腈的醇解示例

在酸催化下，氰基可以醇解直接生成酯。通常使用的催化剂是浓硫酸或氯化氢，只适用于伯醇，因为叔醇和仲醇在硫酸作用下会生成烯，硫酸和释放出的氨成盐。 腈的醇解，醇兼作溶剂，其用量比较大，一般是理论量的4～5倍；硫酸的用量也要超过理论用量的0.5～1倍。 示例1：

NNNHmethanolH2SO4ONONH

1-(4-Cyanophenyl)-piperazine (11 mmol) was dissolved in 5 N a solution of concentrated sulfonic acid and methanol (15 ml) and stirred in a sealed tube at 110℃for 3 h. After evaporation of the solvent, the residue was dissolved in water and extracted with ethyl acetate. Addition of sodium carbonate to the water phase until pH 9 results in the precipitation of a white solid which was filtered off and dried (vacuum). A white powder with Rf 0.59 (CH2Cl2/MeOH = 9:1) was obtained. 4-piperazin-1-yl-benzoic acid methyl ester [1].

示例2

HCl.NNSSNmethanolHClHCl.NNSSOOONO

1-[2,2-Bis(4-cyanobenzylthio)ethyl]-1H-imidazole hydrochloride (1.43 g) was added to methanol (50 mL) which had been saturated with hydrogen chloride at 0℃. The resulting solution was stirred under reflux for 20 h and then concentrated. The gummy residue was partitioned between CH2Cl2 and aqueous NaHCO3, and the CH2Cl2 layer was washed with brine and dried over Na2SO4. Removal of the CH2Cl2 left a gum which was hromatographed on silicic acid (60 g) with CH2Cl2 /CH3OH (95:5), to afford 1.1 g of the free base of the title compound as a viscous oil.

Treatment of a solution of the base in CH3OH-ether with hydrogen chloride provided colorless crystals of 1-[2,2-Bis(4-carbomethoxybenzylthio)ethyl]-1H-imidazole Hydrochloride[2]. 示例3

ONCCN+2CH3CH2OHOOO

向5 L烧瓶中先加入2200 ml无水乙醇，在冷却下慢慢加入1200 ml浓硫酸，再加入470 g（0.5 mol）戊二腈，在水浴上回流16 hs，回收乙醇，将剩余液倒入4 L冰水中，分出上层有状物，用10%碳酸钠溶液洗涤，在用水洗至中性，分出油层，用无水碳酸钠干燥，减压蒸馏，收集122-128oC/2660 Pa馏分[3]。 示例4

示例5

[1]: Patent; Mwassbach, Martin; Publ.: US2001/16207 A1 (2001/08/23), Appl.:

US2001-778302 (2001/02/07)

[2]: Patent; Brwastol-Myers Company; Publ.: US4458079 A1 (1984/07/03), Appl.:

US1980-176422 (1980/08/08)

[3]: 段长强，现代化学试剂手册，第一分册，北京：化学工业出版社。1988：625