Potassium Carbonate → 4-Bromo-3,5-dimethylphenyl 3-(pyridin-3-yl)propiolate

HRID 1483196Notes

Reaction equation

I[C:2]1[CH:3]=[N:4][CH:5]=[CH:6][CH:7]=1.C([O-])([O-])=O.[K+].[K+].[C:14]([O:18][C:19]1[CH:24]=[C:23]([CH3:25])[C:22]([Br:26])=[C:21]([CH3:27])[CH:20]=1)(=[O:17])[C:15]#[CH:16]>C1COCC1.[Cu]I>[N:4]1[CH:5]=[CH:6][CH:7]=[C:2]([C:16]#[C:15][C:14]([O:18][C:19]2[CH:20]=[C:21]([CH3:27])[C:22]([Br:26])=[C:23]([CH3:25])[CH:24]=2)=[O:17])[CH:3]=1

Participants

Conditions

Temperature: 65 °C

Procedure

3-Iodopyridine (226 mg, 1.10 mmol) in THF (2 mL) was degassed under reduced pressure at −78° C., and then nitrogen gas was introduced. To the solution was added K2CO3 (276 mg, 2.00 mmol), CuI (15 mg, 0.079 mmol) and PdCl2(Ph3P)2 (7 mg, 0.01 mmol), and the mixture was stirred at 65° C. 4-bromo-3,5-dimethylphenyl propiolate (6-1) (253 mg, 1.00 mmol) in THF (2 mL) was added by syringe pump over a period of 5 h, and the mixture was stirred an additional 1 h after addition was complete. After being cooled to room temperature, the mixture was filtered. The filtrate was concentrated and purified by silica gel column chromatography to give the title compound 13-1 (88 mg, 27% yield) as a black oil.

Workup

additionnitrogen gas was introduced
stirringthe mixture was stirred an additional 1 h
additionafter addition
temperatureAfter being cooled to room temperature
filtrationthe mixture was filtered
concentrationThe filtrate was concentrated
custompurified by silica gel column chromatography

Sources & evidence

ORD record: ord-e69b31c53b6f440d89aed35f1d475339
Source dataset: uspto-grants-2016_08
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US09416121B2

Reaction notes

Loading…