반응 #1269810
ord-e410db3bddad43c0af03835039675317
반응 방정식
반응 조건
후처리
- 1workup.STIRRINGThe resulting mixture was stirred at about −75° C. for about 30 min
- 2온도slowly warmed to about 25° C. in approximately 2 h
- 3추출The organic material was extracted with hexanes/ether, approximately 1:1
- 4세척The combined extracts were washed with brine
- 5기타dried
- 6기타After removal of the solvent
- 7기타on a rotary evaporator
- 8기타chromatographed on silica gel with hexanes/ethyl acetate, approximately 4:1
실험 절차
A solution of the THPO-ether of 3-butyn-1-ol (approximately 2.88 g, approximately 18.7 mmol) in THF (about 40 ml, dried with sodium benzophenone ketyl) was placed under N2 into a four-neck flask and cooled to about −75° C. Butyl lithium (approximately 18.7 mmol, approximately 9.4 ml of approximately 2.0 M in hexanes) was added slowly via a dropping funnel at about −75° C. The mixture was stirred at this temperature for about 30 min, and then methyl chloroformate (ClCOOMe, about 1.4 ml, about 18.7 mmol) was added. The resulting mixture was stirred at about −75° C. for about 30 min, then slowly warmed to about 25° C. in approximately 2 h and poured into a cold saturated NH4Cl solution. The organic material was extracted with hexanes/ether, approximately 1:1. The combined extracts were washed with brine and dried. After removal of the solvent on a rotary evaporator, the remainder was flash chromatographed on silica gel with hexanes/ethyl acetate, approximately 4:1, to isolate methyl 5-(tetrahydro-2H-pyran-2-yloxy)-2-pentynoate (approximately 2.5 g, approximately 65%). GC-MS (m/z, relative intensity): 211 (1, M+-1), 157 (4), 153 (3), 142 (4), 125 (18), 113 (9), 109 (11), 85 (100), 79 (41), 67 (18), 55 (16), 41 (26). 1H NMR (CDCl3): 1.50-1.64 (m, 4H), 1.72 (m, 1H), 1.83 (m, 1H), 2.66 (t, J=6.6 Hz, 2H, H-4), 3.53 (m, 1H, H-5A), 3.62 (dt, J=9.8, 7.5 Hz, 1H, H-5B), 3.77 (s, 3H, OCH3), 3.87 (m, 2H), 4.65 (br t, J=4.0 Hz, 1H, OCHO). 1H NMR data were in agreement with data obtained for this compound in CCl4 (Rama Rao et al. 1986).