腈加水可以分解为伯酰胺。由于伯酰胺会继续水解为羧酸，一般要控制水解的条件。目前有许多方法报道，有时需要根据底物的特性选择酸性，碱性或中性的水解条件。作为中性的条件，也有文献报道使用镍或钯催化剂的方法。
在酸性条件下与饱和碳相连的氰基，可以在酸中很方便的水解转化为酰胺，并在条件较为剧烈时，很容易进一步水解成酸。但乙烯基或芳基腈的水解条件则要求剧烈得多，一般需要强酸条件，而且一般不会进一步水解。
在碱性条件下，利用过氧化氢氧化的方法可在室温下短时间内水解腈为伯酰胺，这是一个较为可靠的方法。利用NaOH(aq.)-CH2Cl2相转移催化体系，DMSO-K2CO3体系[2]可以用于各种腈水解为伯酰胺。
1.1 盐酸水解腈为伯酰胺示例[3]
In a 3-l. three-necked round-bottomed flask equipped withglass joints are placed 200 g. (1.71 moles) of benzyl cyanide and 800 ml. of 35% hydrochloric acid. The flask is fitted with a reflux condenser, a thermometer,and an efficient mechanical stirrer. At a bath temperature of about 40° themixture is stirred vigorously. Within aperiod of 20–40 minutes the benzyl cyanide goesinto solution. During this time, thetemperature of the reaction mixture rises about 10° above that of the bath. The homogeneous solution is kept in the bathwith, or without, stirring for an additional 20–30 minutes. The warm water in the bath is replaced by tapwater at about 15–20°, and the thermometer is replaced by a dropping funnel from which 800 ml. of cold distilledwater is added with stirring. After theaddition of about 100–150 ml., crystals begin to separate. When the total amount of water has been added,the mixture is cooled externally with ice water for about 30 minutes. The cooled mixture is filtered by suction. Crude phenylacetamideremains on the filter and is washed with two 100-ml. portions of water. The crystals are then dried at 50–80°. The yield of crude phenylacetamideis 190–200 g. (82–86%).
1.2 浓硫酸水解不饱和腈为伯酰胺示例[4]
To 106 g of 84 % sulfuric acid, was added 50 g ofacrylonitrile. After stirring for 30 minat r.t., the resulting mixture was heated to 95 ℃, and stirred for 2 h. After cooling, the solid was collected bysuction, and the filter cake was transferred into a beaker. To the ice-cooled solid, was added aq.ammonia with the speed that keep the temperature less than 50℃. The precipitated ammonium sulphate wasfiltered off, and the filtrate was cooled. The precipitate was collected by filtration, and the filter cake waswashed by water, dried in vacuum to give the desired product.
1.3 H2O2-K2CO3-DMSO体系水解腈为伯酰胺示例[1]
To a stirred solution of 4-chlorobenzonitrile (1.37 g,0.01 mol) in DMSO (3 ml), cooled in a ice bath, was added 30% H2O2(1.2 ml) and K2CO3, the reaction was allowed to warm upto r.t. (strong exothermic effect was observed). After 5 min., distilled water (50 ml) wasadded, cooling applied, and the product was collected by filtration, yield 85%.
1.4 NaOH(aq.)-CH2Cl2相转移催化体系水解腈为伯酰胺[2]
To a magneticallystirred dichloromethane solution (1.5 ml) of o-tolunitrile (0.5 g, 4.27mmol) cooled in an ice bath, are added 30% hydrogen peroxide (2.0 ml),tetrabutylammonium hydrogen sulfate (0.290 g, 0.85 mmol), and a 20% aqueoussolution of sodium hydroxide (1.6 ml). The reaction mixture is allowed to warm up to r.t. and maintained understirring. After 1.6 h, dichloromethaneis added, the organic layer is separated, washed with brine, and dried withsodium sulphate. The solvent is removedunder reduced pressure to leave a white solid from which pure o-toluamide is obtained by chromatography on silicagel. Yield 0.485 g (97%).
2 Ritter反应
碳正离子加成到腈基的氮原子上生成的腈盐加水分解得到相应的酰胺加水可以分解为酰胺。一般能产生碳正离子化合物都可以发生这类反应。由于醇或烯烃在浓硫酸或其他强酸加热条件下反应，一般在次条件下稳定的腈都可用于该类反应。
这类反应通过腈和酸在溶剂中反应，但对于乙腈来说，直接用乙腈中反应即可，对于其他较为复杂，沸点较高的底物，一般用冰醋酸稀释。
一般卤代物用于这一反应比烯烃和醇要差，但用亚硝基四氟硼酸盐（NOBF4）和亚硝基六氟磷酸盐(NOPF6 )可以室温以下反应[5]。这两个试剂也可直接拔除三取代碳上的氢生成碳正离子。
而通过卤素或有机硒等对烯烃加成，得到的碳正性的中间体也可用于对乙腈的加成[7]。如果所用的是环状烯烃，则为反式加成。
2.1 Ritter反应示例一[8]
A solution of 5.3 g (0.1 mol ) of acrylonitrile, 50ml of acetic acid and 7.4 g of tbutylalcohol in an ice-bath wastreated with conc. sulfuric acid (10.1 g, 0.1 mol) with stirring so asto keep the temperature below 40 ℃ during the addition and subsequent reaction (an hour), the reactionmixture was poured onto 200 g of ice, the product filtered and air dried, yield10 g (yield 80 %). The product could berecrystallized from benzene.
2.2 Ritter反应示例二[9]
To a mixture of alcohol (10 mmol) andtrimethylsilyl cyanide (20 mmnol), cooled to - 15°C in an ice-salt bath, undernitrogen, is added concentrated sulfuric acid (30 mmol) dropwise with vigorousstirring (caution: highly exothermic). Afterthe addition, the cold bath is removed and the mixture is stiffed at ambienttemperature for 18 hrs. Tile mixture is then poured onto ice, and neutralizedwith 50% NaOH solution to pH = 7. Theaqueous is extracted with t-BuOMe or CHCl 3, and the combinedorganic extracts are washed with brine, and dried over MgSO4. The crude product is purified by recrystallization(solid) or flash chromatography (oil).
相关反应：Ritter反应
Reference：
1. Synthesis 1989, 949
2. Synthesis 1980, 243
3. Organic Syntheses, Coll. Vol. 1963,4, 760;
4. Org. Syn., Coll. Vol. 1973,5,73; 1955,3, 66,88;
5. J. Org. Chem., 1980,3235
6. Tetrahedron Lett. 2002,1397
7. J. Org. Chem. 1981, 4727
8. J. Am. Chem. Soc. 1951, 4076
9. Tetrahedron Lett. 1996, 8129
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