반응 #157465
ord-0995036285214ab7a941ead28634dfc0
반응 조건
후처리
- 1온도heating
- 2온도The mixture was cooled
- 3세척washed (water, brine)
- 4건조dried over Na2SO4
- 5농축concentrated in vacuo
- 6기타Attempted resolution of the two reaction products by flash chromatography (EtOAc/hexanes)
- 7workup.ADDITIONthus the mixture of products
- 8workup.STIRRINGthe mixture was stirred overnight at room temperature
- 9추출extracted with Et2O (×3)
- 10세척Combined organics were washed (water, brine)
- 11건조dried over Na2SO4
- 12농축concentrated in vacuo
- 13기타The residue was purified by flash chromatography (EtOAc/hexanes)
실험 절차
To a solution of o-cyanophenol (0.595 g; 5.00 mmol) and diisopropylamine (0.060 mL; 0.40 mmol) in PhMe (50 mL) at 70° C. was added NBS (0.980 g; 5.50 mmol) in one portion. The mixture was stirred 2 h, an additional portion of NBS (0.089 g; 0.5 mmol) was added and heating continued until disappearance of starting material was observed (TLC). The mixture was cooled, diluted with EtOAc washed (water, brine), dried over Na2SO4 and concentrated in vacuo. Attempted resolution of the two reaction products by flash chromatography (EtOAc/hexanes), was unsuccessful; thus the mixture of products was dissolved in DMF (10 mL), K2CO3 (2.07 g; 15.0 mmol) and MeI (0.47 mL; 7.5 mmol) were added and the mixture was stirred overnight at room temperature. The mixture was poured into water and extracted with Et2O (×3). Combined organics were washed (water, brine), dried over Na2SO4 and concentrated in vacuo. The residue was purified by flash chromatography (EtOAc/hexanes), affording the title compound as a colorless solid. 1H NMR (400 MHz, DMSO-d6) δ ppm 3.97 (s, 3 H), 7.26 (app. t, J=7.9 Hz, 1 H), 7.86 (dd, J=7.8, 1.5 Hz, 1 H), 8.01 (dd, J=8.1, 1.5 Hz, 1 H). The product obtained above was combined with that of a similar reaction wherein N-methylbenzylamine (0.08 equiv) was substituted for the above diisopropylamine catalyst.