公开(公告)号：US4097517A

公开(公告)日：1978-06-27

申请号：US72224976

申请日：1976-09-10

Applicant: ALLIED CHEM

Inventor： ROGIC MILORAD M ,  DEMMIN TIMOTHY R ,  KLEIN KARL P

IPC: C07C67/00 ,  C07C20060101 ,  C07C41/30 ,  C07C253/00 ,  C07C255/03 ,  C07C255/13 ,  C07C255/19 ,  C07C120/00

CPC classification number: C07C255/00

Abstract: The cleavage forms an ester group and a cyano group. It is effected by use of an ortho ester of a carboxylic acid, or reaction product thereof with the oximino compound or with a Lewis acid such as boron trifluoride in an electrophilic reaction medium. In particular alpha-oximinocyclohexanone dimethyl acetal is cleaved to form omega-cyano methyl valerate by catalytic action of dimethoxy ethylcarbonium tetrafluoroborate in dichloromethane solvent. The cyclic C5, C8, and C12 homologues react similarly; likewise the alkyl-substituted homologues and the nitroso isomers.

Abstract translation: 裂解形成酯基和氰基。 通过在亲电子反应介质中使用羧酸的原酸酯或其与肟基化合物的反应产物或路易斯酸如三氟化硼来实现。 特别是通过二氯甲烷溶剂中四氟硼酸二甲氧基乙基羰基酯的催化作用，将α-肟基环己酮二甲基缩醛裂解形成ω-氰基甲基戊酸甲酯。 循环C5，C8和C12同系物的反应类似; 同样地，烷基取代的同系物和亚硝基异构体。

公开(公告)号：US3928445A

公开(公告)日：1975-12-23

申请号：US42860773

申请日：1973-12-26

Applicant: ALLIED CHEM

Inventor： ROGIC MILORAD M ,  MARES FRANTISEK

IPC: C07C131/04

CPC classification number: C07C255/00

Abstract: 2-Halo-5-cyano alkyl valerate is produced by halogenating a 2alkoxy-3-oximinocyclohexene or the mineral acid salt thereof with at least one equivalent of chlorine, bromine or iodine; treating the 1,2-dihalo-2-alkoxy-3-oximinocyclohexane intermediate thus formed with an alcohol having 1 to 12 carbon atoms, more preferably with ethanol, methanol, propanol, butanol or isobutanol to form the corresponding 2-halo-6oximinocyclohexanone dialkyl ketal or its mineral acid salt; and ring opening of the ketal using a Beckmann cleavage reaction to form 2-halo-5-cyano alkyl valerate. The novel compound thus formed may be converted by reductive amination to form an alkyl ester of lysine which is subsequently hydrolyzed and neutralized to produce lysine.

Abstract translation: 通过用至少一当量的氯，溴或碘将2-烷氧基-3-肟基环己烯或其无机酸盐卤化来制备戊酸2-卤代-5-氰基烷基酯; 用具有1至12个碳原子的醇处理由此形成的1,2-二卤代-2-烷氧基-3-肟基环己烷中间体，更优选用乙醇，甲醇，丙醇，丁醇或异丁醇处理，形成相应的2-卤代-6- 肟基环己酮二烷基缩酮或其无机酸盐; 并使用Beckmann裂解反应开环缩酮形成2-卤代-5-氰基烷基戊酸酯。 由此形成的新化合物可以通过还原胺化转化形成赖氨酸的烷基酯，随后水解和中和以产生赖氨酸。