* 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.
With caesium carbonate; In N,N-dimethyl-formamide; at 20℃;
Step 1: Ethyl 2-(6-(4-chloropyridin-2-yloxy)- 1 -hydroxy-4-methyl- 1 ,3- dihydrobenzo[c] [1,2] oxaborol-3-yl) acetate[0523] To a mixture of ethyl 2-(l ,6-dihydroxy-4-methyl-l ,3- dihydrobenzo[c][l,2]oxaborol-3-yl)acetate (2 g, 8 mmol, 1 eq.) and 4-chloro-2- nitropyridine (2.53 g, 16 mmol, 2 eq.) in 50 ml DMF was added cesium carbonate (7.8 g, 24 mmol, 3 eq.). The reaction was stirred at room temperature overnight. It was then quenched by water, extracted with EtOAc, washed with brine, dried over Na2SO4, and concentrated under reduced pressure. The crude was purified by column chromatography on silica gel (DCM/methanol = 19:1 to 4:1) to give desired product as light yellow oil. MS (ESI) m/z = 721 [2M-H]+.
9-methyl-9H-pyrrolo[2,3-b:4,5-c’]dipyridin-2-amine[ No CAS ]
C16H12N6O2[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
100%
With palladium diacetate; caesium carbonate; 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene; In 1,4-dioxane; at 120℃; for 4h;Inert atmosphere;
1 ,4-Dioxane (20 mL) was degassed for 10 minutes with argon. Then palladium(ll)-acetate (0.017 g, 0.076 mmol) and 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene (0.131 g, 0.227 mmol) were added. The suspension was then heated at 110C for 2 minutes. Then the title compound from Preparative Example 21 (0.150 g, 0.757 mmol), <strong>[65370-42-5]4-chloro-2-nitropyridine</strong> (0.168 g, 1.059 mmol) and cesium carbonate (0.740 g, 2.270 mmol) were added and the stirring was continued at 120C for 4 hours. Water was added and the solid was filtered. The solid was washed with water and dried to afford the title compound (0.246 g, quant.).MS (ESI); m/z = 320.81 [M+H]+
100%
With palladium diacetate; caesium carbonate; 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene; In 1,4-dioxane; at 120℃; for 4h;Inert atmosphere;
(1027) Step A (1028) 1,4-Dioxane (20 mL) was degassed for 10 minutes with argon. Then palladium(II)-acetate (0.017 g, 0.076 mmol) and 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene (0.131 g, 0.227 mmol) were added. The suspension was then heated at 110 C. for 2 minutes. Then the title compound from Preparative Example 21 (0.150 g, 0.757 mmol), <strong>[65370-42-5]4-chloro-2-nitropyridine</strong> (0.168 g, 1.059 mmol) and cesium carbonate (0.740 g, 2.270 mmol) were added and the stirring was continued at 120 C. for 4 hours. Water was added and the solid was filtered. The solid was washed with water and dried to afford the title compound (0.246 g, quant.). (1029) MS (ESI); m/z=320.81 [M+H]+.
With sodium hydrogen sulfide; In N,N-dimethyl-formamide; at 50℃;
4-chloro-2-nitro-pyridine (5000 mg, 31.54 mmol) and NaHS (2122 mg, 37.84 mmol) were dissolvent in DMF (50 mL). Then it was stirred at 50C overnight. Aq NaOH (50 mL) was added to the mixture. The mixture was extracted with EtOAc (10 mL X 3). The aqueous was acidified with aq NaHS04 to PH ~ 4. Then it was extracted with EtOAc (15 mL X 3). The combined organic layers were washed with brine, dried over Na2S04 and concentrated in vacuo to afford crude product, which was purified by washed with EtOAc (10 mL) to afford 2-nitropyridine-4-thio 1(1700 mg, 35% yield). ESI-MS m/z calcd for [C5H4N202S]" [M-H]~: 156.0; found: 155.0.
4-(4,4,5 ,5-tetramethyl-1,3 ,2-dioxaborolan-2-yl)pyridin-2-amine[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
75%
Under nitrogen protection, 550 mL of dioxane, 2-nitro-4-chloropyridine (15.8 g, 0.10 mol) and pinacol borate (25.4 g, 0.10 mol) were sequentially added to the reaction flask. After stirring potassium acetate (14.7 g, 0.15 mol), Finally, the catalyst PdCl2dppf (0.74 g, 0.001 mol) was added, and the temperature was slowly raised to 80-90 C, and the reaction was stirred for 2-3 h. After the completion of the GC reaction, the reaction was stopped by cooling, and the reaction solution was filtered through celite to obtain a dark-black reaction solution. After charging at 1 atm of hydrogen, the mixture was reacted at room temperature overnight. After the reaction was completed, the activated carbon was decolorized, and the filtrate was distilled under reduced pressure until no liquid was poured. /Heptane mixed solvent is cooled and beaten for half an hour, filtered to obtain a light gray crude product, heated again with ethanol, and then cooled down, and the filter cake is rinsed with -20 C anhydrous ethanol, and dried to obtain 16.5 g of an off-white solid. 75%, HPLC purity 99.1%,
With N-ethyl-N,N-diisopropylamine; In 1-methyl-pyrrolidin-2-one; at 150℃; for 24h;
Compound 8 (4g, 0.03mol) was added to a 100mL eggplant-shaped bottle, NMP 30mL was added, stirred, and added sequentially Diisopropylethylamine (10 g, 0.08 mol), compound 9 (4.8 g, 0.03 mol), then reacted at 150 C for 24 h, using thin layer chromatography(TLC) followed the reaction. After 24 h, TLC showed the end of the reaction. Part of the solvent was evaporated under reduced pressure. After suction filtration, drying and recrystallization, 3.20 g of a gray solid compound 10 was obtained in a yield of 50%.
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