公开(公告)号：US3873624A

公开(公告)日：1975-03-25

申请号：US32797973

申请日：1973-01-30

Applicant: ALLIED CHEM

Inventor： MATHEW CHEMPOLIL THOMAS ,  ULMER HARRY EDWARDS

IPC: C07C323/22 ,  C07C45/63 ,  C07C47/14 ,  C07C67/00 ,  C07C313/00 ,  C07C319/14 ,  C07C319/20 ,  C07C323/47 ,  C07C325/00 ,  C07F9/40 ,  C07C47/00

CPC classification number: C07C319/14 ,  C07C45/63 ,  C07C47/14 ,  C07F9/4006 ,  C07C323/22 ,  C07C323/47 ,  C07C323/60

Abstract: AND OXIMATING THE Alpha -FORMYL SULFIDE TO FORM A 2HYDROCARBYLTHIOALDOXIME OF THE FORMULA

WHEREIN X is defined as above, reacting in an aqueous medium the Alpha -haloaldehyde with a thiol salt of the formula R''''''SM, wherein R'''''' and M are defined as above, to form an Alpha formyl sulfide of the formula

WHEREIN R'' and R'''' are defined as above, to form an Alpha haloaldehyde of the formula

Also, 2-hydrocarbylthioaldoximes are prepared by oximating the above Alpha -formyl sulfides by reaction with a source of hydroxylamine. Additionally, 2-hydrocarbylthioaldoximes are prepared by a process which comprises halogenating an aldehyde having the formula

WHEREIN R'' and R'''' independently are hydrogen, hydrocarbon radicals of 1 to 18 carbon atoms selected from the group consisting of alkyl, cycloalkyl, alkenyl, cycloalkenyl and aryl, or substituted hydrocarbon radicals of the above group, and X is a halogen selected from the group consisting of chlorine, bromine, and iodine, with a thiol salt of the formula R''''''SM, wherein R'''''' is a hydrocarbon radical of 1 to 18 carbon atoms selected from the group consisting of alkyl, cycloalkyl, alkenyl, cycloalkenyl and aryl or a substituted hydrocarbon radical of the above group; and M is an alkali or alkaline earth metal, thereby forming an Alpha -formyl sulfide of the formula

An Alpha -formyl sulfide is prepared by a process which comprises reacting in an aqueous medium an Alpha -haloaldehyde of the formula

Abstract translation: 通过一种方法制备α-甲酰基硫化物，该方法包括在水性介质中使式WHEREIN R'和R“的α-卤代醛独立地为氢，1至18个碳原子的烃基选自烷基 ，环烷基，烯基，环烯基和芳基或上述取代的烃基，X是选自氯，溴和碘的卤素，其具有式R“'SM的硫醇盐，其中 R“是选自上述基团的烷基，环烷基，烯基，环烯基和芳基或取代的烃基的1至18个碳原子的烃基; M是碱金属或碱土金属，从而形成下式的α-甲酰硫醚。另外，通过与羟胺源反应，使上述α-甲酰基硫化物肟化，制备2-烃基硫代肟。 另外，2-烃基硫代肟通过一种方法制备，该方法包括卤化具有如上定义的式WHEREIN R'和R“的醛，以形成式WHEREIN X如上所定义的α-卤代醛， 用式R“'SM的硫醇盐介导α-卤代醛，其中R”'和M如上所定义，以形成下式的α-甲酰硫醚，并且将α-甲酰硫醚氧化成形式A 公式的2-羟基乙酰氧基

公开(公告)号：US3907901A

公开(公告)日：1975-09-23

申请号：US34843073

申请日：1973-04-05

Applicant: ALLIED CHEM

Inventor： FEDER RAYMOND L ,  FUHRMANN ROBERT ,  PISANCHYN JOHN ,  ELISHEWITZ SAUL ,  INSINGER THOMAS H ,  MATHEW CHEMPOLIL THOMAS

IPC: C07C409/10 ,  C07C73/08

CPC classification number: C07C409/10 ,  C07C407/00 ,  C07C407/003 ,  C07C409/14

Abstract: An improved continuous process for preparing cumene hydroperoxide and phenol by the controlled liquid phase air oxidation of cumene in the absence of initiators, catalysts, additives or alkalizing agents. A mixture containing cumene having a purity of at least 99.8 percent, and recycle cumene hydroperoxide which has been purified by washing with aqueous alkali metal hydroxide, followed by water wash, is oxidized in a single or multiple stage system by continuously passing through the mixture a stream of gas containing at least 8 mol percent of oxygen at a rate wherein the ratio of the mols of oxygen supplied per hour to the maximum amount of oxygen consumable per hour exdeeds 0.25 and the exit gas contains from 3-10 percent oxygen; and when oxidation is effected in a mutiple stage system the temperature is maintained stepwise from about 120* to about 80*C. while the concentration of cumene hydroperoxide in the reaction mixture is permitted to increase stepwise from about 8 percent to about 40 percent.

Abstract translation: 在不存在引发剂，催化剂，添加剂或碱化剂的情况下，通过异丙苯的受控液相空气氧化来制备氢过氧化异丙苯和苯酚的改进的连续方法。 含有纯度至少为99.8％的异丙基苯的混合物，以及通过用碱金属氢氧化物水溶液洗涤纯化，然后水洗后再循环的异丙基氢过氧化物，在单级或多级系统中通过连续通过混合物a 含有至少8mol％氧气的气体流，其中每小时供应的氧气摩尔数与每小时最大氧消耗量的比例超过0.25，出口气体含有3-10％的氧气; 并且当在多级系统中进行氧化时，温度从约120℃至约80℃逐步维持，而反应混合物中氢过氧化异丙苯的浓度允许从约8％至约40％逐步增加。