通过对环氧化合物的亲核加成或直接还原可以得到各种各样的醇。
环氧化合物和醇反应可以得到邻烷氧基醇、和硫醇反应可以得到邻烷硫基醇、和卤化氢反应生成邻卤醇、和水反应生成邻二醇、和叠氮酸反应生成邻叠氮基醇、和仲胺反应可以得到邻位叔胺基醇、和格氏试剂反应得到碳链增长两个的醇、用硼氢化钠、氢化铝锂或氢气还原环氧化合物可以得到醇。
反应实例
一、环氧化合物和叠氮酸反应生成邻叠氮基醇示例：
To a solution ofcis-2,3-epoxybutane (2 g, 27.74 mmol) in methanol/water (83 ML/8 ML), sodiumazide (2.7 g, 41.61 mmol) and ammonium chloride (2.97 g, 55.48 mmol) wereadded.. The reaction mixture was stirred at reflux temperature for 16 hours..Then cooled to room temperature and evaporated all solvent.. The residue wasextracted with ethyl acetate.. The combined organic phase was dried over MgSO4,filtered and concentrated under reduced pressure to give desired product (2.6g, 82percent). EI-MS m/z 88 (M+N2).
【SmithKline Beecham Corporation;Publ.: US6133319 A1 (2000/10/17), Appl.: US1999-202569 (1999/08/19)】
二、硼氢化钠还原环氧化合物得到醇示例：
A mixture of 39.2 g (71.2mmol) of (2S,3R,4R,5S)-2,5-bis-(N-(((benzyl)oxy) carbonyl) amino) -3,4-epoxy-1,6-diphenylhexanein 600 ml of THF was treated under N2 atmosphere with 13 g (0.36 mol) of sodiumborohydride.. The resulting mixture was treated dropwise with 27.7 ml (0.36mol) of trifluoroacetic acid.. After being stirred for 3.5 h at ambienttemperature, the resulting mixture was quenched with 1N aqueous HCl, dilutedwith water, and stirred for 16 h. The resulting mixture was filtered, washedwith water, and dried to provide 22.85 g (58percent) of the desired compound asa white solid.
【Patent; Abbott Laboratories;Publ.: US5559158 A1 (1996/09/24), Appl.: US1994-297004 (1994/08/31)】
三、环氧化合物和醇反应可以得到邻烷氧基醇示例：
To a solution of sodium(0.12 g) in benzyl alcohol (3.69 g) was added1-tert-butoxy-carbonyl-3,4-epoxypyrrolidine (1.07 g) and the mixture stirred at60.deg. C. for 15 hours.water was added and the mixture extracted withdichloromethane.The organic extract was dried (magnesium sulphate) andevaporated down under reduced pressure.The residue was washed with cold hexaneand dried under vacuum to give the title compound (0.88 g) as a white solid. 1HNMR (CDCl3) : 1.46 (s, 9H), 3.25-3.7 (m, 4H), 3.91 (s, 1H), 4.30 (s, 1H),4.54(m, 2H), 4.70 (d, 1H), 7.3-7.45 (m, 5H).
【Patent; SmithKline BeechamCorporation; Publ.: US2002/82426 A1 (2002/06/27), Appl.: US2002-83910(2002/02/27)】
四、有机金属试剂对环氧加成制备醇示例
To a solution of(1R,2S)-1-(4,5-diphenyloxazol-2-yl)-1,2-epoxycyclohexane (20 g) and CuBr (3.0g) in tetrahydrofuran (400 ml) was dropwise added a solution of3-methoxybenzylmagnesium chloride [prepared from 3-methoxy-benzylchloride (50g) and Mg (9.2 g)] in tetrahydrofuran (500 ml) at -78.deg. C. under N2.. Themixture was stirred for 2 hours at the room temperature and partitioned betweenethyl acetate and water.. The organic layer was washed with 1N-HCl, water, sat.NaHCO3 and brine.. The dried solvent was evaporated in vacuo and the residuewas purified by chromatography on silica gel to give(1R,2S)-1-(4,5-diphenyloxazol-2-yl)-1-hydroxy-2-(3-methoxybenzyl)cyclohexane(29.2 g). IR (Nujol): 3400, 1600 cm-1; NMR (CDCl3): 1.4-2.4 (9H, m), 3.07(1H, d, J=10 Hz), 3.52 (1H, m), 3.74 (3H, s), 6.7-6.9 (4H, m), 7.15 (1H, t, J=8Hz), 7.2-7.8 (10H, m); Mass (m/z): 440 (M+H)+.
【Patent; Fujisawa Pharmaceutical Co., Ltd.;Publ.: US6245790 B1 (2001/06/12), Appl.: US2000-424253 (2000/03/08)】
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