通過對環(huán)氧化合物的親核加成或直接還原可以得到各種各樣的醇。
環(huán)氧化合物和醇反應(yīng)可以得到鄰?fù)檠趸?、和硫醇反?yīng)可以得到鄰?fù)榱蚧?、和鹵化氫反應(yīng)生成鄰鹵醇、和水反應(yīng)生成鄰二醇、和疊氮酸反應(yīng)生成鄰疊氮基醇、和仲胺反應(yīng)可以得到鄰位叔胺基醇、和格氏試劑反應(yīng)得到碳鏈增長兩個(gè)的醇、用硼氫化鈉、氫化鋁鋰或氫氣還原環(huán)氧化合物可以得到醇。
反應(yīng)實(shí)例
一、環(huán)氧化合物和疊氮酸反應(yīng)生成鄰疊氮基醇示例：
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、硼氫化鈉還原環(huán)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、環(huán)氧化合物和醇反應(yīng)可以得到鄰?fù)檠趸际纠?/span>：
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、有機(jī)金屬試劑對環(huán)氧加成制備醇示例
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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