Name: 4316-53-4|4-Methyl-N,N-diphenylaniline|98%
Brand: Ambeed
SKU: A124538
Price: 25.0 USD
Availability: InStock
Rating: 93 (22 reviews)

1
[ 624-31-7 ]
[ 122-39-4 ]
[ 4316-53-4 ]

Yield	Reaction Conditions	Operation in experiment
96%	With copper(l) iodide; 5,6,9,10-tetrahydro-4H,8H-pyrido[3,2,1-ij][1,6]naphthyridine; sodium t-butanolate In toluene at 110℃; for 40h;
92%	With copper; potassium carbonate In 1,2-dichloro-benzene for 16h; Heating;
90%	With potassium <i>tert</i>-butylate In toluene at 120℃; for 12h;

88%	With bis(triphenylphosphine)nickel(II) chloride; ethylmagnesium bromide; triphenylphosphine In tetrahydrofuran at 80℃; for 3h;
80%	With palladium diacetate; copper(l) iodide; cetyltriammonium bromide; potassium carbonate In water; butan-1-ol for 24h; Heating;
79%	With potassium <i>tert</i>-butylate; 1,2-bis(2,6-diisopropylphenylimino)ethane In toluene at 120℃; for 20h;
76%	With potassium phosphate; 8-quinolinol; copper(l) chloride In N,N-dimethyl-formamide at 120℃; for 24h; Inert atmosphere;
75%	With 1,1'-bis-(diphenylphosphino)ferrocene; tris-(dibenzylideneacetone)dipalladium⁽⁰⁾; sodium t-butanolate In toluene at 110℃; for 24h;
70%	With Cu(neocup)(PPh₃)Br; potassium <i>tert</i>-butylate In toluene at 110 - 120℃; for 6h;
69%	With [2,2]bipyridinyl; copper(l) iodide; potassium <i>tert</i>-butylate In toluene at 100℃; for 24h; Inert atmosphere; Sealed tube;
68%	With chloro(1-naphthyl)bis(triphenylphosphine)nickel(II); sodium hydride; triphenylphosphine In toluene; white oil at 120℃; for 12h; Inert atmosphere;
61%	With potassium hydroxide; 1,10-Phenanthroline; copper(l) chloride In o-xylene at 110 - 150℃; for 24h;	1.A Example 1 - Synthesis of cyclo-hexa(diphenyl-4-methylphenylamine) (Compound (9)) viasteps A to I; (A) Compound (1) 4-Methyltriphenylamine; To a flame-dried flask fitted with condenser, nitrogen inlet and outlet, mechanical stirrer and suba-seal was added diphenylamine (50.Og, 295.5mmol (1 molar equivalent)), 4-iodotoluene (128.9g, 591.3mmol (2 molar equivalents)) and 1,10-phenanthroline (10.7g, 59.1mmol (0.2 molar equivalents)). The flask and contents were thoroughly flushed with nitrogen before anhydrous o-xylene (200ml) was added. The reaction mixture was heated to 110°C and then copper (I) chloride (5.9g, 59.1mmol (0.2 molar equivalents)) and potassium hydroxide (132.6g, 2364.0mmol (8 molar equivalents)) were added to the reaction flask. The reaction was heated further with rapid stirring to 150°C for 24 hours before allowing the reaction to cool to room temperature. Water and dichloromethane (DCM) were added to the solution and this was filtered though celite before extracting the product using DCM. The combined organic fractions were dried over magnesium sulphate (MgSO4), filtered and concentrated under vacuum. Purification by column chromatography (silica gel 60; 9: 1, hexane : DCM) followed by recrystallisation from methanol gave compound (1) as a white solid (46.5g, 61%), greater than 99% pure by HPLC.
60%	With potassium carbonate In nitrobenzene at 210 - 220℃; for 12h;
52%	With bromotris(triphenylphosphine)copper(I); caesium carbonate In toluene at 120℃; for 24h;
51%	With [2,2]bipyridinyl; copper(l) iodide; potassium <i>tert</i>-butylate In tetrahydrofuran; toluene at 100℃; for 24h; Inert atmosphere;
	With copper; potassium carbonate; nitrobenzene
	With copper; potassium carbonate In 1,3,5-trimethyl-benzene for 7h; Reflux;	1 50 g of diphenylamine, 64.3 g of 4-iodotoluene, 100 g of potassium carbonate, and 20 g of copper powder were added to mesitylene, and were refluxed for seven hours. Toluene was added to the resulting reaction mixture to dissolve the desired product. The resulting solution was concentrated, filtered with a silica gel column, and then crystallization was carried out from a mixed solvent of toluene/hexane to provide diphenyl-p-tolylamine.
	With tri-tert-butyl phosphine; sodium t-butanolate In xylene for 4h; Heating / reflux;
90 %Chromat.	Stage #1: diphenylamine With 1,10-Phenanthroline; copper (I) tert-butoxide In tetrahydrofuran at 20℃; for 1h; Inert atmosphere; Stage #2: 4-tolyl iodide With 1,10-Phenanthroline In dimethylsulfoxide-d6 at 80℃; Inert atmosphere;
99.1 %Chromat.	With [Na(phen)3][Cu(NPh₂)2]; sodium t-butanolate In toluene at 120℃; for 40h;
92.7 %Spectr.	With copper(l) iodide; 1,10-Phenanthroline; potassium carbonate; sodium t-butanolate In toluene at 20 - 120℃; for 6h;
	With 1,10-Phenanthroline; copper(l) chloride In 5,5-dimethyl-1,3-cyclohexadiene
99 %Chromat.	With copper(l) iodide; 1,10-Phenanthroline; potassium <i>tert</i>-butylate In toluene at 120℃; for 6h;
	With 18-crown-6 ether; copper; potassium carbonate In 1,2-dichloro-benzene at 190℃; Inert atmosphere;

Reference： [1]Wong, Ken-Tsung; Ku, Sung-Yu; Yen, Feng-Wen [Tetrahedron Letters, 2007, vol. 48, # 29, p. 5051 - 5054]
[2]Gauthier, Sylvie; Frechet, Jean M. J. [Synthesis, 1987, # 4, p. 383 - 385]
[3]Nandurkar, Nitin S.; Bhanushali, Mayur J.; Bhor, Malhari D.; Bhanage, Bhalchandra M. [Tetrahedron Letters, 2007, vol. 48, # 37, p. 6573 - 6576]
[4]Chen, Chen; Yang, Lian-Ming [Organic Letters, 2005, vol. 7, # 11, p. 2209 - 2211]
[5]Davydov, D. V.; Beletskaya, I. P. [Russian Chemical Bulletin, 1995, vol. 44, # 6, p. 1141][Izvestiya Akademi Nauk, Seriya Khimicheskaya, 1995, # 6, p. 1181 - 1182]
[6]Liu, Yu-Hua; Chen, Chen; Yang, Lian-Ming [Tetrahedron Letters, 2006, vol. 47, # 52, p. 9275 - 9278]
[7]Qian, Cunwei; Xu, Shaojie; Zong, Qianshou; Fang, Dong [Chinese Journal of Chemistry, 2012, vol. 30, # 8, p. 1881 - 1885]
[8]Location in patent: experimental part Sun, Ying; Chien, Shang-Chieh; Yip, Hin-Lap; Zhang, Yong; Chen, Kung-Shih; Zeigler, David F.; Chen, Fang-Chung; Lin, Baoping; Jen, Alex K.-Y. [Chemistry of Materials, 2011, vol. 23, # 22, p. 5006 - 5015]
[9]Gujadhur, Rattan K.; Bates, Craig G.; Venkataraman [Organic Letters, 2001, vol. 3, # 26, p. 4315 - 4317]
[10]Hernandez-Perez, Augusto C.; Collins, Shawn K. [Angewandte Chemie - International Edition, 2013, vol. 52, # 48, p. 12696 - 12700][Angew. Chem., 2013, vol. 125, # 48, p. 12928 - 12932]
[11]Gao, Cai-Yan; Cao, Xingbo; Yang, Lian-Ming [Organic and Biomolecular Chemistry, 2009, vol. 7, # 19, p. 3922 - 3925]
[12]Current Patent Assignee: MERCK KGAA - WO2006/10555, 2006, A1 Location in patent: Page/Page column 20
[13]Tarasievich; Mikhalevskaya; Kozlov [Russian Journal of Organic Chemistry, 1997, vol. 33, # 8, p. 1100 - 1102]
[14]Gujadhur, Rattan; Venkataraman; Kintigh, Jeremy T [Tetrahedron Letters, 2001, vol. 42, # 29, p. 4791 - 4793]
[15]Wang, Lei; Huang, Wei; Li, Run; Gehrig, Dominik; Blom, Paul W. M.; Landfester, Katharina; Zhang, Kai A. I. [Angewandte Chemie - International Edition, 2016, vol. 55, # 33, p. 9783 - 9787][Angew. Chem., 2016, vol. 128, p. 9935 - 9940,6]
[16]Marsden [Journal of the Chemical Society, 1937, p. 627]
[17]Yakushchenko, Igor K.; Kaplunov, Mikhail G.; Efimov, Oleg N.; Belov, Mikhail Yu; Shamaev, Sergei N. [Physical Chemistry Chemical Physics, 1999, vol. 1, # 8, p. 1783 - 1785]
[18]Current Patent Assignee: BANDO CHEMICAL INDUSTRIES LTD - EP2100880, 2009, A1 Location in patent: Page/Page column 14-15
[19]Current Patent Assignee: INNOVATION NETWORK CORPORATION OF JAPAN; JOLED (in: INCJ) - US6337167, 2002, B1 Location in patent: Example 12
[20]Giri, Ramesh; Hartwig, John F. [Journal of the American Chemical Society, 2010, vol. 132, # 45, p. 15860 - 15863]
[21]Location in patent: experimental part Tseng, Chia-Kai; Lee, Chi-Rung; Han, Chien-Chung; Shyu, Shin-Guang [Chemistry - A European Journal, 2011, vol. 17, # 9, p. 2716 - 2723]
[22]Tseng, Chia-Kai; Tseng, Mei-Chun; Han, Chien-Chung; Shyu, Shin-Guang [Chemical Communications, 2011, vol. 47, # 23, p. 6686 - 6688]
[23]Location in patent: scheme or table Gao, Wen Zheng; Li, Xiang Gao; Wang, Shi Rong; Lv, Hai Jun [Chinese Chemical Letters, 2012, vol. 23, # 2, p. 141 - 144]
[24]Tseng, Chia-Kai; Lee, Chi-Rung; Tseng, Mei-Chun; Han, Chien-Chung; Shyu, Shin-Guang [Dalton Transactions, 2014, vol. 43, # 19, p. 7020 - 7027]
[25]Gudeika, Dalius; Bundulis, Arturs; Mihailovs, Igors; Volyniuk, Dmytro; Rutkis, Martins; Grazulevicius, Juozas V. [Dyes and Pigments, 2017, vol. 140, p. 431 - 440]

2
[ 591-50-4 ]
C₇H₈N^(1-)*Br^(1-)*Mg⁽²⁺⁾ [ No CAS ]
[ 620-84-8 ]
[ 4316-53-4 ]
[ 501-60-0 ]

Yield	Reaction Conditions	Operation in experiment
1: 14% 2: 4% 3: 73%	With [2,2]bipyridinyl; copper(l) iodide In pyridine for 24h; Heating;

Reference： [1]Matsuo, Koji; Shichida, Yoshiaki; Nishida, Hiroshi; Nakata, Satsuki; Okubo, Masao [Journal of Physical Organic Chemistry, 1994, vol. 7, p. 9 - 17]

3
[ 591-17-3 ]
[ 122-39-4 ]
[ 4316-53-4 ]
[ 4316-54-5 ]
[ 4316-55-6 ]

Yield	Reaction Conditions	Operation in experiment
	With potassium hydroxide In toluene at 161 - 163℃; for 8h; Yield given. Yields of byproduct given. Title compound not separated from byproducts;

Reference： [1]Sukata, Kazuaki; Akagawa, Takao [Journal of Organic Chemistry, 1989, vol. 54, # 6, p. 1476 - 1479]

4
[ 106-38-7 ]
[ 122-39-4 ]
[ 4316-53-4 ]
[ 4316-54-5 ]

Yield	Reaction Conditions	Operation in experiment
	With potassium hydroxide In toluene at 165℃; for 8h; Yield given. Yields of byproduct given. Title compound not separated from byproducts;
	With iron(III) oxide; potassium <i>tert</i>-butylate In dimethyl sulfoxide at 130℃; for 36h; regioselective reaction;

Reference： [1]Sukata, Kazuaki; Akagawa, Takao [Journal of Organic Chemistry, 1989, vol. 54, # 6, p. 1476 - 1479]
[2]Location in patent: experimental part Alakonda, Laxhmaiah; Periasamy, Mariappan [Synthesis, 2012, vol. 44, # 7, p. 1063 - 1068]

5
[ 4316-53-4 ]
4,4′-dibromo-4′′-methyltriphenylamine [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
99%	With N-Bromosuccinimide In chloroform Darkness; Cooling with ice;
93%	With N-Bromosuccinimide In N,N-dimethyl-formamide at -78.5℃; for 1.5h;	1.B (B) Compound (2) 4. 4'-Dibromo-4"-rnethvltriphenvlamine; To a flask fitted with nitrogen inlet and outlet, mechanical stirrer and suba-seal was added 4-methyltriarylamine (Compound (1)) (40.0g, 154.4mmol (1 molar equivalent)) and N, N-dimethylformamide (DMF) (120ml). The resulting solution was cooled using dry ice. To the reaction mixture was added a solution of N-bromosuccinimide (NBS) (55.0g, 308.8mmol (2 molar equivalents)) dissolved in DMF (280ml) over 30 minutes, once addition was complete, the dry ice bath was removed. After 1 hour the reaction was complete. The reaction solution was added to water (1L) and the product extracted three times using hexane. The combined organic fractions were dried over MgSC>4, filtered and concentrated under vacuum. The crude product was crystallised from a mixture of methanol and acetone at 0°C to yield compound (2) as an off white solid (59.6g, 93%), 97% pure by HPLC.
90%	With N-Bromosuccinimide In N,N-dimethyl-formamide for 0.25h; Cooling with ice;

	With bromine
129 g	With N-Bromosuccinimide In dichloromethane at 0 - 20℃;	Bis-(4-bromophenyl)-p-tolylamine (Ib) (4-Methylphenyl)diphenylamine (85.2 g, 330 mmol) is dissolved in 1 l of DCM and cooled to 0° C. N-Bromosuccinimide (117 g, 660 mmol) is added in small portions with stirring at such a rate that the reaction temperature does not exceed 5° C. The reaction mixture is warmed to room temperature in an ice bath overnight. 500 ml of a 10% Na2SO3solution are then added, and the phases are separated. The aqueous phase is extracted a number of times with DCM. The organic phase is washed with dist. H2O, dried and freed from solvent. The solid obtained is recrystallised a number of times from 1-butanol, giving 129 g of a colourless solid (94% of theory).

Reference： [1]Wang, Qiwei; He, Zhicai; Wild, Andreas; Wu, Hongbin; Cao, Yong; Schubert, Ulrich S.; Chui, Chung-Hin; Wong, Wai-Yeung [Chemistry - An Asian Journal, 2011, vol. 6, # 7, p. 1766 - 1777]
[2]Current Patent Assignee: MERCK KGAA - WO2006/10555, 2006, A1 Location in patent: Page/Page column 20-21
[3]Lee, Chin-Sheng; Kuo, Cheng-Po; Chang, Chiou-Ling; Chuang, Ching-Nan; Lee, Mandy M.; Sun, Shih-Sheng; Leung, Man-Kit [RSC Advances, 2013, vol. 3, # 43, p. 20227 - 20236]
[4]Yakushchenko, Igor K.; Kaplunov, Mikhail G.; Efimov, Oleg N.; Belov, Mikhail Yu; Shamaev, Sergei N. [Physical Chemistry Chemical Physics, 1999, vol. 1, # 8, p. 1783 - 1785]
[5]Current Patent Assignee: MERCK KGAA - JP2015/534543, 2015, A Location in patent: Paragraph 0112; 0115

6
[ 106-43-4 ]
[ 122-39-4 ]
[ 4316-53-4 ]

Yield	Reaction Conditions	Operation in experiment
99%	With PdCl(π-allyl)(cyclohexyl-(1-methyl-2,2-diphenylcyclopropylphophine)); sodium t-butanolate In tetrahydrofuran; toluene at 100℃; for 0.25h; Inert atmosphere;
99%	With palladium diacetate; sodium t-butanolate; ruphos In neat (no solvent) at 110℃; for 12h; Green chemistry;
98%	With sodium t-butanolate In toluene at 100℃; for 20h;

96%	With tri-tert-butyl phosphine; sodium t-butanolate In toluene at 100℃; for 17h;
94%	With 4-di-tert-butylphosphanyl-1-phenyl-5-(2-methoxyphenyl)-1H-[1,2,3]triazole; sodium t-butanolate In toluene at 110℃; for 20h;
94%	With sodium t-butanolate In toluene at 110℃; for 20h;	9.65 Example 9General Procedure for Pd-Catalysed Amination Reactions[0045] The phosphine ligand compounds of the present invention can be used in conjunction with transition metal catalysts employed in the animation of aryl chlorides. Pd- catalyzed amination of aryl halides has become a powerful method for the synthesis of aniline derivatives. Employing readily available aryl chlorides in this transformation has also become a focus and met with moderate success in recent years. EPO [0046] The procedure for the animation reaction using an unactivated aryl chloride in the presence of a transition metal catalyst and a phosphine ligand is as follows. A Schlenk tube, which was flame-dried under vaccum and backfilled with nitrogen, was charged with an amine (1.2 mmol) and a base such as KO(t-Bu) or NaO(t-Bu) (1.2 equiv.). The flask was evacuated and backfilled with nitrogen three times. Toluene (3 mL), a stock solution of a phosphine ligand (1.0-2.0 mol%) in toluene, a stock solution of a Pd catalyst (0.5-1.0 mol%) in toluene, and aryl chloride (1.0 mmol) were subsequently added. The flask was sealed and the reaction mixture was heated to 80°C or 110°C with vigorous stirring for 20-24 hours. After cooling to room temperature, 10 mL of EtOAc was added and the mixture was washed with 10 mL of 1N NaOH (aq.) and 10 mL of brine. The organic layer was dried over Na2SO4 and concentrated under reduced pressure. The crude product was purified by flash column chromatography on silica gel. The yields of the amination reaction using phosphine ligands described in this example coupled with Pd catalyst are summarized forth in Table 4 below. EPO TABLE 4 EPO EPO EPO EPO EPO EPO EPO EPO EPO In this sample, 5 equiv. of the amine was used.
93%	With johnphos; sodium t-butanolate In toluene at 80℃; for 12h;
91%	With potassium <i>tert</i>-butylate In toluene at 80℃; for 24h;	9.66 Example 9General Procedure for Pd-Catalysed Amination Reactions[0045] The phosphine ligand compounds of the present invention can be used in conjunction with transition metal catalysts employed in the animation of aryl chlorides. Pd- catalyzed amination of aryl halides has become a powerful method for the synthesis of aniline derivatives. Employing readily available aryl chlorides in this transformation has also become a focus and met with moderate success in recent years. EPO [0046] The procedure for the animation reaction using an unactivated aryl chloride in the presence of a transition metal catalyst and a phosphine ligand is as follows. A Schlenk tube, which was flame-dried under vaccum and backfilled with nitrogen, was charged with an amine (1.2 mmol) and a base such as KO(t-Bu) or NaO(t-Bu) (1.2 equiv.). The flask was evacuated and backfilled with nitrogen three times. Toluene (3 mL), a stock solution of a phosphine ligand (1.0-2.0 mol%) in toluene, a stock solution of a Pd catalyst (0.5-1.0 mol%) in toluene, and aryl chloride (1.0 mmol) were subsequently added. The flask was sealed and the reaction mixture was heated to 80°C or 110°C with vigorous stirring for 20-24 hours. After cooling to room temperature, 10 mL of EtOAc was added and the mixture was washed with 10 mL of 1N NaOH (aq.) and 10 mL of brine. The organic layer was dried over Na2SO4 and concentrated under reduced pressure. The crude product was purified by flash column chromatography on silica gel. The yields of the amination reaction using phosphine ligands described in this example coupled with Pd catalyst are summarized forth in Table 4 below. EPO TABLE 4 EPO EPO EPO EPO EPO EPO EPO EPO EPO In this sample, 5 equiv. of the amine was used.
91%	With tris-(dibenzylideneacetone)dipalladium⁽⁰⁾; C₃₃H₄₈N₇P; sodium t-butanolate In toluene at 80℃; for 24h; Inert atmosphere; Schlenk technique; Glovebox;
90%	With bis[chloro(1,2,3-trihapto-allylbenzene)palladium(II)]; N-[2-(di(1-adamantyl)phosphino)phenyl]morpholine; sodium t-butanolate at 110℃; for 21h; Inert atmosphere; neat (no solvent); chemoselective reaction;
88%	With tris(dibenzylideneacetone)dipalladium ⁽⁰⁾; sodium t-butanolate; 2,8,9-tris(2-methylpropyl)-2,5,8,9-tetraaza-1-phosphabicyclo[3.3.3]undecane In toluene Heating;
82%	With potassium hydroxide; bis(tri-tert-butylphosphine)palladium⁽⁰⁾; cetyltrimethylammonim bromide In water; toluene at 90℃; for 24h;
81%	With 2‐(di‐tert‐butylphosphino)‐N,N‐diisopropyl‐5,6‐dimethyl‐1H‐benzo[d]imidazole‐1‐carboxamide; palladium diacetate; potassium carbonate In toluene at 110℃; for 24h; Schlenk technique; Inert atmosphere; Sealed tube;
80%	With 4-(2-(dicyclohexylphosphanyl)phenyl)-1,2,3-triphenyl-1H-pyrrole; bis(dibenzylideneacetone)-palladium⁽⁰⁾; sodium t-butanolate In 1,4-dioxane; water at 20℃; for 0.75h; Inert atmosphere; Sealed tube; Reflux;	2-11 Coupling reaction between aryl chloride and amine: Synthesis of aromatic amine compounds General procedure: Under an argon atmosphere, Pd (dba) 2 (2.9 mg, 0.005 mmol, 0.5 mol%), phosphine compound L1 (3.4 mg, 0.006 mmol, 0.6 mol%), 1,4-dioxane was added to the reaction vessel. (0.9 mL) was added and heated to reflux for 2 minutes. The solution was mixed with 4-chlorotoluene (127 mg, 1 mmol), benzylamine (126 mg, 1.2 mmol, 1.2 equiv), NaOtBu (144 mg, 1.5 mmol, 1.5 equiv), H 2 O (14.4 μL, 0.8 mmol). , 0.8 equiv), 1,4-dioxane (2.1 mL) was added to the reaction vessel sealed. After stirring for 10 minutes at room temperature, the mixture was stirred for 1 hour under reflux. The reaction solution was passed through a short column of sodium sulfate and silica gel and then concentrated. The residue was purified by column chromatography to obtain a coupling product with a yield of 99%. The yield of diarylate was less than 1%.
80%	With 4-(2-(dicyclohexylphosphanyl)phenyl)-1,2,3-triphenyl-1H-pyrrole; water; bis(dibenzylideneacetone)-palladium⁽⁰⁾; sodium t-butanolate In 1,4-dioxane at 110℃; for 0.75h; Sealed tube; chemoselective reaction;
76%	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;
75%	With 1, 3-(di(dicyclohexyl)phosphinyl-2-(2’-N, N-dimethylamine)phenyl)indene; bis(dibenzylideneacetone)-palladium⁽⁰⁾; sodium t-butanolate In 1,2-dimethoxyethane at 90℃; for 24h; Schlenk technique; Inert atmosphere; Glovebox;
65%	Stage #1: diphenylamine With bis(tricyclohexylphosphine)nickel(II) dichloride; isopropylmagnesium chloride; tricyclohexylphosphine In tetrahydrofuran; 1,4-dioxane at 20℃; for 0.0833333h; Inert atmosphere; Stage #2: para-chlorotoluene In tetrahydrofuran; 1,4-dioxane at 20 - 95℃; for 12.16h; Inert atmosphere;
	With PdAu₂; potassium <i>tert</i>-butylate In dimethyl sulfoxide at 100℃; for 24h;
	With C₃₇H₅₀BrO₃PPd In 1,4-dioxane at 80℃; Inert atmosphere; Glovebox; Sealed tube;

Reference： [1]Yokoyama, Naota; Nakayama, Yuji; Nara, Hideki; Sayo, Noboru [Advanced Synthesis and Catalysis, 2013, vol. 355, # 10, p. 2083 - 2088]
[2]Topchiy, Maxim A.; Asachenko, Andrey F.; Nechaev, Mikhail S. [European Journal of Organic Chemistry, 2014, vol. 2014, # 16, p. 3319 - 3322]
[3]Urgaonkar, Sameer; Verkade, John G. [Journal of Organic Chemistry, 2004, vol. 69, # 26, p. 9135 - 9142]
[4]Bedford, Robin B.; Blake, Michael E. [Advanced Synthesis and Catalysis, 2003, vol. 345, # 9-10, p. 1107 - 1110]
[5]Dai, Qian; Gao, Wenzhong; Liu, Duan; Kapes, Lea M.; Zhang, Xumu [Journal of Organic Chemistry, 2006, vol. 71, # 10, p. 3928 - 3934]
[6]Current Patent Assignee: COMMONWEALTH SYSTEM OF HIGHER EDUCATION - WO2006/130842, 2006, A1 Location in patent: Page/Page column 28-29; 35
[7]Wolfe, John P.; Tomori, Hiroshi; Sadighi, Joseph P.; Yin, Jingjun; Buchwald, Stephen L. [Journal of Organic Chemistry, 2000, vol. 65, # 4, p. 1158 - 1174]
[8]Current Patent Assignee: COMMONWEALTH SYSTEM OF HIGHER EDUCATION - WO2006/130842, 2006, A1 Location in patent: Page/Page column 28-29; 35
[9]Kim, So Han; Kim, Min; Verkade, John G.; Kim, Youngjo [European Journal of Organic Chemistry, 2015, vol. 2015, # 9, p. 1954 - 1960]
[10]Tardiff, Bennett J.; Stradiotto, Mark [European Journal of Organic Chemistry, 2012, # 21, p. 3972 - 3977]
[11]Urgaonkar, Sameer; Nagarajan; Verkade, John G. [Organic Letters, 2003, vol. 5, # 6, p. 815 - 818]
[12]Kuwano, Ryoichi; Utsunomiya, Masaru; Hartwig, John F. [Journal of Organic Chemistry, 2002, vol. 67, # 18, p. 6479 - 6486]
[13]Wong, Shun Man; Choy, Pui Ying; Zhao, Qingyang; Yuen, On Ying; Yeung, Chung Chiu; So, Chau Ming; Kwong, Fuk Yee [Organometallics, 2021, vol. 40, # 14, p. 2265 - 2271]
[14]Current Patent Assignee: RES FOUND ITSUU LAB - JP2019/189569, 2019, A Location in patent: Paragraph 0044-0046; 0047-0048
[15]Sai, Masahiro [Advanced Synthesis and Catalysis, 2021, vol. 363, # 24, p. 5422 - 5428]
[16]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]
[17]Yan, Meng-Qi; Yuan, Jia; Pi, Yun-Xiao; Liang, Jin-Hua; Liu, Yan; Wu, Qing-Guo; Luo, Xue; Liu, Sheng-Hua; Chen, Jian; Zhu, Xiao-Lei; Yu, Guang-Ao [Organic and Biomolecular Chemistry, 2015, vol. 14, # 2, p. 451 - 454]
[18]Li, Xin-Le; Wu, Wei; Fan, Xin-Heng; Yang, Lian-Ming [Organic and Biomolecular Chemistry, 2014, vol. 12, # 8, p. 1232 - 1236]
[19]Chen, Zheng; Wang, Shuo; Lian, Chao; Liu, Yuxi; Wang, Dingsheng; Chen, Chen; Peng, Qing; Li, Yadong [Chemistry - An Asian Journal, 2016, vol. 11, # 3, p. 351 - 355]
[20]Arrechea, Pedro Luis; Buchwald, Stephen L. [Journal of the American Chemical Society, 2016, vol. 138, # 38, p. 12486 - 12493]

7
[ 4316-53-4 ]
[ 404825-34-9 ]

Yield	Reaction Conditions	Operation in experiment
85%	With N-iodo-succinimide; acetic acid In tetrahydrofuran at 0 - 20℃; Darkness; Inert atmosphere; Schlenk technique;
55%	With iodine; mercury(II) oxide In ethanol at 78℃; for 3h;
	With potassium iodate; potassium iodide In acetic acid	1 The diphenyl-p-tolylamine was iodinated using 35 g of potassium iodide and 150 g of potassium iodate in acetic acid. The resulting reaction mixture was fractionated by silica gel column chromatography using toluene as an eluent, followed by recrystallization from toluene/hexane to provide 120 g of bis(4-iodophenyl)-p-tolylamine (3) as pale yellow needle crystals.

With N-Bromosuccinimide In tetrahydrofuran; acetic acid

Reference： [1]Zhan, Hongmei; Liu, Qian; Dai, Fengrong; Ho, Cheuk-Lam; Fu, Yingying; Li, Leijiao; Zhao, Li; Li, Hua; Xie, Zhiyuan; Wong, Wai-Yeung [Chemistry - An Asian Journal, 2015, vol. 10, # 4, p. 1017 - 1024]
[2]Plater; Jackson [Journal of the Chemical Society. Perkin Transactions 1 (2001), 2001, # 20, p. 2548 - 2552]
[3]Current Patent Assignee: BANDO CHEMICAL INDUSTRIES LTD - EP2100880, 2009, A1 Location in patent: Page/Page column 14-15
[4]Liu, Xi; Qin, Yi; Zhu, Junlong; Zhao, Xiaoli; Cheng, Tanyu; Jiang, Yanrong; Sun, Haitao; Xu, Lin [Chinese Chemical Letters, 2021, vol. 32, # 4, p. 1537 - 1540]

8
[ 591-50-4 ]
[ 106-49-0 ]
[ 4316-53-4 ]

Yield	Reaction Conditions	Operation in experiment
95%	With [2,2]bipyridinyl; potassium <i>tert</i>-butylate In toluene at 115℃; for 3.5h;
82%	With potassium <i>tert</i>-butylate; 1,2-bis(2,6-diisopropylphenylimino)ethane In toluene at 120℃; for 48h;
65%	With potassium <i>tert</i>-butylate In toluene at 120℃; for 14h; Inert atmosphere;

Reference： [1]Kelkar, Ashutosh A.; Patil, Nandkumar M.; Chaudhari, Raghunath V. [Tetrahedron Letters, 2002, vol. 43, # 40, p. 7143 - 7146]
[2]Liu, Yu-Hua; Chen, Chen; Yang, Lian-Ming [Tetrahedron Letters, 2006, vol. 47, # 52, p. 9275 - 9278]
[3]Location in patent: experimental part Islam; Mondal, Sanchita; Mondal, Paramita; Roy, Anupam Singha; Tuhina, Kazi; Mobarok, Manir [Inorganic Chemistry Communications, 2011, vol. 14, # 9, p. 1352 - 1357]

9
[ 106-38-7 ]
[ 122-39-4 ]
[ 4316-53-4 ]

Yield	Reaction Conditions	Operation in experiment
99%	With palladium diacetate; sodium t-butanolate; ruphos In neat (no solvent) at 110℃; for 12h; Green chemistry;
97%	With tris(dibenzylideneacetone)dipalladium ⁽⁰⁾; di-tert-butylneopentylphosphonium tetrafluoroborate; sodium t-butanolate In toluene at 20℃;
95%	With potassium hydroxide In water for 24h; Reflux; Inert atmosphere;

95%	With bis(η3-allyl-μ-chloropalladium(II)); potassium hydroxide In water for 24h; Reflux; Inert atmosphere;
92%	Stage #1: diphenylamine With ethylmagnesium bromide In diethyl ether at 0 - 40℃; for 2h; Inert atmosphere; Stage #2: para-bromotoluene With lithium bromide; iron(II) chloride In 5,5-dimethyl-1,3-cyclohexadiene at 140℃; for 12h; Inert atmosphere;
91%	With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; tri-tert-butyl phosphine; potassium <i>tert</i>-butylate In 1,4-dioxane at 93℃; for 4h; Inert atmosphere;	1.1; 2.1 First step: under nitrogen protection, 300 g of diphenylamine is dissolved in 3000 mL of 1,4-dioxane, and then 393 g of p-bromotoluene, 435 g of potassium t-butoxide and 12 g of (dppf) PdCl2 and 29 g of tri-tert-butylphosphine are added. The temperature was raised to 93 ° C, kept for 4 hours, and sampled (central control 1, ie TLC detected no diphenylamine). After cooling to room temperature, the system was added to 6000 ml of water, 2000 mL of petroleum ether was added, stirred for 30 minutes, layered, the aqueous phase was extracted once with 2000 mL, the organic phase was combined, the organic phase was washed once with 1000 mL of water, and the organic phase was further diluted with 1000 mL of sodium chloride. After washing once, the organic phase was dried over 50 g of anhydrous sodium sulfate, and the organic phase was passed over 150 g of silica gel (200 to 300 mesh). The crude product was added to 2000 g of methanol at 60 ° C to dissolve the solution, cooled to room temperature (T = 10 to 15 ° C), and filtered to obtain 651 g of wet product (Central Control 2, HPLC > 98.5%), and dried to obtain M1 420 g.The molar yield was 91%.
81%	With active Cu In water microwave irradiation;
81%	With palladium diacetate; sodium t-butanolate; ruphos In neat (no solvent) at 110℃; for 12h; Inert atmosphere; Green chemistry;
80%	With cesium fluoride; bis(dibenzylideneacetone)-palladium⁽⁰⁾; XPhos at 100℃; for 18h; Inert atmosphere; Sealed tube;
71%	With bis(triphenylphosphine)nickel(II) chloride; ethylmagnesium bromide; triphenylphosphine In tetrahydrofuran at 90℃; for 5h;
70%	With water; sodium t-butanolate In N,N-dimethyl-formamide at 120℃; for 3h; Schlenk technique;	Palladium-catalyzed amination of diphenylamine General procedure: An oven-dried Schlenk tube was charged with the aryl halide (2 mmol) and amine (2.5 mmol), FeOA-Pd (0.05 g, 0.04 mmol, 1.5 mol%), base (3 mmol), solvent (5 mL) and additive. The resulting mixture was stirred for the appropriate time and temperature. After reaction completion the reaction mixture was then cooled to room temperature and the catalyst separated using a magnet, taken up in Et2O (4 mL), and washed with brine (5 mL). The resulting solution was dried over anhydrous MgSO4, filtered and concentrated. The crude product was purified by flash chromatography on silica gel.
65%	With chloro(1-naphthyl)bis(triphenylphosphine)nickel(II); sodium hydride; triphenylphosphine In toluene; white oil at 120℃; for 12h; Inert atmosphere;
60%	With sodium t-butanolate In toluene at 70℃; for 24h; Inert atmosphere;
	With potassium hydroxide In toluene at 20℃; for 5h; Heating / reflux;	3 Reactions of Amines with Aryl Halides Example 3 Reactions of Amines with Aryl Halides A 30 mL of reactor equipped with magnetic stir bar was charged with 70 mg (0.13 mmol) of (t-Bu)2PCl)2PdCl2, 0.88 g (5.14 mmol) of 4-bromotoluene, 0.70 g (4.14 mmol) of Ph2NH and 0.48 g (8.55 mmol) of KOH in 2 mL of toluene. The reaction mixture was refluxed for 5 hours. The reaction mixture was cooled to room temperature, transferred to a separatory funnel, and diluted with 100 mL of diethyl ether and 20 mL of H2O. The layers were separated, and organic layer was washed with H2O (2*50 mL), brine (30 mL), and dried over MgSO4, filtered, and solvents removed from the filtrate by rotary evaporation. The resulting residue was chromatographed on silicon gel. The elude was concentrated by rotary evaporation followed by high vacuum to give p-tolyldiphenylamine. LC-MS Found: 260.3 (M++1).
85.7 g	With palladium diacetate; tris-(o-tolyl)phosphine; sodium t-butanolate In toluene for 72h; Reflux;	(4-Methylphenyl)diphenylamine (Ia) Besides the synthesis described here, further syntheses which are described in the literature are available to the person skilled in the art. Diphenylamine (88.34 g, 520 mmol) and 4-bromotoluene (82.0 g, 470 mmol) are dissolved in 900 ml of toluene. Tri-ortho-tolylphosphine (1.46 g, 4.7 mmol), palladium(II) acetate (0.53 g, 2.4 mmol) and sodium tert-butoxide (69.1 g, 700 mmol) are subsequently added to the reaction solution, which is then heated under reflux for 3 days. The mixture is extended with toluene and dist. H2O at room temperature, the organic phase is separated off, and the aqueous phase is extracted a number of times with toluene. The org. phase is dried using MgSO4, filtered through AlOx and evaporated. The residue is brought to precipitation using heptane and recrystallised from isopropanol, giving (4-methylphenyl)diphenylamine as a colourless solid (85.7 g, 70% of theory).

Reference： [1]Topchiy, Maxim A.; Asachenko, Andrey F.; Nechaev, Mikhail S. [European Journal of Organic Chemistry, 2014, vol. 2014, # 16, p. 3319 - 3322]
[2]Hill, Lensey L.; Moore, Lucas R.; Huang, Rongeai; Craciun, Raluca; Vincent, Andrew J.; Dixon, David A.; Chou, Joe; Woltermann, Christopher J.; Shaughnessy, Kevin H. [Journal of Organic Chemistry, 2006, vol. 71, # 14, p. 5117 - 5125]
[3]Hirai, Yoshinori; Uozumi, Yasuhiro [Chemical Communications, 2010, vol. 46, # 7, p. 1103 - 1105]
[4]Hirai, Yoshinori; Uozumi, Yasuhiro [Chemistry - An Asian Journal, 2010, vol. 5, # 8, p. 1788 - 1795]
[5]Hatakeyama, Takuji; Imayoshi, Ryuji; Yoshimoto, Yuya; Ghorai, Sujit K.; Jin, Masayoshi; Takaya, Hikaru; Norisuye, Kazuhiro; Sohrin, Yoshiki; Nakamura, Masaharu [Journal of the American Chemical Society, 2012, vol. 134, # 50, p. 20262 - 20265]
[6]Current Patent Assignee: XUZHOU B&C CHEMICAL CO LTD; SHANGHAI B&C CHEMICAL CO LTD - CN108503553, 2018, A Location in patent: Paragraph 0040; 0041; 0046; 0047; 0048
[7]Yadav, Lal Dhar S.; Yadav, Beerendra S.; Rai, Vijai K. [Synthesis, 2006, # 11, p. 1868 - 1872]
[8]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]
[9]Minami, Yasunori; Komiyama, Takeshi; Shimizu, Kenta; Hiyama, Tamejiro; Goto, Osamu; Ikehira, Hideyuki [Bulletin of the Chemical Society of Japan, 2015, vol. 88, # 10, p. 1437 - 1446]
[10]Chen, Chen; Yang, Lian-Ming [Organic Letters, 2005, vol. 7, # 11, p. 2209 - 2211]
[11]Rafiee, Ezzat; Ataei, Ali; Joshaghani, Mohammad [Tetrahedron Letters, 2016, vol. 57, # 2, p. 219 - 222]
[12]Gao, Cai-Yan; Cao, Xingbo; Yang, Lian-Ming [Organic and Biomolecular Chemistry, 2009, vol. 7, # 19, p. 3922 - 3925]
[13]Nagao, Shinya; Matsumoto, Taisuke; Koga, Yuji; Matsubara, Kouki [Chemistry Letters, 2011, vol. 40, # 9, p. 1036 - 1038]
[14]Current Patent Assignee: COMBIPHOS CATALYSTS - US6878850, 2005, B2 Location in patent: Page/Page column 9
[15]Current Patent Assignee: MERCK KGAA - JP2015/534543, 2015, A Location in patent: Paragraph 0112; 0113

10
[ 108-86-1 ]
[ 106-49-0 ]
[ 4316-53-4 ]

Yield	Reaction Conditions	Operation in experiment
99%	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;
94%	With (6-Dipp)PdCl<SUB>2</SUB>-SPhos; sodium t-butanolate In neat (no solvent) at 110℃; for 24h; Inert atmosphere;
90%	With dichloro{1,10-[di-(2-diizopropylaminoethyl)]-3,3'-o-xylyldibenzimidazolidin-2,2'-diylidene}palladium (II); potassium <i>tert</i>-butylate In 1,2-dimethoxyethane at 80℃; for 15h; Inert atmosphere;

87%	With bis(η3-allyl-μ-chloropalladium(II)); potassium hydroxide In water for 24h; Inert atmosphere; Reflux;
85%	With potassium hydroxide In water for 24h; Reflux; Inert atmosphere;
54 % Chromat.	With Cu(neocup)(PPh₃)Br; potassium <i>tert</i>-butylate In toluene at 110 - 120℃;
89 %Chromat.	With dichlorobis[1,3-bis(3,4-dimethoxybenzyl)imidazolidin-2-yliden]palladium(II); potassium <i>tert</i>-butylate In 1,2-dimethoxyethane at 80℃; for 15h; Inert atmosphere; Schlenk technique;

Reference： [1]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]
[2]Ageshina, Alexandra A.; Sterligov, Grigorii K.; Rzhevskiy, Sergey A.; Topchiy, Maxim A.; Chesnokov, Gleb A.; Gribanov, Pavel S.; Nechaev, Mikhail S.; Asachenko, Andrey F.; Bermeshev, Maxim V.; Melnikova, Elizaveta K. [Dalton Transactions, 2019, vol. 48, # 10, p. 3447 - 3452]
[3]Location in patent: experimental part Demir, Serpil; Özdemir, Ismail; Çetinkaya, Bekir; Arslan, Hakan; VanDerveer, Don [Polyhedron, 2011, vol. 30, # 1, p. 195 - 200]
[4]Hirai, Yoshinori; Uozumi, Yasuhiro [Chemistry - An Asian Journal, 2010, vol. 5, # 8, p. 1788 - 1795]
[5]Hirai, Yoshinori; Uozumi, Yasuhiro [Chemical Communications, 2010, vol. 46, # 7, p. 1103 - 1105]
[6]Gujadhur, Rattan K.; Bates, Craig G.; Venkataraman [Organic Letters, 2001, vol. 3, # 26, p. 4315 - 4317]
[7]Karaca, Emine Özge; Gürbüz, Nevin; Şahin, Onur; Büyükgüngör, Orhan; Özdemir, İsmail [Applied Organometallic Chemistry, 2016, vol. 30, # 12, p. 1050 - 1055]

11
[ 591-50-4 ]
[ 4316-53-4 ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 2 steps 1: 74 percent / active Cu / H₂O / microwave irradiation 2: 81 percent / active Cu / H₂O / microwave irradiation

Reference： [1]Yadav, Lal Dhar S.; Yadav, Beerendra S.; Rai, Vijai K. [Synthesis, 2006, # 11, p. 1868 - 1872]

12
[ 62-53-3 ]
[ 4316-53-4 ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 2 steps 1: 74 percent / active Cu / H₂O / microwave irradiation 2: 81 percent / active Cu / H₂O / microwave irradiation

Reference： [1]Yadav, Lal Dhar S.; Yadav, Beerendra S.; Rai, Vijai K. [Synthesis, 2006, # 11, p. 1868 - 1872]

13
[ 108-86-1 ]
[ 4316-53-4 ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 2 steps 1: 94 percent / KOH; Pd[P(t-Bu₃)]2; cetyltrimethylammonium bromide / toluene; H₂O / 3 h / 90 °C 2: 82 percent / KOH; Pd[P(t-Bu₃)]2; cetyltrimethylammonium bromide / toluene; H₂O / 24 h / 90 °C

Reference： [1]Kuwano, Ryoichi; Utsunomiya, Masaru; Hartwig, John F. [Journal of Organic Chemistry, 2002, vol. 67, # 18, p. 6479 - 6486]

14
[ 62-53-3 ]
[ 4316-53-4 ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 2 steps 1: 94 percent / KOH; Pd[P(t-Bu₃)]2; cetyltrimethylammonium bromide / toluene; H₂O / 3 h / 90 °C 2: 82 percent / KOH; Pd[P(t-Bu₃)]2; cetyltrimethylammonium bromide / toluene; H₂O / 24 h / 90 °C

Reference： [1]Kuwano, Ryoichi; Utsunomiya, Masaru; Hartwig, John F. [Journal of Organic Chemistry, 2002, vol. 67, # 18, p. 6479 - 6486]

15
[ 4316-53-4 ]
N,N-bis{4-[N-(3-methylphenyl)-N-phenylamino]phenyl}tolylamine [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 2 steps 1: 55 percent / mercuric oxide; I₂ / ethanol / 3 h / 78 °C 2: 63 percent / Cu; KOH / decane / 24 h / 173 °C

Reference： [1]Plater; Jackson [Journal of the Chemical Society. Perkin Transactions 1 (2001), 2001, # 20, p. 2548 - 2552]

16
[ 4316-53-4 ]
N,N-bis{4-[N-(3,4-dimethylphenyl)-N-phenylamino]phenyl}tolylamine [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 2 steps 1: 55 percent / mercuric oxide; I₂ / ethanol / 3 h / 78 °C 2: 51 percent / Cu; KOH / decane / 24 h / 173 °C

Reference： [1]Plater; Jackson [Journal of the Chemical Society. Perkin Transactions 1 (2001), 2001, # 20, p. 2548 - 2552]

17
[ 4316-53-4 ]
N,N-bis{4-[N-(2,4-dimethylphenyl)-N-phenylamino]phenyl}tolylamine [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 2 steps 1: 55 percent / mercuric oxide; I₂ / ethanol / 3 h / 78 °C 2: 43 percent / Cu; KO₂CO₃; 18-crown-6 / 1,2-dichloro-benzene / 72 h / 180 °C

Reference： [1]Plater; Jackson [Journal of the Chemical Society. Perkin Transactions 1 (2001), 2001, # 20, p. 2548 - 2552]

18
[ 591-50-4 ]
[ 4316-53-4 ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 2 steps 1: 75 percent / cesium carbonate; Cu(PPh₃)3Br / toluene / 24 h / 110 °C 2: 52 percent / cesium carbonate; Cu(PPh₃)3Br / toluene / 24 h / 120 °C

Reference： [1]Gujadhur, Rattan; Venkataraman; Kintigh, Jeremy T [Tetrahedron Letters, 2001, vol. 42, # 29, p. 4791 - 4793]

19
[ 62-53-3 ]
[ 4316-53-4 ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 2 steps 1: 75 percent / cesium carbonate; Cu(PPh₃)3Br / toluene / 24 h / 110 °C 2: 52 percent / cesium carbonate; Cu(PPh₃)3Br / toluene / 24 h / 120 °C

Reference： [1]Gujadhur, Rattan; Venkataraman; Kintigh, Jeremy T [Tetrahedron Letters, 2001, vol. 42, # 29, p. 4791 - 4793]

20
[ 1821-36-9 ]
[ 4316-53-4 ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 2 steps 1: Ni, Cu, Cr, Na₂SO₄/SiO₂, H₂ / 380 - 400 °C 2: 60 percent / K₂CO₃ / CuCl, Cu / nitrobenzene / 12 h / 210 - 220 °C

Reference： [1]Tarasievich; Mikhalevskaya; Kozlov [Russian Journal of Organic Chemistry, 1997, vol. 33, # 8, p. 1100 - 1102]

21
[ 1132-38-3 ]
[ 4316-53-4 ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 2 steps 1: Ni, Cu, Cr, Na₂SO₄/SiO₂, H₂ / 380 - 400 °C 2: 60 percent / K₂CO₃ / CuCl, Cu / nitrobenzene / 12 h / 210 - 220 °C

Reference： [1]Tarasievich; Mikhalevskaya; Kozlov [Russian Journal of Organic Chemistry, 1997, vol. 33, # 8, p. 1100 - 1102]

22
[ 624-31-7 ]
copper [ No CAS ]
[ 95-50-1 ]
[ 4316-53-4 ]

Yield	Reaction Conditions	Operation in experiment
81.4%	With sodium carbonate; diphenylamine	7 Synthesis of 4-methyltriphenylamine Synthesis of 4-methyltriphenylamine To 30 ml of o-dichlorobenzene, 4.5 g (27 mmol) of diphenylamine, 11.0 g (51 mmol) of p-iodotoluene, 5.5 g (40 mmol) of anhydrous sodium carbonate and 1.1 g of copper powder were added. The mixture was heated and refluxed with stirring for 7 hours. After the reaction was completed, the reaction solution was filtered. The filtrate was successively washed with an aqueous 35% sodium thiosulfate solution and saturated brine. The organic layer was dried with anhydrous sodium sulfate, and thereafter the solvent was removed. The resulting crude reaction product was recrystallized from ethanol to obtain 4-methyltriphenylamine in an amount of 5.7 g (yield: 81.4%).

Reference： [1]Current Patent Assignee: CANON INC. - US6376695, 2002, B1

23
[ 4316-53-4 ]
[ 183994-94-7 ]

Yield	Reaction Conditions	Operation in experiment
91.2%	With N-Bromosuccinimide In tetrachloromethane	7 Synthesis of 4-bromomethyltriphenylamine Synthesis of 4-bromomethyltriphenylamine Into a 300 ml three-necked flask, 6.9 g (39 mmol) of N-bromosuccinimide and 9.1 g (35 mmol) of 4-methyltriphenylamine were placed, and 100 ml of carbon tetrachloride was added thereto. Thereafter, the mixture was heated and refluxed overnight with stirring. After the reaction was completed, the reaction solution was cooled. Subsequently, the reaction was filtered, and the solvent was removed. The reaction product thus obtained was recrystallized from ethanol to obtain 4-bromomethyltriphenylamine in an amount of 10.8 g (yield: 91.2%).
91.2%	With N-Bromosuccinimide In tetrachloromethane	P.7 Synthesis of 4-bromomethyltriphenylamine Synthesis of 4-bromomethyltriphenylamine 6.9 g (39 mmol) of N-bromosuccinimide and 9.1 g (35 mmol) of 4-methyltriphenylamine were loaded in a 300 ml three-neck flask, and 100 m of carbon tetrachloride was added. The components were stirred overnight. Upon completion of the reaction, the reaction solution was cooled and then filtered. The solvent was removed. The reaction mixture obtained was recrystallized with ethanol. As a result, the substance 4-bromomethyltriphenylamine was obtained in an amount of 10.8 g (yield was 91.2%).
	With N-Bromosuccinimide In tetrachloromethane	S.6 Synthesis of 4-bromomethyltriphenylamine Synthesis of 4-bromomethyltriphenylamine 6.9 g (39 mmol) of N-bromosuccinimide and 9.1 g (35 mmol) of 4-methyl triphenylamine were loaded in a 300 mL three-neck flask, and then 100 mL of carbon tetrachloride was added. The mixture was stirred overnight. Upon completion of the reaction, the solution was cooled and then filtered. The solvent was removed. The crude product was recrystallized from ethanol. 4-bromomethyltriphenylamine was resulted in an amount of 10.8 g (91.2%).

Reference： [1]Current Patent Assignee: CANON INC. - US6376695, 2002, B1
[2]Current Patent Assignee: DOW INC; DOCONI ASIA - EP771806, 1997, A1
[3]Current Patent Assignee: DOW INC - EP771809, 1997, A1

24
1,1-diphenyl-4-(p-di-n-propylaminophenyl)-1,3-butadiene [ No CAS ]
[ 4316-53-4 ]
[ 122112-54-3 ]

Yield	Reaction Conditions	Operation in experiment
11.8%		4.1 (1) (1) Synthesis of 4,4'-Diformyl-4"-methyltriphenylamine (8b) Synthesis was conducted in the same manner as in (4) in Example 2 except that 28.73 g (0.111 mol) of 4-methyltriphenylamine (7b) was used in place of triphenylamine (7a). Thus, 3.84 g of 4,4'-diformyl-4"-methyltriphenylamine (8b) was obtained. Theoretical yield, 11.8% m.p., 153.5°-154° C.

Reference： [1]Current Patent Assignee: TAKASAGO INTERNATIONAL CORPORATION - US5573878, 1996, A

25
[ 624-31-7 ]
[ 95-50-1 ]
[ 4316-53-4 ]

Yield	Reaction Conditions	Operation in experiment
81.4%	With copper; potassium carbonate; sodium thiosulfate; diphenylamine	P.7 Synthesis of 4-[4-(triethoxysilyl) butyl] triphenylamine and Synthesis of 4-methyltriphenylamine Practical Example 7 Synthesis of 4-[4-(triethoxysilyl) butyl] triphenylamine and Synthesis of 4-methyltriphenylamine 4.5 g (27 mmol) of diphenylamine, 11.0 g (51 mmol) of p-iodotoluene, 5.5 g (40 mmol) of anhydrous potassium carbonate, and 1.1 g of copper chips were added to 30 ml of o-dichlorobenzene. The mixture was subjected to heating and refluxing for 7 hours under stirring conditions. Upon completion of the reaction, the reaction solution was filtered, the filtrate was washed with a 3-5% aqueous solution of sodium thiosulfate, and then with saturated brine. After drying the organic layer with anhydrous sodium sulfate, the solvent was removed. The reaction mixture obtained was recrystallized with ethanol, and 4-methyltriphenylamine was obtained in an amount of 5.7 g (yield 81.4 %).
	With copper; potassium carbonate; sodium thiosulfate; diphenylamine	S.6 Synthesis of 4-methyltriphenylamine Synthesis Example 6 Synthesis of 4-methyltriphenylamine 4.5 g (27 mmol) of diphenylamine, 11.0 g (51 mmol) of p-iodotoluene, 5.5 g (40 mmol) of anhydrous potassium carbonate, and 1.1 g of copper chips were added to 30 mL of o-dichlorobenzene, and the mixture was refluxed for 7 hours with stirring. Upon completion of the reaction, the solution was filtered, the filtrate was washed with a 3 to 5% aqueous solution of sodium thiosulfate and then with a saturated brine. After drying the organic layer with an anhydrous sodium sulfate, the solvent was removed. The crude product was recrystallized from ethanol, whereby 4-methyltriphenylamine was obtained in an amount of 5.7 g (81.4 %).

Reference： [1]Current Patent Assignee: DOW INC; DOCONI ASIA - EP771806, 1997, A1
[2]Current Patent Assignee: DOW INC - EP771809, 1997, A1

26
[ 4316-53-4 ]
[ 20441-06-9 ]

Yield	Reaction Conditions	Operation in experiment
99%	Stage #1: diphenyl(p-tolyl)amine With methanesulfonic acid In dichloromethane at 0℃; Stage #2: With chloranil In dichloromethane at 0 - 20℃; for 0.0166667h;
86%	Stage #1: diphenyl(p-tolyl)amine With copper(II) perchlorate In acetonitrile at 25℃; for 12h; Stage #2: With potassium carbonate In water; acetonitrile at 25℃; for 0.5h; Further stages.;

Reference： [1]Maddala, Sudhakar; Mallick, Sudesh; Venkatakrishnan, Parthasarathy [Journal of Organic Chemistry, 2017, vol. 82, # 17, p. 8958 - 8972]
[2]Sreenath, Kesavapillai; Suneesh, Chettiyam Veettil; Ratheesh Kumar, Venugopal K.; Gopidas, Karical R. [Journal of Organic Chemistry, 2008, vol. 73, # 8, p. 3245 - 3251]

27
[ 4316-53-4 ]
4-methyltriphenylamine radical cation [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With copper(II) perchlorate In acetonitrile at 25℃;

Reference： [1]Sreenath, Kesavapillai; Suneesh, Chettiyam Veettil; Ratheesh Kumar, Venugopal K.; Gopidas, Karical R. [Journal of Organic Chemistry, 2008, vol. 73, # 8, p. 3245 - 3251]

28
[ 4316-53-4 ]
[ 33513-42-7 ]
4-(N-(4-methylphenyl)-N-phenylamino)benzaldehyde [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	Stage #1: N,N-dimethyl-formamide With trichlorophosphate at 20℃; Neat (no solvent); Stage #2: diphenyl(p-tolyl)amine In N,N-dimethyl-formamide at 70℃; for 1.5h;
	With trichlorophosphate

Reference： [1]Current Patent Assignee: INNOVATION NETWORK CORPORATION OF JAPAN; JOLED (in: INCJ) - US6337167, 2002, B1 Location in patent: Example 13
[2]Jin, Huiyi; Li, Xianggao; Tan, Tingfeng; Wang, Shirong; Xiao, Yin; Tian, Jianhua [Dyes and Pigments, 2014, vol. 106, p. 154 - 160]

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[ 1233934-03-6 ]
[ 4316-53-4 ]
[ 1233934-04-7 ]

Yield	Reaction Conditions	Operation in experiment
86.1%	With trifluorormethanesulfonic acid In 1,4-dioxane at 80℃; Inert atmosphere;