Name: 836-30-6|4-Nitro-N-phenylaniline|98%
Brand: Ambeed
SKU: A886768
Price: 13.0 USD
Availability: InStock
Rating: 90 (27 reviews)

1
[ 836-30-6 ]
[ 1821-27-8 ]
[ 612-36-2 ]

Yield	Reaction Conditions	Operation in experiment
	With nitric acid; acetic acid

Reference： [1]Juillard [Bulletin de la Societe Chimique de France, 1905, vol. <3>33, p. 1173]

2
[ 836-30-6 ]
[ 101-54-2 ]

Yield	Reaction Conditions	Operation in experiment
96%	With water; ammonium chloride; zinc In tetrahydrofuran at 20℃;	Ammonium chloride (48 mg, 9 mmol) in water (1 mL) was added to a stirred solution of (4-nitro-phenyl)-phenyl-amine (200 mg, 0.9 mmol) in THF (4 mL). Zinc powder (48 mg, 7.4 mmol) was then added portion wise and the resulting mixture was stirred at room temperature for 2 hours then filtered over celite. The filtrate was extracted with ethyl acetate and the ethyl acetate was washed with brine solution, dried over Na2SO4 and concentrated to 160 mg (96%) of N-phenyl-benzene-1,4-diamine. LCMS: 185.1 (M+1)+, 93.9%, 1H NMR: (DMSO-d6): 67.2 (t, 2H), 7.0 (d, 2H), 6.8 (m, 2H), 6.7 (d, 2H).
	With acetic acid; zinc
	durch elektrolytische Reduktion;

	With nickel Hydrogenation;
	With ethanol; ammonium chloride; zinc
	With hydrazine hydrate Heating;
	With hydrogen
		1 Use of Prepared Catalyst (1) Reduction of p-nitrodiphenylamine to p-aminodiphenylamine catalyzed by the Pd+2 polymer catalyst. STR12
	With hydrogen In ethanol at 20℃; for 5 - 6h;	1.i A mixture of 4-fluoronitrobenzene (0.02 mol), anilines (0.022 mol), and potassium carbonate (0.022 mol) in 40 ml of anhydrous DMF was heated to 1500C with stirring for overnight. After cooling to room temperature, the reaction mixture was poured into 500 ml of ice water and stirred for 30 min. The precipitates formed were collected by filtration, washed with water and dried in vacuo to give the intermediate. This crude intermediate was dissolved in 100-200 ml of ethanol, and l-2g 10%Pd-C was added. The compound was hydrogenated under ambient pressure at room temperature for 5-6 hours. Then the catalyst was removed by filtration, and the filtrate was concentrated to dryness to give a mixture of crude anilines, which was used for the next step with further purification.
	With hydrogen at 50 - 120℃; for 2.5h;	1.3 hydrogenation step The above-mentioned organic phase ( condensation fluid ) and phase quality 5 wt % of the Raney nickel catalyst into 500 ml stainless steel high-pressure reactor, nitrogen are used, hydrogen replacement three times, in order to ensure that air does not exist in the reaction device. Opening stirring and heating, setting the reaction temperature is 50 °C, the pressure of the hydrogen gas in the reactor to 1.5 MPa, when the reaction temperature reaches 60 °C time, start timing reaction. When the hydrogen pressure in the reactor is less than 1.0 MPa, the, in the cauldron makes up adding hydrogen to the reaction required to 1.5 MPa, so repeatedly hydrogen added to the system. The reaction temperature is kept at 80-120 °C reaction 2h, when the observed when the hydrogen pressure is constant, and then to continue reaction 30 min to stop the reaction. Sampling analysis, control azobenzol content is less than 0.05%. Cooling the pressure relief discharge, filtering and recycling Raney nickel catalyst, to continue to apply to all the next batch of material in the hydrogenation step. From the organic phase (also stock solution) to obtain the target product in 4-aminodiphenylamine (4-ADPA), gas phase chromatography (GC) analysis, delete solvent peak, its content is 98.5%, 4-nitro-diphenylamine and 4-nitrosodi diphenylammonium conversion is 100%.

Reference： [1]Current Patent Assignee: DR REDDY'S LABORATORIES LIMITED; ABBVIE INC - US2009/239848, 2009, A1 Location in patent: Page/Page column 28
[2]Nietzki; Witt [Chemische Berichte, 1879, vol. 12, p. 1402]
[3]Rohde [Zeitschrift fur Elektrochemie und angewandte physikalische Chemie, 1900, vol. 7, p. 339]
[4]Grammaticakis [Bulletin de la Societe Chimique de France, 1954, p. 99,101] Kloetzel et al. [Antibiotics and Chemotherapy, 1954, vol. 4, p. 150]
[5]Ullmann; Dahmen [Chemische Berichte, 1908, vol. 41, p. 3746]
[6]Bumin, K. P.; Il'ina, I. G.; Moiseeva, A. A.; Reutov, O. A. [Journal of general chemistry of the USSR, 1992, vol. 62, # 1.2, p. 155 - 159][Zhurnal Obshchei Khimii, 1992, vol. 62, # 1, p. 188 - 193]
[7]Buchwald, Stephen L.; Mauger, Christelle; Mignani, Gerard; Scholz, Ulrich [Advanced Synthesis and Catalysis, 2006, vol. 348, # 1-2, p. 23 - 39]
[8]Current Patent Assignee: GOODYEAR TIRE & RUBBER CO - US4463191, 1984, A
[9]Current Patent Assignee: BAUSCH HEALTH COMPANIES INC - WO2008/157802, 2008, A1 Location in patent: Page/Page column 11-12
[10]Current Patent Assignee: SINOCHEM HOLDINGS CORPORATION LTD - CN105585507, 2016, A Location in patent: Paragraph 0054; 0055

3
[ 73333-79-6 ]
[ 836-30-6 ]

Yield	Reaction Conditions	Operation in experiment
93%	With potassium hydroxide In tetrahydrofuran; methanol; water at 0 - 70℃; for 12h;	p-Nitro-N,N-diphenylamine (4) A portion of p-nitro-N,N-diphenylbenzamide intermediate (172 mg, 0.54 mmol) was dissolved in anhydrous THF (5 mL), treated with 6 M Claisen’s base (KOH in MeOH/H2O, 5 mL) and then stirred at 70 °C for 12 h. The reaction mixture was then cooled to 0 °C, neutralized with 10% HCl solution, then diluted and extracted with EtOAc (3 × 10 mL), washed with brine (15 mL) dried with Na2SO4, and concentrated under reduced pressure. After workup, the crude mixture was passed through a plug of silica gel (neutralized with 1% Et3N) packed on a fritted funnel and eluted with 5% EtOAc in hexanes with 1% Et3N to remove byproducts, followed by 10-70% gradient of EtOAc in hexanes with 1% Et3N, to afford p-nitro-N,N-diphenylamine 4 as a yellow solid ( 107 mg, 93%).
	With sodium hydroxide

Reference： [1]Padungros, Panuwat; Wei, Alexander [Synthetic Communications, 2014, vol. 44, # 16, p. 2336 - 2343]
[2]Lellmann [Chemische Berichte, 1882, vol. 15, p. 830] Hofmann,A.W. [Justus Liebigs Annalen der Chemie, 1864, vol. 132, p. 166]

4
[ 100-00-5 ]
[ 62-53-3 ]
[ 836-30-6 ]

Yield	Reaction Conditions	Operation in experiment
100%	Stage #1: 4-chlorobenzonitrile; aniline With bis-triphenylphosphine-palladium(II) chloride at 20℃; for 0.166667h; Stage #2: With potassium carbonate for 16h; Reflux;
98%	With C₅₀H₇₂ClPPd; 2,6-bis(2,4,6-triisopropylphenyl)phenyldicyclohexylphosphine; potassium carbonate In <i>tert</i>-butyl alcohol at 100℃; for 6h;
97%	With [1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene](3-chloropyridyl) palladium(II) dichloride; caesium carbonate In 1,2-dimethoxyethane at 80℃; for 24h; Inert atmosphere;

97%	With dichloro(3-chloropyridinyl)(1,3-(diisopropylphenyl)-4,5-bis(dimethylamino)imidazol-2-ylidene)palladium(II); caesium carbonate In 1,2-dimethoxyethane at 80℃; for 24h; Schlenk technique; Sealed tube; Inert atmosphere;
96%	With potassium hydroxide; bis(tri-tert-butylphosphine)palladium⁽⁰⁾; cetyltrimethylammonim bromide In water; toluene at 90℃; for 1h;
96%	With [(2,6-bis(2,4,6-triisopropylphenyl)phenyl)dicyclohexylphosphine](allyl-η³)palladium(II) chloride; potassium hydrogencarbonate In <i>tert</i>-butyl alcohol at 100℃; for 12h; Inert atmosphere; Sealed tube;	48-51 Examples 48-68. General procedure: In the pressure tube, under a nitrogen atmosphere, the aryl halide (1.0 mmol), amine (1.2 mmol), Bicarbonate (1.3mmol), 0.5 mmol% [(TPhos)Pd(all)Cl] and 75 uL of dodecane (As an internal standard for GC analysis) dissolved in 2.0 mL solvent. The tube was sealed and placed at 100°C to react for 12 hours. Add dichloromethane and diatomaceous earth to aid filtration, Analyze by gas chromatography, The product was separated by (petroleum ether/ethyl acetate) column chromatography.
95%	With potassium phosphate; monophosphine 1,2,3,4,5-pentaphenyl-1'-(di-tert-butylphosphino)ferrocene; bis(dibenzylideneacetone)-palladium⁽⁰⁾ In 1,2-dimethoxyethane at 100℃; for 20h;
95%	With potassium phosphate In 1,2-dimethoxyethane	70 4-nitro-diphenylamine (Table 9, Entry 6) Example 70 4-nitro-diphenylamine (Table 9, Entry 6) According to the general procedure B, 4-chloronitrobenzene (80 mg, 0.51 mmol) reacted with aniline (57 mg, 0.60 mmol) using 1 mol % of Pd(dba)2, 2 mol % of Ph5FcP(t-Bu)2, and K3PO4 (254 mg, 1.21 mmol) in DME at 100° C. to give the title compound (102 mg, 95%) as a yellow solid: 1H-NMR (400 MHz, CDCl3): δ 8.12 (d, 2H, J=7.2 Hz), 7.40 (t, 2H, J=7.2 and 8.8 Hz), 6.96 (d, 2H, J=7.2 Hz), 7.24-7.18 (m, 3H), 6.48 (bs, 1H). 13C{1H}-NMR (125 MHz, CDCl3): δ 150.26, 139.51, 139.44, 129.64, 126.18, 124.54, 121.83, 113.59. GC/MS(EI): m/z 214 (M+). Anal. Calcd for C12H10N2O2: C, 67.28; H, 4.71; N, 13.08. Found: C, 67.45; H, 4.75; N, 13.02.
88%	With carbonyl(pentamethylcyclopentadienyl)cobalt diiodide; copper diacetate In neat (no solvent) at 100℃; for 4h;
87%	With potassium hydroxide In N,N-dimethyl-formamide at 100℃; for 5h;	2.3 General Procedure for the O-arylationand N-arylation with Aryl Halides General procedure: A mixture of phenol or amine (1.0 mmol), aryliodide (1.5 mmol), KOH (2 mmol) and BNPs (at) SiO2(CH2)3-TAPC-O-CH2CH2NH2-Pd(0) (0.05 g catalyst equal 0.0725 mmol/g pd) in DMF (2 mL) was stirred at 100 °C. The reaction progress was monitored by TLC. After the completion of the reaction, the catalyst was filtered,washed with ethanol and dried. The reaction mixture was extracted with ethyl acetate (3 × 5) and the organic layer was dried over magnesium sulfate (MgSO4). Then pure products were obtained from recrystallization in n-hexane.
87.9%	With C₃₆H₄₅Cl₃N₄Pd; caesium carbonate In 1,2-dimethoxyethane at 80℃; for 24h; Inert atmosphere;	15 Example 15: Buchwald-Hartwig coupling reaction test of 4-nitrochlorobenzene and aniline Add N-(4-indolyl) azacyclic carbene palladium complex (4mol%), 4-nitrochlorobenzene (1mmol), Cs2CO3 (3mmol), aniline into the reaction tube equipped with a magnetic stir bar. (1.5mmol) and DME (1mL). After argon replacement, the reaction mixture was heated at 80°C for 24h. The reaction solution was diluted with ethyl acetate (2 mL), filtered through Celite, and washed with ethyl acetate. The filtrate was washed with water, the aqueous phase (4 mL) was extracted with ethyl acetate, extracted twice, the organic layers were combined, dried over Na2SO4, filtered, concentrated and purified by silica gel column chromatography (PE:EA=5:1) to obtain the corresponding product.
83%	With copper diacetate at 110℃; for 6h;
80%	With caesium carbonate at 170℃; for 12h;	22 1.06 g (6.7 mmol) of p-chloronitrobenzene, 1.4 g (10.1 mmol) of caesium carbonate and 300 mg (0.7 mmol) of the catalyst from example 1 are stirred in 2 ml of aniline under an argon atmosphere at 170° C. for 12 h. The GC analysis of the crude product indicates the selective formation of the monoarylated compound and 83% conversion; triarylamine is not detected. After workup by column chromatography, 1.14 g (80%) of product are obtained. [0160] GC-MS/EI: 214 (M)
76%	With potassium acetate; 1-butyl-3-methylimidazolium Tetrafluoroborate for 90h; microwave irradiation;
75%	at 170℃; for 12h;	27 [0148] 1.06 g (6.7 mmol) of p-chloronitrobenzene, 1.4 g (10.1 mmol) of caesium carbonate and 500 mg (0.7 mmol) of the catalyst from Example 1 are stirred in 2 ml of aniline under an argon atmosphere at 170° C. for 12 h. The GC analysis of the crude product indicates the selective formation of the monoarylated compound and 83% conversion; triarylamine is not detected. After workup by column chromatography, 1.07 g (75%) of product are obtained. [0149] GC-MS/EI: 214 (M)
68%	With potassium hydroxide In dimethyl sulfoxide at 130℃; for 10h;
63%	at 170℃; for 12h;	33 [0155] 1.06 g (6.7 mmol) of p-chloronitrobenzene, 1.4 g (10.1 mmol) of caesium carbonate and 490 mg (0.7 mmol) of the catalyst from Example 2 are stirred in 2 ml of aniline under an argon atmosphere at 170° C. for 12 h. The GC analysis of the crude product indicates the selective formation of the monoarylated compound and 63% conversion; triarylamine is not detected.
61%	With potassium hydroxide In water at 20℃; for 6h; Green chemistry;
55%	With potassium carbonate In dimethyl sulfoxide for 12h; Reflux; Inert atmosphere;	2.3 General procedure for the N-arylation of aryl amines with aryl halides General procedure: In a 25ml round bottom flask a mixture of 4:1 methanol/water, aryl halide (1mmol), Resin-CuNPs (0.2g), K2CO3 (3mmol) and aryl amine (1.2mmol) were taken and heated at reflux temperature for 12-24h in an oil bath under inert conditions. Resin beads were filtered off at the end of reaction while the solution was still hot. After a work up with dichloromethane and water, the organic layer was separated, dried over anhydrous Na2SO4. The crude products obtained after removal of solvent (Scheme 1) were purified by column chromatography (ethyl acetate: hexane) and identified by mass or 1H NMR spectroscopy (see ESI).
49%	With oxalic acid hydrazide; phosphoric acid trihydrate; tetrabutylammomium bromide; 2,5-hexanedione; copper(II) oxide In water at 120℃; for 24h;
46%	With cerium(IV) oxide; potassium hydroxide In dimethyl sulfoxide at 110℃; for 6h; Air atmosphere;	General procedure for the O-alkylation with 4-nitrochlorobenzene: General procedure: In a 25 mL round bottomed flask was taken a mixture of phenol/amine/thiophenol (1.2 mmol, 0.112 g), 4-nitrochlorobenzene (1 mmol, 0.157 g), base KOH (1.2 mmol, 0.08 g) and 1 mL DMSO was added. Further 2.5 mol % catalyst (4.5 mg) was added to the reaction mixture. The reaction mixture was heated to 110 °C for appropriate time. Reaction is monitored on TLC. After completion of the reaction the catalyst was separated by centrifugation and subsequently washed with dichloromethane. The reaction mixture was diluted with water and the product was extracted by dichoromethane (3 × 10 cm3). The organic layer was dried over anhydrous sodium sulfate and was evaporated under reduced pressure to give the product. The product was purified by column chromatography by using pet ether and ethyl acetate solvent system. The purified product was then confirmed by its spectral analysis after analyzing by IR, 1H NMR, and mass spectra.
8%	With dicyclohexylamino[(2,6-dimethyl)morpholin-4-yl]phenylphosphine; potassium <i>tert</i>-butylate; palladium dichloride In toluene for 48h; Reflux;
	With copper(l) iodide; potassium carbonate
	With copper; potassium carbonate In N,N-dimethyl-formamide at 186 - 194℃; for 4h;
99 % Chromat.	With potassium phosphate tribasic; 2,2'-bis-(diphenylphosphino)-1,1'-binaphthyl Heating;
	With caesium carbonate at 170℃; for 12h;	24 1.06 g (6.7 mmol) of p-chloronitrobenzene, 1.4 g (10.1 mmol) of caesium carbonate and 360 mg (0.7 mmol) of the catalyst from example 2 are stirred in 2 ml of aniline under an argon atmosphere at 170° C. for 12 h. The GC analysis of the crude product indicates the selective formation of the monoarylated compound (comparison with GC-MS/EI of 1101-7) and 91% conversion; triarylamine is not detected.
21 %Chromat.	With C₃₁H₃₇ClN₃NiO₂^(1-)*Li⁽¹⁺⁾; lithium hexamethyldisilazane In dimethyl sulfoxide at 110℃; for 3h; Inert atmosphere; Sealed tube;	2.4 General Amination Procedure of Aryl Halides Using Different Amines General procedure: A representative amination method using chlorobenzene,pentylamine, and KOtBuin DMSO is described here. Allother amination reactions including different aryl halides,primary (1°) and secondary (2°) amines, solvents and baseswere performed using a similar method. A 4mL reactionvial containing a magnetic stir bar was charged with 1.4mLof anhydrous DMSO. The reaction vial, after being sealed with a septum and parafilm, was purged with Ar for 10min.Chlorobenzene [0.4mL, 3.9mmol, 2.25 equivalent (eq.)],pentylamine (0.21mL, 1.8mmol, 1.0eq.), anhydrous powderedKOtBu(70mg, 0.63mmol, 0.3eq.), and 2 (2mg,0.2mol%) were added sequentially. The reaction mixturewas stirred for 5min while continually purging with Ar. Thevial was then sealed with a Teflon screw cap. The reactionmixture was stirred for 3h at 110°C in a preheated oil bath,then allowed to cool to room temperature and filtered bypassing through Celite to remove the base and the catalyst.30L of the solution was then dissolved in 1mL absolute ethanol, and 10μL of decane was added as an internalstandard. Turn over number (TON) was determined usingGC-MS.

Reference： [1]Galaffu, Nicola; Man, Siud Pui; Wilkes, Robin D.; Wilson, John R. H. [Organic Process Research and Development, 2007, vol. 11, # 3, p. 406 - 413]
[2]Zhou, Fabin; Zhang, Lixue; Shi, Ji-cheng [Journal of Catalysis, 2021, vol. 402, p. 238 - 243]
[3]Hoi, Ka Hou; Calimsiz, Selcuk; Froese, Robert D. J.; Hopkinson, Alan C.; Organ, Michael G. [Chemistry - A European Journal, 2012, vol. 18, # 1, p. 145 - 151]
[4]Zhang, Yin; César, Vincent; Lavigne, Guy [European Journal of Organic Chemistry, 2015, vol. 2015, # 9, p. 2042 - 2050]
[5]Kuwano, Ryoichi; Utsunomiya, Masaru; Hartwig, John F. [Journal of Organic Chemistry, 2002, vol. 67, # 18, p. 6479 - 6486]
[6]Current Patent Assignee: GUANGDONG UNIVERSITY OF PETROCHEMICAL TECHNOLOGY - CN112574042, 2021, A Location in patent: Paragraph 0024
[7]Kataoka, Noriyasu; Shelby, Quinetta; Stambuli, James P.; Hartwig, John F. [Journal of Organic Chemistry, 2002, vol. 67, # 16, p. 5553 - 5566]
[8]Current Patent Assignee: YALE UNIVERSITY - US6562989, 2003, B2
[9]Srivastava, Avinash K.; Sharma, Charu; Joshi, Raj K. [Green Chemistry, 2020, vol. 22, # 23, p. 8248 - 8253]
[10]Bahrami, Kiumars; Khodamorady, Minoo [Catalysis Letters, 2019, vol. 149, # 3, p. 688 - 698]
[11]Current Patent Assignee: KUNMING UNIVERSITY OF SCIENCE AND TECHNOLOGY - CN112876516, 2021, A Location in patent: Paragraph 0115-0120
[12]Joshi, Raj Kumar; Sharma, Charu; Sharma, Kamal Nayan; Srivastava, Avinash Kumar [Organic and biomolecular chemistry, 2020, vol. 18, # 18, p. 3599 - 3606]
[13]Current Patent Assignee: LANXESS AG - US2004/198997, 2004, A1 Location in patent: Page/Page column 7
[14]Angrish, Chetna; Kumar, Anil; Chauhan [Indian Journal of Chemistry - Section B Organic and Medicinal Chemistry, 2005, vol. 44, # 7, p. 1515 - 1518]
[15]Current Patent Assignee: LANXESS AG - US2004/192664, 2004, A1 Location in patent: Page/Page column 8
[16]Ghorbani-Choghamarani, Arash; Taherinia, Zahra [New Journal of Chemistry, 2017, vol. 41, # 17, p. 9414 - 9423]
[17]Current Patent Assignee: LANXESS AG - US2004/192664, 2004, A1 Location in patent: Page/Page column 9
[18]Hajipour, Abdol R.; Check, Maryam; Khorsandi, Zahra [Applied Organometallic Chemistry, 2017, vol. 31, # 11]
[19]Barot, Nirav; Patel, Sunil B.; Kaur, Harjinder [Journal of Molecular Catalysis A: Chemical, 2016, vol. 423, p. 77 - 84]
[20]Huang, Manna; Lin, Xiaoqin; Zhu, Xinhai; Peng, Weili; Xie, Jianwei; Wan, Yiqian [European Journal of Organic Chemistry, 2011, # 24, p. 4523 - 4527]
[21]Location in patent: experimental part Agawane, Sandeep M.; Nagarkar, Jayashree M. [Tetrahedron Letters, 2011, vol. 52, # 41, p. 5220 - 5223]
[22]Location in patent: experimental part Park, Song-Eun; Kang, Seung Beom; Jung, Kwang-Ju; Won, Ju-Eun; Lee, Sang-Gyeong; Yoon, Yong-Jin [Synthesis, 2009, # 5, p. 815 - 823]
[23]Current Patent Assignee: Goldberg - DE185663, 1800, C
[24]Liu, Xuan-Gan; Hu, Wei-Xiao [Journal of Chemical Research, 2004, # 8, p. 564 - 565]
[25]Buchwald, Stephen L.; Mauger, Christelle; Mignani, Gerard; Scholz, Ulrich [Advanced Synthesis and Catalysis, 2006, vol. 348, # 1-2, p. 23 - 39]
[26]Current Patent Assignee: LANXESS AG - US2004/198997, 2004, A1 Location in patent: Page/Page column 7
[27]Albkuri, Yahya M.; RanguMagar, Ambar B.; Brandt, Andrew; Wayland, Hunter A.; Chhetri, Bijay P.; Parnell, Charlette M.; Szwedo, Peter; Parameswaran-Thankam, Anil; Ghosh, Anindya [Catalysis Letters, 2020, vol. 150, # 6, p. 1669 - 1678]

5
[ 836-30-6 ]
[ 108-10-1 ]
[ 793-24-8 ]

Yield	Reaction Conditions	Operation in experiment
	With platinum on activated charcoal; isopropyl alcohol at 50 - 150℃; Hydrogenation;

Reference： [1]Current Patent Assignee: du Pont de Nemours & Co. - US2734808, 1951, A

6
[ 836-30-6 ]
[ 79-04-9 ]
[ 118989-62-1 ]

Yield	Reaction Conditions	Operation in experiment
91%	With pyridine for 12h; Heating;
80%	In toluene for 20h; Heating;
	In toluene	4.B.a Step a: Step a: N-[4-Nitrophenyl]-N-phenylchloroacetamide Dissolve 4-nitrodiphenylamine (38mmol) in toluene (450mL) and add chloroacetyl chloride (4.5mL, 57mmol). Reflux the mixture overnight under a nitrogen atmosphere. Evaporate the solvent in vacuoand partition between saturated aqueous sodium hydrogen carbonate and ethyl acetate. Separate the organic phase, dry (MgSO4) and evaporate the solvent in vacuoto give the title compound.

	With triethylamine In dichloromethane for 16h;
	With toluene at 80℃; dann auf 115grad;

Reference： [1]Wadia; Patil [Synthetic Communications, 2003, vol. 33, # 15, p. 2725 - 2736]
[2]Hulinska, Hana; Polivka, Zdenek; Jilek, Jiri; Sindelar, Karel; Holubek, Jiri; et al. [Collection of Czechoslovak Chemical Communications, 1988, vol. 53, # 8, p. 1820 - 1844]
[3]Current Patent Assignee: SANOFI - EP585500, 1994, A1
[4]Location in patent: scheme or table North, Michael; Pizzato, Francesca [Letters in Organic Chemistry, 2009, vol. 6, # 7, p. 552 - 556]
[5]Current Patent Assignee: FIRM J R GEIGY; NOVARTIS AG; Novartis (w/o Sandoz) - DE473526, 1929, C [Fortschr. Teerfarbenfabr. Verw. Industriezweige, vol. 16, p. 1038][Fortschr. Teerfarbenfabr. Verw. Industriezweige, vol. 16, p. 1038]

7
[ 62-53-3 ]
[ 350-46-9 ]
[ 836-30-6 ]

Yield	Reaction Conditions	Operation in experiment
100%	In acetonitrile at 100℃; for 50h;
95.8%	With triethylamine In N,N-dimethyl-formamide at 30℃; for 72h;
87%	With toluene-4-sulfonic acid at 165℃; for 0.666667h; Ionic liquid; Microwave irradiation;	4.1 General procedure for the MW-assisted C-N cross coupling General procedure: In a new sealed pressure regulation 10-mL pressurized vial were placed aryl halide (1 mmol), p-toluenesulfonic acid (1 mmol, 0.172 g), [DBU][HOAc] (1.5 mL), N-nucleophile (2 mmol), and a Teflon-coated magnetic stir bar. The vessel was closed with a snap-on cap, stirred at room temperature for 5 min and then placed into the MW cavity. Microwave irradiation of 100 W at a set temperature of 165°C was used and the reaction mixture was held under these conditions for the specified time. After completion of the reaction (monitored through TLC), the mixture was cooled to room temperature and was poured to a vessel containing distilled water. This was extracted with ethyl acetate (310 mL) and the combined organic phase was washed with brine (210 mL), dried over Na2SO4, and was concentrated under rotary vacuum evaporator. The crude product was purified by column chromatography using a mixture of ethyl acetate/n-hexane as eluent.

62%	With potassium fluoride supported on Clinoptilolite In dimethyl sulfoxide at 110 - 115℃; for 2h;
7%	In tetrahydrofuran at 50℃; for 50h;
	With water; magnesium oxide at 200℃;
	With potassium carbonate In N,N-dimethyl-formamide at 150℃;	1.i A mixture of 4-fluoronitrobenzene (0.02 mol), anilines (0.022 mol), and potassium carbonate (0.022 mol) in 40 ml of anhydrous DMF was heated to 1500C with stirring for overnight. After cooling to room temperature, the reaction mixture was poured into 500 ml of ice water and stirred for 30 min. The precipitates formed were collected by filtration, washed with water and dried in vacuo to give the intermediate. This crude intermediate was dissolved in 100-200 ml of ethanol, and l-2g 10%Pd-C was added. The compound was hydrogenated under ambient pressure at room temperature for 5-6 hours. Then the catalyst was removed by filtration, and the filtrate was concentrated to dryness to give a mixture of crude anilines, which was used for the next step with further purification.

Reference： [1]Kotsuki; Kobayashi; Matsumoto; Suenaga; Nishizawa [Synthesis, 1990, # 12, p. 1147 - 1148]
[2]Brown, Christopher L.; Muderawan, I. Wayan; Young, David J. [Synthesis, 2003, # 16, p. 2511 - 2517]
[3]Singh, Rahul; Allam, Bharat Kumar; Raghuvanshi, Dushyant Singh; Singh, Krishna Nand [Tetrahedron, 2013, vol. 69, # 3, p. 1038 - 1042]
[4]Location in patent: experimental part Khalilzadeh, Mohammad A.; Hosseini, Abolfazl; Pilevar, Afsaneh [European Journal of Organic Chemistry, 2011, # 8, p. 1587 - 1592]
[5]Ibata, Toshikazu; Isogami, Yasushi; Toyoda, Jiro [Bulletin of the Chemical Society of Japan, 1991, vol. 64, # 1, p. 42 - 49]
[6]Lantz; Obellianne [Bulletin de la Societe Chimique de France, 1956, p. 311,315]
[7]Current Patent Assignee: BAUSCH HEALTH COMPANIES INC - WO2008/157802, 2008, A1 Location in patent: Page/Page column 11-12

8
[ 836-30-6 ]
[ 67-64-1 ]
[ 101-72-4 ]

Yield	Reaction Conditions	Operation in experiment
	With platinum on activated charcoal; isopropyl alcohol at 50 - 150℃; Hydrogenation;

Reference： [1]Current Patent Assignee: du Pont de Nemours & Co. - US2734808, 1951, A

9
[ 103-71-9 ]
[ 100-01-6 ]
[ 836-30-6 ]
[ 1821-27-8 ]

Yield	Reaction Conditions	Operation in experiment
3%	With potassium carbonate In nitrobenzene at 190℃; for 4h; other isocyanates, nitroanilines;
3%	With potassium carbonate In nitrobenzene at 190℃; for 4h;

Reference： [1]Viswanathan, N.; Sidhaye, A. R. [Indian Journal of Chemistry - Section B Organic and Medicinal Chemistry, 1981, vol. 20, # 7, p. 611 - 613]
[2]Viswanathan, N.; Sidhaye, A. R. [Indian Journal of Chemistry - Section B Organic and Medicinal Chemistry, 1981, vol. 20, # 7, p. 611 - 613]

10
[ 98-95-3 ]
[ 62-53-3 ]
[ 92-82-0 ]
[ 156-10-5 ]
[ 836-30-6 ]
[ 1227476-15-4 ]

Yield	Reaction Conditions	Operation in experiment
1: 86.9% 2: 8.5% 3: 3.7% 4: 0.7%	In water at 70 - 75℃; for 3.5h;	18 Example 18 Influence of different molar ratios of organic and inorganic hydroxides to betaine on the condensation of aniline with nitrobenzene and, simultaneously, influence of betaine and tetramethylammonium hydroxide (TMAH) on aniline methylation to N-methylaniline (N-MAn) is obvious from the results in Table 10. Example 18 Influence of different molar ratios of organic and inorganic hydroxides to betaine on the condensation of aniline with nitrobenzene and, simultaneously, influence of betaine and tetramethylammonium hydroxide (TMAH) on aniline methylation to N-methylaniline (N-MAn) is obvious from the results in Table 10. Seven-fold molar excess of aniline was added to a prepared aqueous solution of individual components of the reaction system, consisting of TMAH, betaine and potassium hydroxide. After azeotropic distilling off the water, 0.95 mol of nitrobenzene were added to the reaction mixture at 70° C. and at a pressure of 7.3 kPa during 1.5 h. The reaction was completed after further 2 h. Yield (Table 10) of the components in the reaction product has been calculated in relation to the introduced nitrobenzene. N-methylaniline (N-MAn) was expressed in mole per cent, related to the introduced TMAH.
1: 65% 2: 13.2% 3: 15.7% 4: 1.3%	at 80℃; for 6h;	12 Example 12 Influence of a Crown Ether as the Phase Transfer Agent on the Conversion and Yield of the Reaction. Example 12 Influence of a Crown Ether as the Phase Transfer Agent on the Conversion and Yield of the Reaction. Experimental Conditions: Mole ratio of aniline: nitrobenzene: betaine-KOH: 18 dibenzocrown-6-ether=7:1:1.1:0.1; the reaction took place in an inert atmosphere at 80° C. and at a pressure of 7.3 kPa during the overall reaction time of 6 h (Table 6).
1: 65.8% 2: 7.1% 3: 17.2% 4: 1.3%	In water; isopropyl alcohol at 80℃; for 6h;	15 Example 15 Influence of Polarity of Auxiliary Solvents, Forming Azeotropic Mixtures with Water, on the Course of the Reaction of Nitrobenzene with Aniline Under Anaerobic Conditions. Example 15 Influence of Polarity of Auxiliary Solvents, Forming Azeotropic Mixtures with Water, on the Course of the Reaction of Nitrobenzene with Aniline Under Anaerobic Conditions. 0.078 mol of nitrobenzene were dosed into a reaction mixture, consisting of 0.09 mol of KOH (84.0% concentration), 0.09 mol of betaine hydrate, 4 ml of water, 0.51 mol of aniline and 15 ml of an auxiliary solvent, at 80° C. during 1.5 h. Completing the reaction required further 4.5 h, while water was continuously removed from the reaction medium as an azeotrope with the auxiliary solvent. In an experiment with 2-propanol, the azeotrope was distilled off through a short column under an atmospheric pressure. In an experiment with pyridine, the azeotrope distilled at a reduced pressure of 13.3 to 9.3 kPa. In an experiment with cyclohexane water was continuously removed as an azeotrope by means of an azeotropic attachment. The results are given in the following Table 7.

1: 62.2% 2: 21.9% 3: 14% 4: 1.9%	In pyridine; water at 80℃; for 6h;	15 Example 15 Influence of Polarity of Auxiliary Solvents, Forming Azeotropic Mixtures with Water, on the Course of the Reaction of Nitrobenzene with Aniline Under Anaerobic Conditions. Example 15 Influence of Polarity of Auxiliary Solvents, Forming Azeotropic Mixtures with Water, on the Course of the Reaction of Nitrobenzene with Aniline Under Anaerobic Conditions. 0.078 mol of nitrobenzene were dosed into a reaction mixture, consisting of 0.09 mol of KOH (84.0% concentration), 0.09 mol of betaine hydrate, 4 ml of water, 0.51 mol of aniline and 15 ml of an auxiliary solvent, at 80° C. during 1.5 h. Completing the reaction required further 4.5 h, while water was continuously removed from the reaction medium as an azeotrope with the auxiliary solvent. In an experiment with 2-propanol, the azeotrope was distilled off through a short column under an atmospheric pressure. In an experiment with pyridine, the azeotrope distilled at a reduced pressure of 13.3 to 9.3 kPa. In an experiment with cyclohexane water was continuously removed as an azeotrope by means of an azeotropic attachment. The results are given in the following Table 7.
1: 56.9% 2: 8.1% 3: 1% 4: 0.13%	In water at 70 - 75℃; for 3.5h;	18 Example 18 Influence of different molar ratios of organic and inorganic hydroxides to betaine on the condensation of aniline with nitrobenzene and, simultaneously, influence of betaine and tetramethylammonium hydroxide (TMAH) on aniline methylation to N-methylaniline (N-MAn) is obvious from the results in Table 10. Example 18 Influence of different molar ratios of organic and inorganic hydroxides to betaine on the condensation of aniline with nitrobenzene and, simultaneously, influence of betaine and tetramethylammonium hydroxide (TMAH) on aniline methylation to N-methylaniline (N-MAn) is obvious from the results in Table 10. Seven-fold molar excess of aniline was added to a prepared aqueous solution of individual components of the reaction system, consisting of TMAH, betaine and potassium hydroxide. After azeotropic distilling off the water, 0.95 mol of nitrobenzene were added to the reaction mixture at 70° C. and at a pressure of 7.3 kPa during 1.5 h. The reaction was completed after further 2 h. Yield (Table 10) of the components in the reaction product has been calculated in relation to the introduced nitrobenzene. N-methylaniline (N-MAn) was expressed in mole per cent, related to the introduced TMAH.
1: 53% 2: 24% 3: 11.4% 4: 1%	In cyclohexane; water at 80℃; for 6h;	15 Example 15 Influence of Polarity of Auxiliary Solvents, Forming Azeotropic Mixtures with Water, on the Course of the Reaction of Nitrobenzene with Aniline Under Anaerobic Conditions. Example 15 Influence of Polarity of Auxiliary Solvents, Forming Azeotropic Mixtures with Water, on the Course of the Reaction of Nitrobenzene with Aniline Under Anaerobic Conditions. 0.078 mol of nitrobenzene were dosed into a reaction mixture, consisting of 0.09 mol of KOH (84.0% concentration), 0.09 mol of betaine hydrate, 4 ml of water, 0.51 mol of aniline and 15 ml of an auxiliary solvent, at 80° C. during 1.5 h. Completing the reaction required further 4.5 h, while water was continuously removed from the reaction medium as an azeotrope with the auxiliary solvent. In an experiment with 2-propanol, the azeotrope was distilled off through a short column under an atmospheric pressure. In an experiment with pyridine, the azeotrope distilled at a reduced pressure of 13.3 to 9.3 kPa. In an experiment with cyclohexane water was continuously removed as an azeotrope by means of an azeotropic attachment. The results are given in the following Table 7.
1: 46% 2: 8.8% 3: 11.5% 4: 0.7%	In water at 50 - 80℃; for 3.5 - 6h;	7,17,18 Example 7 Reaction of Aniline with Nitrobenzene Under the Conditions, where Water (reaction water and water, introduced as a solvent) is Continually Removed from the Reaction Medium, Particularly by Distillation in the Form of an Azeotrope Water-aniline, while Vacuum in the System is Gradually Decreased. Example 7 Reaction of Aniline with Nitrobenzene Under the Conditions, where Water (reaction water and water, introduced as a solvent) is Continually Removed from the Reaction Medium, Particularly by Distillation in the Form of an Azeotrope Water-aniline, while Vacuum in the System is Gradually Decreased. 114.0 g (0.131 mol) of 20% solution of an equimolar amount of betaine and potassium hydroxide were introduced into a 500 ml three-neck flask, and after heating up to 50° C. water was distilled off under vacuum, until crystalline slurry remained in the flask. 72.3 g of aniline (0.776 mol) were added, and 13.5 g (0.1097 mol) of nitrobenzene were dosed to the reaction mixture during 1.5 h at 80° C. in nitrogen atmosphere under intensive stirring. In the course of aniline adding a pressure of 26 kPa was maintained in the flask, while an azeotrope water-aniline distilled. During the final stage of the reaction in which the reaction mixture was stirred for further 4.5 h, the pressure in the apparatus was gradually reduced from the starting 26 kPa down to 4 kPa at the end of the reaction. After cooling down the reaction mixture was analyzed. A 100% conversion of nitrobenzene was achieved with the following yields (in %) of individual reaction components (calculated in relation to the introduced nitrobenzene): 4-NODFA 82.1%; 4-NO2DFA 11.7%; azobenzene 11.6%; phenazine 1.4%. Example 17 Effect of Water Content on the Reaction of Aniline with Nitrobenzene. A reaction mixture, consisting of aniline, nitrobenzene, potassium hydroxide, betaine and water with mutual molar ratios, given in Table 9, was let to react under intensive stirring at 80° C. at an atmospheric pressure under nitrogen during 6 h. After cooling down and diluting with methanol the obtained solution was analyzed, and the results were expressed in nitrobenzene conversion and yields, related to the charged nitrobenzene. Water in the reaction mixture is a sum of the reaction water, dissolving water and water, introduced by raw material, and it is expressed in mol per 1 mol of nitrobenzene. Example 18 Influence of different molar ratios of organic and inorganic hydroxides to betaine on the condensation of aniline with nitrobenzene and, simultaneously, influence of betaine and tetramethylammonium hydroxide (TMAH) on aniline methylation to N-methylaniline (N-MAn) is obvious from the results in Table 10. Seven-fold molar excess of aniline was added to a prepared aqueous solution of individual components of the reaction system, consisting of TMAH, betaine and potassium hydroxide. After azeotropic distilling off the water, 0.95 mol of nitrobenzene were added to the reaction mixture at 70° C. and at a pressure of 7.3 kPa during 1.5 h. The reaction was completed after further 2 h. Yield (Table 10) of the components in the reaction product has been calculated in relation to the introduced nitrobenzene. N-methylaniline (N-MAn) was expressed in mole per cent, related to the introduced TMAH.
1: 39.1% 2: 17.6% 3: 10.8% 4: 9.8%	at 70℃;	2 Example 2 Results of the Reaction of Aniline with Nitrobenzene, when Using Lithium, sodium, Potassium and Cesium Hydroxide in a Reaction System, Containing Betaine-hydroxide. Example 2 Results of the Reaction of Aniline with Nitrobenzene, when Using Lithium, sodium, Potassium and Cesium Hydroxide in a Reaction System, Containing Betaine-hydroxide. The reaction systems were prepared by the reaction of betaine monohydrate with alkali hydroxides. According to the procedure, described in Example 1, 3 identical reactions were performed at a temperature of 70° C. with various cations of alkali metals, given in Table 2.
1: 24.7% 2: 31.1% 3: 31.6% 4: 10.9%	at 70℃;	2 Example 2 Results of the Reaction of Aniline with Nitrobenzene, when Using Lithium, sodium, Potassium and Cesium Hydroxide in a Reaction System, Containing Betaine-hydroxide. Example 2 Results of the Reaction of Aniline with Nitrobenzene, when Using Lithium, sodium, Potassium and Cesium Hydroxide in a Reaction System, Containing Betaine-hydroxide. The reaction systems were prepared by the reaction of betaine monohydrate with alkali hydroxides. According to the procedure, described in Example 1, 3 identical reactions were performed at a temperature of 70° C. with various cations of alkali metals, given in Table 2.
1: 89 % Chromat. 2: 4 % Chromat. 3: 3.5 % Chromat. 4: 3.5 % Chromat.	With tetramethyl ammoniumhydroxide at 50℃;
1: 22.2 - 40.3 %Chromat. 2: 18.7 - 23.1 %Chromat. 3: 7.3 - 44.1 %Chromat. 4: 1.4 - 9.3 %Chromat.	In methanol at 50 - 130℃; for 4.5h;	1 Example 1 Results of the Reaction of Aniline with Nitrobenzene Under Anaerobic Conditions, when the Reaction System is a Solution of Betaine and Potassium Hydroxide in Methanol at Different Temperatures in the Range of 55 to 130° C. Example 1 Results of the Reaction of Aniline with Nitrobenzene Under Anaerobic Conditions, when the Reaction System is a Solution of Betaine and Potassium Hydroxide in Methanol at Different Temperatures in the Range of 55 to 130° C. For the reaction an apparatus was used which consisted of a 100 ml 3-neck flask with a magnetic stirrer, a thermometer, a dropping funnel and an azeotropic attachment, and was joined with a water-jet pump. 3,5 g (84.02%) of potassium hydroxide (0.052 mol) were dissolved in 6 g of methanol. 6.1 g of betaine (0.052 mol) were added and, after heating up to 50° C., 37.0 g of aniline (0.49 mol) were added. Air in the apparatus was replaced by nitrogen and after heating up to the reaction temperature at first methanol was distilled off at a pressure of 5.2 kPa, and then nitrobenzene, 6.4 g (0.052 mol) on the whole, was dosed under intensive stirring during 1.5 h. The reaction mixture was left to react for further 3 hours, then it was cooled down, diluted by methanol, and analyzed by the method of highly effective liquid chromatography. The yield of reaction components was calculated relative to the amount of nitrobenzene, introduced into the reaction. Further reaction conditions and results achieved are given in Table 1.

Reference： [1]Current Patent Assignee: DUSLO, A.S. - US6388136, 2002, B1 Location in patent: Page column 12-13
[2]Current Patent Assignee: DUSLO, A.S. - US6388136, 2002, B1 Location in patent: Page column 10
[3]Current Patent Assignee: DUSLO, A.S. - US6388136, 2002, B1 Location in patent: Page column 11
[4]Current Patent Assignee: DUSLO, A.S. - US6388136, 2002, B1 Location in patent: Page column 11
[5]Current Patent Assignee: DUSLO, A.S. - US6388136, 2002, B1 Location in patent: Page column 12-13
[6]Current Patent Assignee: DUSLO, A.S. - US6388136, 2002, B1 Location in patent: Page column 11
[7]Current Patent Assignee: DUSLO, A.S. - US6388136, 2002, B1 Location in patent: Page column 8,12
[8]Current Patent Assignee: DUSLO, A.S. - US6388136, 2002, B1 Location in patent: Page column 6-7
[9]Current Patent Assignee: DUSLO, A.S. - US6388136, 2002, B1 Location in patent: Page column 6-7
[10]Stern, Michael K.; Hileman, Fredrick D.; Bashkin, James K. [Journal of the American Chemical Society, 1992, vol. 114, # 23, p. 9237 - 9238]
[11]Current Patent Assignee: DUSLO, A.S. - US6388136, 2002, B1 Location in patent: Page column 6

11
[ 603-33-8 ]
[ 100-01-6 ]
[ 836-30-6 ]

Yield	Reaction Conditions	Operation in experiment
94%	With copper diacetate; triethylamine In dichloromethane for 24h; Ambient temperature;
65%	With copper(II) acetate monohydrate; caesium carbonate In tetrahydrofuran at 80℃; for 12h; chemoselective reaction;
6%	In dichloromethane for 24h; Ambient temperature; under argon;

Reference： [1]Chan, Dominic M. T. [Tetrahedron Letters, 1996, vol. 37, # 50, p. 9013 - 9016]
[2]Jadhav; Pardeshi [RSC Advances, 2016, vol. 6, # 18, p. 14531 - 14537]
[3]Barton, Derek H. R.; Finet, Jean-Pierre; Khamsi, Jamal [Tetrahedron Letters, 1987, vol. 28, # 8, p. 887 - 890]

12
[ 28899-97-0 ]
[ 100-01-6 ]
[ 836-30-6 ]

Yield	Reaction Conditions	Operation in experiment
90%	In dichloromethane for 16h; Ambient temperature;

Reference： [1]Barton, Derek H. R.; Finet, Jean-Pierre; Khamsi, Jamal [Tetrahedron Letters, 1986, vol. 27, # 31, p. 3615 - 3618]

13
[ 28719-46-2 ]
[ 100-01-6 ]
[ 836-30-6 ]

Yield	Reaction Conditions	Operation in experiment
98%	In dichloromethane for 0.75h; Ambient temperature;

Reference： [1]Barton, Derek H. R.; Finet, Jean-Pierre; Khamsi, Jamal [Tetrahedron Letters, 1986, vol. 27, # 31, p. 3615 - 3618]

14
[ 100-25-4 ]
[ 62-53-3 ]
[ 836-30-6 ]

Yield	Reaction Conditions	Operation in experiment
85%	Stage #1: aniline With n-butyllithium In tetrahydrofuran; hexane at -78℃; for 0.0166667h; Inert atmosphere; Stage #2: para-dinitrobenzene In tetrahydrofuran; hexane at -120 - -110℃; for 0.166667h; Inert atmosphere; Stage #3: With potassium permanganate; ammonia In tetrahydrofuran; hexane at -110℃; for 0.0833333h; Inert atmosphere;
77.1%	With potassium <i>tert</i>-butylate In ammonia at -70℃; for 0.333333h;

Reference： [1]Khutorianskyi; Sonawane; Pošta; Klepetářová; Beier [Chemical Communications, 2016, vol. 52, # 45, p. 7237 - 7240]
[2]Iwasaki, Genji; Saeki, Seitaro; Hamana, Masatomo [Chemistry Letters, 1986, p. 31 - 34]

15
[ 17763-80-3 ]
[ 62-53-3 ]
[ 836-30-6 ]

Yield	Reaction Conditions	Operation in experiment
35%	In acetonitrile at 100℃; for 20h;

Reference： [1]Kotsuki; Kobayashi; Suenaga; Nishizawa [Synthesis, 1990, # 12, p. 1145 - 1147]

16
[ 836-30-6 ]
[ 67-63-0 ]
[ 101-72-4 ]

Yield	Reaction Conditions	Operation in experiment
95%	at 60℃; for 4h;

Reference： [1]Banerjee, Ankur A.; Mukesh, Doble [Journal of the Chemical Society. Chemical communications, 1988, # 18, p. 1275 - 1276]

17
[ 836-30-6 ]
[ 350-46-9 ]
[ 1100-10-3 ]

Yield	Reaction Conditions	Operation in experiment
92%	Stage #1: 4-ntrophenyl(phenyl)amine With sodium hydride In N,N-dimethyl acetamide at 20℃; for 0.5h; Stage #2: 4-Fluoronitrobenzene In N,N-dimethyl acetamide at 100℃; for 1h;
	With sodium hydride 1.) DMSO, 25 deg C, 2.) DMSO, 25 deg C; Multistep reaction;

Reference： [1]Location in patent: experimental part Lee, Wen-Ya; Kurosawa, Tadanori; Lin, Shiang-Tai; Higashihara, Tomoya; Ueda, Mitsuru; Chen, Wen-Chang [Chemistry of Materials, 2011, vol. 23, # 20, p. 4487 - 4497]
[2]Vlasov, V. M.; Os'kina, I. A. [Russian Journal of Organic Chemistry, 1994, vol. 30, # 10.1, p. 1587 - 1592][Zhurnal Organicheskoi Khimii, 1994, vol. 30, # 10, p. 1507 - 1512]

18
[ 98-95-3 ]
[ 62-53-3 ]
[ 92-82-0 ]
[ 156-10-5 ]
[ 836-30-6 ]
[ 100-61-8 ]
[ 1227476-15-4 ]

Yield	Reaction Conditions	Operation in experiment
1: 87.9% 2: 6.9% 3: 6% 4: 1% 5: 1%	In water at 70 - 75℃; for 3.5h;	18 Example 18 Influence of different molar ratios of organic and inorganic hydroxides to betaine on the condensation of aniline with nitrobenzene and, simultaneously, influence of betaine and tetramethylammonium hydroxide (TMAH) on aniline methylation to N-methylaniline (N-MAn) is obvious from the results in Table 10. Example 18 Influence of different molar ratios of organic and inorganic hydroxides to betaine on the condensation of aniline with nitrobenzene and, simultaneously, influence of betaine and tetramethylammonium hydroxide (TMAH) on aniline methylation to N-methylaniline (N-MAn) is obvious from the results in Table 10. Seven-fold molar excess of aniline was added to a prepared aqueous solution of individual components of the reaction system, consisting of TMAH, betaine and potassium hydroxide. After azeotropic distilling off the water, 0.95 mol of nitrobenzene were added to the reaction mixture at 70° C. and at a pressure of 7.3 kPa during 1.5 h. The reaction was completed after further 2 h. Yield (Table 10) of the components in the reaction product has been calculated in relation to the introduced nitrobenzene. N-methylaniline (N-MAn) was expressed in mole per cent, related to the introduced TMAH.

Reference： [1]Current Patent Assignee: DUSLO, A.S. - US6388136, 2002, B1 Location in patent: Page column 12-13

19
[ 64-10-8 ]
[ 586-78-7 ]
[ 836-30-6 ]
[ 1932-32-7 ]
[ 1821-27-8 ]
[ 102-07-8 ]

Yield	Reaction Conditions	Operation in experiment
64%	With caesium carbonate; 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene In 1,4-dioxane at 100℃; for 1h;

Reference： [1]Artamkina, Galina A.; Sergeev, Alexey G.; Beletskaya, Irina P. [Tetrahedron Letters, 2001, vol. 42, # 26, p. 4381 - 4384]

20
[ 392-56-3 ]
[ 836-30-6 ]
1,4-bis[N,N'-(phenyl-4-nitrophenyl)]tetrafluorophenylenediamine [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
55%	With sodium hydride In N,N-dimethyl-formamide at 20 - 25℃; for 5.83333h;

Reference： [1]Os'kina; Vlasov [Russian Journal of Organic Chemistry, 2001, vol. 37, # 2, p. 260 - 269]

21
[ 836-30-6 ]
[ 75-03-6 ]
[ 51451-83-3 ]

Yield	Reaction Conditions	Operation in experiment
94%	With tetra-n-propylammonium hydrogensulfate In benzene at 20℃; for 17h;

Reference： [1]Fotsch; Sonnenberg; Chen; Hale; Karbon; Norman [Journal of Medicinal Chemistry, 2001, vol. 44, # 14, p. 2344 - 2356]

23
[ 108-86-1 ]
[ 100-01-6 ]
[ 836-30-6 ]
[ 4316-57-8 ]

Yield	Reaction Conditions	Operation in experiment
1: 35% 2: 11%	With potassium <i>tert</i>-butylate In toluene at 135℃; for 10.5h; high pressure;

Reference： [1]Patil, Nandkumar M.; Kelkar, Ashutosh A.; Nabi, Zahid; Chaudhari, Raghunath V. [Chemical Communications, 2003, # 19, p. 2460 - 2461]

24
[ 100-01-6 ]
[ 108-90-7 ]
[ 836-30-6 ]
[ 4316-57-8 ]

Yield	Reaction Conditions	Operation in experiment
1: 31% 2: 9%	With potassium <i>tert</i>-butylate In toluene at 135℃; for 10.5h; high pressure;

Reference： [1]Patil, Nandkumar M.; Kelkar, Ashutosh A.; Nabi, Zahid; Chaudhari, Raghunath V. [Chemical Communications, 2003, # 19, p. 2460 - 2461]

25
[ 100-00-5 ]
[ 62-53-3 ]
[ 836-30-6 ]
[ 1100-10-3 ]

Yield	Reaction Conditions	Operation in experiment
1: 89% 2: 1%	With potassium carbonate at 190℃; for 4h;
86%	With potassium carbonate In xylene at 189 - 200℃; for 4.5 - 7h;	5; 7 Beispiel 5; 4-NDPA-Kondensation mit in situ erzeugtem Cu-Phosphin-Katalysator mit Cu(I)-Bromid als Vorstufe In einem 1000 ml Vierhalskolben mit mechanischem Rührer, aufgesetzter Vigreux-Kolonne und Wasserabscheider (mit 35ml Xylol gefüllt) wurden 288,9 g (3090 mmol) Anilin, 8,16 g (27 mmol) 2-(Di-t-butylphosphino)biphenyl, 3,87 g (27 mmol) Cu(I)bromid, 83,6 g (605 mmol) gemahlenes Kaliumcarbonat und 157,6 g (1000 mmol) p-NCB unter Rühren und N2-Atmosphäre in das Reaktionsgefäß gegeben und auf Rückflusstemperatur erhitzt. Die anfangs geringe Wasserentwicklung steigerte sich im Verlauf der Reaktion und blieb dann auf niedrigem Niveau konstant. (insg. ca. 9 ml). Die Temperatur des Gemisches stieg von anfangs 189°C auf 200°C. Alle 30 Min. wurden Proben gezogen (unfiltriert) und der Umsatz und das 4-NDPA/Triarylamin-Verhältnis mit HPLC bestimmt. Nach 4,5 h wurde der Versuch beendet. Dabei ergab sich ein Rest-pNCB-Wert von 0,66 Gew.-% (entspricht 99 % Umsatz an pNCB), ein 4-NDPA-Gehalt von 41,2 Gew.-%, der 4,4'-Dinitrotriphenylamin-Gehalt betrug 0,78 % und das 4-NDPA-/Triarylamin-Verhältnis von 52:1 (entspricht 97 % d.Th an 4-NDPA und eine 98 %ige Selektivität, bezogen auf p-NCB). Beispiel 7; 4-NDPA-Kondensation mit in situ erzeugtem Cu-Phosphin-Katalysator (reduzierte Menge) mit Cu(I)-Bromid als Vorstufe In einem 1000 ml Vierhalskolben mit mechanischem Rührer, aufgesetzter Vigreux-Kolonne und Wasserabscheider (mit 35 ml Xylol gefüllt) wurden 288,9 g (3090 mmol) Anilin, 2,42 g (8,1 mmol) 2-(Di-t-butylphosphino)biphenyl, 1,16 g (8,1 mmol) Cu(I)bromid, 83,6 g (605 mmol) gemahlenes Kaliumcarbonat und 157,6 g (1000 mmol) p-NCB unter Rühren und N2-Atmosphäre in das Reaktionsgefäß gegeben und auf Rückflusstemperatur erhitzt. Die anfangs geringe Wasserentwicklung steigerte sich im Verlauf der Reaktion und blieb dann auf niedrigem Niveau konstant. (insg. ca. 7 ml). Die Temperatur des Gemisches stieg von anfangs 189°C auf 198°C. Alle 30 Min. wurden Proben gezogen (unfiltriert) und der Umsatz und das 4-NDPA/Triarylamin-Verhältnis mit HPLC bestimmt. Nach 7h wurde der Versuch beendet. Dabei ergab sich ein Rest-pNCB-Wert von 4,2 Gew.-% (entspricht 89 % Umsatz), ein 4-NDPA-Gehalt von 37,2 Gew.-%, 4,4'-Dinitrotriphenylamin-Gehalt von 1,9 % und 4-NDPA-/Triarylamin-Verhältnis von 33 (entspricht 86 % 4-NDPA-Ausbeute und 97 % Selektivität bezogen auf p-NCB).
86.4%	Stage #1: 4-chlorobenzonitrile; aniline With potassium carbonate In xylene for 0.5h; Heating / reflux; Stage #2: In xylene at 120 - 196℃; for 6h;	8 Beispiel 8; 4-NDPA-Kondensation mit in situ Präparation von Cu-Phosphin-Katalysator mit Cu(I)-Triflat-Benzol-Komplex als Vorstufe In einem 1000 ml Vierhalskolben mit mechanischem Rührer, aufgesetzter Vigreux-Kolonne und Wasserabscheider (mit 35 ml Xylol gefüllt) wurden 288,9 g (3090 mmol) Anilin, 2,14 g (27 mmol) Kupfer-(II)-oxid, 83,6 g (605 mmol) gemahlenes Kaliumcarbonat und 157,6 g (1000 mmol) p-NCB vorgelegt und dann bei einem Stickstoffstrom von ca. 150 L/h bis zum Rückfluss erhitzt. Es schied sich nach kurzer Zeit ca. 0,4 ml Wasser ab. Nach ca. 0,5 h wurde auf etwa 120°C abgekühlt, 4,53 g (8,1 mmol) Cu(I)trifluormethansulfonat Benzol-Komplex und 2,42 g (8,1 mmol) 2-(Di-tert.-butylphosphino)biphenyl-Ligand zugesetzt. Anschließend wurde unter leichtem N2-Strom wieder auf Rückflusstemperatur erhitzt. Daraufhin kam es zunächst zu einer untypisch geringen Wasserentwicklung, die dann aber immer schwächer wurde und spätestens nach 2 h völlig zum Erliegen kam (ca. 0,5 ml). Die Temperatur des Reaktionsgemisches stieg von anfangs 188°C auf 196°C an. Nach 6 h wurde eine Probe gezogen und die Zusammensetzung des Reaktionsgemisches mit HPLC bestimmt. Anschließend wurde der Versuch beendet. Dabei ergab sich ein Rest p-NCB-Wert von 4,0 Gew.-% (entspricht 89 % Umsatz), ein 4-NDPA-Gehalt von 39,6 Gew.-%, 4,4'-Dinitrotriphenylamin-Gehalt von 1,2 % und ein 4-NDPA-/Triarylamin-Verhältnis von 33 (entspricht 86,4 % 4-NDPA-Ausbeute und 86 % Selektivität bezogen auf p-NCB).

82.4%	Stage #1: aniline In xylene at 20℃; for 0.166667h; Stage #2: 4-chlorobenzonitrile With potassium carbonate In xylene at 189 - 196℃; for 5h;	6 Beispiel 6; 4-NDPA-Kondensation mit präformiertem Cu2Br2(2-(Di-t-butylphosphino)-biphenyl)2-Katalysator (reduzierte Menge) In einem 1000 ml Vierhalskolben mit mechanischem Rührer, aufgesetzter Vigreux-Kolonne und Wasserabscheider (mit 35 ml Xylol gefüllt) wurden 3,22 g (3,64 mmol) Cu2Br2(2-(Di- t-butylphosphino)biphenyl)2 unter 50l/h N2-Strom bei Raumtemperatur für 10 min in 372 g (3,99 mol) Anilin gerührt. Anschließend 157,6 g (1,00 mol) para-Nitrochlorbenzol (Abkürzung p-NCB) und 96,6 g (700 mmol) gemahlenes Kaliumcarbonat zugegeben und unter Rückfluss aufgeheizt. Bei Beginn des Rückflusses setzt eine konstante Wasserabscheidung ein. Die Temperatur des Gemisches stieg von anfangs 189°C auf 196°C. Nach 5h wurde die Zusammensetzung des Reaktionsgemisches durch Probennahme (unfiltriert) mit HPLC bestimmt und das 4-NDPA/Triarylamin-Verhältnis mit HPLC bestimmt und der Reaktionsansatz abgekühlt. Dabei ergab sich ein Rest-pNCB-Wert von 6,2 Gew.-% (entspricht 84 % Umsatz), ein 4-NDPA-/Triarylamin-Verhältnis von 59 (entspricht 82,4 % 4-NDPA-Ausbeute und 98 % Selektivität bezogen auf p-NCB).
81%	With potassium carbonate In xylene at 192 - 199℃; for 6.5h; Heating / reflux;	5 Beispiel 5; Cu-Carben-katalysierte Herstellung von 4-Nitrodiphenylamin In einem Mehrhalsrundkolben mit KPG-Rührer mit Teflonblatt, Vigreux-Kolonne, 55 ml-Wasserabscheider mit Xylol befüllt, sowie Stickstoffüberlagerung, Septum, Heizpilz und Isolierung wurden 288,9 g (3090 mmol) Anilin, 83,6 g (605 mmol) Pottasche (Vorbereitung: 60 sek. auf Stufe 1 und 3 x 60 sek. auf Stufe 2 des Labormixers gemahlen, wobei nach jeweils 60 sek. das Mahlgut durch Schütteln aufgelockert wurde), sowie 157,6 g (1000 mmol) 4-Chlornitrobenzol und 9,42 g (16,2 mmol) {1,3-Bis-[N-(N'-methyl)imidazoliden-methyl]-5-methylbenzol}kupfer[II]-bromid unter Rühren vorgelegt. Es entstand eine rot-braune Suspension, die bis auf Rückflusstemperatur erhitzt wurde (Rührer ca. 400 U/min, ganz leichter N2-Strom). Daraufhin kam es zunächst nur zu einer geringen Wasserentwicklung, die sich im Laufe der Reaktion aber steigerte und dann auf niedrigem Niveau konstant blieb (insg. ca. 6,9 ml). Die Probenahme (unfiltriert) erfolgte alle 30 Minuten, die Proben wurden mittels HPLC (6-Punkt Kalibrierung) analysiert. Nach 390 Minuten wurde der Versuch beendet. Die Siedetemperatur des Gemisches lag während der gesamten Versuchsdauer bei etwa 192-199 °C. Dabei ergab sich ein Rest p-NCB-Wert von 6,0 Gew.-% (entspricht 84 % Umsatz), ein 4-NDPA-Gehalt von 32,3 Gew.-%, 4,4'-Dinitrotriphenylamin-Gehalt von 1,2 % und ein 4-NDPA-/Triarylamin-Verhältnis von 27 (entspricht 81 % 4-NDPA-Ausbeute und 96 % Selektivität bezogen auf p-NCB).
79%	Stage #1: 4-chlorobenzonitrile; aniline With potassium carbonate In water; xylene Heating / reflux; Stage #2: In xylene at 80 - 198℃; for 6h;	6 Beispiel 6; Cu-Carben-katalysierte Herstellung von 4-Nitrodipheriylamin in Gegenwart von Cäsium In einem Mehrhalsrundkolben mit KPG-Rührer mit Teflonblatt, Vigreux-Kolonne, 55 ml-Wasserabscheider mit Xylol befüllt, sowie Stickstoffüberlagerung, Septum, Heizpilz und Isolierung wurden 288,9 g (3090 mmol) Anilin, 83.6 g (605 mmol) Pottasche (Vorbereitung: 60 sek. auf Stufe 1 und 3 x 60 sek. auf Stufe 2 des Labormixers gemahlen, wobei nach jeweils 60 sek. das Mahlgut durch Schütteln aufgelockert wurde), sowie 157,6 g (1000 mmol) 4-Chlornitrobenzol und 0,50g (3,78 mmol) Cs als wässrige Lösung wurden unter Rühren vorgelegt. Es entstand eine rot-braune Suspension die bis auf Rückflusstemperatur erhitzt wurde (Rührer ca. 400 U/min, ganz leichter N2-Strom). Nachdem das Wasser ausgekreist war, kühlte man auf ca. 80°C herunter und gab 4,71 g (8,1 mmol) {1,3-Bis-[N-(N'-methyl)-imidazoliden-methyl]-5-methylbenzol}kupfer[II]-bromid hinzu. Nachdem man wieder bis zum Rückfluss aufgeheizt hatte, kam es zunächst nur zu einer geringen Wasserentwicklung, die sich im Laufe der Reaktion aber steigerte und dann auf niedrigem Niveau konstant blieb (insg. ca. 7,2 ml). Die Probeentnahme (unfiltriert) erfolgte alle 30 Minuten, die Proben wurden mittels HPLC (6-Punkt Kalibrierung) analysiert. Nach 360 Minuten wurde der Versuch beendet. Die Siedetemperatur des Gemisches lag während der gesamten Versuchsdauer bei etwa 190-198°C. Dabei ergab sich ein Rest p-NCB-Wert von 6,2 Gew.-% (entspricht 84 % Umsatz), ein 4-NDPA-Gehalt von 33,9 Gew.-%, 4,4'-Dinitrotriphenylamin-Gehalt von 1,92 % und ein 4-NDPA-/Triarylamin-Verhältnis von 17,7 (entspricht 79 % 4-NDPA-Ausbeute und 95 % Selektivität bezogen auf p-NCB).
67%	With potassium carbonate at 200℃; for 4h;	9 Beispiel 9; 4-NDPA-Kondensation Cu-Phosphin-/Phosphit- und Phosphonit-Katalysator im 10 mmol Maßstab Für das Standardsystem werden in den 10ml - Reaktionsgefäßen 1,58 g p-NCB (10 mmol), 0,95 g Pottasche (6,9 mmol), 21,5 mg Cu(II)O (0,25 mmol), 15,5 mg CsHCO3 (0,08 mmol) sowie Anilin 3,75 g (40 mmol) eingewogen. Beim Katalysatorscreening bleiben p-NCB, Pottasche und Anilin unverändert, es werden aber 0,25 mmol der verschiedenen Testkatalysatoren eingesetzt. Auf die Reaktionsgefäße werden mit Molsieb gefüllte Kühlrohre gesetzt. Die Reaktionen werden in einem Rühr-Heiz-Block bei 200°C Blocktemperatur und 530U/min durchgeführt. Nach 4 Stunden wurden die Reaktionen beendet. Nach Abkühlung um etwa 40°C wurde jeweils eine Probe gezogen und mittels HPLC analysiert.
60%	With potassium carbonate In xylene at 203℃; for 5 - 5.5h;	1; 2 Vergleichsbeispiel 1 (analog DE 3 246 151 A1); 4-NDPA-Kondensation mit Cu(II)O-/Cs-Katalysator In einem 1000 ml Vierhalskolben mit mechanischem Rührer, aufgesetzter Vigreux-Kolonne und Wasserabscheider (gefüllt mit 35 ml Xylol) wurden 288,9 g (3090 mmol) Anilin, 2,44 g (12,6 mmol) Cäsiumhydrogencarbonat, 2,14 g (27 mmol) Kupfer-(II)-oxid, 83,6g (605 mmol) gemahlenes Kaliumcarbonat und 157,6 g (1000 mmol) p-NCB zugegeben und die Reaktionsmischung unter Rückfluss erhitzt. Dabei wurde nur ein leichter N2-Strom zur Aufrechterhaltung der Inertgasatmosphäre eingestellt. Ab ca. 189°C setzte die Wasserabscheidung ein, die im Fortlauf der Reaktion andauerte. Die Reaktionstemperatur stieg bis zum Ende der Reaktion nach 5,5 h auf ca. 203°C an . Die Zusammensetzung des Reaktionsgemisches wurde durch HPLC bestimmt. Dabei ergab sich ein Rest p-NCB-Wert von 0,1 Gew.-% (p-NCB-Umsatz > 99%), ein 4-NDPA-Gehalt von 44,8 Gew.-% und 4,4'-Dinitrotriphenylamin-Gehalt von 2,1 % und ein 4-NDPA-/Triarylamin-Verhältnis von 21 (entspricht 87,5 % d. Th. Ausbeute an 4-NDPA und 88 % Selektivität bezogen auf p-NCB).Vergleichsbeispiel 2 (analog DE 3 246 151 A1)4-NDPA-Kondensation mit reduzierter Menge an Cu(II)O-/Cs-Katalysator In einem 1000 ml Vierhalskolben mit mechanischem Rührer, aufgesetzter Vigreux-Kolonne und Wasserabscheider (gefüllt mit 35 ml Xylol) wurden 288,9 g (3090 mmol) Anilin, 733 mg (3,78 mmol) Cäsiumhydrogencarbonat 642 mg (8,1 mmol) Kupfer-(II)-oxid, 83,6g (605 mmol) gemahlenes Kaliumcarbonat und 157,6 g (1000 mmol) 4-Nitrochlorbenzol zugegeben und die Reaktionsmischung unter Rückfluss erhitzt. Dabei wurde nur ein leichter N2-Strom zur Aufrechterhaltung der Inertgasatmosphäre eingestellt. Ab ca. 189°C setzte die Wasserabscheidung ein, die im Fortlauf der Reaktion andauerte. Die Reaktionstemperatur stieg bis zum Ende der Reaktion nach 5 h auf ca. 201°C an. Die Zusammensetzung des Reaktionsgemisches wurde durch HPLC bestimmt. Dabei ergab sich ein Rest p-NCB-Wert von 12,5 Gew.-% (entspricht 63 % Umsatz an p-NCB), ein 4-NDPA-Gehalt von 22,6 Gew.-% und 4,4'-Dinitrotriphenylamin-Gehalt von 1,1 Gew.-% und ein 4-NDPA-/Triarylamin-Verhältnis von 21 (entspricht 60 % d. Th. Ausbeute an 4-NDPA und 95 % Selektivität bezogen auf p-NCB).
1: 41% 2: 10%	With potassium <i>tert</i>-butylate In toluene at 135℃; for 10.5h; high pressure;

Reference： [1]Haider, Joachim; Kunz, Klaus; Scholz, Ulrich [Advanced Synthesis and Catalysis, 2004, vol. 346, # 7, p. 717 - 722]
[2]Current Patent Assignee: LANXESS AG - EP1437340, 2004, A1 Location in patent: Page 7
[3]Current Patent Assignee: LANXESS AG - EP1437340, 2004, A1 Location in patent: Page 8
[4]Current Patent Assignee: LANXESS AG - EP1437340, 2004, A1 Location in patent: Page 7
[5]Current Patent Assignee: LANXESS AG - EP1437341, 2004, A1 Location in patent: Page 8; 9
[6]Current Patent Assignee: LANXESS AG - EP1437341, 2004, A1 Location in patent: Page 9
[7]Current Patent Assignee: LANXESS AG - EP1437340, 2004, A1 Location in patent: Page 8
[8]Current Patent Assignee: LANXESS AG - EP1437340, 2004, A1 Location in patent: Page 8; 9
[9]Patil, Nandkumar M.; Kelkar, Ashutosh A.; Nabi, Zahid; Chaudhari, Raghunath V. [Chemical Communications, 2003, # 19, p. 2460 - 2461]

26
[ 100-25-4 ]
[ 100-59-4 ]
[ 836-30-6 ]

Yield	Reaction Conditions	Operation in experiment
63%	Stage #1: para-dinitrobenzene; phenylmagnesium chloride In tetrahydrofuran at -20℃; for 2h; Stage #2: With sodium tetrahydroborate; iron(II) chloride In tetrahydrofuran at -20 - 20℃; for 2h;

Reference： [1]Sapountzis, Ioannis; Knochel, Paul [Synlett, 2004, # 6, p. 955 - 958]

27
[ 143-66-8 ]
[ 100-01-6 ]
[ 836-30-6 ]

Yield	Reaction Conditions	Operation in experiment
64%	With aluminum oxide; potassium fluoride; copper diacetate for 0.166667h; microwave irradiation;
43%	With copper(II) acetate monohydrate; triethylamine In acetonitrile at 20℃; for 24h;	N-Arylation of Amines 3; General Procedure General procedure: A 10 mL vial was charged with the substrate amine 1 (0.2 mmol), NaBPh4 or NaBAr4 (0.1 mmol), and Cu(OAc)2·H2O (0.2 equiv) in MeCN (2 mL). To this mixture was added Et3N (2.0 equiv). The reaction mixture was then stirred at r.t. for 24 h. After completion of the reaction as monitored by TLC, the mixture was then concentrated through a rotary evaporator to yield the product, which was purified by direct flash column chromatography (Tables 2 and 3).

Reference： [1]Das, Pralay; Basu, Basudeb [Synthetic Communications, 2004, vol. 34, # 12, p. 2177 - 2184]
[2]Yang, Qin; Lei, Xiaoli; Yin, Zhijian; Deng, Zhihong; Peng, Yiyuan [Synthesis, 2019, vol. 51, # 2, p. 538 - 544]

28
[ 100-01-6 ]
[ 98-80-6 ]
[ 836-30-6 ]

Yield	Reaction Conditions	Operation in experiment
98%	With potassium fluoride In dimethyl sulfoxide at 130℃; for 2h; Inert atmosphere;	General procedure for N-arylation reactions General procedure: The mixture of phenylboronic acid (1 mmol), aromatic amine (1.2 mmol) and 0.12 g (2 mmol) of KF in DMSO (4 mL) were added to Cu-IS-AMBA-MNPs (0.06 g, 0.025 mmol) at 130 °C under nitrogen atmosphere for 2 h with vigorous stirring. Then, after completion of the reaction, the catalyst was separated by an external magnet and washed with dry CH2Cl2 three times and checked for its reusability. The solvent of the reaction mixture was evaporated by a rotary evaporator and then ethyl acetate and water were added to the residue. The organic layer was dried over anhydrous MgSO4. The solvent was evaporated under reduced pressure and the crude product was purified by column chromatography using ethyl acetate/n-hexane.
94%	With copper diacetate; potassium carbonate; benzoic acid In ethyl acetate at 20 - 80℃;
86%	With potassium acetate In N,N-dimethyl-formamide at 20℃; for 15h;

85%	With potassium carbonate In methanol at 20℃; for 12h; Irradiation; Green chemistry;
84%	With copper(II)(1,1′-di(2-picolyl)-3,3′-methylenedibenzimidazolium) dihexafluorophosphate In methanol at 20℃;
82%	With triethylamine In N,N-dimethyl-formamide at 60℃; for 2h;	General procedure for Chan-Lam coupling General procedure: In a 50 cm3 round-bottom flask, phenylboronic acid(1.2 mmol), primary amine (1.0 mmol), triethyl amine(2.0 mmol), and 80 mg (0.018 mol% of Cu) Cu-ACP-Am-Fe3O4SiO2 were mixed in 5 cm3 DMF and the reactionwas allowed to stir at 60 °C temperature for 2 h in aerobiccondition. Reactions was monitored by thin-layer chromatography(TLC) using aluminum-backed silica gel 60 (F254)plates. After completion of the reaction, the catalyst wasseparated magnetically using bar magnet. Finally, the resultingsolution was extracted with ethyl acetate and dried overanhydrous Na2SO4.The solvent was removed under reducedpressure and the product was purified by silica gel columnchromatography.
81%	With Cu<SUB>2</SUB>(1,4-benzenedicarboxylate)<SUB>2</SUB>(4,4'-bipyridine); potassium carbonate In methanol; water at 20℃; for 1h;
75%	With copper diacetate; tetrasodium meso-tetra(p-sulfonatophenyl)porphyrin In water at 50℃; for 8h; chemoselective reaction;
69%	With aluminum oxide; potassium fluoride; copper diacetate for 0.166667h; microwave irradiation;
67%	With [Ni(bis(2-acetylthiophene)oxaloyldihydrazone(-2H))(H₂O)₂]_2*2H₂O; 1,8-diazabicyclo[5.4.0]undec-7-ene In acetonitrile at 40℃; for 15h;	2.6. General procedure for C N cross-coupling General procedure: A 10 ml borosilicate vial containing arylboronic acid I (1 mmol),N-nucleophile II (2 mmol), complex (15 mol%), DBU (2 mmol) andacetonitrile (1 ml) was stirred at 40C. The progress of the reactionwas monitored by TLC using ethyl acetate and n-hexane as elu-ent. After completion of reaction, the reaction mixture was filteredto remove the heterogeneous metal catalyst and the filtrate wastreated with ethyl acetate (5 ml) and water (5 ml). The separatedorganic layer was washed twice with water (2 × 5 ml), dried overanhydrous sodium sulfate and concentrated to yield a residue. Theresidue was purified by silica gel column chromatography usinghexane/ethyl acetate to yield clean product III.
66%	With potassium phosphate; 4,4'-dimethyl-2,2'-bipyridines; [Ni(DHASICy)CpCl] In N,N-dimethyl-formamide; toluene at 70℃; for 10h;	3. Typical procedure for the [Ni(DHASICy)CpCl] catalyzed Chan-Lam coupling. General procedure: A flask was charged with [Ni(DHASICy)CpCl] (4.3 mg, 7.5 μmol), 4,4’-dimethyl-2,2’-bipyridyl (1.4 mg, 7.5 μmol), K3PO4 (159.2 mg, 0.75 mmol), phenylboronic acid (91.4 mg, 0.75 mmol), and a stir bar at r.t. (if an amine was solid, it was added to the flask at this point). Solvent (DMF:75 μL, toluene: 0.925 mL (1.425 mL in the case of solid amine)) was added to the resultant vessel at r.t. and stirred well. Amine (0.375 mmol) in toluene (0.3 mL) was added using a syringe, and an additional 0.2 mL of toluene was used to rinse the flask which had been charged with amine (skipped this process in the case of solid amine). The resultant flask was capped with a reflux condenser and the reaction solution was then heated at 70 for 8 h. The reaction was quenched with H2O (5 mL) at r.t., and the resultant mixture was extracted with EtOAc (10 mL ×3). The combined organic layers were washed with brine (10 mL), dried over Na2SO4, filtered, and concentrated under reduced pressure. The crude residue was purified by flash column chromatography on silica gel (30 mL) to afford the cross-coupling product.
65%	With [2,2]bipyridinyl; nickel(II) chloride hexahydrate; 1,8-diazabicyclo[5.4.0]undec-7-ene In acetonitrile at 60℃; for 28h;
45 %Chromat.	With C₂₁H₂₅CuN₃O₆S In dichloromethane at 20℃;
61 %Chromat.	With 1,8-diazabicyclo[5.4.0]undec-7-ene In acetonitrile at 60℃;
84 %Chromat.	With potassium carbonate In ethanol; water at 70℃; for 3h;
95 %Chromat.	With C₃₂H₃₂Cl₂Cu₂N₄O₄; triethylamine In ethanol for 5h;	2.5.1. General procedure for C-N coupling reactions General procedure: In a typical run, an oven-dried 10 ml round bottom flask was charged with a known mole percent of catalyst and base, phenylboronic acid (1.2 mmol) and aniline (1.0 mmol) with ethanol (5 ml). The mixture was stirred at ambient temp (25 °C). After the specified time (5 h)stirring was stopped, water (20 ml) was added, and extraction with ether (2×10 ml) was done. The combined ether extract was washed with water (3×10 ml), dried over anhydrous Na2SO4, and filtered. Solvent was removed under vacuum. The residue was dissolved in hexane and analyzed by GC-MS.
8 %Spectr.	With C₃₀H₂₅N₄O^(1-)3C₂H₃O₂^(1-)2Cu⁽²⁺⁾ In methanol at 20℃; for 24h;

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[15]Jamwal, Babita; Kaur, Manpreet; Sharma, Harsha; Khajuria, Chhavi; Paul, Satya; Clark [New Journal of Chemistry, 2019, vol. 43, # 12, p. 4919 - 4928]
[16]Mukherjee, Aparajita; Basu, Semanti; Bhattacharya, Samaresh [Inorganica Chimica Acta, 2020, vol. 500]
[17]Akatyev, Nikolay; Il'in, Mikhail; Il'in, Mikhail; Peregudova, Svetlana; Peregudov, Alexander; Buyanovskaya, Anastasiya; Kudryavtsev, Kirill; Dubovik, Alexander; Grinberg, Valerij; Orlov, Victor; Pavlov, Alexander; Novikov, Valentin; Volkov, Ilya; Belokon, Yuri [ChemCatChem, 2020, vol. 12, # 11, p. 3010 - 3021]

29
[ 108-86-1 ]
[ 100-01-6 ]
[ 836-30-6 ]

Yield	Reaction Conditions	Operation in experiment
86%	With potassium phosphate In N,N-dimethyl-formamide at 110℃; for 30h;
84%	With C₁₉H₂₀Br₂N₂O₂Ti; potassium carbonate In N,N-dimethyl-formamide at 22 - 34℃; for 4h; Irradiation;	2.4 Typical procedure for C-N cross coupling reaction General procedure: The procedure for the C-N cross coupling reaction was the same for the different heterogeneous photocatalysts. In a typical procedure, to a stirred mixture of bromobenzene (1mmol, 0.093g), aniline derivatives (1mmol) and K2CO3 (1mmol, 0.138g) in DMF (4mL), M1L8 (10) (0.4mol%, 0.0016g) was added. The reaction mixture was located under sunlight irradiation at ambient temperature (a sunny day, in July, in Mashhad between 10 am to 5pm at the temperature ranges of 22-34 °C). The reaction was monitored by TLC. The reaction mixture colour changed from yellow to brown. After completion of the reaction, the catalyst was separated and the desired product was extracted by ethyl acetate (4mL). The obtained crude product was purified by thin layer chromatography using n-hexane/ethyl acetate (50:1).
82%	With iron(III) chloride; caesium carbonate; copper(II) oxide; 1,1'-bi-2-naphthol In N,N-dimethyl-formamide at 110℃; for 24h; Inert atmosphere;

76%	With 4,7-(dipyrrolidin-1-yl)-1,10-phenanthroline; potassium hydroxide; copper(I) bromide In water at 100℃; for 21h; Sealed tube; Inert atmosphere; Green chemistry;
71%	With potassium phosphate; copper(l) iodide; diphenyl pyrrolidine-2-phosphonate hydrochloride In water; N,N-dimethyl-formamide at 110℃; for 30h;
70%	With CuMoO₄; caesium carbonate In dimethyl sulfoxide at 90℃; for 22h; Inert atmosphere;
68%	With toluene-4-sulfonic acid at 165℃; for 0.916667h; Ionic liquid; Microwave irradiation;	4.1 General procedure for the MW-assisted C-N cross coupling General procedure: In a new sealed pressure regulation 10-mL pressurized vial were placed aryl halide (1 mmol), p-toluenesulfonic acid (1 mmol, 0.172 g), [DBU][HOAc] (1.5 mL), N-nucleophile (2 mmol), and a Teflon-coated magnetic stir bar. The vessel was closed with a snap-on cap, stirred at room temperature for 5 min and then placed into the MW cavity. Microwave irradiation of 100 W at a set temperature of 165°C was used and the reaction mixture was held under these conditions for the specified time. After completion of the reaction (monitored through TLC), the mixture was cooled to room temperature and was poured to a vessel containing distilled water. This was extracted with ethyl acetate (310 mL) and the combined organic phase was washed with brine (210 mL), dried over Na2SO4, and was concentrated under rotary vacuum evaporator. The crude product was purified by column chromatography using a mixture of ethyl acetate/n-hexane as eluent.
	at 170℃; for 12h;	28 [0150] 1.05 g (6.7 mmol) of bromobenzene, 1.4 g (10.1 mmol) of caesium carbonate and 500 mg (0.7 mmol) of the catalyst from Example 1 are mixed with 3 g of nitroaniline and stirred under an argon atmosphere at 170° C. for 12 h. The GC analysis of the crude product indicates the selective formation of the monoarylated compound and complete conversion; triarylamine is not detected.
62 %Chromat.	With copper(l) iodide; cesium fluoride In dimethyl sulfoxide at 130℃; for 24h; Inert atmosphere; Glovebox;
39 %Chromat.	With hydrazine hydrate; [Ru(1,2-bis(diphenylphosphino)benzene )(CO)₂Cl₂] at 130℃; for 24h;

Reference： [1]Rao, Honghua; Jin, Ying; Fu, Hua; Jiang, Yuyang; Zhao, Yufen [Chemistry - A European Journal, 2006, vol. 12, # 13, p. 3636 - 3646]
[2]Absalan, Yahya; Ghandi, Khashayar; Gholizadeh, Mostafa; Kovalchukova, Olga; Mahmoudi, Ghodrat; Sarvestani, Hossein Sabet; Shad, Nazanin Noroozi; Strashnov, Pavel [Journal of Photochemistry and Photobiology A: Chemistry, 2021, vol. 417]
[3]Location in patent: body text Wang, Zhe; Fu, Hua; Jiang, Yuyang; Zhao, Yufen [Synlett, 2008, # 16, p. 2540 - 2546]
[4]Engel-Andreasen, Jens; Shimpukade, Bharat; Ulven, Trond [Green Chemistry, 2013, vol. 15, # 2, p. 336 - 340]
[5]Rao, Honghua; Fu, Hua; Jiang, Yuyang; Zhao, Yufen [Journal of Organic Chemistry, 2005, vol. 70, # 20, p. 8107 - 8109]
[6]Panigrahi, Reba; Panda, Subhalaxmi; Behera, Pradyota Kumar; Sahu, Santosh Kumar; Rout, Laxmidhar [New Journal of Chemistry, 2019, vol. 43, # 48, p. 19274 - 19278]
[7]Singh, Rahul; Allam, Bharat Kumar; Raghuvanshi, Dushyant Singh; Singh, Krishna Nand [Tetrahedron, 2013, vol. 69, # 3, p. 1038 - 1042]
[8]Current Patent Assignee: LANXESS AG - US2004/192664, 2004, A1 Location in patent: Page/Page column 8
[9]Gueell, Imma; Ribas, Xavi [European Journal of Organic Chemistry, 2014, vol. 2014, # 15, p. 3188 - 3195]
[10]Mukherjee, Aparajita; Hrovat, David A.; Richmond, Michael G.; Bhattacharya, Samaresh [Dalton Transactions, 2018, vol. 47, # 30, p. 10264 - 10272]

30
[ 836-30-6 ]
[ 7154-66-7 ]
2-bromo-<i>N</i>-(4-nitro-phenyl)-<i>N</i>-phenyl-benzamide [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With dmap; N-ethyl-N,N-diisopropylamine In dichloromethane at 0 - 20℃;

Reference： [1]Campeau, Louis-Charles; Parisien, Mathieu; Jean, Annie; Fagnou, Keith [Journal of the American Chemical Society, 2006, vol. 128, # 2, p. 581 - 590]

31
[ 100-01-6 ]
[ 88284-48-4 ]
[ 836-30-6 ]

Yield	Reaction Conditions	Operation in experiment
85%	With cesium fluoride In acetonitrile at 20℃; for 10h;
85.7%	With cesium fluoride In acetonitrile at 20℃; for 24h;

Reference： [1]Liu, Zhijian; Larock, Richard C. [Journal of Organic Chemistry, 2006, vol. 71, # 8, p. 3198 - 3209]
[2]Lee; Jung; Hahn [Asian Journal of Chemistry, 2013, vol. 25, # 12, p. 6690 - 6692]

32
[ 100-01-6 ]
[ 88284-48-4 ]
[ 836-30-6 ]
[ 4316-57-8 ]

Yield	Reaction Conditions	Operation in experiment
1: 55% 2: 40%	With cesium fluoride In acetonitrile at 20℃; for 72h;

Reference： [1]Liu, Zhijian; Larock, Richard C. [Journal of Organic Chemistry, 2006, vol. 71, # 8, p. 3198 - 3209]

33
[ 100-01-6 ]
[ 108-90-7 ]
[ 836-30-6 ]

Yield	Reaction Conditions	Operation in experiment
30%	With potassium carbonate In methanol; water Reflux; Green chemistry;
27%	With copper(l) iodide; potassium carbonate; pipecolic Acid In N,N-dimethyl-formamide at 110℃; for 36h;
2 %Chromat.	With copper(l) iodide; cesium fluoride In dimethyl sulfoxide at 130℃; for 24h; Inert atmosphere; Glovebox;

Reference： [1]Barot, Nirav; Shaikh, Tauhid; Kaur, Harjinder [New Journal of Chemistry, 2017, vol. 41, # 13, p. 5347 - 5354]
[2]Guo, Xun; Rao, Honghua; Fu, Hua; Jiang, Yuyang; Zhao, Yufen [Advanced Synthesis and Catalysis, 2006, vol. 348, # 15, p. 2197 - 2202]
[3]Gueell, Imma; Ribas, Xavi [European Journal of Organic Chemistry, 2014, vol. 2014, # 15, p. 3188 - 3195]

34
[ 636-98-6 ]
[ 62-53-3 ]
[ 836-30-6 ]

Yield	Reaction Conditions	Operation in experiment
96%	With C₁₀₄H₉₆N₁₆O₈Pd₂⁽⁴⁺⁾*4NO₃^(1-); sodium t-butanolate In toluene at 110℃; for 12h;	Experimental procedure for Buchwald-Hartwig coupling reaction General procedure: In a 50 mL round bottom flask, the mixture of iodobenzene (2 mmol), amine (2.4 mmol), t-BuONa (3 mmol), and 1 as catalyst (0.05 mol %) was taken in toluene (10 mL). The reaction mixture was then heated to 110°C and continued for 12-18 h. The progress of the reaction was monitored by TLC. Upon completion of the reaction the aqueous reaction mixture was extracted with ethyl acetate, washed with brine, dried over MgSO4, concentrated, and purified by column chromatography on silica gel which afforded corresponding coupling products (yield 75-96%).
95%	With potassium hydroxide In N,N-dimethyl-formamide at 100℃; for 4h; Inert atmosphere; Green chemistry;
93%	With potassium hydroxide; copper(II) oxide In dimethyl sulfoxide at 110℃; for 1.2h;

93%	With potassium carbonate In ethanol; water at 20℃; UV-irradiation; Green chemistry;
92%	With CuMoO₄; caesium carbonate In dimethyl sulfoxide at 90℃; for 12h; Inert atmosphere;
90%	With C₂₉H₂₅CuIN₃OPPd; sodium t-butanolate In toluene at 40℃; for 24h;
90%	With copper(II) oxide; potassium hydroxide In dimethyl sulfoxide; <i>tert</i>-butyl alcohol at 110℃; for 24h; Inert atmosphere;
90%	With copper(II) oxide; potassium carbonate In N,N-dimethyl-formamide at 40℃; for 2h;	General procedure for N-arylation of indole and aniline General procedure: In a typical N-arylation procedure, CuO NPs (0.005 g) was added to a mixture of aryl halide (1.0 mmol), indole/aniline (1.0 mmol), and K2CO3 (1.0 mmol) in DMF (5 mL) and stirred at 40 °C for desired time (Table 2). After completion of the reaction, the reaction mixture was cooled to room temperature and diluted with 10 mL of water and extracted with ethyl acetate (2×10 mL). The combined organic extracts were washed with brine and dried over anhydrous MgSO4. Solvent was evaporated under reduced pressure and the product was purified by column chromatography to obtain the desired purity. All the products are known compounds and the spectral data were identical to those reported in the literatures.23-25 The aqueous layer was centrifuged and the catalyst was separated and recovered for the next catalytic run.
90%	With potassium carbonate In water; glycerol for 7h; Irradiation; Green chemistry;
88%	With potassium hydroxide In dimethyl sulfoxide at 120℃; Inert atmosphere;	General experimental procedure for amination reaction General procedure: A mixture of amine (2.0 mmol), aryl halides (1.0 mmol), catalyst (1.0 mol% Pd), and DMSO (6 ml) was stirred for 16 h under nitrogen atmosphere at 120 ◦C. The progress of reaction was monitored by gas chromatography. After completion, the reaction mixture was cooled and filtered to remove the catalyst which could be used for further reaction. The filtrate obtained was purified by flash column chromatography on silica gel to afford the desired product, which was confirmed by GC-MS. All the prepared compounds are known and compared with authentic samples.
88%	With triethylamine In N,N-dimethyl-formamide at 80℃; for 2h;
88%	With potassium hydroxide In N,N-dimethyl-formamide at 130℃; for 0.25h;
85%	With potassium hydroxide In dimethyl sulfoxide; <i>tert</i>-butyl alcohol at 110℃; for 4h;
85%	With toluene-4-sulfonic acid at 165℃; for 0.833333h; Ionic liquid; Microwave irradiation;	4.1 General procedure for the MW-assisted C-N cross coupling General procedure: In a new sealed pressure regulation 10-mL pressurized vial were placed aryl halide (1 mmol), p-toluenesulfonic acid (1 mmol, 0.172 g), [DBU][HOAc] (1.5 mL), N-nucleophile (2 mmol), and a Teflon-coated magnetic stir bar. The vessel was closed with a snap-on cap, stirred at room temperature for 5 min and then placed into the MW cavity. Microwave irradiation of 100 W at a set temperature of 165°C was used and the reaction mixture was held under these conditions for the specified time. After completion of the reaction (monitored through TLC), the mixture was cooled to room temperature and was poured to a vessel containing distilled water. This was extracted with ethyl acetate (310 mL) and the combined organic phase was washed with brine (210 mL), dried over Na2SO4, and was concentrated under rotary vacuum evaporator. The crude product was purified by column chromatography using a mixture of ethyl acetate/n-hexane as eluent.
85%	With triethylamine In N,N-dimethyl-formamide at 80℃; for 3h;
85%	With potassium carbonate In N,N-dimethyl-formamide at 100℃; for 24h;
80%	With N',N'-dimethyl-1H-pyrrole-2-carbohydrazide; copper(II) oxide; sodium hydroxide In <i>tert</i>-butyl alcohol at 25℃; for 15h; Sealed tube;	4 Synthesis of N-p-nitrophenylaniline The 249 mg (1mmol) 4 - nitro-iodobenzene, 140 mg (1.5mmol) aniline, 7.9 mg (0.1mmol) CuO, 30.6 mg (0.2mmol) ligand L4, 60mg (1.5mmol) NaOH, 2 ml t - BuOH, adding 10 ml reaction tube, sealing, 25 °C reaction under the condition 15h. After the stop of the reaction, water, extracted with ethyl acetate, washing, saturated salt water washing, after drying with anhydrous sodium sulfate, filtered, the filtrate is distilled under reduced pressure, purification by silica gel chromatography separation column column, shall be N - nitro phenylaniline 171 mg, yield 80%.
75%	With copper(l) iodide; C₁₉H₁₉N₅O; potassium carbonate In water at 100℃; for 24h; Green chemistry;
73%	With potassium phosphate; copper(l) iodide; N′,N'-bis(2-isopropylphenyl)-1H-pyrrole-2-carbohydrazide In diethylene glycol at 20℃; for 15h; Sealed tube;
68%	With C₃₄H₂₄N₂O₂ In N,N-dimethyl-formamide at 40℃; for 10h; Inert atmosphere; Irradiation;
60%	With potassium carbonate In dimethyl sulfoxide for 12h; Reflux; Inert atmosphere;	2.3 General procedure for the N-arylation of aryl amines with aryl halides General procedure: In a 25ml round bottom flask a mixture of 4:1 methanol/water, aryl halide (1mmol), Resin-CuNPs (0.2g), K2CO3 (3mmol) and aryl amine (1.2mmol) were taken and heated at reflux temperature for 12-24h in an oil bath under inert conditions. Resin beads were filtered off at the end of reaction while the solution was still hot. After a work up with dichloromethane and water, the organic layer was separated, dried over anhydrous Na2SO4. The crude products obtained after removal of solvent (Scheme 1) were purified by column chromatography (ethyl acetate: hexane) and identified by mass or 1H NMR spectroscopy (see ESI).
50%	With potassium hydroxide In neat (no solvent) at 90℃; for 8h;
21%	With potassium hydroxide In neat (no solvent) at 100℃; for 24h; Sealed tube;
85 %Chromat.	With potassium <i>tert</i>-butylate In toluene at 120℃; for 24h; Inert atmosphere;

Reference： [1]Pradhan, Subhashis; Bhattacharyya, Arya; John, Rohith P. [Tetrahedron Letters, 2016, vol. 57, # 14, p. 1532 - 1536]
[2]Veisi, Hojat; Neyestani, Narges; Pirhayati, Mozhgan; Ahany Kamangar, Sheida; Lotfi, Shahram; Tamoradi, Taiebeh; Karmakar, Bikash [RSC Advances, 2021, vol. 11, # 36, p. 22278 - 22286]
[3]Rout, Laxmidhar; Jammi, Suribabu; Punniyamurthy [Organic Letters, 2007, vol. 9, # 17, p. 3397 - 3399]
[4]Singh, Gurpreet; Kumar, Manoj; Bhalla, Vandana [Green Chemistry, 2018, vol. 20, # 23, p. 5346 - 5357]
[5]Panigrahi, Reba; Panda, Subhalaxmi; Behera, Pradyota Kumar; Sahu, Santosh Kumar; Rout, Laxmidhar [New Journal of Chemistry, 2019, vol. 43, # 48, p. 19274 - 19278]
[6]Tsukada, Naofumi; Ohnishi, Nozomi; Aono, Shiori; Takahashi, Fusako [Organometallics, 2012, vol. 31, # 21, p. 7336 - 7338]
[7]Trivedi, Manoj; Ujjain, Sanjeev Kumar; Sharma, Raj Kishore; Singh, Gurmeet; Kumar, Abhinav; Rath, Nigam P. [New Journal of Chemistry, 2014, vol. 38, # 9, p. 4267 - 4274]
[8]Veisi, Hojat; Hemmati, Saba; Javaheri, Hadis [Tetrahedron Letters, 2017, vol. 58, # 32, p. 3155 - 3159]
[9]Kaur, Lovjot; Deol, Harnimarta; Kumar, Manoj; Bhalla, Vandana [Chemistry - An Asian Journal, 2020, vol. 15, # 6, p. 892 - 898]
[10]Islam, Sk. Manirul; Salam, Noor; Mondal, Paramita; Roy, Anupam Singha [Journal of Molecular Catalysis A: Chemical, 2013, vol. 366, p. 321 - 332]
[11]Akhavan, Elham; Hemmati, Saba; Hekmati, Malak; Veisi, Hojat [New Journal of Chemistry, 2018, vol. 42, # 4, p. 2782 - 2789]
[12]Ghasemi, Amir Hossein; Naeimi, Hossein [New Journal of Chemistry, 2020, vol. 44, # 13, p. 5056 - 5063]
[13]Location in patent: experimental part Jammi, Suribabu; Sakthivel, Sekarpandi; Rout, Laxmidhar; Mukherjee, Tathagata; Mandai, Santu; Mitra, Raja; Saha, Prasenjit; Punniyamurthy, Tharmalingam [Journal of Organic Chemistry, 2009, vol. 74, # 5, p. 1971 - 1976]
[14]Singh, Rahul; Allam, Bharat Kumar; Raghuvanshi, Dushyant Singh; Singh, Krishna Nand [Tetrahedron, 2013, vol. 69, # 3, p. 1038 - 1042]
[15]Veisi, Hojat; Ahmadian, Hossein; Mirshokraie, Seyed Ahmad; Didehban, Khadijeh; Zangeneh, Mohammad Mahdi [Applied Organometallic Chemistry, 2019, vol. 33, # 4]
[16]Bahrami, Kiumars; Targhan, Homa [Applied Organometallic Chemistry, 2019, vol. 33, # 4]
[17]Current Patent Assignee: SUN YAT-SEN UNIVERSITY (CHINA) - CN106883132, 2017, A Location in patent: Paragraph 0043-0045
[18]Chakraborti, Gargi; Paladhi, Sushovan; Mandal, Tirtha; Dash, Jyotirmayee [Journal of Organic Chemistry, 2018, vol. 83, # 14, p. 7347 - 7359]
[19]Ding, Xiaomei; Huang, Manna; Yi, Zhou; Du, Dongchen; Zhu, Xinhai; Wan, Yiqian [Journal of Organic Chemistry, 2017, vol. 82, # 10, p. 5416 - 5423]
[20]Deol, Harnimarta; Singh, Gurpreet; Kumar, Manoj; Bhalla, Vandana [Journal of Organic Chemistry, 2020, vol. 85, # 17, p. 11080 - 11093]
[21]Barot, Nirav; Patel, Sunil B.; Kaur, Harjinder [Journal of Molecular Catalysis A: Chemical, 2016, vol. 423, p. 77 - 84]
[22]Mohammadinezhad, Arezou; Akhlaghinia, Batool [New Journal of Chemistry, 2019, vol. 43, # 39, p. 15525 - 15538]
[23]Yang, Chu; Zhang, Feng; Deng, Guo-Jun; Gong, Hang [Journal of Organic Chemistry, 2019, vol. 84, # 1, p. 181 - 190]
[24]Location in patent: experimental part Islam, Manirul; Mondal, Paramita; Tuhina, Kazi; Roy, Anupam Singha; Mondal, Sanchita; Hossain, Dilder [Journal of Organometallic Chemistry, 2010, vol. 695, # 21, p. 2284 - 2295]

35
[ 591-50-4 ]
[ 100-01-6 ]
[ 836-30-6 ]

Yield	Reaction Conditions	Operation in experiment
100%	at 170℃; for 12h;	29 [0151] 1.37 g (6.7 mmol) of iodobenzene, 1.4 g (10.1 mmol) of caesium carbonate and 500 mg (0.7 mmol) of the catalyst from Example 1 are mixed with 3 g of nitroaniline and stirred under an argon atmosphere at 170° C. for 12 h. The GC analysis of the crude product indicates the selective formation of the monoarylated compound (comparison with GC-MS/EI of 1101-4) and complete conversion; triarylamine is not detected.
98%	With silver hexafluoroantimonate; chloro[di(1-adamantyl)-2-dimethylaminophenylphosphine]gold(I) In methanol at 0 - 80℃; Inert atmosphere;
95%	With potassium hydroxide In neat (no solvent) at 90℃; for 5.5h;

91%	With C₂₉H₂₅CuIN₃OPPd; sodium t-butanolate In toluene at 40℃; for 24h;
90%	With potassium carbonate In N,N-dimethyl-formamide at 100℃; for 24h;
88%	With 4,7-(dipyrrolidin-1-yl)-1,10-phenanthroline; potassium hydroxide; copper(I) bromide In water at 100℃; for 21h; Sealed tube; Inert atmosphere; Green chemistry;
85%	With iron(III) chloride; caesium carbonate; copper(II) oxide; 1,1'-bi-2-naphthol In N,N-dimethyl-formamide at 100℃; for 12h; Inert atmosphere;
82%	With potassium hydroxide In N,N-dimethyl-formamide at 100℃; for 7h;	2.3 General Procedure for the O-arylationand N-arylation with Aryl Halides General procedure: A mixture of phenol or amine (1.0 mmol), aryliodide (1.5 mmol), KOH (2 mmol) and BNPs (at) SiO2(CH2)3-TAPC-O-CH2CH2NH2-Pd(0) (0.05 g catalyst equal 0.0725 mmol/g pd) in DMF (2 mL) was stirred at 100 °C. The reaction progress was monitored by TLC. After the completion of the reaction, the catalyst was filtered,washed with ethanol and dried. The reaction mixture was extracted with ethyl acetate (3 × 5) and the organic layer was dried over magnesium sulfate (MgSO4). Then pure products were obtained from recrystallization in n-hexane.
82%	With CuMoO₄; caesium carbonate In dimethyl sulfoxide at 90℃; for 22h; Inert atmosphere;
77%	With copper(l) iodide; C₁₉H₁₉N₅O; potassium carbonate In water at 100℃; for 24h; Green chemistry;
76%	With copper(II) oxide; potassium hydroxide at 110℃; for 10h; Neat (no solvent);
75%	With nickel(II) chloride hexahydrate; triethylamine at 150℃; for 0.333333h; Microwave irradiation; Neat (no solvent);	General procedure for preparation of N-arylated amines 3: Aryl halide (1 mmol), amine (1.5 mmol), NiCl2·6H2O (10 mol % relative to aryl halide) and triethylamine (1.4 equiv) were taken in a 10 mL pressurized microwave vial with snap on cap. The reaction mixture was subjected to microwave exposure for 20 min at 300 W at appropriate temperature as indicated above. The progress of the reaction was monitored by TLC (Thin Layer Chromatography). After the reaction was completed, the reaction mixture was diluted with DCM and the insoluble catalyst was recovered and recycled without loss of activity. The filtrate was concentrated and subjected to column chromatography with n-hexane and ethyl acetate (2-10% depending upon the product) as eluent to afford the pure product.
70%	With potassium hydroxide; copper(II) oxide In dimethyl sulfoxide at 110℃; for 10h;
70%	With potassium hydroxide; air; cadmium(II) acetate dihydrate; ethylene glycol In dimethyl sulfoxide at 110℃; for 10h;
64%	With copper(l) iodide; cesium acetate In dimethyl sulfoxide at 90℃; for 24h; Inert atmosphere;
64%	With toluene-4-sulfonic acid at 165℃; for 0.916667h; Ionic liquid; Microwave irradiation;	4.1 General procedure for the MW-assisted C-N cross coupling General procedure: In a new sealed pressure regulation 10-mL pressurized vial were placed aryl halide (1 mmol), p-toluenesulfonic acid (1 mmol, 0.172 g), [DBU][HOAc] (1.5 mL), N-nucleophile (2 mmol), and a Teflon-coated magnetic stir bar. The vessel was closed with a snap-on cap, stirred at room temperature for 5 min and then placed into the MW cavity. Microwave irradiation of 100 W at a set temperature of 165°C was used and the reaction mixture was held under these conditions for the specified time. After completion of the reaction (monitored through TLC), the mixture was cooled to room temperature and was poured to a vessel containing distilled water. This was extracted with ethyl acetate (310 mL) and the combined organic phase was washed with brine (210 mL), dried over Na2SO4, and was concentrated under rotary vacuum evaporator. The crude product was purified by column chromatography using a mixture of ethyl acetate/n-hexane as eluent.
60%	With potassium carbonate; copper(l) chloride In water at 80℃; for 24h; Inert atmosphere;
58%	With copper(II) acetate monohydrate; caesium carbonate In N,N-dimethyl-formamide at 110℃; for 24h; Inert atmosphere;	4.6. General catalytic procedure for the N-arylation of nitrogen-containing heterocycles with aryl iodides General procedure: To a solution of Cu(OAc)2·H2O (0.01 mmol) in DMF (2 mL) were added aryl iodide (1.2 mmol), nitrogen-containing heterocycle (1.0 mmol), and Cs2CO3 (2 mmol) under nitrogen atmosphere. The mixture was stirred at 110 °C for 24 h. After cooling to ambient temperature, the mixture was partitioned between water and ethyl acetate. The organic layer was separated, and the aqueous layer was extracted with ethyl acetate. The combined organic layers were washed with brine, dried over Na2SO4, and concentrated in vacuo. The residue was purified by flash chromatography on silica gel.
53%	With copper(l) iodide; 2,2'-dihydroxybiphenyl; tetra(n-butyl)phosphonium malonate In 1,4-dioxane at 25℃; for 12h; Inert atmosphere;
45%	With caesium carbonate; 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene In 1,4-dioxane for 120h; Reflux;
20%	With C₂₄H₂₂N₆Ni; sodium t-butanolate In N,N-dimethyl-formamide; acetonitrile at 45℃; for 24h; Inert atmosphere; Schlenk technique;
16%	Stage #1: 4-nitro-aniline With copper(II) acetate monohydrate In dimethyl sulfoxide at 20℃; for 0.5h; Stage #2: With phenylhydrazine In dimethyl sulfoxide at 20℃; for 0.5h; Stage #3: iodobenzene In dimethyl sulfoxide at 20 - 90℃;
79 %Chromat.	With copper(l) iodide; cesium fluoride In dimethyl sulfoxide at 130℃; for 24h; Inert atmosphere; Glovebox;
22 %Chromat.	With copper(l) iodide; cesium fluoride; pyrrole-2-carboxyl acid In dimethyl sulfoxide at 50℃; for 24h; Inert atmosphere; Glovebox; Sealed tube;
69%Chromat.	With hydrazine hydrate; [Ru(1,2-bis(diphenylphosphino)benzene )(CO)₂Cl₂] at 130℃; for 24h;
	With potassium carbonate at 110℃; for 24h; Inert atmosphere;

Reference： [1]Current Patent Assignee: LANXESS AG - US2004/192664, 2004, A1 Location in patent: Page/Page column 8
[2]Akram, Manjur O.; Das, Avishek; Chakrabarty, Indradweep; Patil, Nitin T. [Organic Letters, 2019, vol. 21, # 19, p. 8101 - 8105]
[3]Mohammadinezhad, Arezou; Akhlaghinia, Batool [New Journal of Chemistry, 2019, vol. 43, # 39, p. 15525 - 15538]
[4]Tsukada, Naofumi; Ohnishi, Nozomi; Aono, Shiori; Takahashi, Fusako [Organometallics, 2012, vol. 31, # 21, p. 7336 - 7338]
[5]Bahrami, Kiumars; Targhan, Homa [Applied Organometallic Chemistry, 2019, vol. 33, # 4]
[6]Engel-Andreasen, Jens; Shimpukade, Bharat; Ulven, Trond [Green Chemistry, 2013, vol. 15, # 2, p. 336 - 340]
[7]Location in patent: body text Wang, Zhe; Fu, Hua; Jiang, Yuyang; Zhao, Yufen [Synlett, 2008, # 16, p. 2540 - 2546]
[8]Bahrami, Kiumars; Khodamorady, Minoo [Catalysis Letters, 2019, vol. 149, # 3, p. 688 - 698]
[9]Panigrahi, Reba; Panda, Subhalaxmi; Behera, Pradyota Kumar; Sahu, Santosh Kumar; Rout, Laxmidhar [New Journal of Chemistry, 2019, vol. 43, # 48, p. 19274 - 19278]
[10]Chakraborti, Gargi; Paladhi, Sushovan; Mandal, Tirtha; Dash, Jyotirmayee [Journal of Organic Chemistry, 2018, vol. 83, # 14, p. 7347 - 7359]
[11]Location in patent: experimental part Ahmadi, Seyed Javad; Sadjadi, Sodeh; Hosseinpour, Morteza; Abdollahi, Mojtaba [Monatshefte fur Chemie, 2011, vol. 142, # 8, p. 801 - 806]
[12]Location in patent: experimental part Gupta, Amit Kumar; Tirumaleswara Rao; Singh, Krishna Nand [Tetrahedron Letters, 2012, vol. 53, # 17, p. 2218 - 2221]
[13]Rout, Laxmidhar; Jammi, Suribabu; Punniyamurthy [Organic Letters, 2007, vol. 9, # 17, p. 3397 - 3399]
[14]Rout, Laxmidhar; Saha, Prasenjit; Jammi, Suribabu; Punniyamurthy, Tharmalingam [Advanced Synthesis and Catalysis, 2008, vol. 350, # 3, p. 395 - 398]
[15]Location in patent: experimental part Kubo, Tetsuji; Katoh, Chiharu; Yamada, Ken; Okano, Kentaro; Tokuyama, Hidetoshi; Fukuyama, Tohru [Tetrahedron, 2008, vol. 64, # 49, p. 11230 - 11236]
[16]Singh, Rahul; Allam, Bharat Kumar; Raghuvanshi, Dushyant Singh; Singh, Krishna Nand [Tetrahedron, 2013, vol. 69, # 3, p. 1038 - 1042]
[17]Tang, Lin; Sun, Yu; Zhou, Lingyun; Shao, Taili [Asian Journal of Chemistry, 2013, vol. 25, # 11, p. 6240 - 6242]
[18]Xu, Zhong-Lin; Li, Hong-Xi; Ren, Zhi-Gang; Du, Wei-Yuan; Xu, Wei-Chang; Lang, Jian-Ping [Tetrahedron, 2011, vol. 67, # 29, p. 5282 - 5288]
[19]Yang, Chu-Ting; Fu, Yao; Huang, Yao-Bing; Yi, Jun; Guo, Qing-Xiang; Liu, Lei [Angewandte Chemie - International Edition, 2009, vol. 48, # 40, p. 7398 - 7401][Angewandte Chemie, 2009, vol. 121, # 40, p. 7534 - 7537]
[20]Sa, Sofia; Gawande, Manoj B.; Velhinho, Alexandre; Veiga, Joao Pedro; Bundaleski, Nenad; Trigueiro, Joao; Tolstogouzov, Alexander; Teodoro, Orlando M. N. D.; Zboril, Radek; Varma, Rajender S.; Branco, Paula S. [Green Chemistry, 2014, vol. 16, # 7, p. 3494 - 3500]
[21]Sikari, Rina; Sinha, Suman; Chakraborty, Gargi; Das, Siuli; van Leest, Nicolaas Petrus; Paul, Nanda D. [Advanced Synthesis and Catalysis, 2019, vol. 361, # 18, p. 4342 - 4353]
[22]Location in patent: experimental part Komori, Takashi; Satoh, Nobuhiro; Yokoshima, Satoshi; Fukuyama, Tohru [Synlett, 2011, # 13, p. 1859 - 1862]
[23]Gueell, Imma; Ribas, Xavi [European Journal of Organic Chemistry, 2014, vol. 2014, # 15, p. 3188 - 3195]
[24]Rovira, Mireia; Soler, Marta; Güell, Imma; Wang, Ming-Zheng; Gómez, Laura; Ribas, Xavi [Journal of Organic Chemistry, 2016, vol. 81, # 17, p. 7315 - 7325]
[25]Mukherjee, Aparajita; Hrovat, David A.; Richmond, Michael G.; Bhattacharya, Samaresh [Dalton Transactions, 2018, vol. 47, # 30, p. 10264 - 10272]
[26]Gorginpour, Forough; Zali-Boeini, Hassan; Rudbari, Hadi Amiri [RSC Advances, 2021, vol. 11, # 6, p. 3655 - 3665]

36
[ 591-50-4 ]
[ 836-30-6 ]
[ 10456-04-9 ]
C₁₈⁽¹¹⁾CH₁₄N₂O₃ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
17 % Chromat.	With n-butyllithium; triphenyl-arsane In tetrahydrofuran at 70℃; for 0.0833333h;

Reference： [1]Itsenko, Oleksiy; Blom, Elisabeth; Langstroem, Bengt; Kihlberg, Tor [European Journal of Organic Chemistry, 2007, # 26, p. 4337 - 4342]

37
[ 836-30-6 ]
[ 793-24-8 ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 3 steps 1: 5percent Pd/C 2: 5percent palladium-on-carbon / 85 °C 3: HCOOH / 5percent Pd/C / 85 °C
	Multi-step reaction with 3 steps 1: formic acid / 5percent Pd/C / 85 °C 2: 5percent palladium-on-carbon / 85 °C 3: HCOOH / 5percent Pd/C / 85 °C

Reference： [1]Banerjee, Ankur A.; Mukesh, Doble [Journal of the Chemical Society. Chemical communications, 1988, # 18, p. 1275 - 1276]
[2]Banerjee, Ankur A.; Mukesh, Doble [Journal of the Chemical Society. Chemical communications, 1988, # 18, p. 1275 - 1276]

38
[ 92-82-0 ]
[ 156-10-5 ]
[ 836-30-6 ]
[ 1227476-15-4 ]
[ 101-54-2 ]

Yield	Reaction Conditions	Operation in experiment
99.1%	With hydrogen In methanol; water at 180℃; for 0.116667h;	19,20 Example 19 Example 19 Reaction mixture, obtained by the procedure of Example 7, was diluted by addition of 30% by weight of methanol, the catalyst Raney Ni was added in an amount of 30% by weight in water (related to the amount of nitrobenzene, charged to the reaction). The reaction took place at 60° C. and at a starting pressure of 5 MPa for 7 minutes. A sample of the reaction mixture, taken away, was analyzed for content of 4-ADFA. The overall yield, related to the starting content of 4-NODFA, 4-NO2DFA and 4-FADFA, was 99.1%. The yield of 4-ADFA, related to the reacted nitrobenzene, was 88.5%.Example 20 Batch Solution of the Reaction with Subsequent Processing of the Condensation Mixture, and Isolation of the 4-ADFA Product. For the reaction of aniline with nitrobenzene by the action of the reaction system of a solution of trimethylammonio-acetate with potassium hydroxide a device was used, consisting of a reactor with a volume of 250 l, provided with a rapid agitator, a tempering jacket which was heated by warm water to regulate the temperature in the reactor, a nitrogen inlet under the surface of the reaction mixture, a condensator for condensation of vapours from the reactor, and a receiver for condensate collection which was used as a phase separator, and it was provided with an overflow for recycling the aniline phase with a content of nitrobenzene back to the reactor, while the separated aqueous phase of the condensate was permanently removed from the phase separator. The reactor was further provided with a thermometer and a pressure regulator. 19.1 l of distilled water, 12.8 kg of solid KOH, containing 86.5% of KOH, were inserted into an auxiliary vessel having the volume of 50 l, and after it had dissolved, 26.6 kg of betaine hydrate were added. After dissolving of all components the reaction system in the form of an aqueous solution was prepared to be used in the reaction. 111.8 kg (1.2 kmol) of aniline were inserted into the reactor, and 58.5 kg of the above given solution were added. The reactor was closed and was purged by nitrogen once, while the mixture was stirred. After termination of the reactor purging by nitrogen an absolute pressure of 20 kPa was set in the reactor, and the reactor content was gradually heated up to a temperature of 80° C. After reaching the temperature 21.1 kg of nitrobenzene (0.17 kmol) were started to be dosed into the reactor at such a rate that all nitrobenzene was fed within 1.5 h. The azeotrope aniline-water which was distilled off the reactor was collected in the receiver, where aqueous and aniline phase were separated. The aniline phase contained a certain amount of nitrobenzene and, therefore, it was periodically recycled to the condensation reactor during the whole experiment. After completing the dosing of nitrobenzene pressure in the reactor was gradually reduced to a value of 14 kPa, and the reaction mixture reacted at this pressure and at a temperature of 80° C. for 1.5 h. Then the pressure was gradually reduced to 8 kPa, and at this pressure the reaction mixture reacted for 1.5 h. Finally, pressure in the reactor was reduced to the value 4 kPa, and the reaction mixture was let to complete the reaction within 1.5 h. Finally it was cooled down to 40° C., approximately 15% of methanol were added, it was discharged from the reactor and weighed. An analysis of the reaction mixture has shown that 100% conversion of nitrobenzene took place with the following yield (in %) of individual reaction components (calculated in relation to the introduced nitrobenzene): 4-NODFA 77.0%; 4-NO2DFA 14.3%; 4-phenylazodiphenylamine 0.21%; azobenzene 9.6%; phenazine 1.3%. Note: Content of N-methylaniline was less than 0.05%, related to the introduced betaine. Reaction mixture from the condensation was diluted by methanol in such a way that its content in the diluted condensation mixture was 30% by weight, and it was hydrogenated under conditions, given

Reference： [1]Current Patent Assignee: DUSLO, A.S. - US6388136, 2002, B1 Location in patent: Page column 13

39
[ 98-95-3 ]
[ 62-53-3 ]
[ 92-82-0 ]
[ 156-10-5 ]
[ 836-30-6 ]
[ 1227476-15-4 ]
[ 101-75-7 ]

Yield	Reaction Conditions	Operation in experiment
1: 73.5% 2: 13.5% 3: 9.6% 4: 1.2% 5: 0.17%	In methanol; water at 40 - 80℃; for 6h;	20,21 xample 20 Batch Solution of the Reaction with Subsequent Processing of the Condensation Mixture, and Isolation of the 4-ADFA Product. Example 20 Batch Solution of the Reaction with Subsequent Processing of the Condensation Mixture, and Isolation of the 4-ADFA Product. For the reaction of aniline with nitrobenzene by the action of the reaction system of a solution of trimethylammonio-acetate with potassium hydroxide a device was used, consisting of a reactor with a volume of 250 l, provided with a rapid agitator, a tempering jacket which was heated by warm water to regulate the temperature in the reactor, a nitrogen inlet under the surface of the reaction mixture, a condensator for condensation of vapours from the reactor, and a receiver for condensate collection which was used as a phase separator, and it was provided with an overflow for recycling the aniline phase with a content of nitrobenzene back to the reactor, while the separated aqueous phase of the condensate was permanently removed from the phase separator. The reactor was further provided with a thermometer and a pressure regulator. 19.1 l of distilled water, 12.8 kg of solid KOH, containing 86.5% of KOH, were inserted into an auxiliary vessel having the volume of 50 l, and after it had dissolved, 26.6 kg of betaine hydrate were added. After dissolving of all components the reaction system in the form of an aqueous solution was prepared to be used in the reaction. 111.8 kg (1.2 kmol) of aniline were inserted into the reactor, and 58.5 kg of the above given solution were added. The reactor was closed and was purged by nitrogen once, while the mixture was stirred. After termination of the reactor purging by nitrogen an absolute pressure of 20 kPa was set in the reactor, and the reactor content was gradually heated up to a temperature of 80° C. After reaching the temperature 21.1 kg of nitrobenzene (0.17 kmol) were started to be dosed into the reactor at such a rate that all nitrobenzene was fed within 1.5 h. The azeotrope aniline-water which was distilled off the reactor was collected in the receiver, where aqueous and aniline phase were separated. The aniline phase contained a certain amount of nitrobenzene and, therefore, it was periodically recycled to the condensation reactor during the whole experiment. After completing the dosing of nitrobenzene pressure in the reactor was gradually reduced to a value of 14 kPa, and the reaction mixture reacted at this pressure and at a temperature of 80° C. for 1.5 h. Then the pressure was gradually reduced to 8 kPa, and at this pressure the reaction mixture reacted for 1.5 h. Finally, pressure in the reactor was reduced to the value 4 kPa, and the reaction mixture was let to complete the reaction within 1.5 h. Finally it was cooled down to 40° C., approximately 15% of methanol were added, it was discharged from the reactor and weighed. An analysis of the reaction mixture has shown that 100% conversion of nitrobenzene took place with the following yield (in %) of individual reaction components (calculated in relation to the introduced nitrobenzene): 4-NODFA 77.0%; 4-NO2DFA 14.3%; 4-phenylazodiphenylamine 0.21%; azobenzene 9.6%; phenazine 1.3%. Note: Content of N-methylaniline was less than 0.05%, related to the introduced betaine. Reaction mixture from the condensation was diluted by methanol in such a way that its content in the diluted condensation mixture was 30% by weight, and it was hydrogenated under conditions, given in Example 19. A withdrawn sample of the reaction mixture was analyzed for the content of 4-ADFA. The overall yield of 4-ADFA, related to the starting content of 4-NODFA, 4-NO2DFA and 4-FADFA, was 99.2%. The yield of 4-ADFA in the hydrogenate, related to the nitrobenzene reacted, was 89.9%. After completing the hydrogenation the catalyst Raney Ni was filterred off, and it was washed by methanol and distilled water. The washing solutions were added to the hydrogenate. Methanol was distilled off the diluted hydrogenate at an absolute pressure of 35 kPa and at a temperature of 60 to 70°
1: 58.6% 2: 12.8% 3: 13.2% 4: 0.2% 5: 1.1%	In methanol	6 Example 6 Effect of the Molar ratio Betaine-potassium Hydroxide to Nitrobenzene on the Course of the Reaction. Example 6 Effect of the Molar ratio Betaine-potassium Hydroxide to Nitrobenzene on the Course of the Reaction. By the procedure, given in Example 1, reactions of aniline with nitrobenzene with the molar ratio of 7:1 were performed with the difference that the molar ratio of the reaction System to nitrobenzene was changing from 1:1 to 1.5:1. The reaction system was formed by betaine hydrate and potassium hydroxide with the molar ratio of 1:1 in a methanol solution. Results of the experiments, given in Table 3, have shown the effect of the increasing amount of the reaction system on the yields of the reaction and conversion of nitrobenzene.
1: 35.7 %Chromat. 2: 17.8 %Chromat. 3: 10.9 %Chromat. 4: 0.12 %Chromat. 5: 1.25 %Chromat.	In water at 80℃; for 5h;	4 Example 4 Modified Procedure in which all Reaction Components were Introduced into the Reaction at the Beginning. Example 4 Modified Procedure in which all Reaction Components were Introduced into the Reaction at the Beginning. In a flask, 2.66 g (83.0%) of potassium hydroxide were dissolved in 5.0 ml of water, 5.31 g of betaine hydrate, 24.1 g of aniline and 4.83 g of nitrobenzene were added. The reaction mixture was intensively stirred at 80° C. in nitrogen atmosphere for 5 h. Within this time interval pressure in the apparatus was gradually reduced from 53 kPa down to 2.6 kPa. Finally, the reaction mixture was dissolved in methanol and analyzed by the method of highly effective liquid chromatography. Conversion of nitrobenzene was 75.6%, and the yields (in %) of individual products, calculated relative to the introduced nitrobenzene, were as follows: 4-NODFA 35.7%; 4-NO2DFA 17.8%; 4-FADFA 0.12%; azobenzene 10.9%; phenazine 1.25%.

Reference： [1]Current Patent Assignee: DUSLO, A.S. - US6388136, 2002, B1 Location in patent: Page column 13-15
[2]Current Patent Assignee: DUSLO, A.S. - US6388136, 2002, B1 Location in patent: Page column 7-8
[3]Current Patent Assignee: DUSLO, A.S. - US6388136, 2002, B1 Location in patent: Page column 7

40
[ 98-95-3 ]
[ 62-53-3 ]
[ 156-10-5 ]
[ 836-30-6 ]
[ 1227476-15-4 ]
[ 101-75-7 ]

Yield	Reaction Conditions	Operation in experiment
1: 26.3% 2: 16.8% 3: 40.8% 4: 5.1%	In methanol at 70℃; for 5h;	3 Example 3 Results of the Reaction of Aniline with Nitrobenzene with the Reaction System Betaine-sodium Hydroxide in Methanol Under Aerobic Conditions. Example 3 Results of the Reaction of Aniline with Nitrobenzene with the Reaction System Betaine-sodium Hydroxide in Methanol Under Aerobic Conditions. To a catalyst solution, consisting of 0.066 mol of betaine and 0.066 mol of sodium hydroxide in 15 g of methanol, 0.4 mol of aniline were added. After heating the reaction mixture up to 70° C. nitrobenzene was dosed to the reaction mixture in the course of 1.5 h. Methanol and reaction water were gradually removed from the reaction mixture at a reduced pressure. After completing the nitrobenzene dosing the mixture was stirred for further 3.5 h. After dilution by methanol the mixture was analyzed, and the yield of the reaction products, expressed in %, related to nitrobenzene, charged to the reaction mixture, has achieved: 4-NODFA 26.3%; 4-NO2DFA 16.8%; 4-FADFA 5.1%; azobenzene 40.8%.

Reference： [1]Current Patent Assignee: DUSLO, A.S. - US6388136, 2002, B1 Location in patent: Page column 7

41
[ 98-95-3 ]
[ 62-53-3 ]
[ 156-10-5 ]
[ 836-30-6 ]
[ 1227476-15-4 ]

Yield	Reaction Conditions	Operation in experiment
1: 36% 2: 16.3% 3: 13.8%	at 70℃;	2 Example 2 Results of the Reaction of Aniline with Nitrobenzene, when Using Lithium, sodium, Potassium and Cesium Hydroxide in a Reaction System, Containing Betaine-hydroxide. Example 2 Results of the Reaction of Aniline with Nitrobenzene, when Using Lithium, sodium, Potassium and Cesium Hydroxide in a Reaction System, Containing Betaine-hydroxide. The reaction systems were prepared by the reaction of betaine monohydrate with alkali hydroxides. According to the procedure, described in Example 1, 3 identical reactions were performed at a temperature of 70° C. with various cations of alkali metals, given in Table 2.
1: 18.2 %Chromat. 2: 10.0 %Chromat. 3: 8.5 %Chromat.	In methanol at 50 - 55℃; for 4.5h;	1 Example 1 Results of the Reaction of Aniline with Nitrobenzene Under Anaerobic Conditions, when the Reaction System is a Solution of Betaine and Potassium Hydroxide in Methanol at Different Temperatures in the Range of 55 to 130° C. Example 1 Results of the Reaction of Aniline with Nitrobenzene Under Anaerobic Conditions, when the Reaction System is a Solution of Betaine and Potassium Hydroxide in Methanol at Different Temperatures in the Range of 55 to 130° C. For the reaction an apparatus was used which consisted of a 100 ml 3-neck flask with a magnetic stirrer, a thermometer, a dropping funnel and an azeotropic attachment, and was joined with a water-jet pump. 3,5 g (84.02%) of potassium hydroxide (0.052 mol) were dissolved in 6 g of methanol. 6.1 g of betaine (0.052 mol) were added and, after heating up to 50° C., 37.0 g of aniline (0.49 mol) were added. Air in the apparatus was replaced by nitrogen and after heating up to the reaction temperature at first methanol was distilled off at a pressure of 5.2 kPa, and then nitrobenzene, 6.4 g (0.052 mol) on the whole, was dosed under intensive stirring during 1.5 h. The reaction mixture was left to react for further 3 hours, then it was cooled down, diluted by methanol, and analyzed by the method of highly effective liquid chromatography. The yield of reaction components was calculated relative to the amount of nitrobenzene, introduced into the reaction. Further reaction conditions and results achieved are given in Table 1.
1: 0.15% 2: 0.34% 3: 0.24%	at 70℃;	2 Example 2 Results of the Reaction of Aniline with Nitrobenzene, when Using Lithium, sodium, Potassium and Cesium Hydroxide in a Reaction System, Containing Betaine-hydroxide. Example 2 Results of the Reaction of Aniline with Nitrobenzene, when Using Lithium, sodium, Potassium and Cesium Hydroxide in a Reaction System, Containing Betaine-hydroxide. The reaction systems were prepared by the reaction of betaine monohydrate with alkali hydroxides. According to the procedure, described in Example 1, 3 identical reactions were performed at a temperature of 70° C. with various cations of alkali metals, given in Table 2.

1: 0.6% 2: 0.2% 3: 0.1%	In water at 80℃; for 6 - 7.5h;	5,17 Example 5 Reaction of Aniline with an Excess of Nitrobenzene (as a solvent) in the Presence of the Reaction System Betaine-potassium Hydroxide Under Anaerobic Conditions. Example 5 Reaction of Aniline with an Excess of Nitrobenzene (as a solvent) in the Presence of the Reaction System Betaine-potassium Hydroxide Under Anaerobic Conditions. To a solution of 3.38 g (83%) of potassium hydroxide in 3.0 ml of water 6.85 g of betaine hydrate and 26.8 g of nitrobenzene were added. At a temperature of 80° C. and at a pressure of 20 kPa 4.9 g of aniline were dosed to the reaction mixture in nitrogen atmosphere during 1.5 h. After completing the nitrobenzene dosing the reaction mixture was intensively stirred for further 6 h. After cooling down the reaction mixture was dissolved in methanol. The yields, calculated as related to aniline, charged to the reaction, have achieved: 4-NODFA 1.5%; 4-NO2DFA 0.2%; azobenzene 2.5%. Example 17 Effect of Water Content on the Reaction of Aniline with Nitrobenzene. A reaction mixture, consisting of aniline, nitrobenzene, potassium hydroxide, betaine and water with mutual molar ratios, given in Table 9, was let to react under intensive stirring at 80° C. at an atmospheric pressure under nitrogen during 6 h. After cooling down and diluting with methanol the obtained solution was analyzed, and the results were expressed in nitrobenzene conversion and yields, related to the charged nitrobenzene. Water in the reaction mixture is a sum of the reaction water, dissolving water and water, introduced by raw material, and it is expressed in mol per 1 mol of nitrobenzene.
	With tetramethyl ammoniumhydroxide In water at 75℃; for 2.1h; Dean-Stark;	1 EXAMPLE 1 - Addition of nitrobenzene in a single lot This example illustrates the effect of addition of nitrobenzene in single lot after attaining the desired water to base mole ratio for the start of the coupling reaction, and its impact on volume productivity. The reaction set up was the same as was used for Example A. Initially, aqueous TMAH solution (35% w/w, 480.5 gm, 168.18 gm on a 100% basis, 1.85 moles) was charged. Aniline was charged (1004.2 gm, 10.8 moles) into the reactor and distillation under reduced pressure was continued at 55 mm Hg. Water and aniline were removed by distillation until the molar ratio of water to TMAH was about 4:1. During this process the temperature of the reaction mass increased to 75 °C. After attaining required mole ratio of water to base, nitrobenzene (218.7 gm, 1.78 moles) was added in single lot by using a dropping funnel. After nitrobenzene addition, water and aniline were continuously removed from the reaction by distillation under reduced pressure at 55 mm Hg. Samples of the reaction mass were drawn at hr intervals for analysis by HPLC. The reaction was completed within 1 hour. The reaction end point was determined by HPLC analysis by monitoring the conversion of nitrobenzene. The total reaction time was about 2.1 hrs. Typical selectivity determined by HPLC at 97% nitrobenzene conversion (about 3% NB in distillate) was: 4-NODPA 66.5%, 4-NDPA 13%, azobenzene 19.6% and phenazine 0.9%. The volume productivity of the reaction based on 4-ADPA (4-NODPA+4-NDPA) was calculated to be 68.92 gm/hr/liter. This result shows that when nitrobenzene is added in one lot, the volume productivity yield of 4-NODPA and 4-NDPA, taken together, increases almost two fold as compared to the volume productivity of Example A.
	With tetramethyl ammoniumhydroxide at 65 - 80℃; Flow reactor; Industrial scale;	4 EXAMPLE 4: Coupling aniline with nitrobenzene in continuous manner: This example illustrates the coupling reaction of aniline with nitrobenzene carried out in a continuous manner to obtain a reaction mass having a negligible presence of nitrobenzene with a water to total base molar ratio less than 0.6 and without substantial decomposition of TMAH. a) In a typical pilot plant run aniline (35.86 kg/hr), nitrobenzene (5.93 kg/hr) and TMAH (35% w/w) (11.34 kg/hr) were fed to a pre-mixer, followed by passing through a series of continuous flow reactors at about 50 mm Hg. The temperature of the reaction mass progressively increased from about 65°C in the pre-mixer to about 80°C with distillation of aniline and water from the flowing reaction mass. The last reactor in the series was a continuous plug flow reactor, which was maintained at 10 mm Hg and the reaction mass was passed through this continuous plug flow reactor in a continuous manner with distillation of aniline and water. The temperature of the bottom mass was about 75°C. The output was about 34 kg/hr with a negligible presence of nitrobenzene. Typical selectivity based on nitrobenzene added was about 90% for the total of 4-NODPA and 4- NDPA, azobenzene about 9.2%, and phenazine about 0.5%. The moisture content was around 0.85% w/w by the Dean-Stark method and the TMAH content by analysis around 11.6% w/w giving a water to total base molar ratio of about 0.37. The N-methyl aniline content was around 19 ppm. Thus, it was possible to reduce the water to total base molar ratio to less than 0.6 without appreciable decomposition of TMAH base.

Reference： [1]Current Patent Assignee: DUSLO, A.S. - US6388136, 2002, B1 Location in patent: Page column 6-7
[2]Current Patent Assignee: DUSLO, A.S. - US6388136, 2002, B1 Location in patent: Page column 6
[3]Current Patent Assignee: DUSLO, A.S. - US6388136, 2002, B1 Location in patent: Page column 6-7
[4]Current Patent Assignee: DUSLO, A.S. - US6388136, 2002, B1 Location in patent: Page column 7,12
[5]Current Patent Assignee: NOCIL LIMITED - WO2013/132290, 2013, A2 Location in patent: Page/Page column 19; 20
[6]Current Patent Assignee: NOCIL LIMITED - WO2013/153419, 2013, A1 Location in patent: Page/Page column 28-29

42
[ 98-95-3 ]
[ 62-53-3 ]
[ 92-82-0 ]
[ 156-10-5 ]
[ 836-30-6 ]
[ 17082-12-1 ]

Yield	Reaction Conditions	Operation in experiment
	With tetramethyl ammoniumhydroxide; dihydrogen peroxide In water at 66 - 91℃;	1-15 EXAMPLE 1 [0045] This example provides reference information, for discussion of the effect of using hydrogen peroxide during the coupling reaction in the other examples. The procedure for Runs 1-3 is similar to that of Example 2, except using plant recycle TMAH (26.8 wt. %) and plant recycle aniline, with base concentration and drying at 62 torr and reaction at 60 torr. The procedure for Runs 4-6 is to charge 145.28 g of fresh aniline (1.56 moles) and 87.36 g of aqueous pre-concentrated fresh TMAH solution (36.0 wt. %, 0.345 moles TMAH) to a 500-mL round bottom flask equipped with a thermocouple, heating mantle, subsurface feed tubes for nitrobenzene and peroxide or water and a Teflon paddle stirrer. With pressure at 70 torr, the mixture is heated to remove 18 mL of water, along with aniline, (?30 minutes) and then nitrobenzene feed (36.93 g, 0.30 moles) is started. Temperature rises from about 66-67 C. to 80 C. during the reaction period, while water and aniline are boiled off. Table 1 gives the times for nitrobenzene feed and reaction hold for all six runs. Water and aniline are boiled off during the hold. Batches for Runs 4-6 are quenched with 20 mL of water after the hold period. The hydrogen peroxide charge is 20.40 g (0.03 moles) of a 5 wt. % aqueous solution concurrent with nitrobenzene. Since water can affect selectivity by protecting TMAH from degradation and by shifting reaction equilibriums, water is fed concurrently with nitrobenzene for direct comparison with peroxide. [0046] The example illustrates that both shorter nitrobenzene feed time and the addition of water can increase selectivity, although water is not very effective for the longer feed time. However, peroxide gave the highest selectivity, 1.9% greater than water addition. More importantly, for a commercial process that involves recycles and waste disposal, aqueous peroxide greatly reduced the levels of two key by-products compared to water alone, viz. azobenzene (by 39%) and phenazine (by 36%). Replicate baseline runs by a slightly different procedure gave selectivities of 92.7% and 92.6%, indicating that the experimental results reported herein are very reproducible. Moreover, the replicates indicate that the small selectivity differences, such as 1.9% higher for peroxide vs. water, are indeed significant. EXAMPLE 2 [0047] Some of the runs in the following examples had relatively low conversions, because the procedure used a fixed nitrobenzene feed time plus hold time rather than holding the batches to reaction completion. This example shows the effect of an extended hold period on selectivity. [0048] The procedure is to charge 432.85 g of plant recycle base (24.4 wt. % TMAH, 1.16 moles) to a 1-L water/glycol jacketed reactor. Begin agitation at 150 rpm and boil off 92 mL water at constant pressure of 65 torr, with the water bath temperature starting at 72 C. and increasing by 1 C. per 10 mL of water removed. Then charge 301.50 g (3.24 moles) of fresh aniline via vacuum. Continue to remove water plus aniline at 65 torr, by raising the bath temperature 1 C. per 9 mL of water removed, while continuously charging 120 mL of aniline from a sidearm pressure-vented dropping funnel. When 72 mL of water has been removed (164 mL total), begin co-feeding 123.11 g of nitrobenzene (1.00 moles) and 27.20 g hydrogen peroxide (10 wt. % aqueous solution, 0.08 moles) subsurface via peristaltic pumps over a period of 80 minutes. Continuously add 60 mL of aniline during the reaction step, while holding pressure at 65 torr and boiling off water plus aniline. Gradually increase bath temperature in 0.5 C. increments to achieve 91 C. in the bath and 80-82 C. in the reactor by the end of the reaction step. Initiate the hold period by reducing pressure to 60 torr and increasing the bath and reactor temperatures by another 1 C. Continue removing water plus aniline during an extended hold. [0049] This example shows that holding a low conversion batch to essentially complete conversion had only a minimum impact on selectivity. In the examples following this one, conversion ranged from 73.4% to 100%. These results show that driving conversion from 89.3% to 99.8% reduced selectivity by only 0.5% and going from 96% to 99.8% conversion reduced selectivity by only 0.2%. Therefore, low conversion for some runs in the following examples does not affect the conclusions. EXAMPLE 3 [0050] A 3-factor, 8-run Design of Experiments (DOE) with pressure, nitrobenzene feed rate, and peroxide as variables was executed. Concentration of peroxide (5 wt. % aqueous solution) and H2O2/NB (0.1 molar ratio) were arbitrarily selected for the four runs using peroxide. To a 500-mL round bottom flask equipped with a heating mantle, thermocouple, subsurface feed tubes for nitrobenzene and peroxide and a Teflon paddle stirrer was charged 130.02 g of recycle base (24.4 wt. %), which was then concentrated to 31 wt. % by boiling off 28 mL of water at the pressure indicated in Table 3. Then 145.28 g of aniline was added and another 16 mL of water was removed, along with aniline (44 mL total water). Then nitrobenzene feed of 36.93 g was started, with continued boil off of water and aniline. When peroxide was used, the 20.40 g of 5 wt. % peroxide solution was co-fed with nitrobenzene at an appropriate feed rate to finish with nitrobenzene. Batches were held as described below, then quenched with 20 mL of water. Reactions were run at 80 C. and either 65 or 95 torr (specified in the design) on a 0.3 mole scale. Hold periods were fixed at 20 minutes for the 110 minute nitrobenzene feed and 45 minutes for the 70 minute nitrobenzene feed, both with continued boil off of water and aniline. [0051] Results in Table 3 show that selectivity is consistently higher when peroxide is used at a low level and the range is much smaller (96.1 to 96.6% with vs. 89.8 to 94.8% without) for variations of reaction pressure and nitrobenzene feed rate. Also, with peroxide more 4-NDPA was made relative to azobenzene, whereas without, nearly equimolar amounts were generated. Less 4-NDPA (by 30-40%) was made with peroxide at the longer nitrobenzene feed time and in all runs, much less azobenzene and phenazine were made with peroxide. Example 1 showed that nitrobenzene feed rate can affect selectivity without peroxide and this example shows that peroxide reduces the effect of both nitrobenzene feed rate and reaction pressure, which is unexpected. EXAMPLE 4 [0052] A refining DOE was completed to assess both 1) amount of peroxide and 2) peroxide concentration for the coupling reaction. The procedure was the same as for Example 3, except for the mole ratios and peroxide concentrations listed in Table 4 and a nitrobenzene feed time of about 70 minutes with a 30 minute hold. Table 4 shows that with a fast nitrobenzene feed rate, selectivity is relatively independent of peroxide concentration, especially at the lower molar ratio. This is surprising, because Example 1 showed that adding water can increase selectivity and the runs with 5 wt. % peroxide had 6.33 times the amount of water as 25 wt. % peroxide. The results also show that selectivity can be affected by the amount of oxidant. A comparison of Runs with equal peroxide concentration in Table 4 shows that the higher mole ratio gave lower selectivity in each case. Again, this is surprising, since twice the amount of water was added at the higher mole ratio. So the benefits of water and peroxide are not additive, as the effect of peroxide predominates. EXAMPLE 5 [0053] This example further illustrates the effect of pressure on selectivity when peroxide is used. The batches were made by a procedure similar to Example 2, with a nitrobenzene feed time of 110 minutes, a hold time of 20 minutes, a different sample of plant recycle base (26.8 wt. %) and plant recycle aniline instead of fresh. The results in Table 5 show that pressure does not have an impact on selectivity when 30 wt. % peroxide is used, just as in Example 3 with 5 wt. % peroxide. This is additional evidence that peroxide mitigates the effect of other reaction variables. EXAMPLE 6 [0054] Example 1 showed that shorter nitrobenzene feed time (80 minutes) alone, or with water, or with aqueous peroxide, can increase selectivity. Example 3 showed that for a fixed peroxide concentration and molar ratio, nitrobenzene feed time (about 75 minutes vs. about 110 minutes) had little effect on selectivity. Example 4 showed that with a short nitrobenzene feed time (about 70 minutes), selectivity is relatively independent of peroxide concentration, especially at the lower mole ratio. [0055] This example explores the effect of peroxide concentration on selectivity for a longer nitrobenzene feed time. A series of batches were made by a procedure similar to that of Example 5. Also, peroxide feed for the 0.064 mole ratio runs was via a piston pump (see Example 14). Peroxide concentration was varied from 5 wt. % to 35 wt. %, with H2O2/NB=0.1 and 0.064. The results in Table 6 show that also for a longer nitrobenzene feed time, selectivity is essentially independent of peroxide concentration. Moreover, phenazine level increases only slightly as significantly less water is charged with the peroxide, which is consistent with Example 4. With a longer nitrobenzene feed time, the rate of removal of water relative to the rate of nitrobenzene charge is greater than for a shorter nitrobenzene feed time. So as less water is charged with the peroxide, the batches become even drier. However, even the lowest water charge in Table 6 has significantly higher selectivity than for water alone with a 110 minute nitrobenzene feed in Table 1. This illustrates that although water and peroxide can both play a role in increasing selectivity, the effect of peroxide is more important. Furthermore, since water can influence the rate of formation of the Meisenheimer complex and the rate of its oxidation by nitrobenzene, it should be possible to improve selectivity with peroxide by tuning H2O2/NB to match the Meisenheimer concentration in the batch. EXAMPLE 7 [0056] A series of coupling reactions were done with a fixed peroxide concentration of 5 wt. % to determine the effect of temperature on selectivity. The procedure was as follows: Charge 130.02 g recycle base (24.4 wt. % TMAH) to 500-mL scale coupler and boil off 28 mL of water. Add 145.28 g aniline and remove another 16 mL of water, along with aniline (44 mL total water). Feed 36.93 g nitrobenzene concurrently with 5 wt. % aqueous peroxide solution at H2O2/NB=0.08 molar, both subsurface, while boiling off water and aniline. Complete the co-feed in 100-110 minutes at the temperatures indicated in Table 7 and at a constant pressure of 65 torr. Hold for 30 minutes, while boiling off water and aniline, and then quench with 20 mL of water. [0057] The results in Table 7 illustrate the effect that the rates of formation and intramolecular oxidation of the Meisenheimer complex have on selectivity with peroxide. As temperature is increased, selectivity reaches a maximum at about 80 C. At lower temperatures, the rate of Meisenheimer formation is too low for the rate of peroxide addition, so that oxidation of aniline to azobenzene by peroxide increases. At higher temperatures, the higher rate of intramolecular Meisenheimer oxidation to p-NDPA reduces the amount of Meisenheimer available for reaction with peroxide, so that again oxidation of aniline to azobenzene by peroxide increases. Also, the selectivity at 70 C. is higher than that obtained without peroxide at otherwise comparable reaction conditions. Therefore, the effective range for this example can be extended down to about 65 C. [0058] Thus, 80 C. is an apparent optimum that is dependent on the reaction procedure. Any procedure change that will change the rate of Meisenheimer formation, such as changing the rate of water removal, will affect selectivity with peroxide. This could shift the optimum selectivity to a different temperature. Moreover, selectivity can be increased at lower and higher temperatures simply by adjusting the molar ratio of H2O2/NB to match the rate of formation or rate of intramolecular oxidation of the Meisenheimer. Thus selectivity is highest at 80 C. for this particular reaction procedure with H2O2/NB=0.08 molar. However, the optimum temperature will vary with other variables, such as water level in the reactor and H2O2/NB mole ratio. Furthermore, varying temperature will require a different mole ratio of H2O2/NB for maximum selectivity. Therefore, the effective ranges given in other examples are not absolute. EXAMPLE 8 [0059] Two sets of coupling reactions were done with fixed peroxide concentrations to determine the effective mole ratio range that would give increased selectivity. The procedure for 5 wt. % peroxide was basically the same as for Example 3. Peroxide and nitrobenzene were fed over 105-110 minutes, with a 20 minute hold period for reaction at 80 C. and 65 torr. The procedure for 30 wt. % was similar to Example 5. [0060] FIG. 1 and Table 8 show that the effective range for 5 wt. % peroxide is about H2O2/NB=0.01-0.20, the preferred range is about H2O2/NB=0.03-0.16 and the most preferred range is about H2O2/NB=0.06-0.12. The optimum molar ratio with 5 wt. % peroxide was H2O2/NB=0.07-0.09 for this procedure, which is about the same as the mole % of 4-NDPA that was made from nitrobenzene. So peroxide reacts in high selectivity to make 4-NDPA with minimum formation of azobenzene. This is a surprising result, due to the very large molar excess of aniline that is available to be oxidized to azobenzene. [0061] The effective mole ratio range for 30 wt. % peroxide is about 0.01-0.25. An optimum cannot be derived from the data, but it appears to be within 0.06-0.21, which is shifted higher than for 5 wt. % peroxide. A more preferred range appears to be within 0.08-0.17. So the effective mole ratio range, preferred range and most preferred range for peroxide are expected to vary with some process variables, such as peroxide concentration, impurity levels in recycle streams, reaction temperature, water removal rate and nitrobenzene feed rate. Therefore, these ranges are not absolute for peroxide, but rather representative. It is envisaged that the effective range could extend to H2O2/NB=0.01-0.4 with recycle base or perhaps even somewhat wider. EXAMPLE 9 [0062] An optimization study was done for fresh base with peroxide to examine the effect of base quality. The procedure was similar to Example 3 for 5 and 20 wt. %, with a 126.89 g charge of 25 wt. % base, and to Example 10 for 35 wt. %. As seen in FIG. 2 and Table 9, fresh base gave flatter and wider optimization curves vs. recycle base. Moreover, the optimum mole ratio and effective range varied with concentration, the maximum selectivity was lower vs. recycle base and selectivity increased after the initial optimum was passed. The upturns are due to the higher water charge as mole ratio increased, which did not occur with 35 wt. % peroxide, for which the least water was added. Selectivity rose because water inhibits oxidation of Meisenheimer by nitrobenzene, so that more is oxidized by peroxide. The results show that at the conditions used for Examples 8 and 9, peroxide is more effective with recycle base. Moreover, the salts in recycle base must moderate the effect of water, since the selectivity upturn did not occur with it. Even so, the selectivity increase with fresh base is substantial. The effective range for 35 wt. % peroxide is about 0.01-0.33 and if water was removed faster with 20 wt. % peroxide, the curve tracks to an effective range of about 0.01-0.46. Since nitrobenzene feed rate can extend well beyond 110 minutes for a commercial process, the effective range could wellEXAMPLE 10 [0063] This example further illustrates the effect
	With potassium hydroxide; dihydrogen peroxide; tetramethlyammonium chloride In water at 60℃; for 1h;	2 COMPARATIVE EXAMPLE 2 [0072] This example examines the effect of peroxide with a strong inorganic base and phase transfer catalyst (PTC), by the following procedure. Aniline (99%, 22.58 g, 240 mmoles), nitrobenzene (99%, 4.97 g, 40 mmoles), hydrogen peroxide (50 wt. % aqueous, molar amount indicated below in FIG. 5), water (water is added such that the total water is kept constant at 2.16 g), potassium hydroxide (86% ground powder, 7.83 g, 120 mmoles) and tetramethylammonium chloride (97%, 4.52 g, 40 mmoles) was charged to a 50-mL round bottom flask equipped with a magnetic stirrer. Peroxide was charged to the reaction mixture before adding KOH & TMACI. Then the flask was quickly stoppered and the reaction was allowed to proceed for 1 hour at 60 C. In this example, azoxybenzene and 2-NDPA were obtained as reaction by-products that were not obtained with TMAH. So these by-products were included in the calculation of selectivity. [0073] FIG. 5 shows that with a strong inorganic base and a phase transfer catalyst, selectivity increases steadily as the mole ratio of peroxide/NB is increased from 0 to unity. However, with a strong organic base, i.e. TMAH, there were optimum mole ratios with both fresh and recycle base. It is unexpected that there is an optimum mole ratio with a strong organic base, but not with a strong inorganic base and PTC that generate the same strong organic base in situ. Moreover, the inorganic system gave 2-NDPA+azoxybenzene levels of 1.1% to 2.4%, whereas none was formed with TMAH. Again, it is surprising that these by-products are formed with a strong inorganic base, but not with a strong organic base.

Reference： [1]Current Patent Assignee: EASTMAN CHEMICAL CO - US2004/110986, 2004, A1 Location in patent: Page 4-14
[2]Current Patent Assignee: EASTMAN CHEMICAL CO - US2004/110986, 2004, A1 Location in patent: Page 15-17

43
[ 98-95-3 ]
[ 62-53-3 ]
[ 102-07-8 ]
[ 92-82-0 ]
[ 156-10-5 ]
[ 836-30-6 ]
[ 119-75-5 ]
[ 1227476-15-4 ]

Yield	Reaction Conditions	Operation in experiment
	With sodium hydroxide In dimethyl sulfoxide at 80℃; for 3h;	6 Example 6 The changes in the amounts of 4-NODPA and 4-NDPA, so generated, were observed from this Example, when various types of base were added. A mixture of 1.0g of carbanilide (4.7mmole), 5.8g of nitrobenzene (47mmole), 4.4g of aniline (47mmole) and base (28mmole) was added to 5ml DMSO in a 100ml three-necked flask equipped with a cooler and an agitator, and reacted under the atmosphere of oxygen at 80°C for 3 hours. After the reacting solution was extracted with ethylac'etate, the extract was analyzed on gas chromatography. The results were shown in the following Table 7. From the above Table 7, it was revealed that when sodium hydroxide, potassium hydroxide or sodium hydride as a base was employed, the selectivity or yield of final product was high.
	With sodium hydride In dimethyl sulfoxide at 80℃; for 3h;	6 Example 6 The changes in the amounts of 4-NODPA and 4-NDPA, so generated, were observed from this Example, when various types of base were added. A mixture of 1.0g of carbanilide (4.7mmole), 5.8g of nitrobenzene (47mmole), 4.4g of aniline (47mmole) and base (28mmole) was added to 5ml DMSO in a 100ml three-necked flask equipped with a cooler and an agitator, and reacted under the atmosphere of oxygen at 80°C for 3 hours. After the reacting solution was extracted with ethylac'etate, the extract was analyzed on gas chromatography. The results were shown in the following Table 7. From the above Table 7, it was revealed that when sodium hydroxide, potassium hydroxide or sodium hydride as a base was employed, the selectivity or yield of final product was high.
	With potassium <i>tert</i>-butylate In dimethyl sulfoxide at 80℃; for 3h;	6 Example 6 The changes in the amounts of 4-NODPA and 4-NDPA, so generated, were observed from this Example, when various types of base were added. A mixture of 1.0g of carbanilide (4.7mmole), 5.8g of nitrobenzene (47mmole), 4.4g of aniline (47mmole) and base (28mmole) was added to 5ml DMSO in a 100ml three-necked flask equipped with a cooler and an agitator, and reacted under the atmosphere of oxygen at 80°C for 3 hours. After the reacting solution was extracted with ethylac'etate, the extract was analyzed on gas chromatography. The results were shown in the following Table 7. From the above Table 7, it was revealed that when sodium hydroxide, potassium hydroxide or sodium hydride as a base was employed, the selectivity or yield of final product was high.

Reference： [1]Current Patent Assignee: KUMHO PETRO CHEMICAL CO.,LTD.; GOLDSTAR PETROCHEMICAL - EP1206441, 2004, B1 Location in patent: Page 8
[2]Current Patent Assignee: KUMHO PETRO CHEMICAL CO.,LTD.; GOLDSTAR PETROCHEMICAL - EP1206441, 2004, B1 Location in patent: Page 8
[3]Current Patent Assignee: KUMHO PETRO CHEMICAL CO.,LTD.; GOLDSTAR PETROCHEMICAL - EP1206441, 2004, B1 Location in patent: Page 8

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[ 98-95-3 ]
[ 62-53-3 ]
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[ 156-10-5 ]
[ 836-30-6 ]
[ 1227476-15-4 ]
[ 101-54-2 ]

Yield	Reaction Conditions	Operation in experiment
	With potassium hydroxide In dimethyl sulfoxide at 80℃; for 3h;	8 Example 8 The changes in the amounts of 4-NODPA and 4-NDPA, so generated, were observed from this Example, when various types of solvent were added. A mixture of 1.0g of carbanilide (4.7mmole), 5.8g of nitrobenzene (47mmole), 4.4g of aniline (47mmole) and 1.6g of potassium hydroxide (28mmole) was added to a solvent (10ml) in a 100ml three-necked flask equipped with a cooler and an agitator, and reacted at 80°C for 3 hours in the air. After the reacting solution was extracted with ethylacetate, the extract was analyzed on gas chromatography. The results were shown in the following Table 9. From the above Table 9, it was revealed that the most preferred solvent of this invention was DMSO, and the yield of reactants was high using a co-solvent containing DMF, NMP, dioxane, THF and t-BuOH with DMSO.
	With potassium hydroxide In 1-methyl-pyrrolidin-2-one; dimethyl sulfoxide at 80℃; for 3h;	8 Example 8 The changes in the amounts of 4-NODPA and 4-NDPA, so generated, were observed from this Example, when various types of solvent were added. A mixture of 1.0g of carbanilide (4.7mmole), 5.8g of nitrobenzene (47mmole), 4.4g of aniline (47mmole) and 1.6g of potassium hydroxide (28mmole) was added to a solvent (10ml) in a 100ml three-necked flask equipped with a cooler and an agitator, and reacted at 80°C for 3 hours in the air. After the reacting solution was extracted with ethylacetate, the extract was analyzed on gas chromatography. The results were shown in the following Table 9. From the above Table 9, it was revealed that the most preferred solvent of this invention was DMSO, and the yield of reactants was high using a co-solvent containing DMF, NMP, dioxane, THF and t-BuOH with DMSO.
	With potassium hydroxide In dimethyl sulfoxide; <i>tert</i>-butyl alcohol at 80℃; for 3h;	8 Example 8 The changes in the amounts of 4-NODPA and 4-NDPA, so generated, were observed from this Example, when various types of solvent were added. A mixture of 1.0g of carbanilide (4.7mmole), 5.8g of nitrobenzene (47mmole), 4.4g of aniline (47mmole) and 1.6g of potassium hydroxide (28mmole) was added to a solvent (10ml) in a 100ml three-necked flask equipped with a cooler and an agitator, and reacted at 80°C for 3 hours in the air. After the reacting solution was extracted with ethylacetate, the extract was analyzed on gas chromatography. The results were shown in the following Table 9. From the above Table 9, it was revealed that the most preferred solvent of this invention was DMSO, and the yield of reactants was high using a co-solvent containing DMF, NMP, dioxane, THF and t-BuOH with DMSO.

With potassium hydroxide In tetrahydrofuran; dimethyl sulfoxide at 80℃; for 3h;

8 Example 8 The changes in the amounts of 4-NODPA and 4-NDPA, so generated, were observed from this Example, when various types of solvent were added. A mixture of 1.0g of carbanilide (4.7mmole), 5.8g of nitrobenzene (47mmole), 4.4g of aniline (47mmole) and 1.6g of potassium hydroxide (28mmole) was added to a solvent (10ml) in a 100ml three-necked flask equipped with a cooler and an agitator, and reacted at 80°C for 3 hours in the air. After the reacting solution was extracted with ethylacetate, the extract was analyzed on gas chromatography. The results were shown in the following Table 9. From the above Table 9, it was revealed that the most preferred solvent of this invention was DMSO, and the yield of reactants was high using a co-solvent containing DMF, NMP, dioxane, THF and t-BuOH with DMSO.

Reference： [1]Current Patent Assignee: KUMHO PETRO CHEMICAL CO.,LTD.; GOLDSTAR PETROCHEMICAL - EP1206441, 2004, B1 Location in patent: Page 9
[2]Current Patent Assignee: KUMHO PETRO CHEMICAL CO.,LTD.; GOLDSTAR PETROCHEMICAL - EP1206441, 2004, B1 Location in patent: Page 9
[3]Current Patent Assignee: KUMHO PETRO CHEMICAL CO.,LTD.; GOLDSTAR PETROCHEMICAL - EP1206441, 2004, B1 Location in patent: Page 9
[4]Current Patent Assignee: KUMHO PETRO CHEMICAL CO.,LTD.; GOLDSTAR PETROCHEMICAL - EP1206441, 2004, B1 Location in patent: Page 9

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[ 98-95-3 ]
[ 62-53-3 ]
[ 102-07-8 ]
[ 156-10-5 ]
[ 836-30-6 ]

Yield	Reaction Conditions	Operation in experiment
	With sodium hydroxide; oxygen In dimethyl sulfoxide at 80℃; for 7h;	1 Example 1 A mixture of 1.0g of carbanilide (4.7mmole), 5.8g of nitrobenzene (47mmole), 4.4g of aniline (47mmole) and 20ml DMSO was added to a 100ml three-necked flask equipped with a cooler and an agitator. Then 1.1g of sodium hydroxide (28mmole) was added to the resulting solution 3 times at the interval of 1 hour and reacted under the atmosphere of oxygen at 80°C for 7 hours. At the initial reaction, 100mg of pyrene was added as an internal standard material (this material was also added in other all Examples). The reacting solution was extracted with ethylacetate and from the analysis of gas chromatography, 204 mole% of 4-NDPA and 63 mole% of 4-NODPA were obtained as a basis of the initially-added carbanilide.

Reference： [1]Current Patent Assignee: KUMHO PETRO CHEMICAL CO.,LTD.; GOLDSTAR PETROCHEMICAL - EP1206441, 2004, B1 Location in patent: Page 5

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[ 98-95-3 ]
[ 62-53-3 ]
[ 102-07-8 ]
[ 836-30-6 ]
[ 1227476-15-4 ]

Yield	Reaction Conditions	Operation in experiment
	With potassium hydroxide In DMF (N,N-dimethyl-formamide) at 80℃; for 3h;	8 Example 8 The changes in the amounts of 4-NODPA and 4-NDPA, so generated, were observed from this Example, when various types of solvent were added. A mixture of 1.0g of carbanilide (4.7mmole), 5.8g of nitrobenzene (47mmole), 4.4g of aniline (47mmole) and 1.6g of potassium hydroxide (28mmole) was added to a solvent (10ml) in a 100ml three-necked flask equipped with a cooler and an agitator, and reacted at 80°C for 3 hours in the air. After the reacting solution was extracted with ethylacetate, the extract was analyzed on gas chromatography. The results were shown in the following Table 9. From the above Table 9, it was revealed that the most preferred solvent of this invention was DMSO, and the yield of reactants was high using a co-solvent containing DMF, NMP, dioxane, THF and t-BuOH with DMSO.

Reference： [1]Current Patent Assignee: KUMHO PETRO CHEMICAL CO.,LTD.; GOLDSTAR PETROCHEMICAL - EP1206441, 2004, B1 Location in patent: Page 9

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[ 98-95-3 ]
[ 62-53-3 ]
[ 156-10-5 ]
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Yield	Reaction Conditions	Operation in experiment
1: 76% 2: 20%	Stage #1: aniline With potassium hydroxide at 60℃; for 3h; Stage #2: nitrobenzene at 60℃;	General procedure for reaction of nitrobenzene and aniline General procedure: A 250 ml reactor with a mechanical stirrer was charged with PEG 4000 (35 g) and potassium hydroxide (5.88 g, 95 mmol). For dissolving of KOH small amount of methanol (3 ml) was added and the mixture was heated to 120°C under vigorous stirring for 20 min. The clean homogenous solution obtained was cooled to 60°C, and aniline (60 ml, 0.65 mol) was added inone portion. Then the reactor was connected to vacuum line, and under pressure of 60 mbar dry air was bubbled through the reaction mixtureat flow rate 375 ml min-1, and the air flow was kept at this rate until the reaction was complete. Using a syringe pump nitrobenzene (8.85 g,72 mmol) was introduced at the rate 0.1 ml min-1 keeping the temperatureat 60°C. After additional 1 h excess of aniline was removed by distillation under 0.1 mbar pressure, and the residue was neutralized with HCl solution(10 n, 10.5 ml) to give a solution of (4-nitrosophenyl)phenylamine(10.83 g, 76%) and (4-nitrophenyl)phenylamine (3.85 g, 20%) in PEG 4000/water. For next manipulations and details, see Online Supplementary Materials
	With sodium hydroxide; tetramethyl ammoniumhydroxide; tetramethylammonium carbonate In ethanol at 75℃; for 5h;	3 Example 3 A. Condensation Under vacuum condition, feeding pumps for the above complex base catalyst, aniline and nitrobenzene were simultaneously switched on and adjusted to such flow rate as aniline 150 kg/h, nitrobenzene 30 kg/h and the complex base catalyst 200 kg/h. The aniline, nitrobenzene and complex base catalyst were continuously fed into a falling film reactor to be heated and allowed to condense. Condensation liquid in the falling film reactor was discharged from the bottom into a first reactor to proceed with condensing. Part of condensation liquid from the bottom of the first reactor was conveyed back to the falling film reactor via a circulating pump, forming a local circulating system. Ethanol vapor at 78-90° C. was used as the heat medium of the falling film reactor. Reaction temperature was controlled as 75° C., pressure was controlled as 0.008 MPa (absolute pressure) and flow rate of the circulating liquid was controlled as 1 m3/h. The reactants overflowed from the first reactor into a second reactor. The process conditions of the second reactor, such as operational temperature and pressure, were identical with that of the first reactor. The total residence time of the reactants in the falling film reactor, first reactor and second reactor was controlled as 5 h. Once the condensation reaction became stable, the complex base catalyst recovered according to the procedure as described below could be used, with only a minor amount of fresh complex base catalyst prepared according to example 1 being replenished, and the molar ratio of hydroxide ion to nitrobenzene in the reaction mixture was controlled not less than 1:1. The effluent of the second reactor was found to contain not larger than 0.1 wt.-% of nitrobenzene, 24.9 wt.-% of water and 16.1 wt.-% of 4-nitrosodiphenylamine and 4-nitrodiphenylamine. B. Separation I Thus obtained condensation liquid was continuously fed into the separation I process stage. To the condensation liquid subjected to filtering were introduced carbon dioxide and water until pH of the solution reaches about 8. The layers of system were separated, then calcium hydroxide was added at a rate of 25 kg/h to the obtained aqueous phase. After filtering, the obtained complex base catalyst was concentrated to its initial concentration, then conveyed back to the condensation process. The obtained organic phase contained 4-nitrodiphenylamine and 4-nitrosodiphenylamine. C. Hydrogenation The organic phase containing 4-nitrodiphenylamine and 4-nitrosodiphenylamine obtained by filtration in the separation I was fed to a first-stage hydrogenation reactor equipped with a sealed magnetic stirrer and a cooling and heating system. Hydrogen gas was used to replace the atmosphere of the system and pressurize to 1.3 MPa. A hydrogen gas circulator was switched on and flow rate of circulating hydrogen gas was maintained at 1 Nm3/h. The circulating hydrogen gas was bubbled into the hydrogenation reactors to improve the gas-liquid mass transfer effect during reaction. The flow rate of the organic phase containing 4-nitrodiphenylamine and 4-nitrosodiphenylamine was controlled as 180 kg/h, and the flow rate of methanol was controlled as 48 kg/h. The powdery composite catalyst above-prepared was added simultaneously to the reactor so that the solid-liquid ratio by weight was 6:100. Hydrogenation-reduced liquid overflowed from the first-stage reactor into a second-stage reactor, then into a third-stage reactor, finally into a settler. The reaction temperature was 75-80° C., pressure was 1.3 MPa and total residence time was 5 h. The powdery composite catalyst was recovered as much as possible under the action of a magnetic separator. Solid-liquid mixture containing higher concentration of solid catalyst at the bottom of the settler was returned to the first-stage hydrogenation reactor via a Venturi type solid-liquid conveying device using the power of feeding stocks. The activity of the catalyst in the hydrogenation reaction was judged by monitoring the endpoint of reducing reaction, and thus it could be determined whether powdery composite catalyst for hydrogenation reaction was replenished. The hydrogenation liquid was measured by high performance liquid chromatograph (HPLC) and was found not containing 4-nitrodiphenylamine and 4-nitrosodiphenylamine. D. Separation II The above hydrogenation liquid was conveyed to separation II process stage. The hydrogenation liquid was subjected to filtration to recover a minor amount of the powdery composite catalyst entrained in the hydrogenation liquid. The powdery composite catalyst recovered by filtration was recycled back to the hydrogenation process after regeneration. The filtrate was fed at a flow rate of 228 kg/h to a methanol column, where methanol was obtained from column top and could be reused in the hydrogenation process. The bottoms was fed to an aniline column, where aniline was obtained from the column top and recycled back to the condensation process stage, and crude 4-aminodiphenylamine was obtained from column bottom. The aniline column was operated at a pressure of 0.005 MPa (absolute pressure), a column bottom temperature of 150 to 160° C., and a gas phase temperature of 115 to 125° C. E. Refining The crude 4-aminodiphenylamine from multiple sets of separation II equipment enters one set of refining equipment. The crude product of 4-aminodiphenylamine (containing 78.1 percent of 4-aminodiphenylamine, 21.75 percent of aniline, 0.05 percent of azobenzene and 0.1 percent of phenazine) was continuously fed to rectification column 1 at a flow rate of 120 kg/h via a gear pump. The temperature of still was controlled as 270° C., the temperature of column top was controlled as 110° C., vacuum degree was controlled as 0.094 MPa and reflux ratio was controlled as 5:1. Light components, i.e. aniline, azobenzene and phenazine, were taken out from the column top at a flow rate of about 26.2 kg/h, and conveyed to rectification column 3. The rectification column 3 was operated at conditions of still temperature of 150° C., column top temperature of 90° C., vacuum degree of 0.094 MPa and reflux ratio of 1:1. Aniline was distilled off from column top at a flow rate of 24 kg/h, and azobenzene and phenazine were left in column bottom. Bottoms of the rectification column 1 were conveyed to rectification column 2. The rectification column 2 was operated at conditions of still temperature of 280° C., column top temperature of 170° C., vacuum degree of 0.097 MPa and reflux ratio of 1:1. The finished 4-aminodiphenylamine was obtained at the column top of the rectification column 2. Bottoms of the rectification column 2 were conveyed to batch still. The batch still was operated at conditions of kettle temperature of 285-320° C., vacuum degree of 0.094 MPa and top temperature of 235-250° C., to distill off the residual 4-aminodiphenylamine, which was recycled back to the rectification column 2 to be further distilled. The whole refining process of 4-aminodiphenylamine was continuously carried out. The finished 4-aminodiphenylamine product obtained had a purity of 99.1%, a melting point of 72° C. and a solidifying point of 72.4° C. The yield of the process in industrial scale production was 95.1%.
	With sodium hydroxide; tetramethyl ammoniumhydroxide; water at 75℃;	14 Example 14 Effect on Condensation Reaction Imposed by Water A local circulating system having a total volume of 1L equipped with a vacuum system and a temperature control system was comprised of a miniature reactor, a film reactor and a circulating pump. The system was firstly filled with aniline, and the flow of the circulating pump was set at 2 l/h. A mixing liquid containing nitrobenzene, aniline and the complex base catalyst at a molar ratio of nitrobenzene to aniline to OH- in the complex base catalyst of 1:7:1.15 was fed to the reactor at a certain flow. The system temperature was maintained at 75° C. and the system pressure was maintained at 0.008 MPa (absolute). After the aniline was replaced by reaction liquid and reaction liquid was stable in composition, the feeding flow rate of the reaction mixture was varied to adjust the residence time. The water contents of reaction effluent, measured when the measured content of nitrobenzene was equal to or less than 0.1% and calculated yield based on 4-nitrosodiphenylamine and 4-nitrodiphenylamine generated was 97%, were listed below. Molar ratio of three components in complex base catalyst Tetramethyl ammonium hydroxide:N,N-dimethyl-N,N-bis(ethoxylated (1-4 moles of ethylene oxide) propyl) Water content No. ammonium carbonate:sodium hydroxide in product (%) 1 5:2:2 5.1 2 3:2:2 10.2 3 2:2:2 15.4 4 1:2:1 17.5 5 0.5:2:0.5 19.8 6 Tetramethyl ammonium hydroxide is 1.2 used as catalyst It can be seen that water content at the end of the reaction increases as the proportion of N,N-dimethyl-N,N-bis(ethoxylated (1-4 moles of ethylene oxide) propyl) ammonium carbonate in the complex catalyst increases. Namely, with the use of a complex base catalyst according to the present invention, the range of permitted water content in the reaction mixture at the end of reaction is greatly enlarged, that is, the yield is good enough even when there is a higher content of water in the reaction system. The less the water content is in the later phase of the reaction, the lower the dehydration efficiency is, thus reaction difficulty is reduced in the process according to the present invention. If only the tetramethyl ammonium hydroxide is used as catalyst, the yield cannot reach 97% until the water content of reaction mixture is reduced to 1.2% by dehydration, which imposes difficulty to the reaction control and increases the power consumption.

	With sodium hydroxide; tetramethyl ammoniumhydroxide; water at 75℃;	14 Example 14 Effect on Condensation Reaction Imposed by Water A local circulating system having a total volume of 1L equipped with a vacuum system and a temperature control system was comprised of a miniature reactor, a film reactor and a circulating pump. The system was firstly filled with aniline, and the flow of the circulating pump was set at 2 l/h. A mixing liquid containing nitrobenzene, aniline and the complex base catalyst at a molar ratio of nitrobenzene to aniline to OH- in the complex base catalyst of 1:7:1.15 was fed to the reactor at a certain flow. The system temperature was maintained at 75° C. and the system pressure was maintained at 0.008 MPa (absolute). After the aniline was replaced by reaction liquid and reaction liquid was stable in composition, the feeding flow rate of the reaction mixture was varied to adjust the residence time. The water contents of reaction effluent, measured when the measured content of nitrobenzene was equal to or less than 0.1% and calculated yield based on 4-nitrosodiphenylamine and 4-nitrodiphenylamine generated was 97%, were listed below. Molar ratio of three components in complex base catalyst Tetramethyl ammonium hydroxide:N,N-dimethyl-N,N-bis(ethoxylated (1-4 moles of ethylene oxide) propyl) Water content No. ammonium carbonate:sodium hydroxide in product (%) 1 5:2:2 5.1 2 3:2:2 10.2 3 2:2:2 15.4 4 1:2:1 17.5 5 0.5:2:0.5 19.8 6 Tetramethyl ammonium hydroxide is 1.2 used as catalyst It can be seen that water content at the end of the reaction increases as the proportion of N,N-dimethyl-N,N-bis(ethoxylated (1-4 moles of ethylene oxide) propyl) ammonium carbonate in the complex catalyst increases. Namely, with the use of a complex base catalyst according to the present invention, the range of permitted water content in the reaction mixture at the end of reaction is greatly enlarged, that is, the yield is good enough even when there is a higher content of water in the reaction system. The less the water content is in the later phase of the reaction, the lower the dehydration efficiency is, thus reaction difficulty is reduced in the process according to the present invention. If only the tetramethyl ammonium hydroxide is used as catalyst, the yield cannot reach 97% until the water content of reaction mixture is reduced to 1.2% by dehydration, which imposes difficulty to the reaction control and increases the power consumption.
	With sodium hydroxide; tetramethyl ammoniumhydroxide; tetramethylammonium methyl carbonate at 75℃;	15 Example 15 Anhydrous complex catalyst prepared in example 8 and 651 g of aniline were charged into a four-necked flask with stirring device and thermometer. With stirring, the temperature was elevated to 75° C. and pressure was reduced to 0.008 MPa (absolute pressure). Aniline was returned to the four-necked flask after demixing the water-aniline azeotrope distilled until the water content in the system is less than 0.5%. 123 g of nitrobenzene was dropwise added over 2 h, then the dehydrating was continued for 4 h. It was found via chromatographic analysis that the yield of 4-nitrosodiphenylamine and 4-nitrodiphenylamine was 97.4% and the water content in the system was less than 0.5%.
	With sodium hydroxide; tetramethyl ammoniumhydroxide; tetramethylammonium carbonate at 75℃; for 5h;	13 Example 13 Effect on Reaction Imposed by the Quantity of Aniline and Nitrobenzene A local circulating system having a total volume of 1L equipped with a vacuum system and a temperature control system was comprised of a miniature reactor, a film reactor and a circulating pump. The system was firstly filled with aniline, and the flow of the circulating pump was set at 2 l/h. A mixture, containing nitrobenzene, aniline and the complex base catalyst prepared according to example 1 at a molar ratio of nitrobenzene to aniline to OH- in the complex base catalyst of 1:1:1.8, was fed to the reactor at a flow rate of 200 ml/h. The residence time was 5 h. The system temperature was maintained at 75° C. and the system pressure was maintained at 0.008 MPa (absolute pressure). After the aniline was replaced by reaction liquid and reaction liquid was stable in composition, a sample was taken and analyzed. Nitrobenzene was substantially not detectable. The reaction selectivity was calculated according to the total mole number of 4-nitrosodiphenylamine and 4-nitrodiphenylamine generated. The results obtained under the same conditions except that the ratio of nitrobenzene to aniline was changed were showed in table 1. TABLE 1 Effect on reaction imposed by the quantity of aniline and nitrobenzene Nitrobenzene:aniline Reaction selectivity No. (mol/mol) (%) 1 1:1 90.2 2 1:3 96.1 3 1:5 99.1 4 1:10 99.3 It can be seen from the data showed in table 1 that increasing the molar ratio of aniline to nitrobenzene will enhance the reaction selectivity, increase target products and reduce the by-products. However, in the practice, if the quantity of aniline is too large, the loss of aniline and the energy consumption during separation will increase.
	Stage #1: aniline With tetramethyl ammoniumhydroxide In water at 60 - 75℃; Stage #2: nitrobenzene In water at 75 - 80℃; for 3.41667h;	1 Preparation of 4-ADFA precursors Preparation of 4-ADFA precursors 1242 g of regenerated 25 wt. % tetramethylammonium hydroxide (TMAH) aqueous solution was concentrated to about 36 wt. % at the pressure of about 7.0 kPa and at the temperature of solution increasing from 40°C to 70°C. Then 1516 g of aniline was added, and removing of water continued by distillation of an azeotropic water-aniline mixture at the pressure of about 7.0 kPa and at the temperature of solution increasing from 60°C to 75°C, until a final water/TMAH mole ratio below 3.4 was reached. 376 g of nitrobenzene was added during 145 min, wherein distillation of an azeotropic water-aniline mixture at the pressure of about 7.0 kPa continued (in the end of nitrobenzene addition, the reaction mixture had a temperature of 80°C). After the adding of nitrobenzene was completed, the batch for condensation was stirred for another 1 hour. The distillation rate was adjusted to achieve the water/TMAH mole ratio of 0.55 (or lower) in the end of the reaction (i.e. after adding the complete amount of nitrobenzene plus the time period for finishing the reaction).
	With tetramethyl ammoniumhydroxide at 76℃; for 3h;	1 preparation of (4-nitrosodiphenylamine and 4-nitrodiphenylamine with quaternary ammonium tetramethylammonium hydroxide catalyst) First open nitrobenzene, aniline, quaternary ammonium tetramethylammonium hydroxide catalyst pump through the flow control to control the flow of aniline 13.2 cubic meters / hour, nitrobenzene flow of 2 cubic meters / hour, Were continuously treated in a vacuum degassing tank containing alkali metal hydroxide (30% NaOH) The purpose is to remove the raw materials dissolved and adsorbed acidic substances and some is not conducive to nitrobenzene, aniline condensation reaction of gas, The nitrobenzene (added at 4 different points in the tubular condensation reactor) after alkali metal hydroxide treatment and degassing were 0.6 cubic meters per hour, 0.6 cubic meters per hour, 0.5 cubic meters per hour, 0.3 Cubic / hour, The aniline and quaternary ammonium tetramethylammonium hydroxide catalysts treated with alkali metal hydroxide and degassed were continuously passed into a vacuum state concentrator by controlling the flow rate of 6 cubic meters per hour and then passed through a static mixer to a tubular condensation reactor Internal with a heat transfer tube), Control reaction pressure (vacuum) -0.096 (Mpa); reaction temperature of 76 (); The material was passed through a tubular condensation reactor for a time of 3 (hours) With the addition of nitrobenzene at different points in the tubular condensation reactor and the increase of the material flow through the tubular condensation reactor, the water content will gradually decrease and the condensation reaction will gradually accelerate, By controlling the amount of dewatering until the residual mass of nitrobenzene in the condensate is 1-2%At this time by-product azobenzene, phenazine equal amount of the least,And finally a mixture of 4-nitrosodiphenylamine and 4-nitrodiphenylamine and quaternary ammonium quaternary ammonium hydroxide catalyst is formed. The selectivity to nitrobenzene relative to the conversion was 99.06%.
	Stage #1: aniline With phthalic anhydride In cyclohexane at 160℃; for 1h; Stage #2: nitrobenzene With tetramethyl ammoniumhydroxide; sodium hydroxide In cyclohexane; water at 50 - 80℃; for 3h; Overall yield = 93.3 %;	1.1-1.3; 2.1-2.3; 3.1-3.3; 4.1-4.3; 5.1-5.3; 6.1-6.3 (1) Dissolving phthalic anhydride in cyclohexane, passing it into a microchannel reactor together with aniline, and performing an aminolysis reaction at 160 ° C for 60 min to obtainO-carboxybenzoanilideSolutionamong them,The mass ratio of phthalic anhydride anhydride to cyclohexane is 1:5,The molar ratio of phthalic anhydride to aniline is 1.5:1;(2) an aqueous solution of tetramethylammonium hydroxide and sodium hydroxide,The nitrobenzene, and the o-carboxybenzanilide solution obtained in the step (1) are passed into a microchannel reactor, and the condensation reaction is carried out at 50 ° C for 3 hours to form 4-nitrodiphenylamine and 4-nitrosodiphenylamine;Wherein the molar ratio of nitrobenzene to aniline is 1:1.2, the molar ratio of nitrobenzene to tetramethylammonium hydroxide is 1:1, and the molar ratio of tetramethylammonium hydroxide to sodium hydroxide is 1:2.4. ;(3) mixing the mixed solution obtained in the step (2) with a 22% sodium hydroxide solution, and performing a hydrolysis reaction at 80 ° C under stirring to separate the aqueous phase and the oil phase.The oil phase is distilled off under reduced pressure to remove the organic solvent and unreacted aniline.a mixture of 4-nitrodiphenylamine and 4-nitrosodiphenylamine,The yield (in terms of nitrobenzene) was 93.3%.

Reference： [1]Babkin, Alexander V.; Asachenko, Andrey F.; Uborsky, Dmitry V.; Kononovich, Dmitry S.; Izmer, Vyatcheslav V.; Kudakina, Vera A.; Shnaider, Viktoriya A.; Shevchenko, Nikolay E.; Voskoboynikov, Alexander Z. [Mendeleev Communications, 2016, vol. 26, # 6, p. 555 - 557]
[2]Current Patent Assignee: SINOCHEM HOLDINGS CORPORATION LTD - US2005/65376, 2005, A1 Location in patent: Page/Page column 9-10
[3]Current Patent Assignee: SINOCHEM HOLDINGS CORPORATION LTD - US2005/65376, 2005, A1 Location in patent: Page/Page column 12
[4]Current Patent Assignee: SINOCHEM HOLDINGS CORPORATION LTD - US2005/65376, 2005, A1 Location in patent: Page/Page column 12
[5]Current Patent Assignee: SINOCHEM HOLDINGS CORPORATION LTD - US2005/65376, 2005, A1 Location in patent: Page/Page column 12
[6]Current Patent Assignee: SINOCHEM HOLDINGS CORPORATION LTD - US2005/65376, 2005, A1 Location in patent: Page/Page column 12
[7]Current Patent Assignee: DUSLO, A.S. - WO2015/94128, 2015, A1 Location in patent: Page/Page column 5
[8]Current Patent Assignee: CHINA SUNSINE CHEMICAL HOLDINGS LTD. - CN103864626, 2016, B Location in patent: Paragraph 0035-0036
[9]Current Patent Assignee: KEMAI CHEMICAL - CN109232275, 2019, A Location in patent: Paragraph 0049-0090

48
[ 156-10-5 ]
[ 836-30-6 ]
[ 101-54-2 ]

Yield	Reaction Conditions	Operation in experiment
	With hydrogen In ethanol at 100℃; for 4h;	18 Example 18 Batch Hydrogenating Example 500 g of separation I liquid containing 17.5 weight percent of 4-nitrosodiphenylamine and 3.0 weight percent of 4-nitrodiphenylamine was charged into a 1L autoclave with stirring device and temperature control device. 150 g of ethanol and 5 g of the powdery composite catalyst prepared in example 2 were added thereto. The system atmosphere was replaced with hydrogen gas for three times, and then the system was pressurized to 0.8 MPa. While stirring, the reaction mixture was heated to 100° C. and maintained at this temperature for 4 h. At the end of the reaction, the mixture was cooled, and then discharged after pressure release. The reaction liquid was analyzed via HPLC, and was found containing no 4-nitrosodiphenylamine and 4-nitrodiphenylamine but 14.6% of 4-aminodiphylamine (chromatograph content). Comparison of Powdery Composite Catalyst and Noble Metal Catalyst Pd/C catalyst with 5 wt. % of palladium was compared with the powdery composite catalyst according to the present invention. Experiments were carried out under the same conditions as described in above batch hydrogenating example. The quantities of catalysts used were identical, and both Pd/C catalyst and powdery composite catalyst were recovered and reused after the reaction. Within 21 times of reuse, 4-nitrosodiphenylamine was undetectable in both reaction liquids. However, at the twenty-first time of reuse, the reaction liquid obtained by using Pd/C catalyst was found containing 0.1 wt. % of 4-nitrodiphylamine while the reaction liquid obtained by using the powdery composite catalyst according to the present invention was found containing no 4-nitrodiphylamine. The results showed that the antitoxic performance of the powdery composite catalyst according to the present invention was better than that of the noble metal catalyst.
	With palladium on activated charcoal; hydrogen; aniline In methanol at 60℃; for 3.33333h;	1 Example 1 50 g of a 1% supported palladium carbon catalyst was added to the fixed bed reactor.31.25% methanol and 68.75% aniline were continuously added to the fixed bed reactor by a pump.Warming up to 60 ° C,Preheating the above-mentioned methanol with a concentration of 15% of 4-nitrosodiphenylamine and a concentration of 5% of 4-nitrodiphenylamine,Aniline solution to 60 ° C,The above solution is pumped into the fixed bed reactor.Adjust the solution flow rate to 0.2mL/min,The hydrogen pressure is 0.5 MPa,The hydrogen flow rate is 100 mL/min, and the reaction residence time is 200 min.Timed sampling analysis of reaction materials,The conversion rate of raw materials was 91.1%.The selectivity was 93.2%.Rectification treatment yields p-aminodiphenylamine.

Reference： [1]Current Patent Assignee: SINOCHEM HOLDINGS CORPORATION LTD - US2005/65376, 2005, A1 Location in patent: Page/Page column 13
[2]Current Patent Assignee: CHINA PETROCHEMICAL CORPORATION - CN108623472, 2018, A Location in patent: Paragraph 0017; 0018; 0019; 0020; 0021; 0022

49
[ 836-30-6 ]
[ 96-32-2 ]
methyl [(4-nitro-phenyl)-phenyl-amino]-acetate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	In N,N-dimethyl-formamide	19.a EXAMPLE 19 a) 4-Nitro-diphenylamine (Aldrich) is reacted with methyl bromoacetate in the presence of potassium carbonate in DMF at 70° C. to give methyl [(4-nitro-phenyl)-phenyl-amino]-acetate (brown oil). MS: 287 (M+1).

Reference： [1]Current Patent Assignee: ROCHE HOLDING AG; F (unclear) - US6297266, 2001, B1

50
[ 98-95-3 ]
[ 102-07-8 ]
[ 92-82-0 ]
[ 156-10-5 ]
[ 836-30-6 ]
[ 1227476-15-4 ]
[ 495-48-7 ]

Yield	Reaction Conditions	Operation in experiment
1: 37% 2: 8% 3: 3% 4: 4% 5: 12%	With tetramethyl ammoniumhydroxide In water at 70 - 100℃; for 3h;	1; 2; 3; 4 Experimental Example 1[43] 12.7 g (60 mmole) of carbanilide and 36.9 g (300 mmole) of nitrobenzene were put in a 200 mL, 3-necked round bottom flask equipped with a cooler and a stirrer. After heating the flask to 80 0C, 23.9 g (132 mmole) of TMA(OH) -5H O was added.Reaction was performed for 3 hours while keeping the degree of vacuum at about90-50 mmHg and distilling water. [44] 500 mg of pyrene was added as internal standard at the early step of the reaction(This procedure was applied to all experimental examples and examples). [45] Ethyl acetate was added to the reaction solution. The solution was neutralized with water and acetic acid. The ethyl acetate layer was separated and analyzed by HPLC. [46] Conversion ratio of carbanilide was 99 %. Production yield was 90 mole%4-NDPA and 8 mole% 4-NODPA, based on carbanilide. Byproducts were 8 mole% phenazine, 9 mole% azobenzene and 27 mole% azoxybenzene, based on carbanilide.; [47] Experimental Example 2[48] Production yield of 4-NDPA and 4-NODPA was compared for various nitrobenzene contents. [49] 12.7 g (60 mmole) of carbanilide and 4-10 molar equivalents of nitrobenzene were put in a 200 mL, 3-necked round bottom flask equipped with a cooler and a stirrer.After heating the flask to 80 0C, 21.7 g (120 mmole) of TMA(0H)-5H O was added.Reaction was performed for 3 hours while keeping the degree of vacuum at about90-50 mmHg and distilling water. [50] Ethyl acetate was added to the reaction solution. The solution was neutralized with water and acetic acid. The ethyl acetate layer was separated and analyzed by HPLC. [51] The result is given in Table 1.; [53] Experimental Example 3[54] Production yield of 4-NDPA and 4-NODPA was compared for various base contents. [55] 12.7 g (60 mmole) of carbanilide and 36.9 g (300 mmole) of nitrobenzene were put in a 200 mL, 3-necked round bottom flask equipped with a cooler and a stirrer. After heating the flask to 80 0C, 21.7 g (120 mmole) of TMA(OH) -5H O was added.Reaction was performed for 3 hours while keeping the degree of vacuum at about90-50 rnrnHg and distilling water. [56] Ethyl acetate was added to the reaction solution. The solution was neutralized with water and acetic acid. The ethyl acetate layer was separated and analyzed by HPLC. [57] Conversion ratio of carbanilide was 92 %. Production yield was 84 mole% 4-NDPA and 8 mole% 4-NODPA, based on carbanilide. Byproducts were 4 mole% phenazine, 7 mole% azobenzene and 25 mole% azoxybenzene, based on carbanilide.; [58] Experimental Example 4[59] Production yield of 4-NDPA and 4-NODPA was compared for various reaction temperatures. [60] 6.4 g (30mmole) of carbanilide and 36.9 g (300 mmole) of nitrobenzene were put in a 200 mL, 3-necked round bottom flask equipped with a cooler and a stirrer. Varying temperature, 10.9 g (60 mmole) of TMA(OH)-5H O was added. Reaction was performed for 3 hours while keeping the degree of vacuum at about 90-50 mmHg and distilling water. [61] Ethyl acetate was added to the reaction solution. The solution was neutralized with water and acetic acid. The ethyl acetate layer was separated and analyzed by HPLC. [62] The result is given in Table 2.
1: 29 - 90 %Chromat. 2: 3 - 9 %Chromat. 3: 0 - 8 %Chromat. 4: 0 - 10 %Chromat. 5: 0 - 27 %Chromat.	Stage #1: nitrobenzene; bis(diphenyl)urea With tetramethyl ammoniumhydroxide In water at 70 - 100℃; for 3h; Stage #2: With acetic acid In water; ethyl acetate	1; 2; 3; 4; 6 EXAMPLES Experimental Example 1 12.7 g (60 mmole) of carbanilide and 36.9 g (300 mmole) of nitrobenzene were put in a 200 mL, 3-necked round bottom flask equipped with a cooler and a stirrer. After heating the flask to 80° C., 23.9 g (132 mmole) of TMA(OH).5H2O was added. Reaction was performed for 3 hours while keeping the degree of vacuum at about 90-50 mmHg and distilling water. 500 mg of pyrene was added as internal standard at the early step of the reaction (This procedure was applied to all experimental examples and examples). Ethyl acetate was added to the reaction solution. The solution was neutralized with water and acetic acid. The ethyl acetate layer was separated and analyzed by HPLC. The conversion ratio of carbanilide was 99%. The production yield was 90 mole % 4-NDPA and 8 mole % 4-NODPA, based on carbanilide. By-products included 8 mole % phenazine, 9 mole % azobenzene and 27 mole % azoxybenzene, based on carbanilide. Experimental Example 2 Production yield of 4-NDPA and 4-NODPA was compared for various nitrobenzene contents. 12.7 g (60 mmole) of carbanilide and 4 to 10 molar equivalents of nitrobenzene were put in a 200 mL, 3-necked round bottom flask equipped with a cooler and a stirrer. After heating the flask to 80° C., 21.7 g (120 mmole) of TMA(OH).5H2O was added. Reaction was performed for 3 hours while keeping the degree of vacuum at about 90-50 mmHg and distilling water. Ethyl acetate was added to the reaction solution. The solution was neutralized with water and acetic acid. The ethyl acetate layer was separated and analyzed by HPLC. The results are shown in Table 1. TABLE 1 Nitrobenzene content* (molar Products (mole %)** equivalents) 4-NDPA 4-NODPA Phenazine Azobenzene Azoxybenzene 4 76 9 4 7 24 5 84 8 4 7 25 10 88 4 7 4 12 Molar equivalents of nitrobenzene per initial carbanilide. Production yield per initial carbanilide (mole %). Experimental Example 3 Production yield of 4-NDPA and 4-NODPA was compared for various base contents. 12.7 g (60 mmole) of carbanilide and 36.9 g (300 mmole) of nitrobenzene were put in a 200 mL, 3-necked round bottom flask equipped with a cooler and a stirrer. After heating the flask to 80° C., 21.7 g (120 mmole) of TMA(OH).5H2O was added. Reaction was performed for 3 hours while keeping the degree of vacuum at about 90-50 mmHg and distilling water. Ethyl acetate was added to the reaction solution. The solution was neutralized with water and acetic acid. The ethyl acetate layer was separated and analyzed by HPLC. The conversion ratio of carbanilide was 92%. The production yield was 84 mole % 4-NDPA and 8 mole % 4-NODPA, based on carbanilide. By-products included 4 mole % phenazine, 7 mole % azobenzene and 25 mole % azoxybenzene, based on carbanilide. Experimental Example 4 Production yield of 4-NDPA and 4-NODPA was compared for various reaction temperatures. 6.4 g (30 mmole) of carbanilide and 36.9 g (300 mmole) of nitrobenzene were put in a 200 mL, 3-necked round bottom flask equipped with a cooler and a stirrer. At varying temperatures, as shown below in Table 2, 10.9 g (60 mmole) of TMA(OH).5H2O was added. Reaction was performed for 3 hours while keeping the degree of vacuum at about 90-50 mmHg and distilling water. Ethyl acetate was added to the reaction solution. The solution was neutralized with water and acetic acid. The ethyl acetate layer was separated and analyzed by HPLC. The results are shown in Table 2. TABLE 2 Re- action Products (mole %) temp. 4- 4- (° C.) NDPA NODPA Phenazine Azobenzene Azoxybenzene 100 37 4 3 10 17 80 84 8 4 7 25 70 79 4 3 7 21 Production yield per initial carbanilide (mole %).; Experimental Example 6 Production yield of 4-NDPA and 4-NODPA was compared for various solvents. 12.7 g (60 mmole) of carbanilide and 36.9 g (300 mmole) of nitrobenzene were put in a 200 mL, 3-necked round bottom flask equipped with a cooler and a stirrer. 64 mL of reaction solvent was added to the flask. After heating the flask to 80° C., 21.7 g (120 mmole) of TMA(OH).5H2O was added. Reaction was performed for 3 hours while varying reaction conditions, as shown in Table 4, below. Ethyl acetate was added to the reaction solution. The solution was neutralized with water and acetic acid. The ethyl acetate layer was separated and analyzed by HPLC. The results are shown in Table 4. TABLE 4 Reaction Products (mole %) condition 4- 4- Solvents (mmHg) NDPA NODPA Phenazine Azoxybenzene Toluene 300 35 9 2 - Toluene 760 10 7 - - THF 760 9 3 - - DMSO 760 50 4 - 15 Benzene 760 24 10 2 5 Nitro- 760 29 3 - - benzene *Production yield per initial carbanilide (mole %).

Reference： [1]Current Patent Assignee: KUMHO PETRO CHEMICAL CO.,LTD. - WO2006/123878, 2006, A1 Location in patent: Page/Page column 6-8
[2]Current Patent Assignee: KUMHO PETRO CHEMICAL CO.,LTD. - US2006/258887, 2006, A1 Location in patent: Page/Page column 3-4; 5

51
[ 98-95-3 ]
[ 102-07-8 ]
[ 92-82-0 ]
[ 156-10-5 ]
[ 836-30-6 ]

Yield	Reaction Conditions	Operation in experiment
1: 35% 2: 9% 3: 2%	With tetramethyl ammoniumhydroxide In water; toluene at 80℃; for 3h;	6 Experimental Example 6; [71] Production yield of 4-NDPA and 4-NODPA was compared for various solvents. [72] 12.7 g (60 mmole) of carbanilide and 36.9 g (300 mmole) of nitrobenzene were put in a 200 mL, 3-necked round bottom flask equipped with a cooler and a stirrer. 64 mL of reaction solvent was added to the flask. After heating the flask to 80 0C, 21.7 g (120 mmole) of TMA(OH)-5H O was added. Reaction was performed for 3 hours while varying reaction conditions.[73] Ethyl acetate was added to the reaction solution. The solution was neutralized with EPO water and acetic acid. The ethyl acetate layer was separated and analyzed by HPLC.[74] The result is given in Table 4.
1: 10 - 35 %Chromat. 2: 7 - 9 %Chromat. 3: 0 - 2 %Chromat.	Stage #1: nitrobenzene; bis(diphenyl)urea With tetramethyl ammoniumhydroxide In water; toluene at 80℃; for 3h; Stage #2: With acetic acid In water; ethyl acetate; toluene	6 Experimental Example 6 Production yield of 4-NDPA and 4-NODPA was compared for various solvents. 12.7 g (60 mmole) of carbanilide and 36.9 g (300 mmole) of nitrobenzene were put in a 200 mL, 3-necked round bottom flask equipped with a cooler and a stirrer. 64 mL of reaction solvent was added to the flask. After heating the flask to 80° C., 21.7 g (120 mmole) of TMA(OH).5H2O was added. Reaction was performed for 3 hours while varying reaction conditions, as shown in Table 4, below. Ethyl acetate was added to the reaction solution. The solution was neutralized with water and acetic acid. The ethyl acetate layer was separated and analyzed by HPLC. The results are shown in Table 4. TABLE 4 Reaction Products (mole %)* condition 4- 4- Solvents (mmHg) NDPA NODPA Phenazine Azoxybenzene Toluene 300 35 9 2 - Toluene 760 10 7 - - THF 760 9 3 - - DMSO 760 50 4 - 15 Benzene 760 24 10 2 5 Nitro- 760 29 3 - - benzene *Production yield per initial carbanilide (mole %).

Reference： [1]Current Patent Assignee: KUMHO PETRO CHEMICAL CO.,LTD. - WO2006/123878, 2006, A1 Location in patent: Page/Page column 8-9
[2]Current Patent Assignee: KUMHO PETRO CHEMICAL CO.,LTD. - US2006/258887, 2006, A1 Location in patent: Page/Page column 5

52
[ 98-95-3 ]
[ 102-07-8 ]
[ 92-82-0 ]
[ 156-10-5 ]
[ 836-30-6 ]
[ 495-48-7 ]

Yield	Reaction Conditions	Operation in experiment
1: 24% 2: 10% 3: 5% 4: 2%	With tetramethyl ammoniumhydroxide In water; benzene at 80℃; for 3h;	6 Experimental Example 6; [71] Production yield of 4-NDPA and 4-NODPA was compared for various solvents. [72] 12.7 g (60 mmole) of carbanilide and 36.9 g (300 mmole) of nitrobenzene were put in a 200 mL, 3-necked round bottom flask equipped with a cooler and a stirrer. 64 mL of reaction solvent was added to the flask. After heating the flask to 80 0C, 21.7 g (120 mmole) of TMA(OH)-5H O was added. Reaction was performed for 3 hours while varying reaction conditions.[73] Ethyl acetate was added to the reaction solution. The solution was neutralized with EPO water and acetic acid. The ethyl acetate layer was separated and analyzed by HPLC.[74] The result is given in Table 4.
1: 24 %Chromat. 2: 10 %Chromat. 3: 2 %Chromat. 4: 5 %Chromat.	Stage #1: nitrobenzene; bis(diphenyl)urea With tetramethyl ammoniumhydroxide In water; benzene at 80℃; for 3h; Stage #2: With acetic acid In water; ethyl acetate; benzene	5 Experimental Example 6 Production yield of 4-NDPA and 4-NODPA was compared for various solvents. 12.7 g (60 mmole) of carbanilide and 36.9 g (300 mmole) of nitrobenzene were put in a 200 mL, 3-necked round bottom flask equipped with a cooler and a stirrer. 64 mL of reaction solvent was added to the flask. After heating the flask to 80° C., 21.7 g (120 mmole) of TMA(OH).5H2O was added. Reaction was performed for 3 hours while varying reaction conditions, as shown in Table 4, below. Ethyl acetate was added to the reaction solution. The solution was neutralized with water and acetic acid. The ethyl acetate layer was separated and analyzed by HPLC. The results are shown in Table 4. TABLE 4 Reaction Products (mole %)* condition 4- 4- Solvents (mmHg) NDPA NODPA Phenazine Azoxybenzene Toluene 300 35 9 2 - Toluene 760 10 7 - - THF 760 9 3 - - DMSO 760 50 4 - 15 Benzene 760 24 10 2 5 Nitro- 760 29 3 - - benzene *Production yield per initial carbanilide (mole %).

Reference： [1]Current Patent Assignee: KUMHO PETRO CHEMICAL CO.,LTD. - WO2006/123878, 2006, A1 Location in patent: Page/Page column 8-9
[2]Current Patent Assignee: KUMHO PETRO CHEMICAL CO.,LTD. - US2006/258887, 2006, A1 Location in patent: Page/Page column 4-5

53
[ 98-95-3 ]
[ 102-07-8 ]
[ 156-10-5 ]
[ 836-30-6 ]
[ 1227476-15-4 ]
[ 495-48-7 ]

Yield	Reaction Conditions	Operation in experiment
1: 52% 2: 6% 3: 9% 4: 8%	With sodium hydroxide; tetramethyl ammoniumhydroxide In water at 80℃; for 3h;	5 Experimental Example 5; [65] Production yield of 4-NDPA and 4-NODPA was compared for various mixture bases including TMA(0H)-5H O and inorganic bases.[66] 6.4 g (30mmole) of carbanilide and 36.9 g (300 mmole) of nitrobenzene were put in a 200 mL, 3-necked round bottom flask equipped with a cooler and a stirrer. After heating the flask to 80 0C, 10.9 g (60 mmole) of TMA(0H)-5H O was added. Reaction was performed for 3 hours while keeping the degree of vacuum at about 90-50 mmHg and distilling water.[67] Ethyl acetate was added to the reaction solution. The solution was neutralized with water and acetic acid. The ethyl acetate layer was separated and analyzed by HPLC.[68] The result is given in Table 3.
1: 38% 2: 3% 3: 3% 4: 10%	With potassium hydroxide; tetramethyl ammoniumhydroxide In water at 80℃; for 3h;	5 Experimental Example 5; [65] Production yield of 4-NDPA and 4-NODPA was compared for various mixture bases including TMA(0H)-5H O and inorganic bases.[66] 6.4 g (30mmole) of carbanilide and 36.9 g (300 mmole) of nitrobenzene were put in a 200 mL, 3-necked round bottom flask equipped with a cooler and a stirrer. After heating the flask to 80 0C, 10.9 g (60 mmole) of TMA(0H)-5H O was added. Reaction was performed for 3 hours while keeping the degree of vacuum at about 90-50 mmHg and distilling water.[67] Ethyl acetate was added to the reaction solution. The solution was neutralized with water and acetic acid. The ethyl acetate layer was separated and analyzed by HPLC.[68] The result is given in Table 3.
1: 52 - 85 %Chromat. 2: 6 %Chromat. 3: 9 - 10 %Chromat. 4: 8 - 17 %Chromat.	Stage #1: nitrobenzene; bis(diphenyl)urea With sodium hydroxide; tetramethyl ammoniumhydroxide In water at 80℃; for 3h; Stage #2: With acetic acid In water; ethyl acetate	5 Experimental Example 5 Production yield of 4-NDPA and 4-NODPA was compared for various mixture bases including TMA(OH).5H2O and inorganic bases. 6.4 g (30 mmole) of carbanilide and 36.9 g (300 mmole) of nitrobenzene were put in a 200 mL, 3-necked round bottom flask equipped with a cooler and a stirrer. After heating the flask to 80° C., a mixture of bases, including TMA(OH).5H2O and inorganic bases, was added. Reaction was performed for 3 hours while keeping the degree of vacuum at about 90-50 mmHg and distilling water. Ethyl acetate was added to the reaction solution. The solution was neutralized with water and acetic acid. The ethyl acetate layer was separated and analyzed by HPLC. The results are shown in Table 3. TABLE 3 Products (mole %)* Bases 4-NDPA 4-NODPA Phenazine Azobenzene Azoxybenzene 30 mmole TMA(OH).5H2O + 52 6 - 10 8 30 mmole NaOH30 mmole TMA(OH).5H2O + 85 6 - 9 17 60 mmole NaOH30 mmole TMA(OH).5H2O + 38 3 - 3 10 60 mmole KOH *Production yield per initial carbanilide (mole %).

1: 38 %Chromat. 2: 3 %Chromat. 3: 3 %Chromat. 4: 10 %Chromat.

Stage #1: nitrobenzene; bis(diphenyl)urea With potassium hydroxide; tetramethyl ammoniumhydroxide In water at 80℃; for 3h; Stage #2: With acetic acid In water; ethyl acetate

5 Experimental Example 5 Production yield of 4-NDPA and 4-NODPA was compared for various mixture bases including TMA(OH).5H2O and inorganic bases. 6.4 g (30 mmole) of carbanilide and 36.9 g (300 mmole) of nitrobenzene were put in a 200 mL, 3-necked round bottom flask equipped with a cooler and a stirrer. After heating the flask to 80° C., a mixture of bases, including TMA(OH).5H2O and inorganic bases, was added. Reaction was performed for 3 hours while keeping the degree of vacuum at about 90-50 mmHg and distilling water. Ethyl acetate was added to the reaction solution. The solution was neutralized with water and acetic acid. The ethyl acetate layer was separated and analyzed by HPLC. The results are shown in Table 3. TABLE 3 Products (mole %)* Bases 4-NDPA 4-NODPA Phenazine Azobenzene Azoxybenzene 30 mmole TMA(OH).5H2O + 52 6 - 10 8 30 mmole NaOH30 mmole TMA(OH).5H2O + 85 6 - 9 17 60 mmole NaOH30 mmole TMA(OH).5H2O + 38 3 - 3 10 60 mmole KOH *Production yield per initial carbanilide (mole %).

Reference： [1]Current Patent Assignee: KUMHO PETRO CHEMICAL CO.,LTD. - WO2006/123878, 2006, A1 Location in patent: Page/Page column 8
[2]Current Patent Assignee: KUMHO PETRO CHEMICAL CO.,LTD. - WO2006/123878, 2006, A1 Location in patent: Page/Page column 8
[3]Current Patent Assignee: KUMHO PETRO CHEMICAL CO.,LTD. - US2006/258887, 2006, A1 Location in patent: Page/Page column 4-5
[4]Current Patent Assignee: KUMHO PETRO CHEMICAL CO.,LTD. - US2006/258887, 2006, A1 Location in patent: Page/Page column 4-5

54
[ 98-95-3 ]
[ 102-07-8 ]
[ 156-10-5 ]
[ 836-30-6 ]

Yield	Reaction Conditions	Operation in experiment
1: 29% 2: 3%	With tetramethyl ammoniumhydroxide In water at 80℃; for 3h;	6 Experimental Example 6; [71] Production yield of 4-NDPA and 4-NODPA was compared for various solvents. [72] 12.7 g (60 mmole) of carbanilide and 36.9 g (300 mmole) of nitrobenzene were put in a 200 mL, 3-necked round bottom flask equipped with a cooler and a stirrer. 64 mL of reaction solvent was added to the flask. After heating the flask to 80 0C, 21.7 g (120 mmole) of TMA(OH)-5H O was added. Reaction was performed for 3 hours while varying reaction conditions.[73] Ethyl acetate was added to the reaction solution. The solution was neutralized with EPO water and acetic acid. The ethyl acetate layer was separated and analyzed by HPLC.[74] The result is given in Table 4.
1: 10% 2: 7%	With tetramethyl ammoniumhydroxide In water; toluene at 80℃; for 3h;	6 Experimental Example 6; [71] Production yield of 4-NDPA and 4-NODPA was compared for various solvents. [72] 12.7 g (60 mmole) of carbanilide and 36.9 g (300 mmole) of nitrobenzene were put in a 200 mL, 3-necked round bottom flask equipped with a cooler and a stirrer. 64 mL of reaction solvent was added to the flask. After heating the flask to 80 0C, 21.7 g (120 mmole) of TMA(OH)-5H O was added. Reaction was performed for 3 hours while varying reaction conditions.[73] Ethyl acetate was added to the reaction solution. The solution was neutralized with EPO water and acetic acid. The ethyl acetate layer was separated and analyzed by HPLC.[74] The result is given in Table 4.
1: 9% 2: 3%	With tetramethyl ammoniumhydroxide In tetrahydrofuran; water at 80℃; for 3h;	6 Experimental Example 6; [71] Production yield of 4-NDPA and 4-NODPA was compared for various solvents. [72] 12.7 g (60 mmole) of carbanilide and 36.9 g (300 mmole) of nitrobenzene were put in a 200 mL, 3-necked round bottom flask equipped with a cooler and a stirrer. 64 mL of reaction solvent was added to the flask. After heating the flask to 80 0C, 21.7 g (120 mmole) of TMA(OH)-5H O was added. Reaction was performed for 3 hours while varying reaction conditions.[73] Ethyl acetate was added to the reaction solution. The solution was neutralized with EPO water and acetic acid. The ethyl acetate layer was separated and analyzed by HPLC.[74] The result is given in Table 4.

1: 9 %Chromat. 2: 3 %Chromat.

Stage #1: nitrobenzene; bis(diphenyl)urea With tetramethyl ammoniumhydroxide In tetrahydrofuran; water at 80℃; for 3h; Stage #2: With acetic acid In tetrahydrofuran; water; ethyl acetate

6 Experimental Example 6 Production yield of 4-NDPA and 4-NODPA was compared for various solvents. 12.7 g (60 mmole) of carbanilide and 36.9 g (300 mmole) of nitrobenzene were put in a 200 mL, 3-necked round bottom flask equipped with a cooler and a stirrer. 64 mL of reaction solvent was added to the flask. After heating the flask to 80° C., 21.7 g (120 mmole) of TMA(OH).5H2O was added. Reaction was performed for 3 hours while varying reaction conditions, as shown in Table 4, below. Ethyl acetate was added to the reaction solution. The solution was neutralized with water and acetic acid. The ethyl acetate layer was separated and analyzed by HPLC. The results are shown in Table 4. TABLE 4 Reaction Products (mole %)* condition 4- 4- Solvents (mmHg) NDPA NODPA Phenazine Azoxybenzene Toluene 300 35 9 2 - Toluene 760 10 7 - - THF 760 9 3 - - DMSO 760 50 4 - 15 Benzene 760 24 10 2 5 Nitro- 760 29 3 - - benzene *Production yield per initial carbanilide (mole %).

Reference： [1]Current Patent Assignee: KUMHO PETRO CHEMICAL CO.,LTD. - WO2006/123878, 2006, A1 Location in patent: Page/Page column 8-9
[2]Current Patent Assignee: KUMHO PETRO CHEMICAL CO.,LTD. - WO2006/123878, 2006, A1 Location in patent: Page/Page column 8-9
[3]Current Patent Assignee: KUMHO PETRO CHEMICAL CO.,LTD. - WO2006/123878, 2006, A1 Location in patent: Page/Page column 8-9
[4]Current Patent Assignee: KUMHO PETRO CHEMICAL CO.,LTD. - US2006/258887, 2006, A1 Location in patent: Page/Page column 5

55
[ 98-95-3 ]
[ 102-07-8 ]
[ 156-10-5 ]
[ 836-30-6 ]
[ 495-48-7 ]

Yield	Reaction Conditions	Operation in experiment
1: 50% 2: 4% 3: 15%	With tetramethyl ammoniumhydroxide In water; dimethyl sulfoxide at 80℃; for 3h;	6 Experimental Example 6; [71] Production yield of 4-NDPA and 4-NODPA was compared for various solvents. [72] 12.7 g (60 mmole) of carbanilide and 36.9 g (300 mmole) of nitrobenzene were put in a 200 mL, 3-necked round bottom flask equipped with a cooler and a stirrer. 64 mL of reaction solvent was added to the flask. After heating the flask to 80 0C, 21.7 g (120 mmole) of TMA(OH)-5H O was added. Reaction was performed for 3 hours while varying reaction conditions.[73] Ethyl acetate was added to the reaction solution. The solution was neutralized with EPO water and acetic acid. The ethyl acetate layer was separated and analyzed by HPLC.[74] The result is given in Table 4.
1: 50 %Chromat. 2: 4 %Chromat. 3: 15 %Chromat.	Stage #1: nitrobenzene; bis(diphenyl)urea With tetramethyl ammoniumhydroxide In water; dimethyl sulfoxide at 80℃; for 3h; Stage #2: With acetic acid In water; dimethyl sulfoxide; ethyl acetate	6 Experimental Example 6 Production yield of 4-NDPA and 4-NODPA was compared for various solvents. 12.7 g (60 mmole) of carbanilide and 36.9 g (300 mmole) of nitrobenzene were put in a 200 mL, 3-necked round bottom flask equipped with a cooler and a stirrer. 64 mL of reaction solvent was added to the flask. After heating the flask to 80° C., 21.7 g (120 mmole) of TMA(OH).5H2O was added. Reaction was performed for 3 hours while varying reaction conditions, as shown in Table 4, below. Ethyl acetate was added to the reaction solution. The solution was neutralized with water and acetic acid. The ethyl acetate layer was separated and analyzed by HPLC. The results are shown in Table 4. TABLE 4 Reaction Products (mole %)* condition 4- 4- Solvents (mmHg) NDPA NODPA Phenazine Azoxybenzene Toluene 300 35 9 2 - Toluene 760 10 7 - - THF 760 9 3 - - DMSO 760 50 4 - 15 Benzene 760 24 10 2 5 Nitro- 760 29 3 - - benzene *Production yield per initial carbanilide (mole %).

Reference： [1]Current Patent Assignee: KUMHO PETRO CHEMICAL CO.,LTD. - WO2006/123878, 2006, A1 Location in patent: Page/Page column 8-9
[2]Current Patent Assignee: KUMHO PETRO CHEMICAL CO.,LTD. - US2006/258887, 2006, A1 Location in patent: Page/Page column 5

56
[ 100-00-5 ]
[ 836-30-6 ]

Yield	Reaction Conditions	Operation in experiment
92%		3 EXAMPLE 3 The reaction mixture was worked up in the same manner as in Example 1. Distillation was carried out at 10 to 15 mbar at 150° to 160° C. 216 g of 4-nitrodiphenylamine were obtained. According to liquid chromatographic analysis, this contained 91% by weight, corresponding to a 92% yield based on 4-nitrochlorobenzene.
	With 1-methyl-pyrrolidin-2-one; potassium carbonate; aniline In 5,5-dimethyl-1,3-cyclohexadiene	4 EXAMPLE 4 EXAMPLE 4 2 g of CuO, 12 g of N-methylpyrrolidone and 93 g of aniline were heated to 160° C. The copper oxide dissolved over a period of 20 minutes. This solution was added dropwise over a period of 30 minutes to a mixture, boiling at 180° C., of 157 g of p-nitrochlorobenzene, 93 g of aniline, 10 g of xylene and 100 g of potash. The temperature was then increased to 188° C. and the further reaction carried out in the same way as described in Example 1. Yield of 4-nitrodiphenyl amine 209 g, mp. 117.5° C. 107.2 g of aniline and 6.7 g of p-nitrochlorobenzene were recovered in the same way as in Example 1.
	In <i>N</i>-methyl-acetamide	11 4-Nitrodiphenylamine The yield of 4-nitrodiphenylamine is 86% and conversion of p-nitrochlorobenzene is 96%. The presence of the formanilide reduces tertiary amine byproduct which becomes excessive in the case of reaction in dimethylformamide, for example.

Multi-step reaction with 2 steps 1: copper(II) acetate monohydrate; L-2-O-methyl-chiro-inositol; ammonium hydroxide / 1-methyl-pyrrolidin-2-one / 12 h / 110 °C 2: copper(II) acetate monohydrate; potassium carbonate / 20 h / 110 °C / Inert atmosphere

Reference： [1]Current Patent Assignee: BAYER AG - US4665233, 1987, A
[2]Current Patent Assignee: BAYER AG - US4122118, 1978, A
[3]Current Patent Assignee: EASTMAN CHEMICAL CO - US4187248, 1980, A
[4]Chen, Guoliang; Chen, Yuanguang; Du, Fangyu; Fu, Yang; Wu, Ying; Zhou, Qifan [Synlett, 2019, vol. 30, # 19, p. 2161 - 2168]

57
[ 66-71-7 ]
[ 100-00-5 ]
[ 836-30-6 ]

Yield	Reaction Conditions	Operation in experiment
	With sodium carbonate; aniline In 5,5-dimethyl-1,3-cyclohexadiene; water	21 EXAMPLE 21 EXAMPLE 21 186 g of aniline, 30 ml of xylene, 4.5 g of 1,10-phenanthroline and 2 g of CuO are heated to 150°-155° C. for 20 minutes in a water separator. After 157.5 g of 4-nitrochlorobenzene and 76 g of sodium carbonate have been added, the reaction mixture is boiled in the water separator for 9 hours at 193°-195° C., 9.9 ml of water being produced. The ratio nitrobenzene:4-nitrochlorobenzene:4-nitrodiphenylamine is 2.8:2.7:94.5 parts by weight. After the mixture has been cooled to 110° C., it is filtered off from the salts, and the filter cake is washed with 50 ml of xylene at 90° C. The filtrate and washing liquid are combined, and are subjected to incipient distillation in vacuo (15 mbar, temperature of the heating bath: up to 130° C.). 160 ml of xylene are added to the distillation residue while the latter is still warm, and the mixture is cooled to 5° C. whilst stirring. The product which has crystallized out is filtered off rapidly, and the filter cake is washed with 50 ml of ice-cold xylene and dried: 181 g of finely crystalline 4-nitrodiphenylamine of melting point 122°-125° C. The resulting filtrate is freed from excess xylene by distillation, and is recycled after the addition of 206 g of aniline, 157.5 g of 4-nitrochlorobenzene and 76 g of sodium carbonate. After 11 hours at 193°-195° C., 10.2 ml of water have formed. The 4-nitrochlorobenzene conversion is 97%. The isolation of the 4-nitrodiphenylamine is effected by crystallization, as described above. 177 g of crystalline 4-nitrodiphenylamine of melting point 119°-120° C. are obtained after the product has been dried.

Reference： [1]Current Patent Assignee: BAYER AG - US4404400, 1983, A

58
[ 100-00-5 ]
[ 31432-60-7 ]
[ 836-30-6 ]

Yield	Reaction Conditions	Operation in experiment
	With 1-methyl-pyrrolidin-2-one; sodium hydroxide; potassium carbonate; aniline In 5,5-dimethyl-1,3-cyclohexadiene; water	1 EXAMPLE 1 EXAMPLE 1 93 g of aniline, 157 g of p-nitrochlorobenzene, 2 g of CuO, 150 g of xylene and 12 g of N-methylpyrrolidone were heated under reflux for 20 minutes to 160° C. on a water separator. 100 g of dry potash and 93 g of aniline were then added and the condensation reaction was started by increasing the temperature to 185° C. After 10 hours, 9 g of water had formed and the reaction had ceased. The mixture was suspended in water, sodium hydroxide (5 g) was added and all the volatile constituents were then distilled off with steam. At the same time, the crude nitrodiphenyl amine formed into granules and was isolated and dried. Yield of 4-nitrodiphenyl amine: 209 g, mp.118° C. 106.8 g of aniline and 6.1 g of p-nitrochlorobenzene were recovered from the steam distillation condensate.

Reference： [1]Current Patent Assignee: BAYER AG - US4122118, 1978, A

59
[ 100-00-5 ]
[ 103-70-8 ]
[ 836-30-6 ]

Yield	Reaction Conditions	Operation in experiment
68.6%	With sodium hydroxide In 5,5-dimethyl-1,3-cyclohexadiene; water; potassium	12 Example 12 Example 12 In an experiment without potassium, the reactor charge is 85 grams of formanilide (0.7 mole), 78.5 grams of p-nitrochlorobenzene and 50 grams of xylene. The aqueous reactant is 28 grams of sodium hydroxide (0.7 mole) in 50 ml. of water. The reactor charge is heated to 210° and the aqueous reactant added over a period of 3 hours. The reactor contents are then heated to 215° C. for 1 hour and the yield of 4-nitrodiphenylamine and unreacted p-nitrochlorobenzene determined as described in Example 1. The yield is 68.6% and conversion 84.9%.
	With sodium hydroxide; potassium carbonate In 5,5-dimethyl-1,3-cyclohexadiene; water	11 Example 11 Example 11 To a charge of 157 grams of p-nitrochlorobenzene (1 mole), 169 grams of formanilide (1.4 moles) and 50 grams of xylene at 180° C. is fed over a period of about 4 hours a solution of 58 grams of potassium carbonate (0.42 mole) and 22.5 grams of sodium hydroxide (0.56 mole) in 120 grams of water. Water is removed concurrently from the reaction mixture with the addition of the aforesaid solution. The temperature of the reaction mixture is then raised to 205° C. and heated at such temperature for 11/2 hours. The amounts of 4-nitrodiphenylamine formed and p-nitrochlorobenzene remaining unreacted are then determined, as described in Example 1. The yield of 4-nitrodiphenylamine is 69.3%, and the conversion of the p-nitrochlorobenzene charged is 78.4 or 88.4%.

Reference： [1]Current Patent Assignee: EASTMAN CHEMICAL CO - US4228103, 1980, A
[2]Current Patent Assignee: EASTMAN CHEMICAL CO - US4228103, 1980, A

60
[ 100-02-7 ]
[ 7664-93-9 ]
[ 103-71-9 ]
[ 836-30-6 ]

Yield	Reaction Conditions	Operation in experiment
85.4%	With potassium carbonate	2 EXAMPLE 2 EXAMPLE 2 The same method is followed as in Example 1, but using: 270.4 g (1.94 mol) p-nitrophenol, 750 ml Sulfolan, 9.94 g (0.072 mol) potassium carbonate, 214 g (189 mol) phenyl isocyanate, 4 ml concentrated sulphuric acid. 182.8 g=85.4% of the theoretical yield of 4-nitro-diphenyl amine were obtained; m.p.:130° to 131° C.

Reference： [1]Current Patent Assignee: BAYER AG - US4238407, 1980, A

61
[ 100-02-7 ]
concentrated H₂ SO₄ [ No CAS ]
[ 836-30-6 ]

Yield	Reaction Conditions	Operation in experiment
	With CO₂; potassium carbonate In water; phenyl isocyanate	1 EXAMPLE 1 EXAMPLE 1 150.2 g (1.08 mol) p-nitrophenol are dissolved in 750 ml Sulfolan and 5.52 g (0.04 mol) potassium carbonate in 10 ml water are added. The water is distilled off in vacuo and at 250° C. 129.7 g (1.09 mol) phenyl isocyanate are added dropwise over a period of 1 hour while stirring vigorously. After a further 1.5 hours approximately 24 l of CO2 have evolved. At 150° C. the reaction mixture is reacted with 2.2 ml of concentrated H2 SO4, stirred again briefly and filtered over a glass-sintering suction filter. The Sulfolan is almost completely distilled off in a film evaporator at 1 to 2 mm Hg. 234 g crude product remain, which are recrystallized from 620 ml xylene. 185 g (86.5% of the theoretical yield) 4-nitro-diphenyl amine are obtained. M.P.: 129° to 130° C.

Reference： [1]Current Patent Assignee: BAYER AG - US4238407, 1980, A

62
[ 103-70-8 ]
[ 836-30-6 ]

Yield	Reaction Conditions	Operation in experiment
	With potassium carbonate In 5,5-dimethyl-1,3-cyclohexadiene; 4-chlorobenzonitrile	16 EXAMPLE 16 EXAMPLE 16 Into the reactor described in Example 1 are charged 85 grams (0.7 mole) of formanilide and 50 grams of xylene. The charge is heated to 185°-190° C. and there is fed thereto over a period of about 4 hours in separate streams 78.5 grams (0.5 mole) of p-nitrochlorobenzene and a solution of 29 grams (0.21 mole) of potassium carbonate in 35 grams (0.28 mole) of 45% potassium hydroxide. Heating is continued after the addition for 40 minutes at 180°. The 4-nitrodiphenylamine and unreacted p-nitrochlorobenzene are determined as described in Example 1. The yield of 4-nitrodiphenylamine is 62.1% and the conversion of p-nitrochlorobenzene 72.4%.

Reference： [1]Current Patent Assignee: EASTMAN CHEMICAL CO - US4196146, 1980, A

63
[ 1005197-06-7 ]
[ 62-53-3 ]
[ 836-30-6 ]

Yield	Reaction Conditions	Operation in experiment
57%	With 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene In toluene at 105℃; for 40h;

Reference： [1]Rostovtsev, Vsevolod V.; Bryman, Lois M.; Junk, Christopher P.; Harmer, Mark A.; Carcani, Liane G. [Journal of Organic Chemistry, 2008, vol. 73, # 2, p. 711 - 714]

64
[ 836-30-6 ]
[ 3077-85-8 ]

Yield	Reaction Conditions	Operation in experiment
76%	With air; potassium carbonate; Trimethylacetic acid at 110℃; for 14h;
	With palladium diacetate; potassium carbonate; Trimethylacetic acid Heating;	4 3-Nitro-9H-carbazole A mixture of phenyl trifluoromethanesulfonate (500 mg, 2.21 mmol), palladium acetate (II) (50 mg, 0.22 mmol), (±) 2,2'-bis(diphenylphosphino)-1,1'-binaphthyl (317 mg, 0.66 mmol) and cesium carbonate (1.09 g, 3.31 mmol) in 50 mL of toluene were inertized with argon. Then, 4-nitroaniline (331 mg, 2.43 mmol) was added and the mixture was heated at 110°C overnight. The reaction mixture was allowed to cool to room temperature and filtered through a pad of Celite. The filtrate was diluted with CH2Cl2and water. The phases were separated and the aqueous phase was re-extracted 2 times with CH2Cl2. The combined organic phases were dried over Na2SO4and the resulting solution was dried over anhydrous Na2SO4and purified with flash column chromatography as an eluent EtOAc/hexane (1/6, v/v) to give 4-nitro-N-phenylaniline. The aniline (450 mg, 2 mmol), Pd(OAc)2(23 mg, 0.1 mmol), K2CO3(30 mg, 0.2 mmol), and pivalic acid (408 mg, 4 mmol) was placed into a glass test tube. The uncapped test tube was placed in an oil bath and the mixture was stirred under air at the indicated temperature. The solution was then cooled to room temperature, diluted with EtOAc, washed with a saturated Na2CO3, dried over Na2SO4, concentrated, and purified by flash column chromatography as an eluent of EtOAc/hexane to give 3-nitro-9H-carbazole.

Reference： [1]Liegault, Benoit; Lee, Doris; Huestis, Malcolm P.; Stuart, David R.; Fagnou, Keith [Journal of Organic Chemistry, 2008, vol. 73, # 13, p. 5022 - 5028]
[2]Current Patent Assignee: UNIVERSITY OF TENNESSEE; ONCTERNAL THERAPEUTICS INC - WO2016/172358, 2016, A1 Location in patent: Paragraph 00437-00438

65
[ 64709-82-6 ]
[ 836-30-6 ]
[ 1821-27-8 ]
[ 3665-70-1 ]
[ 382165-80-2 ]

Yield	Reaction Conditions	Operation in experiment
0.08 mmol	With chloroacetic acid; sodium nitrite In benzene at 20℃; Inert atmosphere;

Reference： [1]Location in patent: experimental part Astolfi, Paola; Carloni, Patricia; Damiani, Elisabetta; Greci, Lucedio; Marini, Milvia; Rizzoli, Corrado; Stipa, Pierluigi [European Journal of Organic Chemistry, 2008, # 19, p. 3279 - 3285]

66
[ 62-53-3 ]
[ 586-78-7 ]
[ 836-30-6 ]

Yield	Reaction Conditions	Operation in experiment
100%	With caesium carbonate; 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene In 1,4-dioxane for 24h; Reflux;
92%	With potassium hydroxide In N,N-dimethyl-formamide at 130℃; for 0.316667h;
88%	With CuMoO₄; caesium carbonate In dimethyl sulfoxide at 90℃; for 12h; Inert atmosphere;

85%	With potassium carbonate In water at 100℃; for 1h; Sealed tube; Microwave irradiation;
80%	With copper(II) oxide; potassium carbonate In N,N-dimethyl-formamide at 40℃; for 3h;	General procedure for N-arylation of indole and aniline General procedure: In a typical N-arylation procedure, CuO NPs (0.005 g) was added to a mixture of aryl halide (1.0 mmol), indole/aniline (1.0 mmol), and K2CO3 (1.0 mmol) in DMF (5 mL) and stirred at 40 °C for desired time (Table 2). After completion of the reaction, the reaction mixture was cooled to room temperature and diluted with 10 mL of water and extracted with ethyl acetate (2×10 mL). The combined organic extracts were washed with brine and dried over anhydrous MgSO4. Solvent was evaporated under reduced pressure and the product was purified by column chromatography to obtain the desired purity. All the products are known compounds and the spectral data were identical to those reported in the literatures.23-25 The aqueous layer was centrifuged and the catalyst was separated and recovered for the next catalytic run.
76%	With potassium hydroxide In water at 20℃; for 6h; Green chemistry;
75%	With triethylamine In N,N-dimethyl-formamide at 80℃; for 5h;
75%	With triethylamine In N,N-dimethyl-formamide at 80℃; for 6h;
75%	With copper; caesium carbonate; methyl-alpha-D-glucopyranoside In water; dimethyl sulfoxide at 110℃; Sealed tube; Green chemistry;	General Procedure General procedure: All the reactions were carried out in DMSO-H 2 O (1:1, 2 mL) in asealed vessel. To a 10 mL hydrothermal synthesis reactor was chargedCu powder (6 mg, 0.1 mmol), MG (39 mg, 0.2 mmol), Cs 2 CO 3 (980 mg,3.0 mmol), nitrogen-containing heterocycle (1.5 mmol), amine (3.0mmol), and aryl halide (0.8 mmol). The reaction mixture was stirredfor a specified time at 100-110 °C. After TLC analysis confirmed thecomplete consumption of aryl halides, the mixture was cooled to r.t.(the pH was adjusted if the product was acidic), diluted with EtOAc(10 mL), filtered through a Celite pad, and washed with EtOAc (20-30mL). The organic layer was dried and concentrated. The residue waspurified by silica gel column chromatography to give the product.
74%	With tetrabutylammomium bromide; palladium diacetate; potassium carbonate; 2,6-bis(diphenylphosphino)pyridine In N,N-dimethyl acetamide at 135℃; for 5h; Inert atmosphere;	Typical experimental procedure for the Buchwald-Hartwig reaction General procedure: A round bottomedflask was charged with bromobenzene (4 mmol), aniline (4 mmol),TBAB (3 mmol), and K2CO3 (4 mmol) under a dry nitrogen atmosphere. A solution of (Ph2P)2py (0.05 mol % in 2 mL of DMAc) and a solution of palladiumacetate (0.025 mol % in 2 mL of DMAc) was added through a rubber septum,and the resulting mixture was heated at 135 C for the appropriate time. Uponcompletion of the reaction, the mixture was cooled to room temperature and quenched with H2O. After extraction with CH2Cl2 (3 20 mL), the combinedorganic layer was dried over MgSO4. The solvent was evaporated and the cruderesidue was purified by silica gel chromatography, using n-hexane/EtOAc aseluent to provide the desired product. The products were characterized byNMR spectroscopy
70%	With potassium hydroxide In dimethyl sulfoxide at 130℃; for 8h;
64%	With oxalic acid hydrazide; potassium hydroxide; tetrabutylammomium bromide; 2,5-hexanedione; copper(II) oxide In water at 25℃; for 72h;
63%	With potassium phosphate; copper(l) iodide; N′,N'-bis(2-isopropylphenyl)-1H-pyrrole-2-carbohydrazide In diethylene glycol at 20℃; for 156h; Sealed tube; Molecular sieve;
60%	With (1,3-bis(2,6-diisopropylphenyl)-3,4,5,6-tetrahydropyrimidin-2-ylidene)Pd(cinnamyl, 3-phenylallyl)Cl; sodium t-butanolate In neat (no solvent) at 110℃; for 12h; Inert atmosphere; Green chemistry;
56%	With copper(l) iodide; tetrabutylammomium bromide; potassium hydroxide In water at 70℃; for 16h; Green chemistry;	2.4 General protocol for C-N coupling reaction General procedure: A 10 mL of vial was charged with CuI (10 mg, 0.05 mmol), PSP (0.25 mmol, size less than 90 μM), TBAB (40 mg, 0.25 mmol), base (1.0 mmol), aryl halides (0.5 mmol), arylamine (2.0 mmol), H2O (1.0 mL), and a magnetic stir bar. The vessel was sealed with a septum and placed into an oil bath, which was preheated to 70 °C (90 °C for alkyl amine, 120 °C for imidazole). The reaction mixture was stirred for another 16 h (8 h for imidazole). After allowing the mixture to cool to room temperature, the reaction mixture was filtrated, the precipitates were washed with water and ethyl acetate thoroughly. The filtrate was extracted with ethyl acetate (3×25 mL). The combined organic phases was washed with water and brine, dried over anhydrous Na2SO4, and concentrated in vacuo. The residue was purified by flash column chromatograph on silica gel to afford the desired products.
53%	With copper(l) iodide; N′-phenyl-1H-pyrrole-2-carbohydrazide; tetrabutylammomium bromide; potassium hydroxide In water at 20 - 130℃; Microwave irradiation;
50%	With potassium carbonate In dimethyl sulfoxide for 12h; Reflux; Inert atmosphere;	2.3 General procedure for the N-arylation of aryl amines with aryl halides General procedure: In a 25ml round bottom flask a mixture of 4:1 methanol/water, aryl halide (1mmol), Resin-CuNPs (0.2g), K2CO3 (3mmol) and aryl amine (1.2mmol) were taken and heated at reflux temperature for 12-24h in an oil bath under inert conditions. Resin beads were filtered off at the end of reaction while the solution was still hot. After a work up with dichloromethane and water, the organic layer was separated, dried over anhydrous Na2SO4. The crude products obtained after removal of solvent (Scheme 1) were purified by column chromatography (ethyl acetate: hexane) and identified by mass or 1H NMR spectroscopy (see ESI).
44%	With C₂₀H₂₆N₄O₄; tetrabutylammomium bromide; copper(II) oxide; potassium hydroxide In water at 30℃; for 48h;
34%	With potassium phosphate; copper(l) iodide In diethylene glycol at 70℃; for 14h; Sealed tube;	Synthesis of 1a-s and 2a-q; General Procedure General procedure: A 10 mL vial was charged with CuI (9.5 mg, 0.05 mmol), PSAP (30 mg,0.05 mmol, > 100 mesh), K3PO4 (424 mg, 2 mmol), aryl bromides (1mmol), amines (1.5 mmol), DEG (2 mL), and a magnetic stir bar. The vessel was sealed with a septum and placed into a preheated oil batchat 70 °C. The reaction mixture was held at this temperature for 14 hours. After cooling to r.t., the reaction mixture was filtered, and the precipitates were thoroughly washed with water and EtOAc (3 × 20mL). The combined organic phases were washed with water and brine, dried over anhydrous Na2SO4, and concentrated in vacuo. Theresidue was purified using flash column chromatography on silica gel(eluting with petroleum ether/EtOAc) to afford the desired products.
3 %Chromat.	With C₃₁H₃₇ClN₃NiO₂^(1-)*Li⁽¹⁺⁾; lithium hexamethyldisilazane In dimethyl sulfoxide at 110℃; for 3h; Inert atmosphere; Sealed tube;	2.4 General Amination Procedure of Aryl Halides Using Different Amines General procedure: A representative amination method using chlorobenzene,pentylamine, and KOtBuin DMSO is described here. Allother amination reactions including different aryl halides,primary (1°) and secondary (2°) amines, solvents and baseswere performed using a similar method. A 4mL reactionvial containing a magnetic stir bar was charged with 1.4mLof anhydrous DMSO. The reaction vial, after being sealed with a septum and parafilm, was purged with Ar for 10min.Chlorobenzene [0.4mL, 3.9mmol, 2.25 equivalent (eq.)],pentylamine (0.21mL, 1.8mmol, 1.0eq.), anhydrous powderedKOtBu(70mg, 0.63mmol, 0.3eq.), and 2 (2mg,0.2mol%) were added sequentially. The reaction mixturewas stirred for 5min while continually purging with Ar. Thevial was then sealed with a Teflon screw cap. The reactionmixture was stirred for 3h at 110°C in a preheated oil bath,then allowed to cool to room temperature and filtered bypassing through Celite to remove the base and the catalyst.30L of the solution was then dissolved in 1mL absolute ethanol, and 10μL of decane was added as an internalstandard. Turn over number (TON) was determined usingGC-MS.

Reference： [1]Sa, Sofia; Gawande, Manoj B.; Velhinho, Alexandre; Veiga, Joao Pedro; Bundaleski, Nenad; Trigueiro, Joao; Tolstogouzov, Alexander; Teodoro, Orlando M. N. D.; Zboril, Radek; Varma, Rajender S.; Branco, Paula S. [Green Chemistry, 2014, vol. 16, # 7, p. 3494 - 3500]
[2]Ghasemi, Amir Hossein; Naeimi, Hossein [New Journal of Chemistry, 2020, vol. 44, # 13, p. 5056 - 5063]
[3]Panigrahi, Reba; Panda, Subhalaxmi; Behera, Pradyota Kumar; Sahu, Santosh Kumar; Rout, Laxmidhar [New Journal of Chemistry, 2019, vol. 43, # 48, p. 19274 - 19278]
[4]Nasir Baig; Varma, Rajender S. [RSC Advances, 2014, vol. 4, # 13, p. 6568 - 6572]
[5]Veisi, Hojat; Hemmati, Saba; Javaheri, Hadis [Tetrahedron Letters, 2017, vol. 58, # 32, p. 3155 - 3159]
[6]Hajipour, Abdol R.; Check, Maryam; Khorsandi, Zahra [Applied Organometallic Chemistry, 2017, vol. 31, # 11]
[7]Akhavan, Elham; Hemmati, Saba; Hekmati, Malak; Veisi, Hojat [New Journal of Chemistry, 2018, vol. 42, # 4, p. 2782 - 2789]
[8]Veisi, Hojat; Ahmadian, Hossein; Mirshokraie, Seyed Ahmad; Didehban, Khadijeh; Zangeneh, Mohammad Mahdi [Applied Organometallic Chemistry, 2019, vol. 33, # 4]
[9]Chen, Fengyang; Chen, Guoliang; Chen, Yuanguang; Du, Fangyu; Zhou, Qifan [Synthesis, 2019, vol. 51, # 24, p. 4590 - 4600]
[10]Nadri, Shirin; Rafiee, Ezzat; Jamali, Sirous; Joshaghani, Mohammad [Tetrahedron Letters, 2014, vol. 55, # 30, p. 4098 - 4101]
[11]Ghorbani-Choghamarani, Arash; Taherinia, Zahra [New Journal of Chemistry, 2017, vol. 41, # 17, p. 9414 - 9423]
[12]Zhu, Xinhai; Su, Li; Huang, Liye; Chen, Gong; Wang, Jinlong; Song, Huacan; Wan, Yiqian [European Journal of Organic Chemistry, 2009, # 5, p. 635 - 642]
[13]Ding, Xiaomei; Huang, Manna; Yi, Zhou; Du, Dongchen; Zhu, Xinhai; Wan, Yiqian [Journal of Organic Chemistry, 2017, vol. 82, # 10, p. 5416 - 5423]
[14]Topchiy, Maxim A.; Dzhevakov, Pavel B.; Rubina, Margarita S.; Morozov, Oleg S.; Asachenko, Andrey F.; Nechaev, Mikhail S. [European Journal of Organic Chemistry, 2016, vol. 2016, # 10, p. 1908 - 1914]
[15]Huang, Liye; Yu, Ruina; Zhu, Xinhai; Wan, Yiqian [Tetrahedron, 2013, vol. 69, # 42, p. 8974 - 8977]
[16]Location in patent: experimental part Xie, Jianwei; Zhu, Xinhai; Huang, Manna; Meng, Fei; Chen, Weiwei; Wan, Yiqian [European Journal of Organic Chemistry, 2010, # 17, p. 3219 - 3223]
[17]Barot, Nirav; Patel, Sunil B.; Kaur, Harjinder [Journal of Molecular Catalysis A: Chemical, 2016, vol. 423, p. 77 - 84]
[18]Location in patent: experimental part Meng, Fei; Wang, Chenxia; Xie, Jianwei; Zhu, Xinhai; Wan, Yiqian [Applied Organometallic Chemistry, 2011, vol. 25, # 5, p. 341 - 347]
[19]Yi, Zhou; Huang, Manna; Wan, Yiqian; Zhu, Xinhai [Synthesis, 2018, vol. 50, # 19, p. 3911 - 3920]
[20]Albkuri, Yahya M.; RanguMagar, Ambar B.; Brandt, Andrew; Wayland, Hunter A.; Chhetri, Bijay P.; Parnell, Charlette M.; Szwedo, Peter; Parameswaran-Thankam, Anil; Ghosh, Anindya [Catalysis Letters, 2020, vol. 150, # 6, p. 1669 - 1678]

67
[ 100-02-7 ]
[ 62-53-3 ]
[ 836-30-6 ]

Yield	Reaction Conditions	Operation in experiment
88%	Stage #1: 4-nitro-phenol; aniline With caesium carbonate; chloroacetyl chloride In N,N-dimethyl-formamide at 20℃; for 0.5h; Stage #2: In N,N-dimethyl-formamide at 150℃; Microwave irradiation;

Reference： [1]Location in patent: experimental part Tian, Xiao; Wu, Ren-Min; Liu, Gang; Li, Zhu-Bo; Wei, He-Lin; Yang, Hao; Shin, Dong-Soo; Wang, Li-Ying; Zuo, Hua [ARKIVOC, 2011, vol. 2011, # 10, p. 118 - 126]

68
[ 73655-27-3 ]
[ 836-30-6 ]

Yield	Reaction Conditions	Operation in experiment
66%	With tetrabutylammomium bromide; oxygen; palladium diacetate In dimethyl sulfoxide; toluene at 90℃; for 12h; Schlenk technique; Molecular sieve; Inert atmosphere;

Reference： [1]Hajra, Alakananda; Wei, Ye; Yoshikai, Naohiko [Organic Letters, 2012, vol. 14, # 21, p. 5488 - 5491,4]

69
[ 836-30-6 ]
[ 161886-71-1 ]
[ 101-54-2 ]

Yield	Reaction Conditions	Operation in experiment
	With 5%-palladium/activated carbon; hydrogen at 80℃; for 0.5h; Autoclave;	B EXAMPLE B - Reduction of the coupling reaction product This example illustrates a typical example of reduction of 4-NODPA and 4-NDPA in coupling mass. In 2 liter capacity autoclave, a coupling reaction product (900 gm) containing aniline (54%), TMA salt of 4-NODPA (25%), 4-NDPA (1.8%), phenazine (0.3%), azobenzene (1.8%) was placed. To this product was added water (307 gm) and noble metal catalyst (e.g. 5% Pd/C, 4 weight % loading on 4-NODPA + 4-NDPA). The reaction mixture was heated at 80°C under a hydrogen pressure of 15 kg /cm . At the end of reduction (no hydrogen absorption, typically 30 minutes), the unconverted 4- NODPA and 4-NDPA content was almost negligible (

Reference： [1]Current Patent Assignee: NOCIL LIMITED - WO2013/132290, 2013, A2 Location in patent: Page/Page column 20

70
[ 591-50-4 ]
[ 98-92-0 ]
[ 100-01-6 ]
[ 1752-96-1 ]
[ 836-30-6 ]

Yield	Reaction Conditions	Operation in experiment
1: 47% 2: 36%	With copper(l) iodide; cesium fluoride In dimethyl sulfoxide at 130℃; for 24h; Inert atmosphere; Glovebox;

Reference： [1]Gueell, Imma; Ribas, Xavi [European Journal of Organic Chemistry, 2014, vol. 2014, # 15, p. 3188 - 3195]

71
[ 100-01-6 ]
[ 639-58-7 ]
[ 836-30-6 ]

Yield	Reaction Conditions	Operation in experiment
95%	With triethylamine at 95℃;	General procedure: For CeN coupling, aniline (1 mmol), triphenyltin chloride (0.5mmol) and Et3N (2 mmol) in PEG (2 ml) was added CNT-Kryf/Ni (7 mg)at 95 °C. The progress of the reaction was monitored by TLC. The catalystwas separated by filtration and reused as such for the next experiment.The mixture was washed with water and EtOAc (3 × 5 ml),and then the separated organic layer was dried over MgSO4 and solvent was vaporised to provide the product.
94%	With triethylamine at 20℃; for 15h;
94%	With triethylamine at 90℃; for 9h;

Reference： [1]Aalinejad, Michael; Doustkhah, Esmail; Pesyan, Nader Noroozi [Molecular catalysis, 2020, vol. 494]
[2]Ghorbani-Choghamarani, Arash; Nikpour, Farzad; Ghorbani, Farshid; Havasi, Forugh [RSC Advances, 2015, vol. 5, # 42, p. 33212 - 33220]
[3]Batmani, Hana; Noroozi Pesyan, Nader; Havasi, Forugh [Applied Organometallic Chemistry, 2018, vol. 32, # 8]

72
[ 101-54-2 ]
[ 836-30-6 ]

Yield	Reaction Conditions	Operation in experiment
85%	With 1,9-diperoxynonanedioic acid In acetonitrile at 50℃; for 0.5h;

Reference： [1]Patil, Vilas Venunath; Shankarling, Ganapati Subray [Journal of Organic Chemistry, 2015, vol. 80, # 16, p. 7876 - 7883]

73
[ 836-30-6 ]
2,3-bis(4-bromophenyl)benzo[g]quinoxaline [ No CAS ]
2,3-bis[4-(4-nitro-N-phenylbenzeamino)phenyl]benzo[g]quinoxaline [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
53.17%	With dicyclohexyl-(2',6'-dimethoxybiphenyl-2-yl)-phosphane; tris-(dibenzylideneacetone)dipalladium⁽⁰⁾; sodium t-butanolate In toluene at 100℃; for 10h; Inert atmosphere;	2.2e 2,3-Bis[4-(4-nitro-N-phenylbenzeamino)phenyl]benzo[g]quinoxaline (5): A mixture of compound 1(490 mg, 1 mmol) and 4-nitrodiphenylamine (472 mg,2 mmol) was dissolved in anhydrous toluene (20 mL). To this solution Pd2(dba)3 (37 mg, 0.04 mmol), SPhos(25 mg, 0.06 mmol) and t-BuONa (300 mg, 3.1 mol) were added. The reaction mixture was continuously stirred under nitrogen atmosphere at 100°C for 10 h. Reaction mixture was then cooled to room temperature and extracted with chloroform. The solid thus obtained was then purified by column chromatography (eluent: n-hexane: chloroform ratio as 60:40) to obtaina bright yellow solid. Yield: 210 mg (53.17%), M.p.:314°C. IR (KBrνmax cm-1): 3051, 2921, 1580 (-C=N),1489, 1286 (-C-N str), 1108; 1H NMR (300 MHz,CDCl3): δ (ppm) 8.89 (s, 2H, ArH), 8.18 (dd, 2H,ArH, J = 3.3, 3.0 Hz), 8.08 (d, 4H, ArH, J = 9.3Hz ), 7.62 (d, 6H, ArH , J = 6.6 Hz), 7.03-7.42 (m,18H, ArH); 13C NMR: 152.72, 147.52, 145.33, 141.30,134.54, 131.72, 130.21, 128.69, 127.62, 126.83,126.36, 125.47, 124.59, 120.05; HRMS calcd forC48H33N6O4 757.2558, found 757.2577. Anal.Calcd for C48H32N6O4: C (76.17), H (4.25), N (8.46), O (11.10).Found: C (76.17), H (4.23), N (8.49), O (11.12).

Reference： [1]Shaikh, Azam M.; Sharma, Bharat K.; Kamble, Rajesh M. [Journal of Chemical Sciences, 2015, vol. 127, # 9, p. 1571 - 1579]

74
[ 24067-17-2 ]
[ 62-53-3 ]
[ 836-30-6 ]

Yield	Reaction Conditions	Operation in experiment
95%	With potassium fluoride; In dimethyl sulfoxide; at 130℃; for 2h;Inert atmosphere;	General procedure: The mixture of phenylboronic acid (1 mmol), aromatic amine (1.2 mmol) and 0.12 g (2 mmol) of KF in DMSO (4 mL) were added to Cu-IS-AMBA-MNPs (0.06 g, 0.025 mmol) at 130 C under nitrogen atmosphere for 2 h with vigorous stirring. Then, after completion of the reaction, the catalyst was separated by an external magnet and washed with dry CH2Cl2 three times and checked for its reusability. The solvent of the reaction mixture was evaporated by a rotary evaporator and then ethyl acetate and water were added to the residue. The organic layer was dried over anhydrous MgSO4. The solvent was evaporated under reduced pressure and the crude product was purified by column chromatography using ethyl acetate/n-hexane.

Reference： [1]Research on Chemical Intermediates,2019,vol. 45,p. 2727 - 2747
[2]Chemical Communications,2016,vol. 52,p. 1170 - 1173
[3]Applied Organometallic Chemistry,2020,vol. 34
[4]Applied Organometallic Chemistry,2018,vol. 32
[5]Organic Letters,2019,vol. 21,p. 4540 - 4543

75
[ 124-38-9 ]
[ 836-30-6 ]
[ 13744-88-2 ]

Yield	Reaction Conditions	Operation in experiment
24%	With C₃₇H₄₆N₄; 9-bora-bicyclo[3.3.1]nonane In toluene at 100℃; for 1.5h; Glovebox; Inert atmosphere; Schlenk technique;

Reference： [1]Chen, Wen-Ching; Shen, Jiun-Shian; Jurca, Titel; Peng, Chun-Jung; Lin, Yen-Hsu; Wang, Yi-Ping; Shih, Wei-Chih; Yap, Glenn P. A.; Ong, Tiow-Gan [Angewandte Chemie - International Edition, 2015, vol. 54, # 50, p. 15207 - 15212][Angew. Chem., 2015, vol. 54-127, # 50, p. 15422 - 15427,6]

76
[ 100-01-6 ]
[ 100-63-0 ]
[ 836-30-6 ]

Yield	Reaction Conditions	Operation in experiment
75%	With iron(II) phthalocyanine; copper(I) bromide In toluene at 25℃;	8 Synthesis of 4-nitrodiphenylamine A reaction flask was added 4-nitroaniline 0.138 g (1 mmol), phenylhydrazine 0.216 g(2 mmol), FePc 0.086 g (0.15 mmol), CuBr0.015 g (0.1 mmol) and 10 ml of toluene, 25 °C reaction ; TLC until complete reaction was followed over; after the reaction, the crudeproduct obtained was purified by column chromatography (petroleum ether: ethyl acetate =100: 1) to give the desired product (yield 75%).
58%	With tetrabenzoporphyrinatocobalt(II); copper diacetate In acetonitrile at 0℃; for 13h; chemoselective reaction;	3.8 4.2.1. General procedure for N-arylation of amines (2) with arylhydrazines (1). General procedure: Into a 25 mL round-bottom flask, amine (2) (1 mmol), Cu(OAc)2 (0.02 g, 0.1 mmol) and acetonitrile (4 mL) were added, the mixture was stirred and cooled to 0 °C. Then, CoPc (0.057 g, 0.1 mmol) was added, the solution of arylhydrazine (1) (2 mmol) in acetonitrile (2 mL) was added successively at a rate of 0.2 mmol per hour while stirring for 13 h in air. After completion of the reaction monitored by TLC analysis (developing solvent: ethyl acetate/petroleum ether (1:8)), the mixture was filtered, concentrated, and the residue was further purified by column chromatography using ethyl acetate/petroleum ether (1:100) as eluent to afford N-aryl amine 3.

Reference： [1]Current Patent Assignee: WUXI GREEN SEPARATION TECHNOLOGY INST - CN104262167, 2016, B Location in patent: Paragraph 0076-0079
[2]Sun, Wang-Bin; Zhang, Pei-Zhi; Jiang, Tao; Li, Cheng-Kun; An, Li-Tao; Shoberu, Adedamola; Zou, Jian-Ping [Tetrahedron, 2016, vol. 72, # 41, p. 6477 - 6483]

77
[ 62-53-3 ]
[ 100-16-3 ]
[ 836-30-6 ]

Yield	Reaction Conditions	Operation in experiment
50%	With cobalt(II) phthalocyanine; copper(II) sulfate In chloroform at 20℃;	24 Synthesis of 4-nitrodiphenylamine In the reaction flask aniline 0.093 g (1 mmol), 4- dinitrophenylhydrazine 0.306 g(2 mmol), CoPc 0.057 Ke (0.1 mmol), Cu (SO 4) 20.026 g (0.1 mmol) and 10 ml ofchloroform, 20 °C reaction; TLC until the reaction was followed completely finished; thecrude product after the reaction was subjected to column chromatography (petroleumether: ethyl acetate = 100: 1) to give the desired product (50% yield).
25%	With tetrabenzoporphyrinatocobalt(II); copper diacetate In acetonitrile at 0℃; for 13h; chemoselective reaction;	3.23 4.2.1. General procedure for N-arylation of amines (2) with arylhydrazines (1). General procedure: Into a 25 mL round-bottom flask, amine (2) (1 mmol), Cu(OAc)2 (0.02 g, 0.1 mmol) and acetonitrile (4 mL) were added, the mixture was stirred and cooled to 0 °C. Then, CoPc (0.057 g, 0.1 mmol) was added, the solution of arylhydrazine (1) (2 mmol) in acetonitrile (2 mL) was added successively at a rate of 0.2 mmol per hour while stirring for 13 h in air. After completion of the reaction monitored by TLC analysis (developing solvent: ethyl acetate/petroleum ether (1:8)), the mixture was filtered, concentrated, and the residue was further purified by column chromatography using ethyl acetate/petroleum ether (1:100) as eluent to afford N-aryl amine 3.

Reference： [1]Current Patent Assignee: WUXI GREEN SEPARATION TECHNOLOGY INST - CN104262167, 2016, B Location in patent: Paragraph 0156-0159
[2]Sun, Wang-Bin; Zhang, Pei-Zhi; Jiang, Tao; Li, Cheng-Kun; An, Li-Tao; Shoberu, Adedamola; Zou, Jian-Ping [Tetrahedron, 2016, vol. 72, # 41, p. 6477 - 6483]

78
[ 98-95-3 ]
[ 62-53-3 ]
[ 836-30-6 ]

Yield	Reaction Conditions	Operation in experiment
	With 3-methyl-1-butylimidazole hydroxide; tetramethyl ammoniumhydroxide In water at 60℃; for 3h;	1.1; 1.2 condensation step In the equipped with a mechanical stirrer, thermometer, condenser, and constant pressure dropping funnel receiving flask of 500 ml in four flasks, the concentration of added to 25 wt % of the aqueous solution of tetramethyl ammonium hydroxide 48g (0.132mol), aniline 144g (1.55mol) and 3-methyl-1-butylimidazole hydroxide 2.4g (as nitrobenzene amount of 10 wt %), the temperature of the 1st opening stirring and heating to 60 °C, and vacuum, regulating the vacuum degree of vacuum to 1st 0.08 MPa (absolute pressure), when the receiving flask is a dripping of condensed water, slowly dropping nitrobenzene 24g (0.195mol), dropping time is 40 min. After dripping, the vacuum degree of the vacuum accent to 2nd 0.092 MPa (absolute pressure), controlling the reaction to 2nd temperature 85 °C, to continue heating and stirring 1.5h, sampling with the high performance liquid chromatography analysis (HPLC), the conversion of nitrobenzene to 98%, active ingredient selectivity of 88%.After completion of the reaction, 60 g of water was added to the above-mentioned condensate, and the mixture was allowed to stand in a separatory funnel. The lower aqueous phase can be directly applied to the above-mentioned condensation reaction, and the upper organic phase is subjected to hydrogenation reduction because of containing the basic ionic liquid 3-methyl-1-butylimidazole hydroxide and the catalyst tetramethylammonium hydroxide.

Reference： [1]Current Patent Assignee: SINOCHEM HOLDINGS CORPORATION LTD - CN105585507, 2016, A Location in patent: Paragraph 0050; 0051; 0052; 0053

79
[ 17763-67-6 ]
[ 100-01-6 ]
[ 836-30-6 ]

Yield	Reaction Conditions	Operation in experiment
	With palladium diacetate; caesium carbonate; 2,2'-bis-(diphenylphosphino)-1,1'-binaphthyl In toluene at 110℃; Inert atmosphere;	4 3-Nitro-9H-carbazole A mixture of phenyl trifluoromethanesulfonate (500 mg, 2.21 mmol), palladium acetate (II) (50 mg, 0.22 mmol), (±) 2,2'-bis(diphenylphosphino)-1,1'-binaphthyl (317 mg, 0.66 mmol) and cesium carbonate (1.09 g, 3.31 mmol) in 50 mL of toluene were inertized with argon. Then, 4-nitroaniline (331 mg, 2.43 mmol) was added and the mixture was heated at 110°C overnight. The reaction mixture was allowed to cool to room temperature and filtered through a pad of Celite. The filtrate was diluted with CH2Cl2and water. The phases were separated and the aqueous phase was re-extracted 2 times with CH2Cl2. The combined organic phases were dried over Na2SO4and the resulting solution was dried over anhydrous Na2SO4and purified with flash column chromatography as an eluent EtOAc/hexane (1/6, v/v) to give 4-nitro-N-phenylaniline. The aniline (450 mg, 2 mmol), Pd(OAc)2(23 mg, 0.1 mmol), K2CO3(30 mg, 0.2 mmol), and pivalic acid (408 mg, 4 mmol) was placed into a glass test tube. The uncapped test tube was placed in an oil bath and the mixture was stirred under air at the indicated temperature. The solution was then cooled to room temperature, diluted with EtOAc, washed with a saturated Na2CO3, dried over Na2SO4, concentrated, and purified by flash column chromatography as an eluent of EtOAc/hexane to give 3-nitro-9H-carbazole.

Reference： [1]Current Patent Assignee: UNIVERSITY OF TENNESSEE; ONCTERNAL THERAPEUTICS INC - WO2016/172358, 2016, A1 Location in patent: Paragraph 00437-00438

80
[ 100-01-6 ]
[ 65-85-0 ]
[ 836-30-6 ]

Yield	Reaction Conditions	Operation in experiment
78%	With potassium hydroxide In dimethyl sulfoxide at 130℃; for 2h;	General Procedure for the Synthesis of Secondary Amines The reaction was conducted at 130°C in DMSO (3mL) with substituted amine (3 mmol), substituted benzoic acid (1.3mmol), KOH (7 mmol), and 200 mL of the solution containing CuNP- or NiNP-PNF. The progress of the reaction was monitored by TLC. After reaction completion, the mixture was cooled to room temperature and was extracted with ethyl acetate (220mL). The organic extract was washed twice with water and dried with anhydrous Na2SO4, and then filtered and the solvent was evaporated to give the corresponding aryl amine. The crude product was purified by preparative TLC.

Reference： [1]Ghorbani-Choghamarani, Arash; Taherinia, Zahra [Australian Journal of Chemistry, 2017, vol. 70, # 10, p. 1127 - 1137]

81
[ 24067-17-2 ]
[ 586-96-9 ]
[ 836-30-6 ]

Yield	Reaction Conditions	Operation in experiment
91%	With triethyl phosphite In toluene at 20℃; for 0.75h;

Reference： [1]Roscales, Silvia; Csákÿ, Aurelio G. [Organic Letters, 2018, vol. 20, # 6, p. 1667 - 1671]

82
[ 1919-18-2 ]
[ 62-53-3 ]
[ 836-30-6 ]

Yield	Reaction Conditions	Operation in experiment
87%	With potassium carbonate In toluene at 90℃; for 8h;

Reference： [1]Hajipour, Abdol R.; Abolfathi, Parisa [Applied Organometallic Chemistry, 2018, vol. 32, # 4]

83
[ 836-30-6 ]
[ 110-12-3 ]
N-(1,4-dimethylpentyl)-N'-phenyl-p-phenylenediamine [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
99.3%	Stage #1: 4-ntrophenyl(phenyl)amine; 5-Methyl-2-hexanone at 120 - 125℃; for 1h; Stage #2: With palladium on activated charcoal; hydrogen at 155 - 163℃; for 1h;	4 The operating conditions were the same as in Example 1, but the starting material used in step (1) was p-nitrodiphenylamine.Result: The upper part of the distillation still 1 obtained in the step (2) was sampled, analyzed by gas spectrum analysis, the content of 5-methyl-2-hexanone was 94.55%, and 5-methyl-2-hexanone was not detected. N-(1,4-dimethylpentyl)-N'-phenyl-p-phenylenediamine was not detected.Step (3) Reaction liquid 3 was obtained. Gas chromatographic analysis, 5-methyl-2-hexanone content 0.74%, 5-methyl-2-hexanol 0.09%, N-(1,4-dimethylpentyl)-N'-phenyl The content of p-phenylenediamine is 97.01%.[0041] The finished product obtained in step (4) was detected to be neither p-aminodiphenylamine nor p-nitrodiphenylamine, containing N-(1,4-dimethylpentyl)-N'-phenyl-p-phenylene The amine content was 99.30%.

Reference： [1]Current Patent Assignee: CHINA PETROCHEMICAL CORPORATION - CN107814725, 2018, A Location in patent: Paragraph 0038-0041

84
[ 1190059-22-3 ]
[ 836-30-6 ]
2-(4-((4-nitrophenyl)(phenyl)amino)phenyl)-1H-anthra[1,2-d]imidazole-6,11-dione [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With dicyclohexyl-(2',6'-dimethoxybiphenyl-2-yl)-phosphane; tris-(dibenzylideneacetone)dipalladium⁽⁰⁾; sodium t-butanolate In toluene at 100℃; for 24h; Inert atmosphere;	2.2a General method for the synthesis of compounds1-5: General procedure: In a three-necked round bottom flask equipped witha reflux condenser and argon inlet and outlet ports, 2-(4-bromo)phenyl-anthra[1,2-d]imidazole-6,11-dione (6) (1.0mmol) and diarylamine (1.2 mmol) were dissolved in anhydroustoluene (20 mL) under argon atmosphere. The palladiumcatalyst [Pd2(dba)3] (5-8 mol%), 2-dicyclohexylphoshpino-2’,6’-dimethyl biphenyl (SPhos) (10-15 mol%) andsodium-t-butoxide (3.1 mol) were added to the reactionmixture. The reaction mixture was thoroughly stirred underargon atmosphere while the temperature was slowly raised to100 °C. Reaction mixture was stirred at this temperature for24 h. Reaction mixture was cooled to room temperature andextracted with chloroform (3 × 50 mL) followed by waterwash (3 × 50 mL). All the organic layers were combinedand dried over anhydrous Na2SO4 and evaporated to get thecrude product which was further purified by silica gel columnchromatography.

Reference： [1]Sharma, Bharat K; Shaikh, Azam M; Chacko, Sajeev; Kamble, Rajesh M [Journal of Chemical Sciences, 2018, vol. 130, # 5]

85
[ 636-98-6 ]
[ 100-01-6 ]
[ 836-30-6 ]
[ 4316-57-8 ]

Yield	Reaction Conditions	Operation in experiment
1: 88% 2: 18%	With caesium carbonate In N,N-dimethyl-formamide at 120℃; for 24h; Sealed tube;

Reference： [1]Garnier, Tony; Danel, Mathieu; Magné, Valentin; Pujol, Anthony; Bénéteau, Valérie; Pale, Patrick; Chassaing, Stefan [Journal of Organic Chemistry, 2018, vol. 83, # 12, p. 6408 - 6422]

86
[ 836-30-6 ]
[ 90172-60-4 ]
4-fluoro-N-(4-(phenylamino)phenyl)benzamide [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
85%	With manganese; 1,10-Phenanthroline; trimethylsilyl iodide In 1-methyl-pyrrolidin-2-one at 120℃; for 24h; Inert atmosphere;

Reference： [1]Cheung, Chi Wai; Ma, Jun-An; Hu, Xile [Journal of the American Chemical Society, 2018, vol. 140, # 22, p. 6789 - 6792]

87
[ 905718-45-8 ]
[ 62-53-3 ]
[ 836-30-6 ]

Yield	Reaction Conditions	Operation in experiment
91%	Stage #1: [(4-nitrophenyl)(phenyl)iodonium trifluoromethanesulfonate] With sodium carbonate Inert atmosphere; Sealed tube; Stage #2: aniline In toluene at 110℃; for 4h; Inert atmosphere; Sealed tube; regiospecific reaction;

Reference： [1]Purkait, Nibadita; Kervefors, Gabriella; Linde, Erika; Olofsson, Berit [Angewandte Chemie - International Edition, 2018, vol. 57, # 35, p. 11427 - 11431][Angew. Chem., 2018, vol. 130, # 35, p. 11597 - 11601,5]

Purity	Size	Price	VIP Price	USA Stock *0-1 Day	Global Stock *5-7 Days	Quantity
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CAS No. :	836-30-6	MDL No. :	MFCD00007301
Formula :	C₁₂H₁₀N₂O₂	Boiling Point :	-
Linear Structure Formula :	-	InChI Key :	XXYMSQQCBUKFHE-UHFFFAOYSA-N
M.W :	214.22	Pubchem ID :	13271
Synonyms :

Signal Word:	Warning	Class:	N/A
Precautionary Statements:	P261-P305+P351+P338	UN#:	N/A
Hazard Statements:	H315-H319-H335	Packing Group:	N/A
GHS Pictogram:

[ CAS No. 836-30-6 ] {[proInfo.proName]}

Quality Control of [ 836-30-6 ]

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Application In Synthesis of [ 836-30-6 ]

[ 836-30-6 ] Synthesis Path-Downstream 1~87

Precautionary Statements-General

Prevention

Response

Storage

Disposal

Physical hazards

Health hazards

Environmental hazards

Inquiry

Precautionary Statements-General
Code	Phrase
P101	If medical advice is needed,have product container or label at hand.
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P103	Read label before use
Prevention
Code	Phrase
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Response
Code	Phrase
P301	IF SWALLOWED:
P304	IF INHALED:
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P321
P322
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P342	If experiencing respiratory symptoms:
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P371	In case of major fire and large quantities:
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P376	Stop leak if safe to do so. Oxidising gases (section 2.4) 1
P377	Leaking gas fire: Do not extinguish, unless leak can be stopped safely.
P378
P380	Evacuate area.
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P390	Absorb spillage to prevent material damage.
P391	Collect spillage. Hazardous to the aquatic environment
P301 + P310	IF SWALLOWED: Immediately call a POISON CENTER or doctor/physician.
P301 + P312	IF SWALLOWED: call a POISON CENTER or doctor/physician IF you feel unwell.
P301 + P330 + P331	IF SWALLOWED: Rinse mouth. Do NOT induce vomiting.
P302 + P334	IF ON SKIN: Immerse in cool water/wrap in wet bandages.
P302 + P350	IF ON SKIN: Gently wash with plenty of soap and water.
P303 + P361 + P353	IF ON SKIN (or hair): Remove/Take off Immediately all contaminated clothing. Rinse SKIN with water/shower.
P304 + P312	IF INHALED: Call a POISON CENTER or doctor/physician if you feel unwell.
P304 + P340	IF INHALED: Remove victim to fresh air and Keep at rest in a position comfortable for breathing.
P304 + P341	IF INHALED: If breathing is difficult, remove victim to fresh air and keep at rest in a position comfortable for breathing.
P305 + P351 + P338	IF IN EYES: Rinse cautiously with water for several minutes. Remove contact lenses, if present and easy to do. Continue rinsing.
P306 + P360	IF ON CLOTHING: Rinse Immediately contaminated CLOTHING and SKIN with plenty of water before removing clothes.
P307 + P311	IF exposed: call a POISON CENTER or doctor/physician.
P308 + P313	IF exposed or concerned: Get medical advice/attention.
P309 + P311	IF exposed or if you feel unwell: call a POISON CENTER or doctor/physician.
P332 + P313	IF SKIN irritation occurs: Get medical advice/attention.
P333 + P313	IF SKIN irritation or rash occurs: Get medical advice/attention.
P335 + P334	Brush off loose particles from skin. Immerse in cool water/wrap in wet bandages.
P337 + P313	IF eye irritation persists: Get medical advice/attention.
P342 + P311	IF experiencing respiratory symptoms: call a POISON CENTER or doctor/physician.
P370 + P376	In case of fire: Stop leak if safe to Do so.
P370 + P378	In case of fire:
P370 + P380	In case of fire: Evacuate area.
P370 + P380 + P375	In case of fire: Evacuate area. Fight fire remotely due to the risk of explosion.
P371 + P380 + P375	In case of major fire and large quantities: Evacuate area. Fight fire remotely due to the risk of explosion.
Storage
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P401
P402	Store in a dry place.
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Disposal
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