经典化学合成反应操作增加版氰转化为酰胺

1、6. 基酰6.1.1 盐酸水解腈为伯酰胺示例HCl,Ina3-l.three-neckedround-bottomedflaskequippedwithglasssare placed 6. 基酰6.1.1 盐酸水解腈为伯酰胺示例HCl,Ina3-l.three-neckedround-bottomedflaskequippedwithglasssare placed 200g.moles) of benzyl cyanide and 800 ml. of 35% hydrochloric acid. The flask is fitted reflux condenser, a thermo

2、meter, and an efficient mechanical At a bath of about 40 the mixture is stirred riod of 2040 minutes the cyanide o During this time, the temperature of the reaction mixture about 10 t of the The homogeneous solution is he bath with, without, stirring for anadditional 2030 The warm he bath isreplaced

3、 tap water at about 1520, and the thermometer is replaced by a funnel from 800 ml. of cold distilled water is added with After the addition of about ml., crystals o When the total amount of water has been added, the is cooled externally with ice water for about 30 The cooled mixture is filtered Crud

4、e phenylacetamide remains on the filter and is washed with two 100-portions of The crystals are then dried at The yield of phenylacetamide is190200g.Page1of浓硫酸水解不饱和腈为伯酰胺示例2. To 106 g of 84 % sulfuric acid, was added 50 g of After stirring for 30 min r.t., the resulting mixture was heated to 95 , and

5、 stirred for 2 After cooling, the was collected 浓硫酸水解不饱和腈为伯酰胺示例2. To 106 g of 84 % sulfuric acid, was added 50 g of After stirring for 30 min r.t., the resulting mixture was heated to 95 , and stirred for 2 After cooling, the was collected by suction, and the filter cake was o a Totheice-solid, was

6、added aq. ammonia with the t keep the temperature n 50. ed ammonium sulphate was filtered off, and the filtrate was cooled. The was collected by filtration, and the filter cake was washed by water, dried in vacuum to thedesired体系水解腈为伯酰胺示例H2O2-K2CO3-30%H2O2,ODMSO,rt,5To a stirred solution of 4-chloro

7、benzonitrile (1.37 g, 0.01 mol) in DMSO (3 ml), cooled in a icebath,wasadded30% H2O2 (1.2ml)andK2CO3, thereactionwasallowedtowarmuptor.t. (strong exothermic effect was observed). After 5 min., distilled water (50 ml) was added,coolingapp d, andtheproduct wascollected byfiltration, yield 相转移催化体系水解腈为伯

8、酰胺NaOH(aq.)- -+(nC H )N 49O30%H2O2, 20%NaOH,20-25Toamagneticallystirrednesolution(1.5ml)ofo-itrile(0.5g,4.27mmol)cooledinice bath, are added 30% hydrogen peroxide (2.0 ml), tetrabutylammonium hydrogen (0.290 g, 0.85 mmol), and a 20% aqueous solution of sodium hydroxide (1.6 Page2ofreaction mixture i

9、s allowed to warm up to r.t. and ained under stirring. After 1.6 ne is added, anic layer is separated, washed with brine, and dried sodium Thesolvent isremoved under reduced re to leave awhite solid whichreaction mixture is allowed to warm up to r.t. and ained under stirring. After 1.6 ne is added,

10、anic layer is separated, washed with brine, and dried sodium Thesolvent isremoved under reduced re to leave awhite solid whichpureo-toluamideisobtainedbychromatographyonsilicagel. Yield0.485gRitterO CN AcOH, 20oC, 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O 0oC-r

11、t,OMeOH (1.5eq), PPA 150oC, 7。如果所用的是环状烯烃，则为反式加成, reflux, 1 Page3ofRitter 反应示例一H2SO4, +40oC, 1 OA solution of 5.3 g (0.1 mol ) of acrylonitrile, 50 ml of acetic acid and 7.4 g of tbutylalcohol in an ice-bath was treated with conc. sulfuricacid (10.1 g, 0.1 mol) with stirring so as Ritter 反应示例一H2SO4,

12、+40oC, 1 OA solution of 5.3 g (0.1 mol ) of acrylonitrile, 50 ml of acetic acid and 7.4 g of tbutylalcohol in an ice-bath was treated with conc. sulfuricacid (10.1 g, 0.1 mol) with stirring so as to the temperature below 40 during the addition and subsequent reaction (an hour), reaction mixture was

13、poured onto 200 g of ice, the product filtered and air dried, yield 10 (yield 80Theproduct couldberecrystallized fromRitter 反应示例二hrt,18 To amixtureofalcohol(10mmol)and trimethylsilyl cyanide(20mmnol), cooledto-15C analt bath, undernitrogen, isadded concentrated sulfuric acid(30mmol)dropwise vigorous stirring(caution:highlyAfter theaddition,the cold bathisandthemixtureisstiffedatambienttemperaturefor18hrs.Tilemixtureisthenpouredice, and neutralizedwith50%NaOHsolutiontopH=Theaqueousisextracted t-BuOMeorCHCl3,andtheanicextractsarewashedwithbrine,anddriedThecrudeproduct ispurifiedbyrecrysta