* All experimental methods are cited from the reference, please refer to the original source for details. We do not guarantee the accuracy of the content in the reference.
A mixture of 350 mg of 2,2’-Bipyridine N,N-dioxide and 630 mg Pd/C (5percent) in 38mL of ethanol was purged with N2 gas. The suspension was then heated to reflux under nitrogen and, after the complex was completely dissolved, 2.7mL of hydrazine hydrate in 10 mL ethanol was added dropwise over a period of 20 min. The resulting solution was held at reflux for 15 h. When completed, the mixture was immediately filtered under reduced pressure, and washed with boiling ethanol. After removal of the solvent, the yellow precipitate was ground in 20 mL of water and left at 2 °C overnight. The white solid that separated was vacuum filtered, washed with cold water and dried at 50 °C. Yield: 195 mgof white powder (83percent).
Reference：
[1] Chemical Communications, 1999, # 24, p. 2521 - 2522
[2] New Journal of Chemistry, 2001, vol. 25, # 12, p. 1553 - 1566
[3] RSC Advances, 2016, vol. 6, # 20, p. 16482 - 16488
[4] European Journal of Inorganic Chemistry, 2014, vol. 2014, # 31, p. 5322 - 5330
[5] Dalton Transactions, 2004, # 24, p. 4130 - 4138
[6] New Journal of Chemistry, 2018, vol. 42, # 19, p. 16183 - 16192
[7] Journal of Organometallic Chemistry, 2015, vol. 791, p. 175 - 182
[8] Journal of the American Chemical Society, 1958, vol. 80, p. 2745,2747
[9] Tetrahedron Letters, 2004, vol. 45, # 1, p. 121 - 123
[10] Synlett, 2011, # 2, p. 223 - 226
[11] European Journal of Inorganic Chemistry, 2016, vol. 2016, # 10, p. 1470 - 1479
[12] Patent: CN104478922, 2017, B, . Location in patent: Paragraph 0069; 0072
2
[ 1762-41-0 ]
[ 18511-69-8 ]
Reference：
[1] Journal of the Chemical Society, Perkin Transactions 2: Physical Organic Chemistry (1972-1999), 1996, # 4, p. 613 - 618
3
[ 7275-43-6 ]
[ 18511-69-8 ]
Reference：
[1] Tetrahedron Letters, 2004, vol. 45, # 1, p. 121 - 123
[2] Synlett, 2011, # 2, p. 223 - 226
[3] European Journal of Inorganic Chemistry, 2016, vol. 2016, # 10, p. 1470 - 1479
[4] Patent: CN104478922, 2017, B,
[5] New Journal of Chemistry, 2018, vol. 42, # 19, p. 16183 - 16192
4
[ 366-18-7 ]
[ 18511-69-8 ]
Reference：
[1] Spectrochimica Acta - Part A: Molecular and Biomolecular Spectroscopy, 2009, vol. 72, # 5, p. 1117 - 1121
[2] Synlett, 2011, # 2, p. 223 - 226
[3] Journal of Organometallic Chemistry, 2015, vol. 791, p. 175 - 182
[4] European Journal of Inorganic Chemistry, 2016, vol. 2016, # 10, p. 1470 - 1479
[5] Patent: CN104478922, 2017, B,
5
[ 14432-12-3 ]
[ 18511-69-8 ]
Reference：
[1] Beilstein Journal of Organic Chemistry, 2014, vol. 10, p. 814 - 824
6
[ 638352-65-5 ]
[ 18511-69-8 ]
Reference：
[1] Beilstein Journal of Organic Chemistry, 2014, vol. 10, p. 814 - 824
7
[ 18511-69-8 ]
[ 1189458-67-0 ]
Yield
Reaction Conditions
Operation in experiment
36%
With pyridine hydrofluoride; sodium nitrite In toluene at -4 - 20℃; for 18 h; Inert atmosphere
To a mixture of 4,4′-diamino-2,2′-bipyridine (7h)(2.00 g, 10.7 mmol), hydrogen fluoride-pyridine (65percentHF, 31.5 g, 1.02 mol), and toluene (30 mL) ina polyethylene cup equipped with a poly(tetrafluoroethylene) coated magnetic stir bar was addedsodium nitrite (1.85 g, 26.8 mmol, 2.5 equiv) at −4 °C. The mouth of the reaction vessel was coveredwith polyethylene wrapping and the reaction mixture was stirred for 18 hours at room temperature.After the pyridine layer was separated from the reaction mixture with a pipette, the separated layerwas basified with aqueous sodium hydroxide until the pH reached 10 and then filtered. The filtratewas extracted with ethyl acetate and the combined organic layer was dried over anhydrous sodiumsulfate. Evaporation of the solvent and sublimation of the residue in vacuo afforded 7d (0.752 g,36percent). 7d: colorless needles. 1H NMR (300 MHz, CDCl3) δ 8.64 (dd, J = 8.4 Hz, 5.4 Hz, 2H), 8.18(dd, J = 9.9 Hz, 2.4 Hz, 2H), 7.08 (ddd, J = 7.8 Hz, 5.4 Hz, 2.4 Hz, 2H). 19F NMR (283 MHz,CDCl3) δ −111.68 to −111.59 (m).Synthesis
With hydrazine hydrate In ethanol for 8h; Heating;
100%
With hydrazine hydrate In ethanol for 8h; Heating;
78%
With palladium 10% on activated carbon; hydrazine hydrate In ethanol for 12h; Inert atmosphere; Reflux;
75%
Stage #1: 4,4'-dinitro-2,2'-bipyridyl-N,N'-dioxide With palladium 10% on activated carbon In ethanol Inert atmosphere; Reflux;
Stage #2: With hydrazine hydrate In ethanol for 15h; Inert atmosphere; Reflux;
69%
With hydrazine hydrate In ethanol for 8h; Heating;
57%
Stage #1: 4,4'-dinitro-2,2'-bipyridyl-N,N'-dioxide With palladium 10% on activated carbon In ethanol Inert atmosphere; Reflux;
Stage #2: With hydrazine hydrate In ethanol Inert atmosphere; Reflux;
2.2.3. 4,4'-diamino-2,2'-bipyridine [19]
A mixture of 4,4'-dinitro-2,2'-bipyridine-N,N'-dioxide (1.50 g,5.4 mmol) and Pd/C (10%, 1.50 g) in ethanol (180 mL) was purgedwith N2 gas. The suspension was heated and refluxed under nitrogenand after the complex was completely dissolved, hydrazinehydrate (13 mL, 0.4 mol) in ethanol (45 mL) was added dropwiseover a period of 1 h. The resulting solution was refluxed for 15 h,filtered through a Celite bed while still hot, and washed with hotethanol (4 45 mL). After removal of the solvent water (120 mL)was poured on the yellow precipitate and left overnight at 2 °C.While the yellow precipitate dissolved, a white solid appeared,which was filtered, washed with cold water and dried at 50 °C toyield 0.57 g (57%) of the desired 4,4'-diamino-2,2'-bipyridineligand. M.p. >250 °C. 1H NMR (300 MHz, DMSO-d6, 25 °C): δ 8.03(d, 2H), d 7.54 (d, 2H), d 6.45 (dd, 2H), d 6.02 (s, 4H).
54%
Stage #1: 4,4'-dinitro-2,2'-bipyridyl-N,N'-dioxide With palladium 10% on activated carbon In ethanol Inert atmosphere; Reflux;
Stage #2: With hydrazine hydrate In ethanol for 16h; Reflux;
53%
With hydrazine hydrate; 5%-palladium/activated carbon for 15h; Inert atmosphere; Reflux;
5,6-diamino-1,10-phenanthrolin
A mixture of 350 mg of 2,2’-Bipyridine N,N-dioxide and 630 mg Pd/C (5%) in 38mL of ethanol was purged with N2 gas. The suspension was then heated to reflux under nitrogen and, after the complex was completely dissolved, 2.7mL of hydrazine hydrate in 10 mL ethanol was added dropwise over a period of 20 min. The resulting solution was held at reflux for 15 h. When completed, the mixture was immediately filtered under reduced pressure, and washed with boiling ethanol. After removal of the solvent, the yellow precipitate was ground in 20 mL of water and left at 2 °C overnight. The white solid that separated was vacuum filtered, washed with cold water and dried at 50 °C. Yield: 195 mgof white powder (83%).
With iron; acetic acid
With hydrazine hydrate In ethanol for 15h; Heating;
With 10% palladium on activated charcoal; hydrazine In ethanol
With palladium 10% on activated carbon In ethanol Heating;
With palladium 10% on activated carbon; hydrazine hydrate In ethanol at 78℃; for 15h; Inert atmosphere;
2.3 Example 2
3. Add 120 g of 1.1 g (0.30 mol) of 4,4'-dinitro-2,2'-bipyridyl-N,N'-dioxide, 1.0 g of 10% Pd/C under an inert atmosphere. Ethanol was dissolved by heating, and a mixed solution containing 8.6 mL of hydrazine hydrate (80%) and 30 mL of ethanol was added dropwise, and the mixture was refluxed at 78° C. for 15 h. The mixture was filtered while hot, the filter cake was washed with hot ethanol, and the filtrate was suspended to remove the solvent to give a yellow powder. Recrystallize from 5 mL of double distilled water to give a white needle. That is BipyNH2.
6 Ruthenium tris(4,4'-diamino-2,2'-bipyridine)
Example 6 Ruthenium tris(4,4'-diamino-2,2'-bipyridine) 4,4'-diamino-2,2'-bipyridine [BiPy(di-amino)] (5.21 g, 28.02 mmol)(Carbosynth) was dissolved in 35 mL of ethylene glycol, followed by RuCl3.3H2O (1.22 g, 4.67 mmol). The reaction mixture was refluxed for 80 hours at 190-200° C. It was then cooled to RT and transferred to a 500 mL beaker. Na2S2O4 solution (7.2 g Na2S2O4 in 150 mL water) was dripped to reaction mixture over a period of a half hour. The reaction mixture in the beaker was cooled in an ice bath for 1.5 hours. The solid product was collected by vacuum filtration and washed with deionized water (3*20 mL), refrigerated methanol (10 mL), and diethyl ether (120 mL) respectively. The black powder, ruthenium tris(4,4'-diamino-2,2'-bipyridine), was collected and dried in a vacuum oven at 60° C. for 24 hours. (product: 2.79, yield: 73%) and its spectra are: ESI: C30H30N12Ru Calc. 660. found Mol Wt. 660.
With pyridine hydrofluoride; sodium nitrite; In toluene; at -4 - 20℃; for 18h;Inert atmosphere;
To a mixture of 4,4?-diamino-2,2?-bipyridine (7h)(2.00 g, 10.7 mmol), hydrogen fluoride-pyridine (65%HF, 31.5 g, 1.02 mol), and toluene (30 mL) ina polyethylene cup equipped with a poly(tetrafluoroethylene) coated magnetic stir bar was addedsodium nitrite (1.85 g, 26.8 mmol, 2.5 equiv) at -4 C. The mouth of the reaction vessel was coveredwith polyethylene wrapping and the reaction mixture was stirred for 18 hours at room temperature.After the pyridine layer was separated from the reaction mixture with a pipette, the separated layerwas basified with aqueous sodium hydroxide until the pH reached 10 and then filtered. The filtratewas extracted with ethyl acetate and the combined organic layer was dried over anhydrous sodiumsulfate. Evaporation of the solvent and sublimation of the residue in vacuo afforded 7d (0.752 g,36%). 7d: colorless needles. 1H NMR (300 MHz, CDCl3) delta 8.64 (dd, J = 8.4 Hz, 5.4 Hz, 2H), 8.18(dd, J = 9.9 Hz, 2.4 Hz, 2H), 7.08 (ddd, J = 7.8 Hz, 5.4 Hz, 2.4 Hz, 2H). 19F NMR (283 MHz,CDCl3) delta -111.68 to -111.59 (m).Synthesis
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