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    • 4. 发明授权
    • Preparation of 1,1-dihalogeno-alkenes
    • 制备1,1-二卤代烯烃
    • US4424166A
    • 1984-01-03
    • US237005
    • 1981-02-23
    • Fritz MaurerUwe PriesnitzHans-Jochem Riebel
    • Fritz MaurerUwe PriesnitzHans-Jochem Riebel
    • C07C69/743C07C17/00C07C17/26C07C17/263C07C21/02C07C21/17C07C22/00C07C22/02C07C22/04C07C22/08C07C45/00C07C49/567C07C51/00C07C61/40C07C67/00C07C231/00C07C231/12C07C233/38C07C253/00C07C255/48C07C121/48C07C61/35C07C121/66
    • C07C17/263
    • In the preparation of a 1,1-dihalogenoalkene of the formula ##STR1## in which R.sup.1 is a hydrogen atom or an optionally substituted alkyl, alkenyl, alkynyl, cycloalkyl, aralkyl, aralkenyl or aryl radical, and R.sup.2 is an optionally substituted alkyl, alkenyl, alkynyl, cycloalkyl, aralkyl, aralkenyl or aryl radical, or R.sup.1 and R.sup.2 together form an optionally branched and/or optionally benzo-fused hydrocarbon chain, and X.sup.1 and X.sup.2 each independently is a halogen atom, wherein a carbonyl compound of the formula ##STR2## is reacted with a trihalogenoacetate of the formula ##STR3## in which X.sup.3 is a halogen atom, and M.sup..sym. is an alkali metal ion or one equivalent of an alkaline earth metal ion, in the presence of an approximately equimolar amount of a phosphorus-containing compound, the improvement which comprises employing as said phosphorus-containing compound a phosphorous acid trialkyl ester or a phosphorous acid triamide and effecting the reaction at a temperature between about 0.degree. and 200.degree. C. A preferred end product is ##STR4## and the preferred phosphorus-containing compound is trimethyl phosphite, triethyl phosphite, tripropyl phosphite or phosphorous acid tris-dimethyl-amide.
    • 在制备其中R 1为氢原子或任选取代的烷基,烯基,炔基,环烷基,芳烷基,芳烯基或芳基的式“IMAGE”的1,1-二卤代烯烃中,R 2为任选取代的烷基, 烯基,炔基,环烷基,芳烷基,芳烯基或芳基,或R 1和R 2一起形成任选支链和/或任选的苯并稠合烃链,并且X 1和X 2各自独立地为卤素原子,其中式 与式(X3)中的X为卤素原子的式(III)的三卤代乙酸酯反应,M(+)​​为碱金属离子或1当量碱土金属离子,在大约等摩尔量存在下 的含磷化合物,其改进包括使用磷酸三烷基酯或亚磷酸三酰胺作为所述含磷化合物,并在约0℃至200℃的温度下进行反应。 优选的最终产物是“IMAGE”,优选的含磷化合物是亚磷酸三甲酯,亚磷酸三乙酯,亚磷酸三丙酯或亚磷酸三 - 二甲基 - 酰胺。
    • 6. 发明授权
    • Process for the preparation of halogenoalkenes
    • 卤代烯烃的制备方法
    • US4330482A
    • 1982-05-18
    • US218394
    • 1980-12-18
    • Hellmut Hoffmann
    • Hellmut Hoffmann
    • C07C69/743C07B31/00C07B37/04C07C17/00C07C17/263C07C45/00C07C45/68C07C49/567C07C67/00C07C253/00C07C255/06C07C255/48C07F9/38C07F9/40C07C21/19C07C121/48
    • C07F9/4065C07C45/68C07C49/567C07F9/4018C07F9/4056
    • In the process for the production of a halogenoalkene of the formula ##STR1## in which R.sup.1 is an optionally substituted alkyl, alkenyl, alkinyl, cycloalkyl, cycloalkenyl, aralkyl, aralkenyl or aryl radical or an optionally substituted heterocyclic radical,R.sup.2 represents a halogen atom, a cyano group, an optionally substituted alkyl, alkenyl, alkinyl, cycloalkyl, aralkenyl, aryl, alkylcarbonyl, arylcarbonyl, alkoxycarbonyl or aminocarbonyl radical or an optionally substituted heterocyclic radical, andX is a halogen atom,in which an .alpha.-hydroxy-phosphonic acid ester of the formula ##STR2## in which R.sup.3 each independently is an alkyl or phenyl radical, or the two radicals R.sup.3 together are an alkanediyl (alkylene) radical,is reacted with a phosphorus-containing olefinating agent of the formula ##STR3## in which Z.sup.1 is the phosphorus-containing radical ##STR4## R.sup.4 and R.sup.5 each independently is an alkyl, phenyl, alkoxy or phenoxy radical or together are an alkanedioxy radical, andR.sup.6 is an alkyl or phenyl radical,in the presence of a base at a temperature between about -70.degree. and +150.degree. C., the improvement which comprises effecting the reaction in the presence of a halogen carrier. The end products are useful as intermediates such as in synthesizing pyrethroid-like insecticides.
    • 在制备其中R 1为任选取代的烷基,烯基,炔基,环烷基,环烯基,芳烷基,芳烯基或芳基或任选取代的杂环基团的式IMAMA的卤代烯烃的方法中,R 2表示卤素原子 ,氰基,任选取代的烷基,烯基,炔基,环烷基,芳烯基,芳基,烷基羰基,芳基羰基,烷氧基羰基或氨基羰基或任选取代的杂环基,X是卤素原子,其中α-羟基膦酸 其中R 3各自独立地是烷基或苯基,或者两个基团R 3一起是烷二基(亚烷基)基团的式“IMAGE”的酸酯与式“IMAGE”的含磷烯烃化合物在 其中Z 1是含磷基团R 4和R 5各自独立地是烷基,苯基,烷氧基或苯氧基,或者一起是烷二氧基,R 6是烷基 1或苯基,在碱存在下,温度在约-70℃至+ 150℃之间,其改进包括在卤素载体存在下进行反应。 最终产物可用作合成拟除虫菊酯类杀虫剂的中间体。
    • 8. 发明授权
    • Process for the preparation of cyclopropane derivatives, intermediates
in the synthesis of pyrethroid insecticides
    • 制备环丙烷衍生物的方法,中间体合成拟除虫菊酯类杀虫剂
    • US4284582A
    • 1981-08-18
    • US177453
    • 1980-08-12
    • Albert E. KayeAlan C. Tucker
    • Albert E. KayeAlan C. Tucker
    • B01J23/00B01J27/00B01J31/00C07C67/00C07C253/00C07C255/45C07C255/48C07C120/00C07C121/48
    • C07C255/45
    • Compounds of formula: ##STR1## wherein both groups X are chlorine, bromine or trifluoromethyl, or one X is chlorine or bromine and the other is trifluoromethyl, and Y is --CN or --COOR in which R is an alkyl group, are obtained by (A) reacting a compound of the formula: ##STR2## wherein X.sup.1 is chlorine or bromine, with a compound of the formula:X.sub.2 C.dbd.CH--CH.dbd.C(CH.sub.3).sub.2in the presence of metallic copper or at least one copper salt and a base, or (B) reacting a compound of the formula:Y--CH.sub.2 --CNwith a compound of the formula:X.sub.2 C.dbd.CH--CH.dbd.C(CH.sub.3).sub.2and chlorine or bromine, in the presence of at least one reducible copper salt and a base, or (C) reacting a compound of formula:X--CH.sub.2 --CNwith a compound of the formula: ##STR3## wherein X.sup.1 is chlorine or bromine, in the presence of at least one copper salt.The compounds are intermediates in the synthesis of pyrethroid insecticides.
    • 其中两个基团X为氯,溴或三氟甲基,或一个X为氯或溴,另一个为三氟甲基,Y为-CN或其中R为烷基的-COOR,分别为 (A)在金属铜或至少一种铜盐的存在下使下式的化合物:其中X 1是氯或溴与下式的化合物:X2C = CH-CH = C(CH3) 和(B)使下式化合物与下式化合物的反应:式中:X 2 C = CH-CH = C(CH 3)2和氯或溴的化合物在至少一种 或者(C)在至少一种铜盐存在下使式:X-CH 2 -CN的化合物与下式的化合物:其中X 1是氯或溴反应。 这些化合物是合成拟除虫菊酯杀虫剂的中间体。