公开(公告)号：US3839407A

公开(公告)日：1974-10-01

申请号：US33657073

申请日：1973-02-28

申请人： ALLIED CHEM

发明人： ROGIC M ,  VITRONE J

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

CPC分类号： C07C255/00 ,  C07C2603/16

摘要： 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.