In the field of chemistry, the synthetic routes of compounds are constantly being developed and updated. I will also mention this compound in other articles. 89878-14-8, 3-(Diethylboryl)pyridine, other downstream synthetic routes, hurry up and to see.
89878-14-8, Researchers who often do experiments know that organic synthesis is a process of preparing more complex target molecules from simple raw materials through one or more chemical reactions. Generally, it requires fewer steps,and cheap raw materials. 89878-14-8, name is 3-(Diethylboryl)pyridine. A new synthetic method of this compound is introduced below.
A 500 mL Parr bottle was charged with 2.0 g of 10% palladium on carbon (50% water) and covered with 50 mL ethanol. 2-methyl-5-nitroanisole (10.0 g, 59.8 mmol) was dissolved in 100 mL ethanol and added to the catalyst suspension. The reaction was hydrogenated at 50 psi for 3 h. The catalyst was filtered through a celite plug. The filter cake was washed with 150 mL ethanol and the filtrated concentrated under reduced pressure to yield 8.05g (98%) of 5-amino-2-methylanisole as a clear oil. ‘H NMR (400 MHz, CDC13) 8 6. 90 (d, 1 H), 6.23 (m, 2H), 3.78 (s, 3H), 2.11 (s, 3H). 5-amino-2-methylanisole (8.05 g, 58.7 mmol) was dissolved in 244 mL water and 8.1 mL concentrated H2SO4 and cooled to 0C. NAN02 (4.86 g, 70.4 mmol) in 61 mL water was added dropwise with stirring. Reaction was stirred 30 minutes at 0C. Urea (0.70 g, 11.7 mmol) was added and stirring continued for an additional 30 minutes. The pale yellow solution was transferred to a dropping funnel and added slowly to a stirred solution of potassium iodide (19.48 g, 117.4 mmol) in 122 mL water. The solution was stirred at ambient temperature for 1 h after completion of the addition. The reaction was extracted with diethyl ether (3 x 300 mL). The organic extracts were combined and washed with 1 M Na2S203 (2 x 200 mL), dried over NA2SO4, filtered and concentrated under reduced pressure to yield 9.60 g (66%) of 5- iodo-2-methyl anisole as a brown oil. 1H NMR (400 MHz, CDC13) 8 7.19 (dd, 1H), 7.10 (d, 1H), 6.86 (t, 1H), 3.81 (s, 3H), 2.15 (s, 3H). 5-iodo-2-methyl anisole (9.60 g, 38.70 mmol) and diethyl- (3-pyridyl) borane (5.70 g, 38.70 mmol) were dissolved in 60 mL tetrahydrofuran in a 250 mL round bottom flask equipped with a magnetic stirrer. Sodium carbonate (8.20 g, 77.40 mmol) and 30 mL water were added followed by tetrakis (triphenylphosphine) palladium (0) (0.90g, 0.77 mmol) and 15 mL ethanol. The mixture was heated at reflux for 24 h under nitrogen then cooled to ambient temperature. The mixture was diluted with 200 mL water and extracted with diethyl ether (2 x 200 mL). The organic phases were combined and extracted with’N HCI (3 x 150 mL). The acidic extractions were combined and made basic with 5N aqueous sodium hydroxide. This basic layer was extracted with diethyl ether (3 x 150 mL) and the extracts were combined and dried over anhydrous sodium sulfate, filtered and concentrated under reduced pressure to yield 7. 71G (99%) of 2-methyl-5- (3-pyridyl)- anisole as a brown oil. MS (LC-MS) 200.1 (M + H) +. ‘H NMR (400 MHz, CDGI3) 8 8.87 (s, 1 H), 8.60 (d, 1 H), 8.03 (dd, 1 H), 7.50 (m, 1 H), 7.25 (d, 1H), 7.08 (d, 1 H), 7.00 (s, 1 H), 3.92 (s, 3H), 2.27 (s, 3H). A 500 mL L hydrogenation vessel was charged with 0.77 g platinum (II) oxide and purged with nitrogen. 2-methyl-5- (3-pyridyl)-anisole (7.71 g, 38.7 mmol) was added as a solution in 150 mL acetic acid. The suspension was hydrogenated at 45 psi for 18 h. The catalyst was filtered through celite and the filter plug was washed with 200 mL acetic acid. The filtrate was concentrated under reduced pressure. The resultant oil was taken up in 300 mL water and made basic with 5N aqueous sodium hydroxide. This basic layer was extracted with ethyl acetate (2 x 300 mL) and the extracts were combined and dried over anhydrous sodium sulfate,,. filtered and concentrated under reduced pressure. The resultant oil was taken up in 300 mL hot ethanol. L- (+)-tartaric acid (5.81 g, 38.7 mmol) in 50 mL hot ethanol was added into the ethanol solution and was allowed to stir at ambient temperature for 24 h, forming a white precipitate that was collected by filtration. The white solid was recrystallized from hot 5% H2O/ETHANOL (200 mL) to yield 4.88 g (35%) of 5- (3-PIPERIDINYL)-2- methylanisole-L-tartaric acid salt as a white solid. The mother liquors were combined and concentrated under reduced pressure. The resultant oil was taken up in 500 mL diethyl ether and washed with 300 mL saturated aqueous NAHCO3. The organic layer was dried over anhydrous sodium sulfate, filtered and concentrated under reduced pressure. The resultant oil was taken up in 200 mL hot ethanol. D- (-)-tartaric acid (3.75 g, 25.0 mmol) in 50 mL hot ethanol was added and was allowed to stir at ambient temperature for 48 h, forming a white precipitate that was collected by filtration. The white solid was recrystallized from hot 5% H20/ETHANOL (300 mL) to yield 5.36 g (39%) of 5- (3-PIPERIDINYL)-2-METHYLANISOLE-D-TARTARIC acid salt as a white solid. ‘H NMR (400 MHz, DMSOd6) 8 7.06 (d, 1 H), 6.82 (d, 1 H), 6.71 (dd, 1 H), 3.87 (s, 2H), 3.77 (s, 3H), 3.27 (m, 2H), 2.97 (t, 1H), 2.86 (q, 2H), 2.09 (s, 3H), 1.85 (d, 2H), 1.69 (m, 2H). 3- (3-methoxy-4-methylphenyl)-1 H-piperidine-L-tartaric acid salt (4.88 g, 13.73 mmol) was slowly dissolved in hydrobromic acid (50 mL) and the resulting mixture heated at 140 C for 2 h. After cooling to ambient temperature, the hydrobromic acid and water were distilled off and the resulting brown oil was azeotroped with to…
In the field of chemistry, the synthetic routes of compounds are constantly being developed and updated. I will also mention this compound in other articles. 89878-14-8, 3-(Diethylboryl)pyridine, other downstream synthetic routes, hurry up and to see.
Reference:
Patent; PFIZER PRODUCTS INC.; WO2004/48334; (2004); A1;,
Pyridine – Wikipedia,
Pyridine | C5H5N – PubChem