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酰胺通过五氯化磷脱水得到亚胺酰氯中间体，消除一个Cl离子生成腈正离子，Cl-亲核进攻αN-碳得到腈和卤代烃。
反应实例
【J. Am. Chem. Soc., 1962, 84, 769】
【J. Am. Chem. Soc., 1949, 71, 2808】
A solution of 1.240 mmol ofN-tert-butyl-4-(6,7-dihydro-5H-[2]pyridin-7-yl)benzamide and 1.0 ml of thionylchloride in 30 ml of chloroform is stirred under reflux for 6 hours. The reaction mixture is cooled to roomtemperature and evaporated. The residueis taken up in dichloromethane and mixed with saturated aqueous sodiumbicarbonate solution. The organic phaseis separated and the aqueous phase is extracted with dichloromethane (2x). The combined organic phases are dried withsodium sulphate and concentrated. Theresidue is dissolved in diethyl ether and the title compound is converted intothe hydrochloride salt by adding ethereal HCI solution (2N). The solid is stirred in diethyl ether/acetone(1: 1), filtered and dried. The titlecompound is obtained as a dark grey solid. Rf (free base) = 0.36 (EtOAc)
【Reference: WO2005/118540 】
A 5 L round bottom flask was charged with N,N'-di-tert-butyl-5-(2,3-difluoro-6-nitro-phenoxy)-isophthalamide (21; 564 g) and 1.3 L ofphosphorus oxychloride. The mixture washeated to between 90 deg C. ~ 100.deg. C. for 2 h, after which approximately1/2 of the POCl3was removed by distillation. Toluene was added (1 L) and additional liquidwas distilled. After cooling the mixtureovernight, a crude was obtained by filtration. Additional material was obtained by recovery from the mother liquid. The combined solids were stirred in MeOH (0.7L) for between 1 and 3 h, filtered and dried in a vacuum oven between 50~80 degC.at 25 Torr with a nitrogen bleed to afford 339 g of 22 (90percent theory).
【Reference: US2005/234236】
At ice-water bath, oxalyl chloride (0.345 ml) wasadded dropwise to a solution of 1.0 g of ethyl1-{4-[2-(t-butylaminocarbonyl)phenyl]phenyl}methyl-4-(1-hydroxy-1-methylethyl)-2-propylimidazole-5-carboxylate in 10 ml of methylene chloride. The mixture was stirred at the sametemperature for 2 hours. The reactionmixture was diluted with an aqueous solution of sodium hydrogencarbonate andethyl acetate, and the ethyl acetate layer was separated, dried over anhydrousmagnesium sulfate and concentrated by evaporation under reduced pressure. The residue was purified by silica gel columnchromatography, using 1:1 EtOAc/hex (v/v) as the eluent, to give 0.69 g of thetitle compound as crystals.
【Reference: US5616599】
参考资料
Comprehensive Organic Name Reactions and Reagents, by Zerong Wang，2900-2903.
相关反应
