公开(公告)号：US3857510A

公开(公告)日：1974-12-31

申请号：US28568172

申请日：1972-09-01

Applicant: ALLIED CHEM

Inventor： ROGIC M ,  FUHRMANN R

IPC: C07D201/08 ,  C07D53/06

CPC classification number: C07D201/08

Abstract: A method of cleaving ketones at a carbon-carbon bond adjacent to the ketonic carbon to produce a terminal carboxylic ester and a terminal oxime group, which comprises, nitrosating the ketone in the presence of a polar aprotic solvent and an alcohol. The products are useful intermediates, particularly as intermediates in the production of polyamides, and as solvents. A method of synthesizing Epsilon -caprolactam from the intermediate omega hydroximino hexanoate, produced by cleaving cyclohexanone, hydrogenating the intermediate omega -aminohexanoate ester and cyclizing the corresponding ester thus formed, to Epsilon caprolactam.

Abstract translation: 一种在与碳酮碳相邻的碳 - 碳键处切割酮的方法，以产生末端羧酸酯和末端肟基，其包括在极性非质子溶剂和醇的存在下亚硝化酮。 该产品是有用的中间体，特别是作为生产聚酰胺和作为溶剂的中间体。 通过裂解环己酮，氢化中间体ω-氨基己酸酯并将由此形成的相应的酯环化为ε-己内酰胺从中间体ω-羟肟基己酸酯合成ε-己内酰胺的方法。

公开(公告)号：US3839407A

公开(公告)日：1974-10-01

申请号：US33657073

申请日：1973-02-28

Applicant: ALLIED CHEM

Inventor： ROGIC M ,  VITRONE J

IPC: C07C69/00 ,  B01J21/00 ,  B01J31/00 ,  C07B61/00 ,  C07C20060101 ,  C07C67/00 ,  C07C253/00 ,  C07C255/19 ,  C07C255/45 ,  C07C255/46 ,  C07C121/02

CPC classification number: C07C255/00 ,  C07C2603/16

Abstract: 1. A PROCESS FOR CLEAVAGE OF A BOND IN A KETAL, JOINING THE KETAL GROUP AND A METHYLENIC CARBON ATOM, WHICH PROCESS COMPRISES: FORMING A REACTION MIXTURE BY PROVIDING SUCH KETAL, IN WHICH ANY SUBSTITUENTS ARE APROTIC, IN AN ANHYDROUS LIQUID REACTION MEDIUM COMPRISING AN EFFECTIVE PROPORTION OF A POLAR APROTIC SOLVENT INERT PER SE AT THE REACTION TEMPERATURE TO SAID KETAL; AND BY PROVIDING IN SAID REACTION MEDIUM (1) NITROUS ACID ESTER IN AMOUNT NOT GREATER THAN ABOUT TWO MOLAR EQUIVALENTS PER MOL OF UNREACTED KETAL PROVIDED; (2) ACID CAPABLE OF EXCHANGING ITS ANION WITH THE ESTER GROUP OF SAID NITROUS ACID ESTER UNDER THE REACTION CONDITIONS, IN TOTAL AMOUNT NOT GREATER THAN ABOUT ONE EQUIVALENT PER MOL OF TOTAL NITRITE PROVIDED IN THE REACTION MIXTURE; AND (3) A PRIMARY ALCOHOL CONTAINING AT LEAST TWO CARBON ATOMS IN AMOUNT INCLUDING SUCH AS IS FORMED IN THE REACTION AND SUCH AS IS ADDED TO THE MIXTURE, OF AT LEAST ABOUT 1/2 EQUIVALENT PER MOL OF KETAL PROVIDED IN THE REACTIN MIXTURE; AND SUBJECTING THE REACTION MIXTURE TO TEMPERATURE IN THE RANGE BETWEEN (-70*C.) AND THE BOILING POINT OF THE SOLVENT UNDER THE PREVAILING PRESSURE, AND TIME SUFFICIENT FOR PRODUCING REACTION IN SAID REACTION MIXTURE AT THE SAID BOND WITH CLEAVAGE THEREOF AND FORMATION OF A CYANO GROUP AND AN ESTER GROUP AT THE POINT OF CLEAVAGE.