Name: 1202-34-2|Di(pyridin-2-yl)amine|99%
Brand: Ambeed
SKU: A621225
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1
[ 504-29-0 ]
[ 109-09-1 ]
[ 1202-34-2 ]

Yield	Reaction Conditions	Operation in experiment
99%	With lithium amide; sodium t-butanolate In toluene at 100 - 110℃; for 1h; Inert atmosphere; Sealed vial;
94%	With caesium carbonate; 2,2'-bis-(diphenylphosphino)-1,1'-binaphthyl In 1,4-dioxane at 100℃; for 15h;
75.5%	With potassium <i>tert</i>-butylate In toluene at 3120℃; for 36h; Inert atmosphere;	Synthesis of 2,2′-dipyridylamine 1 Potassium t-butoxide (15.50 g, 138.1 mmol) was added to a solutionof 2-aminopyridine (10.00 g, 106.2 mmol) and 2-chloropyridine (13.27 g, 116.8 mmol) in toluene (100 mL), and the mixture was stirredat 120 °C for 36 h under a nitrogen atmosphere. After cooling to roomtemperature and removing solvent under vacuum, the crude productwas extracted with ether and the combined ethers then washed withwater three times. The organic layer was dried with magnesium sulfate,filtered and the solvent was removed under reduced pressure. Theresidue was purified by chromatography on silica gel to yield a whitesolid,31 13.73 g (75.5%). m.p. 90.3-91.6 °C (lit.32 94-95 °C), 1H NMR: δ8.28-8.27 (m, 2H), 8.19 (brs, 1H), 7.61-7.55 (m, 4H), 6.85-6.83 (m, 2H).

30%	Stage #1: 2-aminopyridine With potassium <i>tert</i>-butylate In benzene for 2h; Reflux; Stage #2: 2-chloropyridine In benzene for 72h; Reflux;	10 Example 10 Di-(pyridin-2-yl) amine (DP A) Example 10 Di-(pyridin-2-yl) amine (DP A): (Fig: 10) Synthetic Procedure: The mixture of 2-aminopyridine (4g, 42.49mmol) and potassium tert-butoxide (5.72g, 50.97mmol) in 60mL of benzene were refluxed in a 250mL round bottom flask for 2 h. Then 2-chloropyridine (4.82mL, 42.45mmol) was added and continued to reflux for 72 h. Benzene was removed using rotary evaporator. Crude product was extracted with dichloromethane and washed with water. The organic layer was dried over anhydrous sodium sulphate and solvent was evaporated on the rotary evaporator under reduced pressure. Product was purified by column chromatography on silica gel by eluting with 60% ethyl acetate in hexane. Pure product was dried under high vacuum. It was further purified by recrystallization using a mixture of dichloromethane and hexane (25:75). Yield: 2.16g (30%). NMR (200 MHz, CDC13): δ ppm: 6.86 (t, 2H, J=6Hz), 7.59 (m, 4H), 7.81 (s, 1H), 8.26 (d, 2H, J=4Hz).
	With zinc(II) chloride at 200℃;
	With barium(II) oxide
	With barium(II) oxide at 200 - 220℃; im Rohr;
87 %Chromat.	With potassium carbonate In ethanol at 100℃; for 4h; chemoselective reaction;

Reference： [1]Lundgren, Rylan J.; Sappong-Kumankumah, Antonia; Stradiotto, Mark [Chemistry - A European Journal, 2010, vol. 16, # 6, p. 1983 - 1991]
[2]Yin, Jingjun; Zhao, Matthew M.; Huffman, Mark A.; McNamara, James M. [Organic Letters, 2002, vol. 4, # 20, p. 3481 - 3484]
[3]Pan, Dan; Wu, Aiqun; Li, Pengfei; Xu, Haitang; Lei, Fuhou; Shen, Liqun [Journal of Chemical Research, 2014, vol. 38, # 12, p. 715 - 718]
[4]Current Patent Assignee: COUNCIL OF SCIENTIFIC AND INDUSTRIAL RESEARCH (IN) - WO2015/104722, 2015, A1 Location in patent: Page/Page column 12-13
[5]Tschitschibabin; Seide [Zhurnal Russkago Fiziko-Khimicheskago Obshchestva, 1914, vol. 46, p. 1232][Chemisches Zentralblatt, 1915, vol. 86, # I, p. 1065]
[6]Diepolder; Deuerlein [Journal fur praktische Chemie (Leipzig 1954), 1923, vol. <2>106, p. 48]
[7]Steinhaeuser; Diepolder [Journal fur praktische Chemie (Leipzig 1954), 1916, vol. <2> 93, p. 395]
[8]Adam, Mohamed Shaker S.; Ullah, Farman; Makhlouf, Mohamed M. [Journal of the American Ceramic Society, 2020, vol. 103, # 8, p. 4632 - 4653]

2
[ 504-29-0 ]
[ 109-04-6 ]
[ 1202-34-2 ]

Yield	Reaction Conditions	Operation in experiment
90%	With tris-(dibenzylideneacetone)dipalladium⁽⁰⁾; 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene In 1,4-dioxane at 100℃; for 15h;
87%	With tris(dibenzylideneacetone)dipalladium ⁽⁰⁾; 1,3-bis-(diphenylphosphino)propane; sodium t-butanolate In toluene at 70℃; for 4h;
67%	Stage #1: 2-aminopyridine With sodium hydride In tetrahydrofuran; mineral oil at 30℃; for 0.5h; Stage #2: 2-bromo-pyridine In tetrahydrofuran; mineral oil at 70℃; for 18h; Inert atmosphere;	2.3.1. N-pyridin-(2-ylpyridin) -2-amine (3) In a THF (50 mL), 2-amino pyridine ( 1 ) (1.88 g, 0.02 mole) was dissolved completely. After the dissolution of starting reagents, sodium hydride (60% dispersion in mineral oil) (1.2 g, 0.03 mole) was put in portion-wise to it and the blend was mixed for 30 min at 30 °C. Later, 2-bromopyridine (2) (2.10 g, 0.022 mole) was added and further heated to 70 °C for 18 h in a nitrogen atmosphere. Once completion of the reaction, the brown-colored solution was obtained. Then, the solvent was evaporated on a rotary evaporator and the resulting crude sticky gel mass obtained was rinse with water and further 2-3 times extracted with ethyl acetate. The col- lected organic phase was dried with anhydrous sodium sulfate and further evaporator on rotavap. The purification of sticky residue was done by column chromatography on silica gel ( n -hexane: ethyl acetate = 9:1). Offwhite colored solid. Yield: 2.291 g (67%), Melt- ing point = 90 °C, 1 H NMR (500 MHz, CDCl 3 , TMS) 8.28 (ddd, J = 5.0, 1.8, 0.8 Hz, 2H), 8.01 (s, 1H), 7.62 -7.55 (m, 4H), 6.86 -6.83 (m, 2H). 13 C NMR (126 MHz, CDCl 3 ) 154.1, 147.7, 137.7, 116.3, 111.7.

58%	With barium(II) oxide at 220℃; for 14h;
51%	With sodium hydride In toluene for 24h; Reflux;
	With copper; potassium carbonate at 180℃;
	With tris(dibenzylideneacetone)dipalladium ⁽⁰⁾; 2,2'-bis-(diphenylphosphino)-1,1'-binaphthyl; sodium t-butanolate In toluene; <i>tert</i>-butyl alcohol at 80℃;
	With 1,3-bis-(diphenylphosphino)propane; sodium t-butanolate In toluene at 80℃; for 36h;
	With tris-(dibenzylideneacetone)dipalladium⁽⁰⁾
94 %Chromat.	With potassium carbonate In ethanol at 100℃; for 4h; chemoselective reaction;
	With palladium diacetate; bis[2-(diphenylphosphino)phenyl] ether; sodium t-butanolate In toluene at 110℃; for 24h; Schlenk technique; Inert atmosphere;	Synthesis of aD: (a) 2,2′-dipyridylamine (aD ligand): A reported procedure was followed (cite); bis(2-diphenylphosphinophenyl) ether (498.99 mg, 926.51 μmol), 2-bromopyridine (3.66, 23.16 mmol), 2-aminopyridine (2.18 g, 23.16 mmol) and t-BuONa (3.12 g, 32.43 mmol) were purged with nitrogen gas in a re-sealable shlenk flask where a degassed dry toluene is cannula transferred. Pd(OAc)2 catalyst was added to the air free flask and refluxed in a 110° C. oil bath for 24 hours. The reaction mixture is cooled to room temperature and diluted with THF and ethyl ether. The solid precipitate was filtered, concentrated, and purified via silica gel column chromatography (2% MeOH/CH2Cl2). An alternative route is to purchase the commercially available 2,2′-dipyridylamine.
	With palladium diacetate; sodium t-butanolate In toluene at 110℃; for 24h; Schlenk technique; Inert atmosphere;	a Synthesis of aD: (a) 2,2′-dipyridylamine (aD ligand): A reported procedure was followed (cite); bis(2-diphenylphosphinophenyl) ether (498.99 mg, 926.51 μmol), 2-bromopyridine (3.66, 23.16 mmol), 2-aminopyridine (2.18 g, 23.16 mmol) and t-BuONa (3.12 g, 32.43 mmol) were purged with nitrogen gas in a re-sealable shlenk flask where a degassed dry toluene is cannula transferred. Pd(OAc)2 catalyst was added to the air free flask and refluxed in a 110° C. oil bath for 24 hours. The reaction mixture is cooled to room temperature and diluted with THF and ethyl ether. The solid precipitate was filtered, concentrated, and purified via silica gel column chromatography (2% MeOH/CH2Cl2). An alternative route is to purchase the commercially available 2,2′-dipyridylamine.
	With palladium⁽⁰⁾

Reference： [1]Qian, Guangyin; Liu, Bingxin; Tan, Qitao; Zhang, Siwen; Xu, Bin [European Journal of Organic Chemistry, 2014, vol. 2014, # 22, p. 4837 - 4843]
[2]Wagaw, Seble; Buchwald, Stephen L. [Journal of Organic Chemistry, 1996, vol. 61, # 21, p. 7240 - 7241]
[3]Jachak, Mahesh; Khopkar, Sushil; Patel, Khushbu; Patil, Yogesh; Shankarling, Ganapati [Journal of Molecular Structure, 2021, vol. 1233]
[4]Kaplan, G. M.; Frolov, A. N.; El'tsov, A. V. [Journal of Organic Chemistry USSR (English Translation), 1991, vol. 27, # 1.2, p. 177 - 182][Zhurnal Organicheskoi Khimii, 1991, vol. 27, # 1, p. 201 - 206]
[5]Patil, Dinesh S.; Sonigara, Keval K.; Jadhav, Manoj M.; Avhad, Kiran C.; Sharma, Suryapratap; Soni, Saurabh S.; Sekar, Nagaiyan [New Journal of Chemistry, 2018, vol. 42, # 6, p. 4361 - 4371]
[6]Carboni; Pardi [Annali di Chimica, 1959, vol. 49, p. 1220,1224]
[7]Usui, Shinya; Suzuki, Takayoshi; Hattori, Yoshifumi; Etoh, Kazuma; Fujieda, Hiroki; Nishizuka, Makoto; Imagawa, Masayoshi; Nakagawa, Hidehiko; Kohda, Kohfuku; Miyata, Naoki [Bioorganic and Medicinal Chemistry Letters, 2005, vol. 15, # 6, p. 1547 - 1551]
[8]Huang, Kevin S.; Haddadin, Makhluf J.; Kurth, Mark J. [Journal of Organic Chemistry, 2002, vol. 67, # 7, p. 2382 - 2385]
[9]Glinton, Kwame; Latifi, Reza; Cockrell, David S.; Bardeaux, Matthew; Nguyen, Bachkhoa; Tahsini, Laleh [RSC Advances, 2019, vol. 9, # 39, p. 22417 - 22427]
[10]Adam, Mohamed Shaker S.; Ullah, Farman; Makhlouf, Mohamed M. [Journal of the American Ceramic Society, 2020, vol. 103, # 8, p. 4632 - 4653]
[11]Current Patent Assignee: UNIVERSITY OF SOUTHERN CALIFORNIA - US2020/243772, 2020, A1 Location in patent: Paragraph 0160
[12]Current Patent Assignee: UNIVERSITY OF SOUTHERN CALIFORNIA - US2020/239456, 2020, A1 Location in patent: Paragraph 0163
[13]Cabanillas-Gonzalez, Juan; Costa, Rubén D.; Di Nasso, Davide; Elie, Margaux; Fresta, Elisa; Gaillard, Sylvain; Linares, Mathieu; Lohier, Jean-François; Mahoro, Gilbert Umuhire; Renaud, Jean-Luc; Wannemacher, Reinhold; Zhang, Qi [Dalton Transactions, 2021, vol. 50, # 32, p. 11049 - 11060]

3
[ 1202-34-2 ]
[ 74-88-4 ]
[ 123368-97-8 ]

Yield	Reaction Conditions	Operation in experiment
91%	Stage #1: di(pyridin-2-yl)amine With potassium hydroxide In dimethyl sulfoxide at 20℃; for 0.5h; Stage #2: methyl iodide In dimethyl sulfoxide at 20℃; for 1h;	Synthesis of N-methyl-2,2'-dipyridylamine (ligand 11).3 Potassium hydroxyde (1.64 g, 29.2 mmol, 5 eq) was added to a solution of 2,2'-dipyridylamine (1.00 g,5.8 mmol, 1 eq) in DMSO (30 ml). After stirring for 30min at room temperature, iodomethane (437 μl,7.0 mmol, 1.2 eq) was added and the reaction mixture was stirred at room temperature for an additional1 hour. The reaction was quenched with 50 ml of water and extracted with diethyl ether (3x50 ml). Thecombined organic layers were washed with brine (50 ml) and dried over MgSO4. The solvent wasremoved under vacuum. The crude product was purified by flash chromatography on silica gel (eluentpentane/ethyl acetate 1/1) to give N-methyl-2,2'-dipyridylamine as a colorless oil (984 mg, 91% yield).1H-NMR (CDCl3, 400 MHz): δ 3.64 (s, 3H), 6.87 (t, J = 7.5, 4.5 Hz, 2H), 7.17 (d, J = 8.3 Hz, 2H), 7.55(t, J = 8.3, 7.5 Hz, 2H), 8.35 (d, J = 4.5 Hz, 2H) ppm.
89%	Stage #1: di(pyridin-2-yl)amine With potassium hydroxide In dimethyl sulfoxide for 0.75h; Stage #2: methyl iodide In dimethyl sulfoxide at 20℃; for 20h;
89%	Stage #1: di(pyridin-2-yl)amine With potassium hydroxide In dimethyl sulfoxide for 0.75h; Schlenk technique; Inert atmosphere; Stage #2: methyl iodide In dimethyl sulfoxide at 25℃; for 20h; Schlenk technique; Inert atmosphere;

73%	In acetonitrile at 20℃; electrolysis (0.1 M Bu₄NBr, Pt electrode, 1.1 F per mole); with other alkyl halides;
73%	With tetrabutylammomium bromide In acetonitrile electrolysis;
73%	In acetonitrile at 20℃; electrolysis (Pt electrode, 0.1 M Bu₄NBr, 1.1 F per mole);
53.3%	Stage #1: di(pyridin-2-yl)amine With potassium hydroxide In dimethyl sulfoxide at 20℃; for 0.75h; Stage #2: methyl iodide In dimethyl sulfoxide at 20℃; for 1h;	Synthesis of the ligands General procedure: The ligands, namely (2,20-dipyridyl)methylamine (dpma),(2,20-dipyridyl)ethylamine (dpea), (2,20-dipyridyl)-1-propylamine(dppa), (2,20-dipyridyl)-1-butylamine (dpba), and (2,20-dipyridyl)-1-hexylamine (dpha), were synthesizedusing the same procedure [15] starting from 2,20-dipyridylamineand their respective bromo alkyl halides. For dpma,methyl iodide was used as a precursor.To a suspension of potassium hydroxide (1.3 g,0.02 mol) in 15 mL of DMSO, 2,20-dipyridylamine(0.0855 g, 0.5 mmol) was added. The mixture was stirredat room temperature for 45 min after which the respectivealkyl halide (0.5 mmol) was added. After stirring at roomtemperature for a further period of 60 min, 20 mL of waterwas added. The solution was extracted with diethyl ether(30 mL), and the organic extracts dried over MgSO4. Thesolvent was removed in vacuo to yield the desired ligand.All ligands were characterized by NMR spectroscopy andLC-MS and used for complex formation without furtherpurification.dpma Brown oil, yield 49.3 mg (53.3 %). 1H NMR(CDCl3, 400 MHz): d = 8.23 (ddd, 2H), 7.44 (ddd, 2H),7.06 (td, 2H), 6.76 (dd, 2H), 3.53 (s, 3H). 13C NMR(CDCl3, 400 MHz): 157.6, 148.1, 137.1, 116.9, 114.4 and36.1. TOF MS ES?: m/z [M ? H]? = 186.01.

Reference： [1]Sauvageot, Elodie; Lafite, Pierre; Duverger, Eric; Marion, Ronan; Hamel, Matthieu; Gaillard, Sylvain; Renaud, Jean-Luc; Daniellou, Richard [Journal of Organometallic Chemistry, 2016, vol. 808, p. 122 - 127]
[2]Swarts, Andrew J.; Mapolie, Selwyn F. [Dalton Transactions, 2014, vol. 43, # 26, p. 9892 - 9900]
[3]Swarts, Andrew J.; Zheng, Feng; Smith, Vincent J.; Nordlander, Ebbe; Mapolie, Selwyn F. [Organometallics, 2014, vol. 33, # 9, p. 2247 - 2256]
[4]Dorokhov, V. A.; Baryshnikova, T. K.; Gordeev, M. F.; Niyazymbetov, M. E.; Petrosyan, V. A. [Bulletin of the Academy of Sciences of the USSR Division of Chemical Science, 1991, vol. 40, # 1.2, p. 138 - 141][Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, 1991, # 1, p. 155 - 159]
[5]Dorokhov, V. A.; Baryshnikova, T. K.; Gordeev, M. F.; Niyazymbetov, M. E.; Petrosyan, V. A. [Bulletin of the Academy of Sciences of the USSR Division of Chemical Science, 1989, vol. 38, # 7.2, p. 1573][Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, 1989, vol. 38, # 7, p. 1708 - 1709]
[6]Dorokhov, V. A.; Baryshnikova, T. K.; Gordeev, M. F.; Niyazymbetov, M. E.; Petrosyan, V. A. [Bulletin of the Academy of Sciences of the USSR Division of Chemical Science, 1991, vol. 40, # 1.2, p. 138 - 141][Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, 1991, # 1, p. 155 - 159]
[7]Kinunda, Grace; Jaganyi, Deogratius [Transition Metal Chemistry, 2016, vol. 41, # 2, p. 235 - 248]

4
[ 1202-34-2 ]
[ 2530-83-8 ]
C₁₉H₂₉N₃O₅Si [ No CAS ]

Reference： [1]Recueil des Travaux Chimiques des Pays-Bas,1996,vol. 115,p. 191 - 197

5
[ 109-09-1 ]
[ 1202-34-2 ]

Yield	Reaction Conditions	Operation in experiment
62%	With lithium amide; tris(dibenzylideneacetone)dipalladium ⁽⁰⁾; johnphos In toluene at 100℃; for 19h;

Reference： [1]Huang; Buchwald [Organic letters, 2001, vol. 3, # 21, p. 3417 - 3419]

6
[ 1202-34-2 ]
[ 7511-49-1 ]
[ 391594-50-6 ]

Reference： [1]Angewandte Chemie - International Edition,2001,vol. 40,p. 4042 - 4045
[2]Journal of Materials Chemistry,2002,vol. 12,p. 206 - 212

7
[ 108-77-0 ]
[ 1202-34-2 ]
[ 432551-43-4 ]

Yield	Reaction Conditions	Operation in experiment
72%	With N-ethyl-N,N-diisopropylamine In tetrahydrofuran for 48h; Heating;
68%	With sodium hydroxide In toluene for 24h; Reflux;	Syntheses The ligand (abbreviated TRA) was synthesized accordingto a literature method [23]. Briefly, 2,4,6-trichloro-1,3,5-triazine (2.39 g, 13 mmol) was mixed with 2,2′-dipyridylamine(10.00 g, 58.4 mmol) in toluene (100 mL) containingsodium hydroxide (1.97 g, 51 mmol) and the mixture refluxed for 24 h. The solution was allowed to cool and waterwas added. The product thus obtained was recrystallizedusing hexanes and methylene chloride to yield 5.2 g (68%)of an off-white solid. Elemental analysis for TRA CH2Cl2,C33.25H24.5Cl0.5N12;Calc.: C 65.48, H 4.05, N 27.56. Found:C 65.34, H 3.90, N 27.54. 1H NMR (600 MHz, DMSO-d6)δ ppm: 7.31-7.41 (m, 6H), 7.62 (d, J = 7.63 Hz, 6H), 7.93(td, J = 7.78, 2.05 Hz, 6H), 8.40-8.43 (m, 6H). IR (cm-1):1586, 1535, 1458, 1432, 1370, 1310, 1288, 1233, 1134,1097, 1049, 995, 876, 805, 776, 739, 666
55%	With sodium hydroxide In toluene for 24h; Heating;

30%

With N-ethyl-N,N-diisopropylamine In tetrahydrofuran at 0 - 48℃; for 68h;

The synthesis was via sequential substitution of the three chlorides of cyanuric chloride by 2,2'-dipyridylamine. 2,4,6-trichloro-[1,3,5]-triazine (cyanuric chloride) (0.307 g, 1.67 mmol) was dissolved in 25 mL tetrahydrofuran (THF) and 3 equivalent moles of N,N-diisopropylethylamine (DIPEA, 'Hünig's base' 0.646 g, 5.00 mmol) added while stirring. The resulting yellow solution was cooled down to 0 °C. Subsequently, a solution of 2, 2'-dipyridylamine (0.856 g, 5.00 mmol) in THF (20 mL) was added drop-wise and the reaction mixture stirred at 0 °C for 1 h. The reaction mixture was warmed to room temperature and refluxed for 48 h at 67 °C. The resultant white precipitate was isolated on a glass filter washed with THF ( mL) and with ethanol ( mL) to remove DIPEA. 2,4,6-tris(dipyridin-2-ylamino)-[1,3,5]-triazine (tdat), Yield 0.296 g (30%). 1H NMR (400 MHz, CDCl3, 303 K) δ 8.35 (6H, d, py), 7.51 (6H, dd, py), 7.42 (6H, d, py), 7.03 (6H, dd, py) ppm, 13C NMR (100 MHz, CDCl3, 303 K) δ 165.8, 154.9, 148.2, 137.3, 122.9, 120.8 ppm. Anal. Calc. for C33H24N12, C, 67.34, H, 4.11, N, 28.55, Found C, 66.98, H, 4.08, N, 28.80; TOF MS ES+ (m/z): [M+Na]+ = 611.2141.

Reference： [1]De Hoog, Paul; Gamez, Patrick; Driessen, Willem L; Reedijk, Jan [Tetrahedron Letters, 2002, vol. 43, # 38, p. 6783 - 6786]
[2]Beckford, Floyd A.; Niece, Madison B.; Lassiter, Brittany P.; Beebe, Stephen J.; Holder, Alvin A. [Journal of Biological Inorganic Chemistry, 2018, vol. 23, # 8, p. 1205 - 1217]
[3]Pang, Jun; Tao, Ye; Freiberg, Stephan; Yang, Xiao-Ping; D'Iorio, Marie; Wang, Suning [Journal of Materials Chemistry, 2002, vol. 12, # 2, p. 206 - 212]
[4]Asman, Panyako Wangoli [Inorganica Chimica Acta, 2018, vol. 469, p. 341 - 352]

8
[ 1202-34-2 ]
[ 626-39-1 ]
[ 432551-42-3 ]

Yield	Reaction Conditions	Operation in experiment
57%	Stage #1: di(pyridin-2-yl)amine; 1,3,5-trisbromobenzene With copper(ll) sulfate pentahydrate; potassium carbonate In dichloromethane; water at 20℃; Stage #2: at 210℃; for 8h; Inert atmosphere;	1,3,5-tris(di-2-pyridylamino)benzene (tdab) was prepared according to literature procedure using 1,3,5-tribromobenzene and di-2-pyridylamine via copper-mediated Ullmann condensation [34]. A mixture of 1,3,5-tribromobenzene (0.525g, 1.67mmol) in dichloromethane (30mL), 14 di-2-pyridylamine (0.856g, 5mmol) in dichloromethane (20mL), 29 potassium carbonate (0.8976g, 6.448mmol) in 19 water (10mL) and copper (II) sulphate pentahydrate (0.1355g, 0.5428mmol) in water (10mL) was stirred overnight at room temperature and evaporated to dryness under vacuum. The dried mixture was ground in a mortar and 5 drops of chloromethane added and heated at 210°C for 8h under nitrogen. The mixture was cooled to room temperature and dissolved in a mixture of dichloromethane (50mL) and water (50mL). The organic layer was washed with water (3×50 3×50 mL), dried over Na2SO4, and concentrated to give a yellow residue that was purified by chromatographic column using tetrahydrofuran (THF) and 33 hexane (3:1) v/v to obtain a brown solid. The brown solid was recrystallized from a mixture of CH2Cl2 - hexane to give a white crystalline compound. (0011) 1,3,5-tris(di-2-pyridylamino)benzene (tdab), Yield, 0.302g, (57%). 1H NMR (400MHz, CDCl3, 303K) δ 8.28 (6H, d, py), 7.56 (6H, dd, py), 7.14 (6H, d, py), 6.91 (6H, dd, py), 3.16 (3H, s, ph) ppm, 13C NMR (100MHz, CDCl3, 303K) δ 158.0, 148.7, 146.8, 137.9, 120.6, 118.9, 117.9ppm. Anal. Calcd for C36H27N9: C, 73.83, H, 4.65, N, 21.52, Found C, 73.41, H, 4.81, N, 21.88.
45%	With potassium carbonate; copper(II) sulfate at 210℃; for 8h;

Reference： [1]Asman, Panyako Wangoli [Inorganica Chimica Acta, 2018, vol. 469, p. 341 - 352]
[2]Pang, Jun; Tao, Ye; Freiberg, Stephan; Yang, Xiao-Ping; D'Iorio, Marie; Wang, Suning [Journal of Materials Chemistry, 2002, vol. 12, # 2, p. 206 - 212]

9
[ 1202-34-2 ]
[ 30363-03-2 ]
[ 432551-44-5 ]

Reference： [1]Journal of Materials Chemistry,2002,vol. 12,p. 206 - 212

10
[ 1202-34-2 ]
[ 1079-66-9 ]
[ 472959-76-5 ]

Yield	Reaction Conditions	Operation in experiment
100%	With n-butyllithium In diethyl ether; hexane at 20℃; for 48h;

Reference： [1]Schareina, Thomas; Kempe, Rhett [Angewandte Chemie - International Edition, 2002, vol. 41, # 9, p. 1521 - 1523]

11
[ 1202-34-2 ]
[ 21510-43-0 ]
N-(4-(5-phenyl-1,3,4-oxadiazol-2-yl)phenyl)-di(pyridin-2-yl)amine [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
60%	With potassium carbonate; copper(II) sulfate at 180℃; for 6h;
59%	With 1,3-dimethyl-3,4,5,6-tetrahydro-2(1H)-pyrimidinone; copper(l) iodide; 18-crown-6 ether; potassium carbonate at 180℃; for 48h; Inert atmosphere;

Reference： [1]Shavaleev, Nail M.; Barbieri, Andrea; Bell, Zoee R.; Ward, Michael D.; Barigelletti, Francesco [New Journal of Chemistry, 2004, vol. 28, # 3, p. 398 - 405]
[2]Location in patent: experimental part Wu, Jing; Li, Hong-Yan; Kang, Ling-Chen; Li, Dong-Ping; Li, Huan-Rong; Zhou, Xin-Hui; Sui, Yan; Zheng, You-Xuan; Zuo, Jing-Lin; You, Xiao-Zeng [Journal of Photochemistry and Photobiology A: Chemistry, 2010, vol. 211, # 2-3, p. 135 - 142]

12
[ 623-24-5 ]
[ 1202-34-2 ]
[ 916162-36-2 ]

Yield	Reaction Conditions	Operation in experiment
66%	With potassium hydroxide In N,N-dimethyl-formamide at 40℃; for 40h;
66%	Stage #1: di(pyridin-2-yl)amine With potassium hydroxide In N,N-dimethyl-formamide at 40℃; for 0.333333h; Stage #2: 1,4-bis(bromomethyl)benzene In N,N-dimethyl-formamide at 40℃; for 40h;	1,4-Bis(di-2-pyridylaminomethyl)benzene (L3) Di-2-pyridylamine(1.00 g, 5.84 mmol) and potassium hydroxide (1.33 g,23.7 mmol) were stirred in DMF (30 mL) at 40 °C for 20 min. 1,3-Bis(bromomethyl)benzene (0.699 g, 2.65 mmol) was added andstirring was continued at 40 °C for a further 40 h. The solvent wasremoved under reduced pressure and the residue partitionedbetween dichloromethane (200 mL) and water (150 mL). Theorganic layer was washed twice with water (2150 mL) and thenthe combined aqueous phases washed with dichloromethane (2100 mL). The combined dichloromethane layers were dried(Na2SO4) and then evaporated, resulting in a pale yellow solid.This was recrystallized from acetone-water yielding 780 mg (66%)as a yellow powder; mp 181-183 °C. Found: C, 75.47; H, 5.44; N,19.01. Calc. for C28H24N6: C, 75.65; H, 5.44; N, 18.91%. 1HNMR(500 MHz, CDCl3, 296 K) d 8.28 (4H, d, py), 7.47 (4H, t, py), 7.22 (4H,s, ph), 7.13 (4H, d, py), 6.82 (4H, dd, py), 5.43 (4H, s, CH2). 13C NMR(500 MHz, CDCl3, 296 K) d 157.1, 148.1, 137.6, 137.1, 126.9, 117.1,114.5, 51.02. MS (HR-ESI): m/z 444.2078; C28H24N6 requires444.2063.
59%	With potassium hydroxide In water; N,N-dimethyl-formamide at 20℃; for 24h; Inert atmosphere; Schlenk technique;

Reference： [1]Antonioli, Bianca; Bray, David J.; Clegg, Jack K.; Gloe, Kerstin; Gloe, Karsten; Kataeva, Olga; Lindoy, Leonard F.; McMurtrie, John C.; Steel, Peter J.; Sumby, Christopher J.; Wenzel, Marco [Dalton Transactions, 2006, # 40, p. 4783 - 4794]
[2]Rohman, Mostofa Ataur; Sutradhar, Dipankar; Sangilipandi; Mohan Rao; Chandra, Asit K.; Mitra, Sivaprasad [Journal of Photochemistry and Photobiology A: Chemistry, 2017, vol. 341, p. 115 - 126]
[3]Asman, Wangoli Panyako; Jaganyi, Deogratius [International Journal of Chemical Kinetics, 2017, vol. 49, # 8, p. 545 - 561]

13
[ 1202-34-2 ]
[ 111-25-1 ]
N-hexyl-N-(pyridin-2-yl)pyridin-2-amine [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
54.6%	Stage #1: di(pyridin-2-yl)amine With potassium hydroxide In dimethyl sulfoxide at 20℃; for 0.75h; Stage #2: 1-bromo-hexane In dimethyl sulfoxide at 20℃; for 1h;	Synthesis of the ligands General procedure: The ligands, namely (2,20-dipyridyl)methylamine (dpma),(2,20-dipyridyl)ethylamine (dpea), (2,20-dipyridyl)-1-propylamine(dppa), (2,20-dipyridyl)-1-butylamine (dpba), and (2,20-dipyridyl)-1-hexylamine (dpha), were synthesizedusing the same procedure [15] starting from 2,20-dipyridylamineand their respective bromo alkyl halides. For dpma,methyl iodide was used as a precursor.To a suspension of potassium hydroxide (1.3 g,0.02 mol) in 15 mL of DMSO, 2,20-dipyridylamine(0.0855 g, 0.5 mmol) was added. The mixture was stirredat room temperature for 45 min after which the respectivealkyl halide (0.5 mmol) was added. After stirring at roomtemperature for a further period of 60 min, 20 mL of waterwas added. The solution was extracted with diethyl ether(30 mL), and the organic extracts dried over MgSO4. Thesolvent was removed in vacuo to yield the desired ligand.All ligands were characterized by NMR spectroscopy andLC-MS and used for complex formation without furtherpurification.
45%	Stage #1: di(pyridin-2-yl)amine With sodium hydride In dimethyl sulfoxide at 60℃; for 12h; Stage #2: 1-bromo-hexane at 60℃; for 24h;

Reference： [1]Kinunda, Grace; Jaganyi, Deogratius [Transition Metal Chemistry, 2016, vol. 41, # 2, p. 235 - 248]
[2]Horie, Masaki; Yamaguchi, Isao; Yamamoto, Takakazu [Macromolecules, 2006, vol. 39, # 22, p. 7493 - 7501]

14
[ 1202-34-2 ]
[ 18226-42-1 ]
[ 609769-95-1 ]

Yield	Reaction Conditions	Operation in experiment
49%	With potassium hydroxide In dimethyl sulfoxide for 48h;
49%	Stage #1: di(pyridin-2-yl)amine With potassium hydroxide In dimethyl sulfoxide for 1h; Stage #2: 1,3,5-Tris(bromomethyl)benzene In dimethyl sulfoxide for 48h;	1,3,5-Tris(di-2-pyridylaminomethyl)benzene (L4) This wasprepared by an adaptation of a published procedure.7 Di-2-pyridylamine (1.00 g, 5.84 mmol) and potassium hydroxide (1.31 g,23.4 mmol) were stirred in DMSO (5 mL) for 1 h. 1,3,5-Tris(bromomethyl)benzene19 (0.675 g, 1.89 mmol) was then addedand the solution stirred for an additional 48 h. Water was addeddropwise until the solution turned cloudy. On standing, a yellowprecipitate formed which wasfiltered off, washed with water andrecrystallized from an ethyl acetate-petroleum ether (bp 30-60 °C)mixture. Yield, 0.583 g (49%); mp 158-160 °C. Found: C, 74.33; H,5.07; N, 19.80. Calc. for C39H33N9: C, 74.62; H, 5.30; N, 20.08%. 1HNMR (500 MHz, CDCl3, 296 K) d 8.20 (6H, d, py), 7.37 (6H, t, py), 7.07(3H, s, ph), 6.91 (6H, d, py), 6.78 (6H, dd, py), 5.34 (6H, s, CH2). 13CNMR (125.76 MHz, CDCl3, 296 K) d 157.0, 148.0, 139.4, 137.0, 123.6,116.9, 114.5, 51.18. MS (HR-ESI): m/z 628.2937. C39H34N9+ requires628.2953.
	Stage #1: di(pyridin-2-yl)amine With potassium hydroxide In dimethyl sulfoxide for 1h; Stage #2: 1,3,5-Tris(bromomethyl)benzene In dimethyl sulfoxide for 48h;	a 1,3,5-Tris(di-2-pyridylaminomethyl)benzene was prepared by reacting di-2-pyridylamine (0.856g, 5mmol) with potassium hydroxide (1.121g, 20mmol) in 5mL of DMSO. The mixture was stirred for 1h and 17 1,3,5-tris(bromomethyl)benzene (0.595g, 1.667mmol) added and stirred for an additional 48h. Water was added drop-wise to induce crystallization. On standing, a yellow powder formed and was filtered off, washed with plenty of water and recrystallized from an ethyl acetate-petroleum ether mixture. The synthesized ligands were characterized using 1H, 13C NMR, mass spectrometry and elemental analysis.

Reference： [1]Antonioli, Bianca; Bray, David J.; Clegg, Jack K.; Gloe, Kerstin; Gloe, Karsten; Kataeva, Olga; Lindoy, Leonard F.; McMurtrie, John C.; Steel, Peter J.; Sumby, Christopher J.; Wenzel, Marco [Dalton Transactions, 2006, # 40, p. 4783 - 4794]
[2]Rohman, Mostofa Ataur; Sutradhar, Dipankar; Sangilipandi; Mohan Rao; Chandra, Asit K.; Mitra, Sivaprasad [Journal of Photochemistry and Photobiology A: Chemistry, 2017, vol. 341, p. 115 - 126]
[3]Asman, Panyako Wangoli [Inorganica Chimica Acta, 2018, vol. 469, p. 341 - 352]

15
[ 1202-34-2 ]
[ 100-39-0 ]
[ 26422-90-2 ]

Yield	Reaction Conditions	Operation in experiment
60%	Stage #1: di(pyridin-2-yl)amine With potassium hydride In N,N-dimethyl-formamide at 0℃; for 1.5h; Inert atmosphere; Stage #2: benzyl bromide In N,N-dimethyl-formamide at 70 - 75℃; for 48h; Inert atmosphere;
46%	Stage #1: di(pyridin-2-yl)amine With potassium hydroxide In dimethyl sulfoxide for 0.666667h; Schlenk technique; Inert atmosphere; Stage #2: benzyl bromide In dimethyl sulfoxide at 20℃; for 24h; Schlenk technique; Inert atmosphere;
26%	With sodium hydroxide In N,N-dimethyl-formamide at 75℃; for 24h;

21%	With potassium hydroxide In N,N-dimethyl-formamide at 20℃; for 24h; Inert atmosphere;	2.2 Synthesis of ligands General procedure: Three ligands; di-2-pyridylaminobenzene, di-2-pyridylaminomethylbenzene, and 1,3,5-tris(bromomethyl)benzene were synthesized according to literature procedures [32],[33a]. A weighed amount of bromoalkyl halide (0.855g, 5.00mmol) was dissolved in 3mL DMF at room temperature and 2,2′-dipyridylamine (0.856g, 5.00mmol) and KOH (1.137g, 20.26mmol) in 5.00mL DMF added drop wise. The resulting solution was stirred under nitrogen at room temperature for 24h and dried under vacuum. The residue was washed with water and extracted into CHCl3 (3×50 3×50 mL). The extracts were dried over anhydrous sodium sulphate and filtered. The filtrate was dried under vacuum and chromatographed on silica gel with CHCl3:CH3OH (5:1) v/v. The resulting yellow product was recrystallized from an acetone-water mixture.Di-2-pyridylaminomethylbenzene, Yield, 0.277 g, (21%). 1H NMR (400 MHz, CDCl3, 303 K) δ 8.40 (2H, d, py), 7.60 (2H, t, py), 7.37 (2H, d, py), 7.27 (2H, d, ph), 7.20 (1H, t, ph), 7.16 (2H, d, ph), 6.94 (2H, t, py), 5.55 (2H, s, CH2) ppm, 13C NMR (100 MHz, CDCl3, 303 K) δ 157.5, 148.6, 139.8, 137.4, 128.0, 117.4, 114.4, 51.3 ppm. Anal. Calcd for C17H15N3, C, 78.13, H, 5.79, N, 16.08, Found C, 77.78, H, 5.55, N, 16.48, TOF MS ES+ (m/z): [M+H]+ = 262.134.
21%	With potassium hydroxide In water; N,N-dimethyl-formamide at 20℃; for 24h; Inert atmosphere; Schlenk technique;
16%	With potassium hydroxide In N,N-dimethyl-formamide at 20℃; for 15h;

Reference： [1]Licciulli, Sebastiano; Thapa, Indira; Albahily, Khalid; Korobkov, Ilia; Gambarotta, Sandro; Duchateau, Robbert; Chevalier, Reynald; Schuhen, Katrin [Angewandte Chemie - International Edition, 2010, vol. 49, # 48, p. 9225 - 9228]
[2]Vaquero, Mónica; Ruiz-Riaguas, Alba; Martínez-Alonso, Marta; Jalón, Félix A.; Manzano, Blanca R.; Rodríguez, Ana M.; García-Herbosa, Gabriel; Carbayo, Arancha; García, Begoña; Espino, Gustavo [Chemistry - A European Journal, 2018, vol. 24, # 42, p. 10662 - 10671]
[3]Bulatov, Evgeny; Haukka, Matti [Dalton Transactions, 2019, vol. 48, # 10, p. 3369 - 3379]
[4]Asman, Panyako Wangoli [Inorganica Chimica Acta, 2018, vol. 469, p. 341 - 352]
[5]Asman, Wangoli Panyako; Jaganyi, Deogratius [International Journal of Chemical Kinetics, 2017, vol. 49, # 8, p. 545 - 561]
[6]Antonioli, Bianca; Bray, David J.; Clegg, Jack K.; Gloe, Kerstin; Gloe, Karsten; Kataeva, Olga; Lindoy, Leonard F.; McMurtrie, John C.; Steel, Peter J.; Sumby, Christopher J.; Wenzel, Marco [Dalton Transactions, 2006, # 40, p. 4783 - 4794]

16
[ 1202-34-2 ]
[ 91-13-4 ]
[ 916162-33-9 ]

Yield	Reaction Conditions	Operation in experiment
37%	With potassium hydroxide In water; N,N-dimethyl-formamide at 20℃; for 24h; Inert atmosphere; Schlenk technique;
26%	Stage #1: di(pyridin-2-yl)amine With potassium hydroxide In dimethyl sulfoxide for 1h; Stage #2: α,α'-dibromo-o-xylene In dimethyl sulfoxide
25%	With potassium hydroxide In dimethyl sulfoxide for 40h;

25%

Stage #1: di(pyridin-2-yl)amine With potassium hydroxide In dimethyl sulfoxide for 1h; Stage #2: α,α'-dibromo-o-xylene In dimethyl sulfoxide for 40h;

1,2-Bis(di-2-pyridylaminomethyl)benzene (L1) Di-2 pyridylamine(1.00 g, 5.84 mmol) and potassium hydroxide (1.33 g,23.7 mmol) were stirred in DMSO (5 mL) for 1 h; 1,2 bis(bromomethyl)benzene (0.70 g, 2.65 mmol) was added and thereaction mixture was stirred for a further 40 h. Water was thenadded until the solution turned cloudy. The yellow precipitate thatformed was isolated and recrystallized from an ethyl acetate-petroleum ether (bp 30-60 °C) solution to yield yellow crystals.Yield, 0.29 g (25%); mp 144-146 °C. Found: C, 75.37; H, 5.38; N,19.04. Calc. for C28H24N6: C, 75.65; H, 5.44; N, 18.91%. 1H NMR(500 MHz, CDCl3, 296 K) d 8.32 (4H, d, py), 7.53 (4H, t, py), 7.27 (2H,d, ph), 7.22 (4H, d, py), 7.04 (2H, t, ph), 6.86 (4H, dd, py), 5.64 (4H, s,CH2). 13C NMR (125.76 MHz, CDCl3, 296 K) d 157.1 (C5), 148.2 (C1),137.2 (C7), 136.1 (C3), 126.5, 126.4 (C8, C9), 117.2 (C2), 114.6 (C4),48.6 (C6). MS (HR-ESI): m/z 444.2079; C28H24N6 requires 444.2063.

Reference： [1]Asman, Wangoli Panyako; Jaganyi, Deogratius [International Journal of Chemical Kinetics, 2017, vol. 49, # 8, p. 545 - 561]
[2]Location in patent: experimental part Gupta, Gajendra; Gloria, Sairem; Therrien, Bruno; Das, Babulal; Mohan Rao, Kollipara [Journal of Organometallic Chemistry, 2011, vol. 696, # 3, p. 702 - 708]
[3]Antonioli, Bianca; Bray, David J.; Clegg, Jack K.; Gloe, Kerstin; Gloe, Karsten; Kataeva, Olga; Lindoy, Leonard F.; McMurtrie, John C.; Steel, Peter J.; Sumby, Christopher J.; Wenzel, Marco [Dalton Transactions, 2006, # 40, p. 4783 - 4794]
[4]Rohman, Mostofa Ataur; Sutradhar, Dipankar; Sangilipandi; Mohan Rao; Chandra, Asit K.; Mitra, Sivaprasad [Journal of Photochemistry and Photobiology A: Chemistry, 2017, vol. 341, p. 115 - 126]

17
[ 1202-34-2 ]
[ 626-15-3 ]
[ 916162-34-0 ]

Yield	Reaction Conditions	Operation in experiment
83%	With potassium hydroxide In N,N-dimethyl-formamide at 40℃; for 40h;
83%	Stage #1: di(pyridin-2-yl)amine With potassium hydroxide In N,N-dimethyl-formamide at 40℃; for 0.333333h; Stage #2: 1,3-bis-(bromomethyl)benzene In N,N-dimethyl-formamide at 40℃; for 40h;	1,3-Bis(di-2-pyridylaminomethyl)benzene (L2) Di-2pyridylamine(1.00 g, 5.84 mmol) and potassium hydroxide (1.33 g,23.7 mmol) were stirred in DMF (30 mL) at 40 C for 20 min. 1,3-bis (bromomethyl)benzene (0.699 g, 2.65 mmol) was added andstirring was continued at 40 °C for a further 40 h. The solvent wasremoved under reduced pressure and the residue partitionedbetween dichloromethane (200 mL) and water (150 mL). Theorganic layer was washed twice with water (2150 mL) and thenthe combined aqueous phases washed with dichloromethane (2100 mL). The combined dichloromethane layers were dried(Na2SO4) and then evaporated, resulting in a pale yellow solid.This was recrystallized from acetone-water yielding 980 mg (83%)of a yellow crystalline solid; mp 133-134 °C. Found: C, 75.46; H,5.49; N, 19.03. Calc. for C28H24N6: C, 75.65; H, 5.44; N, 18.91%. 1H NMR (500 MHz, CDCl3, 296 K) d 8.25 (4H, d, py), 7.53 (4H, t, py), 7.27(2H, d, ph), 7.22 (4H, d, py), 7.04 (2H, t, py), 6.86 (4H, t, py), 5.64 (4H,s, CH2). 13C NMR (500 MHz, CDCl3, 296 K) d 157.0 (C5), 148.1 (C1),139.3 (C7), 137.1 (C3), 128.4 (C9), 125.3 (C10), 125.1 (C8), 117.2 (C2),114.5 (C4), 51.20 (C6).
46%	With potassium hydroxide In water; N,N-dimethyl-formamide at 20℃; for 24h; Inert atmosphere; Schlenk technique;

Reference： [1]Antonioli, Bianca; Bray, David J.; Clegg, Jack K.; Gloe, Kerstin; Gloe, Karsten; Kataeva, Olga; Lindoy, Leonard F.; McMurtrie, John C.; Steel, Peter J.; Sumby, Christopher J.; Wenzel, Marco [Dalton Transactions, 2006, # 40, p. 4783 - 4794]
[2]Rohman, Mostofa Ataur; Sutradhar, Dipankar; Sangilipandi; Mohan Rao; Chandra, Asit K.; Mitra, Sivaprasad [Journal of Photochemistry and Photobiology A: Chemistry, 2017, vol. 341, p. 115 - 126]
[3]Asman, Wangoli Panyako; Jaganyi, Deogratius [International Journal of Chemical Kinetics, 2017, vol. 49, # 8, p. 545 - 561]

18
[ 52776-76-8 ]
[ 1202-34-2 ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 2 steps 1: 39 percent / aq. potassium hydroxide; p-toluenesulfonyl chloride / CHCl₃ / 2 h / 20 °C 2: 68 percent / hydrochloric acid / 12 h / Heating

Reference： [1]Solekhova; Kurbatov [Russian Journal of Organic Chemistry, 2005, vol. 41, # 1, p. 128 - 130]

19
[ 1202-34-2 ]
[ 43091-72-1 ]
[ 155204-28-7 ]

Yield	Reaction Conditions	Operation in experiment
64.5%	With sodium amide In toluene for 24h; Heating / reflux;	5 1-[N-N-bis-(2-pyridyl)-2-aminoethyl]-4-(2-methoxyphenyl)-piperazine hydrochloride To a solution of 1.71 g of bis-(2-pyridyl)amine in 50 ml of toluene, under stirring at room temperature, was added 0.55 g of 95% sodium amide, followed by 2.54 g of 1-(2-chloroethyl)-4-(2-methoxyphenyl)-piperazine. The reaction mixture was refluxed for 24 hours and then cooled to room temperature. It was carefully diluted with 10 ml of methanol and then stirred for 15 minutes. 20 ml of water and 20 ml of ethyl acetate were added. Then, after 10 minutes further stirring, phase separation was carried out, and the aqueous phase was subsequently re-extracted with ethyl acetate. The combined organic phases were then washed with water, dried on sodium sulphate, and then evaporated to complete dryness under vacuum. The crude residue was then purified by flash chromatography (petroleum ether : ethyl acetate : 2.2N methanolic ammonia, gradient from 6 : 4 : 0.2 to 4 : 6 : 0.2). The recovered fractions were then evaporated to complete dryness, yielding 2.51 g (64.5%) of the title product as a base. This material was subsequently dissolved in 45 ml of ethyl acetate, to which was added 1 molar equivalent of 1M ethanolic hydrogen chloride. Overnight resting at 0°C afforded the title product, in crystalline form, which melted at 218-220°C. 1H-NMR (DMSO-d6, δ): 8.40 (dd, 2H, pyridine H6); 7.74 (ddd, 2H, pyridine H4); 7.28 (dd, 2H, pyridine H3); 6.90 - 7.15 (m, 6H, pyridine H5, phenyl CHs); 4.58 (t, 2H, PyNCH2); 4.35 - 5.15 (br, 1H, NH+); 3.80 (s, 3H, OCH3); 2.95 - 3.35 (m, 10H, piperazine protons and PyNCH2CH2).
	With sodium amide In toluene for 24h; Heating / reflux;	5 To a solution of 1.71 g of bis-(2-pyridyl)amine in 50 mL of toluene, under stirring at room temperature, was added 0.55 g of 95% sodium amide, followed by 2.54 g of 1-(2-chloroethyl)-4-(2-methoxyphenyl)piperazine. The obtained reaction mixture was then refluxed for 24 h, followed by cooling to room temperature and subsequent careful dilution with 10 mL of methanol. Afterwards, after 15 min of stirring, 20 mL of water and 20 mL of ethyl acetate were added. Then, after 10 min of further stirring, phase separation was carried out, and the aqueous phase was subsequently re-extracted with ethyl acetate. The combined organic phases were then washed with water, dried on sodium sulphate, and then evaporated to complete dryness under vacuum. The crude residue was then purified by flash chromatography (petroleum ether-ethyl acetate-2.2 N solution of ammonia in methanol; gradient from 6:4:0.2 to 4:6:0.2). The recovered fractions were then evaporated to complete dryness, yielding 2.51 g (64.5%) of the title product as a base. This material was subsequently dissolved in 45 mL of ethyl acetate, to which was added 1 molar equivalent of hydrochloric acid (1 M solution in ethanol). Overnight resting at 0° C. afforded the title product, in crystalline form, which melted at 218-220° C.
	With sodium amide In toluene for 24h; Heating / reflux;	5 To a solution of 1.71 g of bis-(2-pyridyl)amine in 50 mL of toluene, under stirring at room temperature, was added 0.55 g of 95% sodium amide, followed by 2.54 g of 1-(2-chloroethyl)-4-(2-methoxyphenyl)piperazine. The obtained reaction mixture was then refluxed for 24 h, followed by cooling to room temperature and subsequent careful dilution with 10 mL of methanol. Afterwards, after 15 min of stirring, 20 mL of water and 20 mL of ethyl acetate were added. Then, after 10 min of further stirring, phase separation was carried out, and the aqueous phase was subsequently re-extracted with ethyl acetate. The combined organic phases were then washed with water, dried on sodium sulphate, and then evaporated to complete dryness under vacuum. The crude residue was then purified by flash chromatography (petroleum ether-ethyl acetate-2.2 N solution of ammonia in methanol; gradient from 6:4:0.2 to 4:6:0.2). The recovered fractions were then evaporated to complete dryness, yielding 2.51 g (64.5%) of the title product as a base. This material was subsequently dissolved in 45 mL of ethyl acetate, to which was added 1 molar equivalent of hydrochloric acid (1 M solution in ethanol). Overnight resting at 0° C. afforded the title product, in crystalline form, which melted at 218-220° C.

Reference： [1]Current Patent Assignee: RECORDATI SPA - EP1000046, 2003, B1 Location in patent: Page/Page column 11
[2]Current Patent Assignee: RECORDATI SPA - US6894052, 2005, B1 Location in patent: Page/Page column 16-17
[3]Current Patent Assignee: RECORDATI SPA - US6894052, 2005, B1 Location in patent: Page/Page column 16-17

20
[ 1202-34-2 ]
[ 6329-74-4 ]
sodium perchlorate [ No CAS ]
[ 6046-93-1 ]
{(5-bromosalicylamidato bis(2-pyridyl)amine) copper(II)} perchlorate [ No CAS ]

Reference： [1]Indian Journal of Chemistry, Section A: Inorganic, Physical, Theoretical and Analytical,1989,vol. 28,p. 673 - 677

21
[ 1202-34-2 ]
copper(II) nitrate trihydrate [ No CAS ]
[ 5550-12-9 ]
bis{(guanosine 5'-monophosphate)(di-2-pyridylamine)aquacopper(II)} trihydrate [ No CAS ]

Reference： [1]Nippon Kagaku Kaishi/Journal of the Chemical Society of Japan,
Nippon Kagaku Kaishi,1988,vol. 63,p. 611 - 620

22
[ 1202-34-2 ]
[ 12257-42-0 ]
[ 108792-65-0 ]

Reference： [1]Inorganica Chimica Acta,1986,vol. 115,p. 65 - 74

23
[ 1202-34-2 ]
[ 12257-42-0 ]
[ 108792-55-8 ]

Reference： [1]Inorganica Chimica Acta,1986,vol. 115,p. 65 - 74

24
[ 5027-32-7 ]
[ 1202-34-2 ]
[ 6147-53-1 ]
(((CH₃CO)2CH)2)4Co₄((C₅H₄N)2NH)4 [ No CAS ]
3Co⁽²⁺⁾*4CH₃COO^(1-)*2(C₅H₄N)2NH^(1-)=Co₃(O₂CCH₃)4((C₅H₄N)NH(C₅H₄N))2 [ No CAS ]

Reference： [1]Journal of the American Chemical Society,1998,vol. 120,p. 9398 - 9399

25
[ 1295-35-8 ]
[ 1202-34-2 ]
[ 107-13-1 ]
[ 165462-08-8 ]

Reference： [1]Inorganica Chimica Acta,1995,vol. 230,p. 249 - 252
Inorg. Chim. Acta,

26
[ 5027-32-7 ]
[ 1202-34-2 ]
[ 16712-25-7 ]
[ 245483-57-2 ]

Reference： [1]Canadian Journal of Chemistry,1999,vol. 77,p. 1424 - 1435

27
[ 553-26-4 ]
[ 5027-32-7 ]
[ 1202-34-2 ]
[ 16712-25-7 ]
[Cu₂(C₁₀H₁₂O₄)(2,2'-dipyridylamine)2(4,4'-dipyridyl)](CF₃CO₂)2 [ No CAS ]

Reference： [1]Canadian Journal of Chemistry,1999,vol. 77,p. 1424 - 1435

28
[ 5027-32-7 ]
[ 1202-34-2 ]
[ 6147-53-1 ]
[Co(C₁₀H₁₂O₄)(2,2'-dipyridylamine)4](CH₃CO₂)2(H₂O)2/CH₃OH [ No CAS ]

Reference： [1]Canadian Journal of Chemistry,1999,vol. 77,p. 1424 - 1435

29
sodium hexaflorophosphate [ No CAS ]
[ 1202-34-2 ]
copper(II) nitrate trihydrate [ No CAS ]
[ 471-47-6 ]
[Cu2(μ-oxamato)(N,N,N',N'-tetramethylethylenediamine)2](PF6)2 *3H2O [ No CAS ]

Reference： [1]Inorganica Chimica Acta,1980,vol. 41,p. 155 - 160

30
[ 1202-34-2 ]
copper(II) nitrate trihydrate [ No CAS ]
[ 471-46-5 ]
[Cu2(μ-oxamido)(2,2'-dipyridylamine)2(NO3)2] [ No CAS ]

Reference： [1]Inorganica Chimica Acta,1980,vol. 41,p. 155 - 160

31
[ 1202-34-2 ]
copper(II) nitrate trihydrate [ No CAS ]
[ 471-46-5 ]
[Cu2(μ-oxamido)(2,2'-dipyridylamine)2](NO3)2 * 4H2O [ No CAS ]

Reference： [1]Inorganica Chimica Acta,1980,vol. 41,p. 155 - 160

32
[ 1202-34-2 ]
copper(II) nitrate trihydrate [ No CAS ]
[ 471-47-6 ]
[Cu2(μ-oxamate)(2,2'-dipyridylamine)2](NO3)2 [ No CAS ]

Reference： [1]Inorganica Chimica Acta,1980,vol. 41,p. 155 - 160

33
[ 1202-34-2 ]
copper(II) choride dihydrate [ No CAS ]
[ 51940-44-4 ]
chloro(8-ethyl-5,8-dihydro-5-oxo-2-(1-piperazinyl)pyrido[2,3-d]pyrimidine-6-carboxylate)(2,2'-dipyridylamine)copper(II) [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
65%	With sodium acetate In methanol stoich., acette added to a soln. of acid, stirred for 30 min, a soln. ofCu salt and amine added dropwise, refluxed for 1 h; concd. (vac.), slowly evapd.; elem. anal.;

Reference： [1]Efthimiadou, Eleni K.; Katsaros, Nikos; Karaliota, Alexandra; Psomas, George [Inorganica Chimica Acta, 2007, vol. 360, # 15, p. 4093 - 4102]

34
[ 1202-34-2 ]
zinc(II) nitrate hexahydrate [ No CAS ]
[ 1863-63-4 ]
[ 1000608-52-5 ]

Reference： [1]Inorganic Chemistry Communications,2007,vol. 10,p. 287 - 291

35
[ 12092-47-6 ]
[ 1202-34-2 ]
[ 108792-64-9 ]

Reference： [1]Inorganica Chimica Acta,1986,vol. 115,p. 65 - 74
[2]Inorganica Chimica Acta,1986,vol. 115,p. 65 - 74

36
[ 15231-91-1 ]
[ 1202-34-2 ]
[ 1084338-24-8 ]

Yield	Reaction Conditions	Operation in experiment
50%	With sodium t-butanolate In toluene at 50℃; for 3h; Heating / reflux;	1.3 After 2,2'-dipyridylamine (5.0 g, 29 mmol), 2-bromo-6~naphthol(5.4 g, 24.2 mmol), and NaOt-Bu (7 g, 72.6 mmol) were put into toluene(250 mU, the mixture was heated to 50 0C . Pd(P(t-Bu)3)2 (61.5 mg, 0.12mmol) was added and then heated and agitated for 3 hours. Thetemperature was cooled to normal temperature, celite was added, and theagitation was performed for 10 min. The suspension solution was filteredby using a filter in which silica gel was provided by 1.5 cm. The filtratewas distilled under reduced pressure and recrystallized with ethanol (200mL) to obtain formul 1-C (3.8 g, yield 50%). MS: [M+ H]+ = 314

Reference： [1]Current Patent Assignee: LG CHEM CO.,LTD. - WO2008/143440, 2008, A1 Location in patent: Page/Page column 67

37
[ 1202-34-2 ]
[ 589-87-7 ]
[ 467238-86-4 ]

Yield	Reaction Conditions	Operation in experiment
54%	With potassium carbonate In N,N-dimethyl acetamide at 20 - 160℃; for 8.16667h;	1.1 After 2,2'-dipyridylamine (5.0 g, 29 mmol) and 4-bromoiodobenzene(9.1 g, 32.1 mmol) were dissolved in 70 ml of dimethyl acetamide (DMAC), CuCl (0.4 g, 2.9 mmol), 2,2'- dipyridyl (0.45 g, 2.9 mmol), and K2CO3 (8 g,58 mmol) were added, and the mixture was agitated at a room temperaturefor 10 min and agitated at 160 C for 8 hours. If the reaction was finished,the cooling was performed to a normal temperature, the extraction wasperformed with water and THF (tetrahydrofurane), water was removedwith MgSO4, THF was removed under reduced pressure, silica gel shortcolumn was performed by using hexane and THF, and the precipitation wasformed with water and ethanol (EtOH). The precipitate was filtered toprepare the compound of formula 1-A (5.2 g, yield 54%) that was the whitesolid. MS: [M+ H]+ = 327

Reference： [1]Current Patent Assignee: LG CHEM CO.,LTD. - WO2008/143440, 2008, A1 Location in patent: Page/Page column 65-66

38
[ 1202-34-2 ]
[ 561064-15-1 ]
[ 1084339-08-1 ]

Yield	Reaction Conditions	Operation in experiment
30%	With sodium t-butanolate In toluene at 50℃; for 3h; Heating / reflux;	4.1 After 2,2'-dipyridylamine (17.7 g, 103.7 mmol), 2,6-dibromo-9,10-bis(2-naphthyl)anthracene (25.4 g, 43.2 mmol), and NaOt-Bu (12.5 g, 129.6mmol) were put into toluene (346 mL), the mixture was heated to 50 C .Pd(P(t-Bu)3)2 (220.5 mg, 0.43 mmol) was added and then heated andagitated for 3 hours. The temperature was cooled to normal temperature,celite was added, and the agitation was performed for 10 min. Thesuspension solution was filtered by using a filter in which silica gel wasprovided by 1.5 cm. The filtrate was distilled under reduced pressure andrecrystallized with ethanol (200 mL) to obtain a comopound of formul 2-11 (10 g, yield 30%). MS: [M+ H]+ = 769

Reference： [1]Current Patent Assignee: LG CHEM CO.,LTD. - WO2008/143440, 2008, A1 Location in patent: Page/Page column 90-91

39
[ 474688-76-1 ]
[ 1202-34-2 ]
[ 1084338-71-5 ]

Yield	Reaction Conditions	Operation in experiment
70%	With sodium t-butanolate;bis(tri-t-butylphosphine)palladium(0); In toluene; at 50℃; for 3h;Heating / reflux;	After 2,2'-dipyridylamine (5.0 g, 29 mmol), 2-bromo-9,10-dinaphthylanthracene (12.3 g, 24.2 mmol), and NaOt-Bu (7 g, 72.6 mmol) were put into toluene (250 mL), the mixture was heated to 50 "C . Pd(PCt-Bu)3)2 (61.5 mg, 0.12 mmol) was added and then heated and agitated for 3hours. The temperature was cooled to normal temperature, celite wasadded, and the agitation was performed for 10 min. The suspensionsolution was filtered by using a filter in which silica gel was provided by1.5 cm. The filtrate was distilled under reduced pressure andrecrystallized with ethanol (200 mL) to obtain a comopound of formul 1-11(10.1 g, yield 70%). MS: [M+ H]+ = 600

Reference： [1]Patent: WO2008/143440,2008,A1 .Location in patent: Page/Page column 78-79

40
[ 1202-34-2 ]
[ 16523-54-9 ]
[ 472959-98-1 ]

Yield	Reaction Conditions	Operation in experiment
64%	Stage #1: di(pyridin-2-yl)amine With n-butyllithium In hexane at -20 - 20℃; Stage #2: chlorodicyclohexylphosphane In hexane at -20 - 20℃;

Reference： [1]Blank, Benoit; Madalska, Martyna; Kempe, Rhett [Advanced Synthesis and Catalysis, 2008, vol. 350, # 5, p. 749 - 758]

41
[ 1202-34-2 ]
tetrakis(acetonitrile)copper(I)tetrafluoroborate [ No CAS ]
[ 74-85-1 ]
[ 91128-09-5 ]

Yield	Reaction Conditions	Operation in experiment
84%	Stage #1: tetrakis(acetonitrile)copper(I)tetrafluoroborate; ethene In methanol at 20℃; for 5h; Inert atmosphere; Stage #2: di(pyridin-2-yl)amine In methanol Inert atmosphere;	2.2.4 Synthesis of [Cu(DPyA)(C₂H₄)](BF₄) (4a) Ethylene was charged into a solution of [CuI(MeCN)4]BF4 (1.573g, 5.00mmol) in 30mL methanol under ambient conditions. The mixture was stirred for 5h and a solution of 2,2′-dipyridylamine (DPyA, 0.856g, 5mmol) in 10mL MeOH was added dropwise, and a white solid was rapidly formed. The mixture was reduced to half its volume and 60mL ether was added, and then the resulting white solid was collected via filtration and dried under vacuum to give 1.468g 4a (84% yield). IR (cm-1): 3353s, 3262m, 3226m, 3159m, 3084m, 1644s, 1616m, 1586s, 1566 w, 1532s, 1482s b, 1437s, 1383s, 1276m, 1268m, 1235s, 1165s, 1016s b, 911s, 871 w, 829m, 767s, 654m, 613 w, 526s, 418s.
60%	In methanol byproducts: MeCN; under Ar; Cu-contg. compd. (1.0 mmol) and a ligand (1.0 mmol) were charged to sep. Schlenk flasks in dry box; MeOH was added to flask with ligand; stirring; C2H4 satd. MeOH was added to the flask with Cu-contg. compd.; stirring and addn of H-dpa soln.; stirring for 2 h; the soln. was filtered and n-pentane was added to ppt.the complex; then it was filtered;

Reference： [1]Davidson, Royce A.; Hao, Jingjun; Rheingold, Arnold L.; Miller, Joel S. [Polyhedron, 2017, vol. 133, p. 348 - 357]
[2]Allen, John J.; Barron, Andrew R. [Dalton Transactions, 2009, # 5, p. 878 - 890]

42
[ 1202-34-2 ]
[ 2050-47-7 ]
[ 914785-98-1 ]

Reference： [1]New Journal of Chemistry,2009,vol. 33,p. 1290 - 1300

43
[ 1202-34-2 ]
[ 14040-11-0 ]
[ 75-09-2 ]
[ 15522-59-5 ]
[ 1200628-21-2 ]
[W₂(2,2'-dipyridylamine-H)3Cl₂](tetraphenylborate)*2(dichloromethane) [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	In further solvent(s) under N2; to mixt. of W(CO)6 (1.14 mmol) and ligand (1.71 mmol) was added 1,2-dichlorobenzene; stirring for 12 h (250°C); filtering; filtrate was dried under reduced pressure; solid was extd. with CH2Cl2 and filtered into (NBu4)(BPh4) (0.57 mmol); layering with Et2O; ppt. was collected by filtration and recrystd. 2 times from CH2Cl2/Et2O;

Reference： [1]Nippe, Michael; Victor, Eric; Berry, John F. [Inorganic Chemistry, 2009, vol. 48, # 24, p. 11889 - 11895]

44
[ 1202-34-2 ]
[ 66990-32-7 ]
[ 1214913-78-6 ]

Yield	Reaction Conditions	Operation in experiment
72%	With dmap; dicyclohexyl-carbodiimide In dichloromethane at 20℃; for 32h; Inert atmosphere;

Reference： [1]Location in patent: experimental part Jose, D. Amilan; Koenig, Burkhard [Organic and Biomolecular Chemistry, 2010, vol. 8, # 3, p. 655 - 662]

45
[ 1202-34-2 ]
cadmium(II) nitrate tetrhydrate [ No CAS ]
[ 1863-63-4 ]
[ 1217263-75-6 ]

Reference： [1]Polyhedron,2010,vol. 29,p. 773 - 786

46
[ 1202-34-2 ]
[ 29823-18-5 ]
[ 1238944-67-6 ]

Yield	Reaction Conditions	Operation in experiment
51%	Stage #1: di(pyridin-2-yl)amine With sodium hydride In N,N-dimethyl-formamide at 20℃; for 0.166667h; Stage #2: ethyl 7-bromoheptanoate With potassium iodide In N,N-dimethyl-formamide at 20 - 90℃;	3 NaH (112 mg, 2.92 mmol) was added to di-pyridyl-2-yl-amine, I, (500 mg, 2.92 mmol) in DMF (10 mL) at rt. After 10min, Kl (727 mg, 4.38 mmol) and ethyl 7- bromoheptanoate (0.854 mL, 4.38 mmol) were added, and the reaction mixture was stirred at 9O0C for 18h. Aqueous 0.1 M Na2S2O3 (100 mL) and EtOAc (100 mL) were added, the phases were separated, and the organic phase was washed with brine (100 mL) then dried over MgSO4, filtered, and subsequently evaporated under reduced pressure. The resulting residue was purified by silica gel column chromatography eluting with hexane/EtOAc (90:10 to 75:25) to furnish Il as a colourless oil (490 mg, 51%).1H NMR (400 MHz, CDCI3) δH: 8.35 (dd, J=1.8, 5.3Hz, 2H), 7.52 (dt, J=2.0,7.0Hz, 2H), 7.08 (d, J=8.0Hz, 2H), 6.86 (dd, J=5.5, 7.0Hz, 2H), 4.18 (t, J=7.5Hz, 2H), 4.12 (q, J=7.0Hz, 2H), 2.27 (t, J=7.5Hz, 2H), 1.71 (td, J=7.0, 14.6Hz, 2H),1.61 (td, J=I. Z, 14.6Hz, 2H), 1.43-1.30 (m, 4H), 1.25 (t, J=7.0Hz, 3H). MW:327.42. LCMS (ES): found 327.9 [MH]+.

Reference： [1]Current Patent Assignee: KARUS THERAPEUTICS LIMITED - WO2010/86646, 2010, A1 Location in patent: Page/Page column 27-28

47
[ 1202-34-2 ]
[ 14273-90-6 ]
[ 1238944-66-5 ]

Yield	Reaction Conditions	Operation in experiment
24%	Stage #1: di(pyridin-2-yl)amine With sodium hydride In N,N-dimethyl-formamide at 20℃; Stage #2: methyl 6-bromohexanoate With potassium iodide In N,N-dimethyl-formamide at 20 - 90℃;	2 NaH (112 mg, 2.92 mmol) was added to di-pyridin-2-yl-amine (500 mg, 2.92 mmol) in DMF (10 ml.) at it After 10 min, Kl (485 mg, 2.92 mmol) and methyl 6- bromohexanoate, I (0.464 ml_, 2.92 mmol) were added, and the reaction mixture was stirred at 9O0C for 21 h. Brine (200 mL) and EtOAc (200 mL) were then added, the phases were separated, and the aqueous phase was extracted with EtOAc (100 mL). The organic phases were combined, dried over MgSO4, filtered, and subsequently evaporated under reduced pressure. The resulting residue was purified by silica gel column chromatography using CH2CI2/Me0H (100:0.5 to 100:1) as eluant to furnish Il as a colourless oil (206 mg, 24%). 1H NMR (400 MHz, CDCI3) δH: 8.35 (dd, J=2.5, 1.8Hz, 2H), 7.47-7.56 (m, 2H), 7.07 (d, J=9.2Hz, 2H), 6.86 (dd, J=6.4, 5.6Hz, 2H), 4.15-4.21 (m, 2H), 3.65 (s, 3H), 2.29 (t, J=7.5Hz, 2H), 1.61-1.77 (m, 4H), 1.34-1.45 (m, 2H). MW: 299.37. LCMS (ES): found 300.3 [MH]+, 322.3 [MNa]+.

Reference： [1]Current Patent Assignee: KARUS THERAPEUTICS LIMITED - WO2010/86646, 2010, A1 Location in patent: Page/Page column 26

48
ammonium hexafluorophosphate [ No CAS ]
[ 1202-34-2 ]
[ 92361-49-4 ]
[ 1246811-06-2 ]

Reference： [1]Journal of Molecular Structure,2010,vol. 979,p. 205 - 213

49
[ 1202-34-2 ]
[ 111693-13-1 ]
[ 7732-18-5 ]
[ 6155-57-3 ]
[Pd(2,2'-dipyridylamine)]2[saccharinate]2*2H₂O [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
85%	In methanol; water aq. suspn. of PdCl2(dpya) (0.5 mmol) mixed with MeOH soln. of ligand (1 mmol), refluxed overnight, cooled to room temp., filtered, aq. soln. of Na(sac)*2H2O (1 mmol) added, mixt. stirred at 60°C for 2 h; concd., crystd. in 1 d, elem. anal.;

Reference： [1]Guney, Emel; Yilmaz, Veysel T.; Buyukgungor, Orhan [Inorganica Chimica Acta, 2010, vol. 363, # 11, p. 2416 - 2424]

50
[ 1202-34-2 ]
[ 111693-14-2 ]
[ 7732-18-5 ]
[ 6155-57-3 ]
[Pt(2,2'-dipyridylamine)]2[saccharinate]2*2H₂O [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
80%	In methanol; water aq. suspn. of PtCl2(dpya) (0.5 mmol) mixed with MeOH soln. of ligand (1 mmol), refluxed overnight, cooled to room temp., filtered, aq. soln. of Na(sac)*2H2O (1 mmol) added, mixt. stirred at 60°C for 2 h; concd., crystd. in 1 d, elem. anal.;

Reference： [1]Guney, Emel; Yilmaz, Veysel T.; Buyukgungor, Orhan [Inorganica Chimica Acta, 2010, vol. 363, # 11, p. 2416 - 2424]

51
[ 1202-34-2 ]
[ 753-89-9 ]
[ 1258543-20-2 ]

Yield	Reaction Conditions	Operation in experiment
74%	Stage #1: di(pyridin-2-yl)amine With potassium hydride In N,N-dimethyl-formamide at 0℃; for 1.5h; Inert atmosphere; Stage #2: neopentyl chloride In N,N-dimethyl-formamide at 70 - 75℃; for 48h; Inert atmosphere;
74%	Stage #1: di(pyridin-2-yl)amine With potassium hydride In N,N-dimethyl-formamide at 0℃; for 1.5h; Inert atmosphere; Stage #2: neopentyl chloride In N,N-dimethyl-formamide at 0 - 75℃; for 48h; Inert atmosphere;	1.1.1 1.1 Synthesis of N-neopentyl-2,2'-dipyridylamineIn a two-necked flask equipped with condenser 2,2'-dipyridylamine (10 g, 54.5 mmol) was dissolved in dry DMF (100 ml) and the resulting solution was stirred under N2 at 0°C for 15 min. Potassium hydride (1.2 eq., 65.4 mmol) was added portion wise and the resulting solution was stirred at 0°C for 1.5h. 1-chloro-2,2-dimethylpropane (1.3 eq, 71 mmol) was added in one portion and the resulting yellow/green solution was refluxed at 70-75°C for 2 days after which 10 ml of ethanol were added to quench the reaction. After stirring the reaction solution for 20 min, the solvent was evaporated under reduced pressure and the resulting thick yellow oil was treated with ether (30 ml). The resulting yellow suspension was filtered and the liquid organic phase was evaporated under reduced pressure to give yellow oil which was purified by column chromatography on silica gel (Hexane/AcOEt 7/3). The pure product was obtained as white crystalline material (9.72 g, 74% yield).

Reference： [1]Licciulli, Sebastiano; Thapa, Indira; Albahily, Khalid; Korobkov, Ilia; Gambarotta, Sandro; Duchateau, Robbert; Chevalier, Reynald; Schuhen, Katrin [Angewandte Chemie - International Edition, 2010, vol. 49, # 48, p. 9225 - 9228]
[2]Current Patent Assignee: UNIVERSITY OF OTTAWA; LYONDELLBASELL INDUSTRIES N.V. - WO2011/85951, 2011, A1 Location in patent: Page/Page column 17

52
[ 1202-34-2 ]
zinc(II) nitrate hexahydrate [ No CAS ]
[ 35453-19-1 ]
[ 1288844-65-4 ]

Reference： [1]Russian Journal of Coordination Chemistry,2011,vol. 37,p. 176 - 179

53
[ 1202-34-2 ]
[ 31588-18-8 ]
copper(II) nitrate [ No CAS ]
[Cu(2-phenyl-3-hydroxy-4(H)-quinoline^(1-))(bis(2-pyridyl)amine)]NO₃*0.5H₂O [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	In ethanol; water elem. anal.;

Reference： [1]Buchtik, Roman; Travnicek, Zdenek; Vanco, Jan; Herchel, Radovan; Dvorak, Zdenek [Dalton Transactions, 2011, vol. 40, # 37, p. 9404 - 9412]

54
[ 1202-34-2 ]
[ 110871-86-8 ]
[ 7646-85-7 ]
bis(5-amino-1-cyclopropyl-7-((3R,5S)-3,5-dimethylpiperazin-1-yl)-6,8-difluoro-4-oxo-1,4-dihydroquinoline-3-carboxylato)(2,2'-bipyridylamine)zinc [ No CAS ]

Reference： [1]Dalton Transactions,2011,vol. 40,p. 9461 - 9473

55
[ 1202-34-2 ]
[ 4181-20-8 ]
[ 147970-27-2 ]

Reference： [1]Dalton Transactions,2012,vol. 41,p. 5280 - 5293

56
[ 1202-34-2 ]
[ 1218812-58-8 ]
[ 1218812-57-7 ]

Yield	Reaction Conditions	Operation in experiment
41%	With 18-crown-6 ether; Cu bronze; potassium carbonate In N,N-dimethyl-formamide at 145℃; for 30h; Inert atmosphere;	3 Example 3: Preparation of Monomer Compound L² A mixture of 15 2,2′-dipyridylamine (5.27 g, 30.76 mmol), 12 (4-bromophenyl)-di(4-pyridyl)amine (2.50 g, 7.69 mmol), anhydrous 7 potassium carbonate (2.66 g, 19.23 mmol), bronze powder (4.93 g, 77.64 mmol), 18-crown-6 (200 mg, 0.76 mmol), and 16 DMF (125 mL) was heated at 145 degrees C. under nitrogen for 30 hours. The reaction was cooled and worked up by a procedure similar to that for L1. A yellowish solid was collected from a silica gel column, and was further purified by recrystallization from dichloromethane and petroleum ether, to afford a white solid of 17 N,N-di(2-pyridyl)-N′,N′-di(4-pyridyl)-1,4-phenylenediamine (L2, 1.32 g, yield: 41%). 1H NMR (CDCl3, Bruker 400 MHz): 8.43 (d, J=4.4 Hz, 4H, pyridyl-H), 8.37 (d, J=3.6 Hz, 2H, pyridyl-H), 7.60-7.65 (m, 2H, pyridyl-H), 7.21 (d, J=8.8 Hz, 2H, phenylene-H), 7.14 (d, J=8.8 Hz, 2H, phenylene-H), 6.98-7.09 (m, 8H, pyridyl-H). Anal. Calcd (%) for C26H20N6: C, 74.98; H, 4.84; N, 20.18. Found: C, 74.53; H, 4.72; N, 19.89. IR (KBr pellet, cm-1): 1575(vs), 1505(s), 1490(s), 1467(s), 1431(vs), 1324(s), 1305.13(s), 1276(s), 1218(m), 1163(w), 1103(w), 991(m), 811(m), 777(m), 737(w), 654(w), 622(m), 530(m).
	With potassium carbonate In N,N-dimethyl-formamide	3 Preparation of Monomer Compound L2 Example 3 Preparation of Monomer Compound L2 A mixture of 2,2'-dipyridylamine (5.27 g, 30.76 mmol), (4-bromophenyl)-di(4-pyridyl)amine (2.50 g, 7.69 mmol), anhydrous potassium carbonate (2.66 g, 19.23 mmol), bronze powder (4.93 g, 77.64 mmol), 18-crown-6 (200 mg, 0.76 mmol), and DMF (125 mL) was heated at 145 degrees C. under nitrogen for 30 hours. The reaction was cooled and worked up by a procedure similar to that for L1. A yellowish solid was collected from a silica gel column, and was further purified by recrystallization from dichloromethane and petroleum ether, to afford a white solid of N,N-di(2-pyridyl)-N',N'-di(4-pyridyl)-1,4-phenylenediamine (L2, 1.32 g, yield: 41%). 1H NMR (CDCl3, Bruker 400 MHz): 8.43 (d, J=4.4 Hz, 4H, pyridyl-H), 8.37 (d, J=3.6 Hz, 2H, pyridyl-H), 7.60-7.65 (m, 2H, pyridyl-H), 7.21 (d, J=8.8 Hz, 2H, phenylene-H), 7.14 (d, J=8.8 Hz, 2H, phenylene-H), 6.98-7.09 (m, 8H, pyridyl-H). Anal. Calcd (%) for C26H20N6: C, 74.98; H, 4.84; N, 20.18. Found: C, 74.53; H, 4.72; N, 19.89. IR (KBr pellet, cm-1): 1575(vs), 1505(s), 1490(s), 1467(s), 1431(vs), 1324(s), 1305.13 (s), 1276(s), 1218(m), 1163(w), 1103(w), 991(m), 811(m), 777(m), 737(w), 654(w), 622(m), 530(m).

Reference： [1]Current Patent Assignee: EAST CHINA UNIVERSITY OF SCIENCE AND TECHNOLOGY - US10087289, 2018, B2 Location in patent: Page/Page column 18
[2]Current Patent Assignee: EAST CHINA UNIVERSITY OF SCIENCE AND TECHNOLOGY - US2012/214962, 2012, A1

57
[ 1202-34-2 ]
[ 5292-43-3 ]
tert-butyl 2-(di(pyridine-2-yl)amino)acetate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
88%	Stage #1: di(pyridin-2-yl)amine With potassium hydroxide In dimethyl sulfoxide at 20℃; for 16h; Stage #2: bromoacetic acid <i>tert</i>-butyl ester With potassium iodide In dimethyl sulfoxide at 20℃; for 2h;	1 [00134] Example 1. Synthesis of Tert-butyl 2-(di(pyridine-2-yl)amino)acetate (DPA). Tert-butyl 2-(di(pyridine-2-yl)amino)acetate was prepared with modification to irin et al., 2007, J. Inorg. Chem., 3686-3694, the entire contents of which are incorporated herein by reference. Potassium hydroxide (3.0 g, 53.6 mmol, 4.6 equiv) was added to a solution of2,2'-dipyridylamine (2.0 g, 1 1.7 mmol) in 40 ml DMSO and stirred at room temperature for 16 hours (h). Potassium iodide (200 mg, 1 .2 mmol, 0.1 equiv) and tert-butyl bromoacetate (4 ml, 2.3 equiv) were added to the mixture, and the reaction was stirred for 2 h at room temperature. The reaction mixture was extracted with diethyl ether (3 x 50 ml). The organic fractions were combined and dried over magnesium sulfate, and the solvent was removed by rotary evaporation. The crude product was isolated by flash chromatography (Si02, hexane/ethyl acetate = 8:2) to give a yellow oil. DPA was obtained (Yield: 2.92 g (88%)), and confirmed by NMR (CDC13, 300 MHz): δ 8.33 (ddd, J = 5.0, 1.9, 0.9 Hz; 2H), 7.53 (m, 2H), 7.23 (m, 2H), 6.88 (ddd, J = 7.2, 5.0, 0.9 Hz; 2H), 4.84 (s, 2H), 1.42 (s, 9H). ESI- MS (cation): 286 m/z (M + H+) obsd, 286 m/z calcd.
88%	Stage #1: di(pyridin-2-yl)amine With potassium hydroxide In dimethyl sulfoxide at 20℃; for 16h; Stage #2: bromoacetic acid <i>tert</i>-butyl ester With potassium iodide In dimethyl sulfoxide at 20℃; for 2h;	1 Example 1. Synthesis ofTert-butyl 2-(di(pyridine-2-yl)amino)acetate (DP A). [00144] Example 1. Synthesis ofTert-butyl 2-(di(pyridine-2-yl)amino)acetate (DP A). Tert- butyl 2-(di(pyridme-2-yl)arrrino)acetate was prepared with modification to irin et al, 2007, J. Inorg, Chem., 3686-3694, the entire contents of which are incorporated herein by reference. Potassium hydroxide (3.0 g, 53.6 mmol, 4.6 equiv) was added to a solution of 2,2'- dipyridylamine (2.0 g, 11.7 mmol) in 40 ml DMSO and stirred at room temperature for 16 hours (h). Potassium iodide (200 mg, 1.2 mmol, 0.1 equiv) and ie/f-butyi bromoacetate (4 ml, 2.3 equiv) were added to the mixture, and the reaction was stirred for 2 h at room temperature. The reaction mixture was extracted with diethyl ether (3 x 50 mi). The organic fractions were combined and dried over magnesium sulfate, and the solvent was removed by rotary evaporation. The crude product was isolated by flash chromatography (SiO?, hexane/'ethyl acetate = 8:2) to give a yellow oil. DPA was obtained (Yield: 2.92 g (88%)), and confirmed by " H NMR (CDCI3, 300 MHz): δ 8.33 (ddd, J = 5.0, 1.9, 0.9 Hz: 2H), 7.53 (m, 2H), 7.23 (m, 2H), 6.88 (ddd, J = 7.2, 5.0, 0.9 Hz: 2H), 4.84 (s, 2H), 1.42 (s, 9H). ESI-MS (cation): 286 m/z (M + H+) obsd, 286 m/z calcd.

Reference： [1]Current Patent Assignee: CALIFORNIA INSTITUTE OF TECHNOLOGY - WO2012/155004, 2012, A2 Location in patent: Page/Page column 19
[2]Current Patent Assignee: CALIFORNIA INSTITUTE OF TECHNOLOGY - WO2014/200497, 2014, A1 Location in patent: Paragraph 0060; 00144

58
[ 74-83-9 ]
[ 1202-34-2 ]
[ 123368-97-8 ]

Yield	Reaction Conditions	Operation in experiment
23%	Stage #1: di(pyridin-2-yl)amine With sodium hydride In tetrahydrofuran at 0℃; for 0.25h; Inert atmosphere; Stage #2: methyl bromide In tetrahydrofuran at 20℃; for 18h; Inert atmosphere; Reflux;	4 [00137] Example 4. Synthesis of N-alkyl-N-(pyridin-2-yl)pyridin-2 -amine (MeDPA), EtDPA, PropylDPA, HexylDPA): To a slurry of sodium hydride (70 mg, 2.9 mmol) in THF (10 ml) was added HDP A (500 mg, 2.9 mmol) in 5 ml THF at 0 °C under 1 atm Ar. The reaction was purged with argon for 15 min, and the appropriate 1 -bromomethane (3.8 mmol) was added dropwise and warmed to room temperature. The reaction was stirred an additional 18 h under argon at reflux temperature. The reaction mixture was extracted with dilute sodium bicarbonate, and the aqueous phase was extracted with CH2C12 (3 x 40 ml). The organic fractions were combined and dried over magnesium sulfate, and the solvent was removed in vacuo. MethylDPA was obtained (10 mmol scale, Yield: 0.44 g, 23%), and confirmed by 1H-NMR (CDC13): 8.35 (d of d, 2H); 7.54 (t, 2H); 7.17 (d, 2H); 6.86 (t, 2H), 3.62 (s, 3H). ESI-MS: 186 m/z [M+H]+.
23%	Stage #1: di(pyridin-2-yl)amine With sodium hydride In tetrahydrofuran at 0℃; for 0.25h; Inert atmosphere; Stage #2: methyl bromide In tetrahydrofuran at 0℃; for 18h; Inert atmosphere; Reflux;	4 Example 4. Synthesis ofN-alkyl-N-(pyridin-2-yl)pyridin-2-amine (MeDPA), EtDPA, PropylDPA, HexylDPA) [00147] Example 4. Synthesis ofN-alkyl-N-(pyridin-2-yl)pyridin-2-amine (MeDPA), EtDPA, PropylDPA, HexylDPA): To a slurry of sodium hydride (70 nig, 2.9 mmol) in THF (10 ml) was added HDPA (500 mg, 2.9 mmol) in 5 ml THF at 0 C'C under 1 aim Ar. The reaction was purged with argon for 15 min, and the appropriate 1-bromome hane (3.8 mmol) was added dropwise and warmed to room temperature. The reaction was stirred an additional 18 h under argon at reflux temperature. The reaction mixture was extracted with dilute sodium bicarbonate, and the aqueous phase was extracted with CH2CI2 (3 x 40 ml). The organic fractions were combined and dried over magnesium sulfate, and the solvent was removed in vacuo. MethylDPA was obtained (10 mmol scale, Yield: 0.44 g, 23%), and confirmed by 1H- NMR (CDCI3): 8.35 (d of d, 2H); 7.54 (t, 2H); 7.17 (d, 2H); 6.86 (t, 2H), 3.62 (s, 3H). ESI-MS: 186 m/z [M+H]+.

Reference： [1]Current Patent Assignee: CALIFORNIA INSTITUTE OF TECHNOLOGY - WO2012/155004, 2012, A2 Location in patent: Page/Page column 20
[2]Current Patent Assignee: CALIFORNIA INSTITUTE OF TECHNOLOGY - WO2014/200497, 2014, A1 Location in patent: Paragraph 00147

59
[ 1202-34-2 ]
[Rh(NH₃)4phzi]TFA₃ [ No CAS ]
[Rh(HDPA)2phzi]Cl₃ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
38%	Stage #1: di(pyridin-2-yl)amine; [Rh(NH₃)4phzi]TFA₃ In ethanol at 90℃; for 48h; Inert atmosphere; Stage #2: With magnesium chloride	12 [00149] Example 12. Synthesis of [Rh(HDPA)2phzi]Cl3. A solution of[Rh(NH3)4phzi]TFA3 (53.2 mg, 69.2 μηιο) in ethanol (25 mL) was added to a 100-mL schlenk flask and sparged with argon for 10 min. A solution of HDP A (0.346 mmol) in ethanol (25 mL) was then added and the resulting light yellow solution sparged with argon for an additional 10 min, then subsequently heated to 90° C. The solution was allowed to stir for 48 hours, after which the solvent was evaporated in vacuo and the resulting red solid purified via column chromatography (Cis-derivatized silica, eluting with 12.5% acetonitrile in 0.1% TFA(aq)). The fractions containing product were identified by HPLC, combined, and lyophilized to give a red solid. The chloride salt can be obtained from a Sephadex QAE anion exchange column equilibrated with 0.1M MgCl2. [Rh(HDPA)2phzi]Cl3 was obtained (Yield: 21.5 mg, 38%), and confirmed by NMR (300 MHz, d6-DMSO): δ 7.04 (m, 4H), 7.81 (m, 5H), 7.92 (m, 5H), 8.03 (m, 4H), 8.14 (m, 3H), 8.27 (m, 3H), 8.73 (s, IH), 9.37 (s, IH), 12.65 (s, IH), 13.02 (s, IH). ESI-MS: calc. 701.16 (M-2H+)., obs. 701.1 (M-2H+), 351.3 (M-H2+). UV-Vis (H20, pH 7): 318 nm (44,600 M"1 cm"1), 350 nm (33,200 M"1, cm"1), 400 nm (9,100 M"1, cm"1).

Reference： [1]Current Patent Assignee: CALIFORNIA INSTITUTE OF TECHNOLOGY - WO2012/155004, 2012, A2 Location in patent: Page/Page column 22

60
[ 1202-34-2 ]
[ 31588-18-8 ]
copper(II) tetrafluoroborate monohydrate [ No CAS ]
[Cu(qui)(ambpy)]BF₄ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
70%	In ethanol; water at 20℃;	2.3 Synthesis of [Cu(qui)(bpy)]BF4·H2O (1), [Cu(qui)(phen)]BF4 (2), [Cu(qui)(ambpy)]BF4 (3), [Cu(qui)(mphen)]BF4·H2O (4), [Cu(qui)(nphen)]BF4 (5) and [Cu(qui)(bphen)]BF4 (6) General procedure: To a solution of 2-phenyl-3-hydroxy-4(1H)-quinolinone (237 mg, 1 mmol) in ethanol (50 mL), the corresponding bidentate N-donor ligand (L) (1 mmol) dispersed in EtOH (5 mL) was added while stirring. To this mixture, a solution of Cu(BF4)2·H2O (237 mg, 1 mmol) in H2O (5 mL) was slowly added while stirring. The reaction mixture was stirred at room temperature for a few hours, and subsequently left to stand for several days at room temperature. The obtained solid product was filtered off, washed with a small amount of cold water and ethanol, and dried in the air at 40 °C.

Reference： [1]Buchtik, Roman; Travnicek, Zdenek; Vanco, Jan [Journal of Inorganic Biochemistry, 2012, vol. 116, p. 163 - 171]

61
[ 1202-34-2 ]
copper(II) choride dihydrate [ No CAS ]
[ 93106-60-6 ]
[ 1421369-55-2 ]

Reference： [1]Chemistry and biodiversity,2012,vol. 9,p. 2810 - 2824

62
[ 108-77-0 ]
[ 1202-34-2 ]
[ 348603-47-4 ]

Yield	Reaction Conditions	Operation in experiment
95%	Stage #1: 1,3,5-trichloro-2,4,6-triazine With N-ethyl-N,N-diisopropylamine In tetrahydrofuran Stage #2: di(pyridin-2-yl)amine In tetrahydrofuran at 0℃;
63.2%	Stage #1: di(pyridin-2-yl)amine With n-butyllithium In tetrahydrofuran; hexane for 1h; Schlenk technique; Inert atmosphere; Stage #2: 1,3,5-trichloro-2,4,6-triazine In tetrahydrofuran; hexane at 0 - 20℃; for 4.5h; Schlenk technique; Inert atmosphere;	2.1.2.1. Synthesis of 4,6-dichloro-N,N-di(pyridin-2-yl)-1,3,5-triazin-2-amine (1). 2,2-dipyridylamine (5 g, 29.2 mmol) was placed in aschlenk flask with a stir. Dry THF (50 mL) was injected with a syringeinto the fask under nitrogen atmosphere. Then the solution was cooledin an ice bath and stirred for 30 min. Then, 1.6M n-butyllithium inhexane solution (19.7 mL, 31.5 mmol) was added slowly into thesolution. The mixture was stirred for 1 h at room temperature, and itscolor became yellow slurry. Then, the slurry solution was slowlydropped into a stirred solution of 2,4,6-trichloro-1,3,5-triazine (2.0 g,10.8 mmol) in dry THF (20 mL) at 0 °C for 30 min. After stirring for4 h at room temperature, the mixture was poured into water andextracted with CH2Cl2. The layers were separated, and the organiclayers were collected and dried over anhydrous magnesium sulfate. Thesolvent was removed by rotary evaporation, and the residue waspurified by column chromatography to give a yellow solid (5.3 g,yield 63.2%). 1H NMR (400 MHz, CD2Cl2) δ (ppm) 8.46-8.47 (d,J=8.0, 2H) 7.84-7.89 (t, J=8.0, 2H) 7.50-7.52 (d, J=8.0, 2H)7.29-7.32 (t, J=6.0, 2H)
55%	With N-ethyl-N,N-diisopropylamine In tetrahydrofuran at 0℃; for 1h;

Reference： [1]Wannarit, Nanthawat; Roubeau, Olivier; Youngme, Sujittra; Gamez, Patrick [European Journal of Inorganic Chemistry, 2013, # 5-6, p. 730 - 737]
[2]Park, So-Ra; Kim, Su-Mi; Choi, Yongseon; Lee, Ja Yeon; Lee, Ji-Hoon; Suh, Min Chul [Dyes and Pigments, 2019, vol. 170]
[3]Nassirinia, Nassim; Amani, Saeid; Teat, Simon J.; Roubeau, Olivier; Gamez, Patrick [Chemical Communications, 2014, vol. 50, # 8, p. 1003 - 1005]

63
[ 1202-34-2 ]
copper(II) choride dihydrate [ No CAS ]
[ 530-78-9 ]
[ 1435489-16-9 ]

Yield	Reaction Conditions	Operation in experiment
60%		General procedure: A methanolic (10 mL) solution containing <strong>[530-78-9]flufenamic acid</strong>(0.2 mmol, 52 mg) and KappaOmicronEta (0.2 mmol, 11 mg) after 1 h stirring was added slowly, and simultaneously with a methanolic solution of bipyam (0.2 mmol, 34 mg), to a methanolic solution (10 mL) ofCuCl22H2O (0.2 mmol, 34 mg) and stirred for 15 additional min. Green crystals of [Cu(fluf)(bipyam)Cl] 2 suitable for X-ray structure determination were collected after a week. Yield: 66 mg, 60%. Anal.Calcd. for [Cu(fluf)(bipyam)Cl] (C24H20ClCuF3N4O2) (MW = 552.43):C 52.18, H 3.65, N 10.14; found C 52.29, H 3.34, N 10.04. IR (KBr disk):numax, cm-1; nu asym(CO2): 1590 (vs); nusym(CO2): 1410 (vs); Delta =180 cm-1; UV-vis: lambda, nm(epsilon, M-1 cm-1) as nujol mull: 842(sh), 705,421 (sh), 328, 297; in DMSO: 845(sh) (15), 702 (105), 420 (sh) (180),325 (10,300), 300 (13,500). mueff = 1.98 BM. The complex is soluble in DMF and DMSO (LambdaM = 6 mho cm2 mol-1, in 1 mM DMSO).

Reference： [1]Journal of Inorganic Biochemistry,2013,vol. 123,p. 53 - 65

64
[ 1202-34-2 ]
[ 7732-18-5 ]
[ 6046-93-1 ]
[ 144052-40-4 ]
Cu₂(2,2' dipyidylamine)2(m-xylenediphosphonic acid(-2H))2 [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
90%	With hydrogen fluoride at 135℃; for 48h; High pressure; Heating;	2.13. Synthesis of Cu(2,20 dipyidylamine)(HO3PC8H8PO3H) (13) A solution of copper(II) acetate monohydrate(0.094 g,0.47 mmol), 2,20 dipyridylamine (0.074 g,0.432 mmol),m-xylene diphosphonic acid (0.152 g,0.57 mmol), (10 mL,556 mmol) and HF (500 lL, 14.5 mmol) with the mole ratio of1:0.92:1.2:1183:30.8 was stirred briefly before heating to 135 Cfor 48 h. The initial and final pH values were 1 and 1, respectively.Green rods suitable for X-ray diffraction were isolated in 90% yield.IR (KBr pellet, cm1): 3434(m), 2920(w), 2366(w), 2344(w),1605(m), 1585(w), 1533(w), 1490(s), 1435(m), 1233(w), 1159(s),1122(m), 1100(s), 948(m), 805(w), 765(m), 705(m), 530(w),203(m), 465(w). Anal. Calc. for C36H38Cu2N6O12P4: C, 43.3; H,3.84; N, 8.42. Found: C, 42.7; H, 3.76; N, 8.22%.

Reference： [1]Smith, Tiffany M.; Vargas, Jose; Symester, Diona; Tichenor, Michael; O'Connor, Charles J.; Zubieta, Jon [Inorganica Chimica Acta, 2013, vol. 403, p. 63 - 77]

65
[ 104-92-7 ]
[ 1202-34-2 ]
1-(N,N-bis(2-pyridyl)amino)-4-methoxybenzene [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
65%	With copper(II) sulfate; potassium hydroxide at 180℃; for 6h;	3.3 Synthesis of Compound 3 Synthesis of Compound 3 (0087) Dipyridylamine (5.84 mmol; 1 g), 4-bromoanisole (8.76 mmol; 1.64 g), potassium hydroxide (8.75 mmol; 0.5 g) and copper sulfate (0.18 mmol; 30 mg) as a catalyst were mixed and stirred while being heated at a temperature of 180° C. for 6 hours. After completion of the reaction, the mixture was allowed to cool and chloroform and water were added thereto. After the mixture was washed with water, the solvent was vacuum-distilled on magnesium sulfate thereby obtaining an intended product. The intended product was dissolved in chloroform and refined with a column MeOH/CHCl3 (1/10) thereby producing Compound 3 at a yield of 65%. Compound 3 was identified with NMR.

Reference： [1]Current Patent Assignee: ENEOS HOLDINGS INC; NAGOYA INSTITUTE OF TECHNOLOGY; ENEOS (in: ENEOS Holdings) - US8471018, 2013, B2 Location in patent: Page/Page column 34; 35

66
[ 1202-34-2 ]
[ 98-05-5 ]
[ 6046-93-1 ]
molybdenum(VI) oxide [ No CAS ]
[{Cu(2,2′-dipyridylamine)(H₂O)}₂Mo₆O₁₈(O₃AsC₆H₅)₂] [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
15%	With ammonium fluoride In water at 135℃; for 72h; Autoclave;	2.7 _{RRN 17}Synthesis of [{Cu(2,2′dipyridylamine)(H₂O)}₂Mo₆O₁₈(O₃AsC₆H₅)₂] (6 A solution of MoO3 (0.191 g, 1.33 mmol), copper(II) acetate monohydrate (0.046 g, 0.23 mmol), 2,2′ dipyridylamine (0.041 g, 0.24 mmol), phenylarsonic acid (0.111 g, 0.55 mmol), ammonium fluoride (0.068 g, 1.84 mmol), and H2O (10 mL, 556 mmol) with the mole ratio of 1:0.17:0.18:0.41:1.38:418 was stirred briefly before heating to 135 °C for 72 h. The initial and final pH values were 3 and 3, respectively. Purple rods suitable for X-ray diffraction were isolated in 15% yield. IR (KBr pellet, cm-1): 3429(s), 3097(w), 2919(w), 2373(m), 2344(m), 1654(m), 1646(m), 1626(m), 1560(w), 1476(m), 1458(w), 965(w), 888(s), 773(s), 669(s), 652(s), 592(s). Anal. Calc. for C32H32As2Cu2Mo6N6O26: C, 21.7; H, 1.81; N, 4.75. Found: C, 21.5; H, 1.75; N, 4.62%.

Reference： [1]Smith, Tiffany M.; Strauskulage, Luke; Perrin, Kathryn A.; Zubieta, Jon [Inorganica Chimica Acta, 2013, vol. 407, p. 48 - 57]

67
[ 1202-34-2 ]
[ 42104-58-5 ]
[ 7664-39-3 ]
vanadia [ No CAS ]
[ 6046-93-1 ]
2Cu⁽²⁺⁾*2C₁₀H₉N₃*C₈H₈O₆P₂^(4-)*V₂F₂O₄ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
40%	In water at 120℃; for 96h;	Synthesis of [Cu2(2,20-dpa)2V2F2O4(1,2-O3PC8H8PO3)] (5) A solution of vanadium(V) oxide (0.092 g, 0.51 mmol), copper(II) acetate monohydrate (0.200 g, 1.00 mmol), 2,2’-dipyridylamine(0.152 g, 0.89 mmol), o-xylene-diphosphonic acid (0.116 g,0.43 mmol), H2O (10 mL, 556 mmol) and HF (400 lL, 11.6 mmol)with the mole ratio of 1:1.96:1.75:0.84:1090:22.7 was stirredbriefly before heating to 120 C for 4 days. The initial and finalpH values were 1 and 1, respectively. Green rods suitable for Xraydiffraction were isolated in 40% yield. IR (KBr pellet, cm1):3299(w), 3248(w), 3207(w), 3145(w), 3083(w), 3041(w),2915(w), 1702(w), 1637(s), 1588(m), 1529(s), 1482(s), 1434(m),1232(m), 1160(m), 1087(s), 1052(s), 1026(s), 982(s), 928(s),840(m), 803(w), 785(w), 759(s), 559(m), 513(m), 441(w). Anal.Calc. for C14H13CuFN3O5PV: C, 35.9; H, 2.78; N, 8.98. Found: C,35.8; H, 2.69; N, 8.95%.

Reference： [1]Smith, Tiffany M.; Strauskulage, Luke; Perrin, Kathryn A.; Symester, Diona; Freund, Steven R.; Vargas, Jose; Spinu, Leonard; Zubieta, Jon [Inorganica Chimica Acta, 2014, vol. 411, p. 134 - 147]

68
[ 1202-34-2 ]
vanadia [ No CAS ]
[ 6046-93-1 ]
[ 144052-40-4 ]
2Cu⁽²⁺⁾*2C₁₀H₉N₃*C₈H₈O₆P₂^(4-)*V₂O₅ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
90%	With hydrogen fluoride In water at 135℃; for 48h;	Synthesis of [Cu2(2,2’-dpa)2V2O5(1,3-O3PC8H8PO3)] (2) A solution of vanadium(V) oxide (0.077 g, 0.42 mmol), copper(II) acetate monohydrate (0.207 g, 1.04 mmol), 2,20-dipyridylamine(0.083 g, 0.48 mmol), m-xylene-diphosphonic acid(0.055 g, 0.21 mmol), H2O (5 mL, 278 mmol) and HF (100 lL,2.9 mmol) with the mole ratio of 1:2.48:1.14:0.5:662:6.9 was stirredbriefly before heating to 135 C for 48 h. The initial and final pHvalues were 2 and 2, respectively. Green plates suitable for X-raydiffraction were isolated in 90% yield. IR (KBr pellet, cm1):3929(w), 3241(w), 3187(w), 3131(w), 3075(w), 3011(w),1643(m), 1585(m), 1529(m), 1479(s), 1436(m), 1326(w),1239(m), 1187(s), 1151(m), 1114(m), 1055(m), 989(m), 940(s),865(m), 819(s), 865(m), 819(s), 692(w), 647(w), 583(w), 531(m),433(m). Anal. Calc. for C28H26Cu2N6O11P2V2: C, 36.8; H, 2.85; N,9.20. Found: C, 37.3; H, 3.02; N, 9.18%.

Reference： [1]Smith, Tiffany M.; Strauskulage, Luke; Perrin, Kathryn A.; Symester, Diona; Freund, Steven R.; Vargas, Jose; Spinu, Leonard; Zubieta, Jon [Inorganica Chimica Acta, 2014, vol. 411, p. 134 - 147]

69
[ 1202-34-2 ]
[ 3722-27-8 ]
C₂₆H₄₂N₅⁽³⁺⁾*3Br^(1-) [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
90%	With N-ethyl-N,N-diisopropylamine In dichloromethane at 130℃; for 10h;	Preparation of ionic liquid 1.(Br)₃ A mixed solution of 2,2'-dipyridylamine (10 mmol, 1.71 g) in dichloromethane (4.0 mL), 1-(3-bromopropyl)-1-methylpyrrolidinium bromide salt (25 mmol, 7.2 g), and N,N-diisopropylethylamine (8.0 mL) was heated to 130 °C for 10 h. The reaction mixture was then allowed to cool down to room temperature, followed by the addition of 20 mL acetone. The organic solvent was decanted to obtain an oily mixture. The mixture was then washed with chloroform for several times to remove unreacted starting materials. A pale yellow hygroscopic solid of ionic liquid, 1.(Br)3, was obtained with 90% yield (6.2 g) after dried under vacuum. 1H NMR (400 MHz D2O): δ 2.25 (s, 8H), 2.40-2.62 (m, 4H), 3.09 (s, 6H), 3.43-3.80 (m, 12H), 4.58 (t, 4H, J= 8 Hz), 7.02 (t, 2H, J= 8 Hz), 7.46 (d, 2H, J= 8 Hz), 7.911 (t, 2H, J= 8 Hz), 8.14 (d, 2H, J= 8 Hz); 13C NMR (400 MHz, D2O): δ 21.25, 23.42, 48.13, 50.53, 61.03, 64.64, 114.48, 116.49, 140.98, 143.22, 156.31; ESI-MS m/z: [M -3Br-]3+= 141.5, [M -2Br-]2+= 251.6, 252.6; Elemental analysis: Calcd. for C26H42N5Br3·H2O: C, 47.00; H, 6.37; N, 10.54. Found: C, 47.05; H, 6.40; N, 10.56.

Reference： [1]Wong, Wing-Leung; Lee, Lawrence Yoon Suk; Ho, Kam-Piu; Zhou, Zhong-Yuan; Fan, Ting; Lin, Zhenyang; Wong, Kwok-Yin [Applied Catalysis A: General, 2014, vol. 472, p. 160 - 166]

70
[ 1202-34-2 ]
[ 1005112-71-9 ]
C₃₂H₅₄N₅⁽³⁺⁾*3Br^(1-) [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
80%	With N-ethyl-N,N-diisopropylamine In dichloromethane at 130℃; for 10h;	5 Preparation of ionic liquid 2.(Br)₃ A mixed solution of 2,2'-dipyridylamine (10.3 mmol, 1.8 g) in dichloromethane (4.0 mL), 1-(6-bromohexyl)-1-methylpyrrolidinium bromide salt (22 mmol, 7.4 g), and N,N-diisopropylethylamine (4.0 mL) was heated to 130 °C for 10 h. The reaction mixture was then allowed to cool down to room temperature. After 20 mL of THF was added, the organic solvent was decanted to obtain an oily mixture. The mixture was then washed with acetonitrile for several times to remove unreacted starting materials. A pale yellow hygroscopic solid of ionic liquid, 2.(Br)3, was obtained with 80% yield (6.2 g) after dried under vacuum. 1H NMR (400 MHz D2O): δ 1.39-1.53 (m, 8H), 1.74-1.85 (m, 4H), 1.85-1.94 (m, 4H), 2.15-2.30 (m, 8H), 3.01 (s, 6H), 3.41-3.59 (m, 12H), 4.34-4.38 (t, 4H, J = 7 Hz), 6.88-6.92 (t, 2H, J = 7 Hz), 7.30 (d, 2H, J = 9 Hz), 7.78-7.83 (t, 2H, J = 7 Hz), 8.02 (d, 2H, J = 9 Hz); 13C NMR (400 MHz, D2O): δ 21.21, 22.93, 25.10, 25.29, 28.22, 48.02, 53.35, 63.96, 64.20, 113.53, 115.91, 140.98, 142.19, 155.94; ESI-MS m/z: [M -3Br-]3+ = 169, [M -2Br-]2+ = 293.5, 294.5; Elemental analysis: Calcd. for C32H54N5Br3·H2O: C, 50.14; H, 7.36; N, 9.14. Found: C, 50.22; H, 7.41; N, 9.19.

Reference： [1]Wong, Wing-Leung; Lee, Lawrence Yoon Suk; Ho, Kam-Piu; Zhou, Zhong-Yuan; Fan, Ting; Lin, Zhenyang; Wong, Kwok-Yin [Applied Catalysis A: General, 2014, vol. 472, p. 160 - 166]

71
[ 1202-34-2 ]
manganese(II) chloride tetrahydrate [ No CAS ]
[ 13710-19-5 ]
[Mn₂(μ²-tolf-O,O′)₂(tolf-O,O′)₂(2,2'-bipyridylamine)₂] [ No CAS ]

Reference： [1]Inorganic Chemistry,2014,vol. 53,p. 2040 - 2052

72
[ 1202-34-2 ]
[ 1584141-23-0 ]
[Zn(2-hydroxy-4-methoxybenzophenone-H)₂(2,2'-dipyridylamine)] [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
68%	In methanol at 20℃; for 2h;	Synthesis of [Zn(keto)2(enR)] (2-4 and 6-8) General procedure: A methanolic solution (10 mL) of bipy (1 mmol, 156 mg), phen(1 mmol, 180 mg) or dpamH (1 mmol, 171 mg) was added slowly to a methanolic solution (10 mL) of [Zn(keto)2(H2O)2] (1 or 5) (1 mmol)under stirring at room temperature. The reaction mixture was stirredfor 2 h, reduced in volumeand left for slowevaporation. The pale yellowmicrocrystalline product was filtered off and dried under vacuum.

Reference： [1]Mrkalić, Emina; Zianna, Ariadni; Psomas, George; Gdaniec, Maria; Czapik, Agnieszka; Coutouli-Argyropoulou, Evdoxia; Lalia-Kantouri, Maria [Journal of Inorganic Biochemistry, 2014, vol. 134, p. 66 - 75]

73
[ 1202-34-2 ]
Sodium orthovanadate [ No CAS ]
[ 6046-93-1 ]
[{Cu₂(2,2′-dipyridylamine)₄}V₄O₁₂] [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
50%	With ammonium fluoride In water at 135℃; for 48h; High pressure;	2.1. Synthesis of [{Cu₂(2,2′-dpam)₄}V₄O₁₂] (1) A solution of sodium orthovanadate (0.244g, 1.33mmol), copper(II) acetate monohydrate (0.046g, 0.23mmol), 2,2′-dipyridylamine (0.041g, 0.239mmol), ammonium fluoride (0.050g, 1.35mmol) and H2O (10mL, 556mmol) with the mole ratio of 1:0.17:0.18:1.02:418 was stirred briefly before heating to 135°C for 2days. The initial and final pH values were 8 and 7, respectively. Green blocks suitable for X-ray diffraction were isolated in 50% yield. IR (KBr pellet, cm-1): 3466(w), 3185(w), 3064(w), 2819(w), 1642(m), 1580(m), 1529(m), 1473(s), 1432(m), 1236(m), 1158(m), 1056(w), 952(m), 908(s), 787(s), 641(s).Anal.Calc. for C40H36Cu2N12O12V4: C, 39.7; H, 2.98; N, 13.9. Found: C, 39.6; H, 3.11; N, 13.7%.

Reference： [1]Smith, Tiffany M.; Freund, Steven R.; Lau, Adam; Varges, Jose; Spinu, Leonard; Zubieta, Jon [Inorganica Chimica Acta, 2014, vol. 414, p. 91 - 96]

74
[ 1202-34-2 ]
copper(II) choride dihydrate [ No CAS ]
[ 7732-18-5 ]
sodium adipate [ No CAS ]
C₃₂H₃₄Cu₂N₆O₈*2H₂O [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
75%	In ethanol at 20℃;	Preparation of the copper compound 1 Under aerobic conditions, an ethanolic solution (5 mL) of 2,2'-dipyridylamine (0.052 g, 0.30 mmol) was added, with stirring at room temperature, to an ethanolic solution (3 mL) of CuCl2*2H2O (0.051 g, 0.30 mmol). A pale green precipitate appeared quickly in the green solution; an aqueous solution of sodium adipate (0.2 mol L-1) was then slowly added with stirring until complete dissolution of the precipitate (ca. 10 mL). Slow evaporation of the resulting solution at room temperature afforded green crystals of [Cu2(adp)2(2,2'-dpa)2](H2O)2 (1).

Reference： [1]Setifi, Zouaoui; Setifi, Fatima; Ghazzali, Mohamed; El-Ghozzi, Malika; Avignant, Daniel; Pérez, Olivier; Reedijk, Jan [Polyhedron, 2014, vol. 75, p. 68 - 72]

75
[ 1202-34-2 ]
nickel(II) chloride hexahydrate [ No CAS ]
sodium adipate [ No CAS ]
2Ni⁽²⁺⁾*4C₁₀H₉N₃*C₆H₈O₄^(2-)*2Cl^(1-) [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
68%	In ethanol at 20℃;	Preparation of the copper compound 1 General procedure: Under aerobic conditions, an ethanolic solution (5 mL) of 2,2'-dipyridylamine (0.052 g, 0.30 mmol) was added, with stirring at room temperature, to an ethanolic solution (3 mL) of CuCl2*2H2O (0.051 g, 0.30 mmol). A pale green precipitate appeared quickly in the green solution; an aqueous solution of sodium adipate (0.2 mol L-1) was then slowly added with stirring until complete dissolution of the precipitate (ca. 10 mL). Slow evaporation of the resulting solution at room temperature afforded green crystals of [Cu2(adp)2(2,2'-dpa)2](H2O)2 (1).

Reference： [1]Setifi, Zouaoui; Setifi, Fatima; Ghazzali, Mohamed; El-Ghozzi, Malika; Avignant, Daniel; Pérez, Olivier; Reedijk, Jan [Polyhedron, 2014, vol. 75, p. 68 - 72]

76
[ 1202-34-2 ]
[ 148-04-9 ]
[ 1644640-81-2 ]

Yield	Reaction Conditions	Operation in experiment
84.6%	With zinc(II) nitrate hexahydrate; nitric acid In ethanol; water for 24h;	Preparation of the microcrystalline product Into 100 cm3 of an aqueous solution containing0.74 g (2.5 mmol) of Zn(NO3)2·6H2O, first 5 cm3 of HNO3 solution (c = 1 mol dm-3),then 0.43 g of dipya (2.5 mmol) dissolved in 10 cm3 of an EtOH/H2O mixture (3:1 volumeratio) was added. The pH value of this mixture was 2. Then, 50 cm3 of an aqueous solution ofNa4pyr (0.32 g; 1.25 mmol) was slowly added under stirring. The final pH value was 4. Afterstanding for 24 h, the obtained precipitate was filtered and rinsed with H2O, EtOH and Et2O.Yield: 84.6 %; Anal. Calcd. for C20H15N3O8: C, 56.48; H, 3.55; N, 9.88 %. Found: C, 56.27,H, 3.62, N, 9.91 %; FT-IR (KBr, cm-1): 3470 (bw), 3117 (m), 3097 (m), 3061 (m), 3024 (m),2993 (m), 2920 (w), 1715 (m), 1660 (s), 1604 (s), 1562 (s), 1451 (s), 1311 (w), 1292 (w), 1270(w), 1250 (w), 1170 (m), 1151 (m), 1005 (m), 955 (m), 901 (m), 771 (s), 748 (s), 594 (m), 559(w), 532 (m). The compound was soluble in DMSO but insoluble in H2O and EtOH.

Reference： [1]Poleti, Dejan; Rogan, Jelena; Radovanović, Lidija; Rodić, Marko [Journal of the Serbian Chemical Society, 2014, vol. 79, # 6, p. 637 - 648]

77
[ 1202-34-2 ]
[ 1711-02-0 ]
4-iodo-N,N-di(pyridin-2-yl)benzamide [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
92%	With potassium carbonate In acetonitrile at 85℃; for 12h; Inert atmosphere; Darkness;	2.1 2.2.1 4-iodo-N,N-di(pyridin-2-yl)benzamide (c) In a round-bottom flask under argon, protected from light and equipped with a reflux condenser, were introduced 1.053 g (3.960 mmol, 1 eq.) of 4-iodobenzoyl chloride, 677 mg (3.960 mmol, 1 eq.) of di(pyridin-2-yl)amine and 546 mg (3.960 mmol, 1 eq.) of potassium carbonate (K2CO3). Distilled acetonitrile (50 mL) was added, and the reaction mixture was stirred at 85 °C overnight. The resulting mixture was filtered while hot to remove the salts. During the cooling, colorless crystals grew up in the filtrate, which was evaporated under reduced pressure to obtain 4-iodo-N,N-di(pyridin-2-yl)benzamide c as a white powder; yield 1.460 g (3.641 mmol), 92%.
92%	With potassium carbonate In acetonitrile at 85℃; Inert atmosphere; Darkness;

Reference： [1]Wenzel, Margot; Bigaeva, Emilia; Richard, Philippe; Le Gendre, Pierre; Picquet, Michel; Casini, Angela; Bodio, Ewen [Journal of Inorganic Biochemistry, 2014, vol. 141, p. 10 - 16]
[2]Wenzel, Margot; De Almeida, Andreia; Bigaeva, Emilia; Kavanagh, Paul; Picquet, Michel; Le Gendre, Pierre; Bodio, Ewen; Casini, Angela [Inorganic Chemistry, 2016, vol. 55, # 5, p. 2544 - 2557]

78
[ 67-56-1 ]
[ 1202-34-2 ]
cobalt(II) chloride hexahydrate [ No CAS ]
[ 93106-60-6 ]
[Co(enrofloxacin)₂(2,2'-bipyridylamine)]·4.5MeOH·1.25H₂O [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
60%	With potassium hydroxide; for 0.5h;	General procedure: The methanolic solution (10 mL) of <strong>[93106-60-6]enrofloxacin</strong> (0.4 mmol, 144 mg) and KOH (0.4 mmol, 22 mg) was added, after a 30-min stirring, to a methanolic solution (10 mL) of CoCl2?6H2O (0.2 mmol, 48 mg) followed by the addition of 2 mL of py. The resultant red-orange solution was stirred for 30 min and left for slow evaporation. Orange crystals of [Co(erx)2(py)2]·MeOH·6H2O, 2·MeOH·6H2O (140 mg, yield: 65%) suitable for X-ray structure determination, were collected after twenty days. Anal. Calcd. for [Co(erx)2(py)2]·MeOH·6H2O (C49H68CoF2N8O13) (MW = 1074.04): C 54.80, H 6.38, N 10.43; found C 55.13, H 6.25, N 10.80

Reference： [1]European Journal of Medicinal Chemistry,2014,vol. 86,p. 189 - 201

79
[ 17084-13-8 ]
[ 1202-34-2 ]
[ 578743-87-0 ]
(1,3-bis(2,6-di-iso-propylphenyl)imidazol-2-ylidene) (2,2’-dipyridylamine) copper hexafluorophosphate [ No CAS ]

Reference： [1]Inorganic Chemistry,2014,vol. 53,p. 9181 - 9191
[2]RSC Advances,2019,vol. 9,p. 22417 - 22427
[3]Journal of Organometallic Chemistry,2019,vol. 893,p. 21 - 31

80
[ 1202-34-2 ]
[ 61-68-7 ]
[ 7646-85-7 ]
C₄₀H₃₈N₅O₄Zn [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
65%		General procedure: A methanolic solution (10 mL) of mefenamic acid (0.4 mmol, 97 mg) and KOH (0.4 mmol, 22 mg) after 1 h stirring was added dropwise slowly and simultaneously with a methanolic solution (10 mL) of bipy (0.2 mmol, 31 mg) to a methanolic solution (10 mL) of ZnCl2 (0.2 mmol, 27 mg). The resultant solution was left for slow evaporation. Colorless crystals of [Zn(mef)2(bipy)], 2 (100 mg, 71 %) suitable for X-ray structure determination, were collected after a few days

Reference： [1]Journal of Inorganic Biochemistry,2013,vol. 128,p. 85 - 96

81
[ 1202-34-2 ]
[ 2417-72-3 ]
methyl 4-[bis(pyridin-2-yl)amino]methyl}benzoate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
62%	Stage #1: di(pyridin-2-yl)amine With sodium hydride In N,N-dimethyl-formamide; mineral oil at 20℃; for 0.25h; Stage #2: Methyl 4-(bromomethyl)benzoate In N,N-dimethyl-formamide; mineral oil at 90℃; for 1h; Inert atmosphere;	NaH (83mg, 2.l8mmol) was added to 2,2’-dipyridylamine, 2 (373mg, 2.l8mmol) in DMF (5mL) at rt. After 15 mm, methyl-4-(bromomethyl)benzoate (1) (500mg,2.l8mmol) was added, and the reaction mixture was subsequently stirred at 90°C for lh under Ar(g). Once cooled to rt, the reaction mixture was poured onto brine (50mL) and extracted twice with EtOAc (2 x 25mL). The organic phases were combined, dried over MgSO4, filtered, and subsequently concentrated in vacuo. The resulting residue was purified by silica gel column chromatography withhexanes/EtOAc (4:1) to furnish 3 as a white solid (429mg, 62%). LCMS (ES): found 319.9 [M+H].
62%	Stage #1: di(pyridin-2-yl)amine With sodium hydride In N,N-dimethyl-formamide at 20℃; for 0.25h; Stage #2: Methyl 4-(bromomethyl)benzoate In N,N-dimethyl-formamide at 90℃; for 1h; Inert atmosphere;	A NaH (83mg, 2.18mmol) was added to 2,2'-dipyridylamine, 2 (373mg, 2.18mmol) in DMF (5ml_) at rt. After 15 min, methyl-4-(bromomethyl)benzoate (1 ) (500mg, 2.18mmol) was added, and the reaction mixture was subsequently stirred at 90°C for 1 h under Ar(g). Once cooled to rt, the reaction mixture was poured onto brine (50m L) and extracted twice with EtOAc (2 x 25m L). The organic phases were combined, dried over MgS04, filtered, and subsequently concentrated in vacuo. The resulting residue was purified by silica gel column chromatography with hexanes/EtOAc (4: 1 ) to furnish 3 as a white solid (429mg, 62%). LCMS (ES): found 319.9 [M+H]+.
62%	Stage #1: di(pyridin-2-yl)amine With sodium hydride In N,N-dimethyl-formamide at 20℃; for 0.25h; Stage #2: Methyl 4-(bromomethyl)benzoate In N,N-dimethyl-formamide at 90℃; for 1h; Inert atmosphere;	A Example A (0198) -[Bis(pyridin-2-yl)amino]methyl}-N-hydroxybenzamide Example A (0198) -[Bis(pyridin-2-yl)amino]methyl}-N-hydroxybenzamide (0199) (0200) A (0201) NaH (83mg, 2.18mmol) was added to 2,2'-dipyridylamine, (2) (373mg, 2.18mmol) in DMF (5ml_) at rt. After 15min, methyl-4-(bromomethyl)benzoate (1) (500mg, 2.18mmol) was added, and the reaction mixture was subsequently stirred at 90°C for 1 h under Ar(g). Once cooled to rt, the reaction mixture was poured onto brine (50ml_) and extracted with EtOAc (2 x 25ml_). The organic phases were combined, dried over MgS04, filtered and subsequently concentrated in vacuo. The resulting residue was purified by silica gel column chromatography with hexane/EtOAc (4:1) to furnish (3) as a white solid (429mg, 62%).

Reference： [1]Current Patent Assignee: KARUS THERAPEUTICS LIMITED - WO2014/181137, 2014, A1 Location in patent: Page/Page column 23
[2]Current Patent Assignee: KARUS THERAPEUTICS LIMITED - WO2017/29514, 2017, A1 Location in patent: Page/Page column 48
[3]Current Patent Assignee: KARUS THERAPEUTICS LIMITED - WO2017/208032, 2017, A1 Location in patent: Page/Page column 28

82
[ 1202-34-2 ]
[ 55243-02-2 ]
2,7-bis(di-2-pyridinyl)-1,8-naphthyridine [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
68%	With 1,3-bis-(diphenylphosphino)propane; caesium carbonate; palladium dichloride In N,N-dimethyl-formamide at 120℃; for 48h; Inert atmosphere;	Preparation of 2,7-bis(di-2-pyridinyl)-1,8-naphthyridine (1) A mixture of 2,2'-dipyridinylamine (0.38 g, 2.2 mmol), 2,7-dichloro-1,8-naphthyridine (0.2 g, 1 mmol), Cs2CO3 (0.82 g,2.5 mmol), PdCl2 (4 mg, 0.02 mmol) and 1,2-bis(diphenylphosphino)propane (16 mg, 0.04 mmol) in DMF (5 mL) was heated at 120 C for 48 h. After cooling, water (10 mL) was added and the mixture was extracted with CH2Cl2 (20 mL 3). The extracts were combined, dried over MgSO4 and concentrated. The residue was chromatographied on silica gel with elution of CH2Cl2/ether (v:v 1:2). After concentration, the desired compound 1 was obtained as yellow solids (0.32 g, 68%): 1H NMR (400 MHz, CDCl3): d 8.35 (d, J 5.6 Hz,4H, Py-H), 7.87 (d, J 8.8 Hz, 2H, Naph-H), 7.64 (t, J 6.0 Hz, 4H, Py-H), 7.23 (d, J 8.8 Hz, 4H, Py-H), 7.18 (ddd, J 8.6, 8.2,1.8 Hz, 4H, Py-H), 7.03 (d, J 8.8 Hz, 2H, Naph-H).13C NMR (100 MHz, CDCl3):d 158.4, 156.5, 155.2, 148.6, 137.7, 137.1, 120.1, 119.7, 117.0, 116.3. ESIMS:m/z calcd. for 469.18C28H21N8 ([M H]), found 469.30. Anal.Calcd for C28H20N8: C, 71.78; H, 4.30; N, 23.92. Found:C, 71.52; H,4.47; N, 23.64.

Reference： [1]Tang, Wei-Hung; Liu, Yi-Hung; Peng, Shie-Ming; Liu, Shiuh-Tzung [Journal of Organometallic Chemistry, 2014, vol. 775, p. 94 - 100]

83
[ 109-04-6 ]
[ 1202-34-2 ]
[ 10428-50-9 ]

Yield	Reaction Conditions	Operation in experiment
54%	With copper(l) iodide; potassium phosphate monohydrate In N,N-dimethyl-formamide at 130℃; for 24h; Inert atmosphere;	Tris(2-pyridinyl)amine A mixture of 2-bromopyridine (90 mg, 0.57 mmol), 2,2'-dipyridinylamine (80 mg, 0.47 mmol), K3PO4.H2O (0.32 g, 1.4 mmol) and CuI (9 mg, 0.05 mmol) in DMF (5 mL) was heated at 130 C for 24 h. After cooling, water (10 mL) was added and the mixture was extracted with CH2Cl2 (20 mL 3). The extracts were dried over MgSO4 and concentrated. The residue was chromatographied on silica gel with elution of hexane/ethyl acetate (v:v 4:1). After concentration, the desired compound was obtained as brown solids(76 mg, 54%). The spectral data is essentially identical to the literaturereported. 1H NMR (400 MHz, CDCl3): d 8.36 (br, 3H, Py-H), 7.60 (br, 3H, Py-H), 7.03 (br, 3H, Py-H), 6.97 (br, 3H, Py-H). 13CNMR (100 MHz, CDCl3): d 157.4, 148.9,137.8, 119.4, 118.6. ESI-HRMS:m/z calcd. for 249.1140C15H13N4 ([M H]), found 249.1136.

Reference： [1]Tang, Wei-Hung; Liu, Yi-Hung; Peng, Shie-Ming; Liu, Shiuh-Tzung [Journal of Organometallic Chemistry, 2014, vol. 775, p. 94 - 100]

84
[ 1202-34-2 ]
[ 3030-47-5 ]
[(N,N,N′,N″,N″-pentamethyldiethylenetriamine)Na(2,2′-dipyridylamide)]2 [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
81%	Stage #1: di(pyridin-2-yl)amine With butylsodium In hexane for 0.75h; Inert atmosphere; Schlenk technique; Stage #2: N,N,N',N'',N'''-pentamethyldiethylenetriamine In hexane at -30℃; for 24h; Inert atmosphere; Schlenk technique;

Reference： [1]Armstrong, David R.; Brouillet, Etienne V.; Kennedy, Alan R.; Garden, Jennifer A.; Granitzka, Markus; Mulvey, Robert E.; Trivett, Joshua J. [Dalton Transactions, 2014, vol. 43, # 38, p. 14409 - 14423]

85
[ 1202-34-2 ]
[ 3033-62-3 ]
[(N,N,N′,N′-tetramethyldiaminoethylether)Na(2,2′-dipyridylamide)]2 [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
37%	Stage #1: di(pyridin-2-yl)amine With butylsodium In hexane for 1h; Inert atmosphere; Schlenk technique; Stage #2: Bis<2-(N,N-dimethylamino)aethyl>aether In hexane at -30℃; for 48h; Inert atmosphere; Schlenk technique;

Reference： [1]Armstrong, David R.; Brouillet, Etienne V.; Kennedy, Alan R.; Garden, Jennifer A.; Granitzka, Markus; Mulvey, Robert E.; Trivett, Joshua J. [Dalton Transactions, 2014, vol. 43, # 38, p. 14409 - 14423]

86
[ 1202-34-2 ]
2C₈H₇O₃^(1-)*Zn⁽²⁺⁾*2H₂O [ No CAS ]
[Zn(3-OCH₃-salo)₂(2,2'-dipirydylamine)] [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
67.4%	In methanol at 20℃; for 2h;	2.4.2. Synthesis of [Zn(3-OCH₃-salo)₂(enR)] (2-5) General procedure: A methanolic solution (10 mL) of the enR base was added slowly to a methanolic solution (10 mL) of [Zn(3-OCH3-salo)2(H2O)2] (1) (1 mmol, 403.4 mg) under stirring at room temperature. The reaction mixture was stirred for 2 h, reduced in volume and left for slow evaporation. A pale yellow microcrystalline product was formed, filtered off and air-dried in every case.

Reference： [1]Anastasiadou, Despoina; Zianna, Ariadni; Gdaniec, Maria; Sigalas, Michael P.; Coutouli-Argyropoulou, Evdoxia; Czapik, Agnieszka; Lalia-Kantouri, Maria [Polyhedron, 2014, vol. 87, p. 275 - 285]

87
[ 1202-34-2 ]
2C₈H₇O₃^(1-)*Zn⁽²⁺⁾*2H₂O [ No CAS ]
C₂₆H₂₃N₃O₆Zn [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
67.4%	In methanol at 20℃; for 2h;	6 2.4.2. Synthesis of [Zn(3-OCH₃-salo)₂(enR)] (2-5) General procedure: A methanolic solution (10 mL) of the enR base was added slowly to a methanolic solution (10 mL) of [Zn(3-OCH3-salo)2(H2O)2] (1) (1 mmol, 403.4 mg) under stirring at room temperature. The reaction mixture was stirred for 2 h, reduced in volume and left for slow evaporation. A pale yellow microcrystalline product was formed, filtered off and air-dried in every case.

Reference： [1]Anastasiadou, Despoina; Zianna, Ariadni; Gdaniec, Maria; Sigalas, Michael P.; Coutouli-Argyropoulou, Evdoxia; Czapik, Agnieszka; Lalia-Kantouri, Maria [Polyhedron, 2015, vol. 87, p. 275 - 285]

88
[ 67-56-1 ]
[ 1202-34-2 ]
copper(II) choride dihydrate [ No CAS ]
[ 13710-19-5 ]
[Cu(tolfenamate)₂(2,2′-bipyridylamine)]·0.5MeOH [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
60%		General procedure: A methanolic (20 mL) solution containing tolfenamic acid (0.4 mmol,104 mg) and KOH (0.4 mmol, 22 mg) after 1 h stirring was added slowlyand simultaneouslywith a methanolic solution of bipy (0.4 mmol, 62mg)to a methanolic solution (5 mL) of CuCl2·2H2O (0.4 mmol, 68mg) andstirred for 15 min. Green crystals of [Cu(tolf-O,O?)(bipy)Cl] 1 (80 mg,65%) suitable for X-ray structure determination were collected after a week.Complexes 2-4 were prepared in a similar way. More specifically,Htolf (0.8 mmol, 208 mg) was dissolved in methanol (20 mL) and KOH(0.8 mmol, 44 mg) was added. After 1 h stirring, the solution was addedslowly to a methanolic solution (5 mL) of CuCl2·2H2O (0.4 mmol,68 mg) followed by the addition of a methanolic solution (5 mL) of bipy(0.4 mmol, 62 mg) for 2, bipyam (0.4 mmol, 68 mg) for 3 and phen(0.4mmol, 72 mg) for 4 andwas stirred for 30 min. Dark greenmicrocrystallineproduct of [Cu(tolf-O,O?)2(bipy)], 2 (97 mg, 70%) was collectedafter five days. Green crystals of [Cu(tolf-O,O?)2(bipyam)]·0.5MeOH,3·0.5MeOH (95 mg, 60%) suitable for X-ray structure determination,were deposited after two weeks. Dark green crystals of [Cu(tolf-O,O?)(tolf-O)(phen)(MeOH)], 4 (95 mg, 60%) suitable for X-ray structure determination, were deposited after three days.

Reference： [1]Journal of Inorganic Biochemistry,2015,vol. 149,p. 68 - 79

Purity	Size	Price	VIP Price	USA Stock *0-1 Day	Global Stock *5-7 Days	Quantity
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CAS No. :	1202-34-2	MDL No. :	MFCD00006247
Formula :	C₁₀H₉N₃	Boiling Point :	-
Linear Structure Formula :	-	InChI Key :	HMMPCBAWTWYFLR-UHFFFAOYSA-N
M.W :	171.20	Pubchem ID :	14547
Synonyms :

Num. heavy atoms :	13
Num. arom. heavy atoms :	12
Fraction Csp3 :	0.0
Num. rotatable bonds :	2
Num. H-bond acceptors :	2.0
Num. H-bond donors :	1.0
Molar Refractivity :	51.58
TPSA :	37.81 Å²

GI absorption :	High
BBB permeant :	Yes
P-gp substrate :	No
CYP1A2 inhibitor :	Yes
CYP2C19 inhibitor :	No
CYP2C9 inhibitor :	No
CYP2D6 inhibitor :	No
CYP3A4 inhibitor :	No
Log Kp (skin permeation) :	-5.93 cm/s

Log Po/w (iLOGP) :	1.2
Log Po/w (XLOGP3) :	1.99
Log Po/w (WLOGP) :	2.22
Log Po/w (MLOGP) :	0.97
Log Po/w (SILICOS-IT) :	1.71
Consensus Log Po/w :	1.62

[ CAS No. 1202-34-2 ] {[proInfo.proName]}

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Physicochemical Properties

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Druglikeness

Water Solubility

Medicinal Chemistry

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Application In Synthesis of [ 1202-34-2 ]

[ 1202-34-2 ] Synthesis Path-Downstream 1~88

Precautionary Statements-General

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Lipinski :	0.0
Ghose :	None
Veber :	0.0
Egan :	0.0
Muegge :	1.0
Bioavailability Score :	0.55

Log S (ESOL) :	-2.71
Solubility :	0.337 mg/ml ; 0.00197 mol/l
Class :	Soluble
Log S (Ali) :	-2.41
Solubility :	0.666 mg/ml ; 0.00389 mol/l
Class :	Soluble
Log S (SILICOS-IT) :	-4.21
Solubility :	0.0104 mg/ml ; 0.000061 mol/l
Class :	Moderately soluble

PAINS :	0.0 alert
Brenk :	0.0 alert
Leadlikeness :	1.0
Synthetic accessibility :	2.07

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:

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P309	IF exposed or if you feel unwell:
P310	Immediately call a POISON CENTER or doctor/physician.
P311	Call a POISON CENTER or doctor/physician.
P312	Call a POISON CENTER or doctor/physician if you feel unwell.
P313	Get medical advice/attention.
P314	Get medical advice/attention if you feel unwell.
P315	Get immediate medical advice/attention.
P320
P302 + P352	IF ON SKIN: wash with plenty of soap and water.
P321
P322
P330	Rinse mouth.
P331	Do NOT induce vomiting.
P332	IF SKIN irritation occurs:
P333	If skin irritation or rash occurs:
P334	Immerse in cool water/wrap n wet bandages.
P335	Brush off loose particles from skin.
P336	Thaw frosted parts with lukewarm water. Do not rub affected area.
P337	If eye irritation persists:
P338	Remove contact lenses, if present and easy to do. Continue rinsing.
P340	Remove victim to fresh air and keep at rest in a position comfortable for breathing.
P341	If breathing is difficult, remove victim to fresh air and keep at rest in a position comfortable for breathing.
P342	If experiencing respiratory symptoms:
P350	Gently wash with plenty of soap and water.
P351	Rinse cautiously with water for several minutes.
P352	Wash with plenty of soap and water.
P353	Rinse skin with water/shower.
P360	Rinse immediately contaminated clothing and skin with plenty of water before removing clothes.
P361	Remove/Take off immediately all contaminated clothing.
P362	Take off contaminated clothing and wash before reuse.
P363	Wash contaminated clothing before reuse.
P370	In case of fire:
P371	In case of major fire and large quantities:
P372	Explosion risk in case of fire.
P373	DO NOT fight fire when fire reaches explosives.
P374	Fight fire with normal precautions from a reasonable distance.
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.
P381	Eliminate all ignition sources if safe to do so.
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
Code	Phrase
P401
P402	Store in a dry place.
P403	Store in a well-ventilated place.
P404	Store in a closed container.
P405	Store locked up.
P406	Store in corrosive resistant/ container with a resistant inner liner.
P407	Maintain air gap between stacks/pallets.
P410	Protect from sunlight.
P411
P412	Do not expose to temperatures exceeding 50 oC/ 122 oF.
P413
P420	Store away from other materials.
P422
P402 + P404	Store in a dry place. Store in a closed container.
P403 + P233	Store in a well-ventilated place. Keep container tightly closed.
P403 + P235	Store in a well-ventilated place. Keep cool.
P410 + P403	Protect from sunlight. Store in a well-ventilated place.
P410 + P412	Protect from sunlight. Do not expose to temperatures exceeding 50 oC/122oF.
P411 + P235	Keep cool.
Disposal
Code	Phrase
P501	Dispose of contents/container to ...
P502	Refer to manufacturer/supplier for information on recovery/recycling