Process for production of .beta.-dihalogenoethenylcyclopropane
derivatives
    1.
    发明授权
    Process for production of .beta.-dihalogenoethenylcyclopropane derivatives 失效
    生产β-二卤代乙酰基环丙烷衍生物的方法

    公开(公告)号:US4740612A

    公开(公告)日:1988-04-26

    申请号:US825966

    申请日:1986-02-05

    CPC分类号: C07C45/65 C07C45/69

    摘要: A novel process for producing a .beta.-dihalogenoethenylcyclopropane derivative of the formula, ##STR1## wherein R.sub.1 is a hydrogen atom or an alkyl group, R.sub.3 is a hydrogen atom, lower alkyl, acyl, carboxyl or alkoxycarbonyl group and R is a hydrogen atom or a lower alkyl group and each of Y.sub.1 and Y.sub.2 is a fluorine, chlorine or bromine atom respectively, which is an acidic moiety of the useful synthetic insecticides of the pyrethrin type, which process comprises a combination of a series of sequential steps starting from alkyl 3-butenyl ketone derivative of the formula (I), which may be shown according to the following reaction scheme: ##STR2## According to this process, objective compound of the formula (VI) having any cis/trans ratio can be produced by selecting the reaction condition of the Stages II-1, II-2, and IV-2.

    摘要翻译: 一种制备下式的β-二卤代乙酰基环丙烷衍生物的新方法,其中R1是氢原子或烷基,R3是氢原子,低级烷基,酰基,羧基或烷氧基羰基,R是氢原子或 低级烷基,Y1和Y2各自分别是氟,氯或溴原子,它们是除虫菊酯类有用的合成杀虫剂的酸性部分,该方法包括从烷基3开始的一系列顺序步骤的组合 (VI)的目标化合物,其具有任何顺式(Ⅵ)的式(Ⅵ)的化合物, /反式比可以通过选择阶段II-1,II-2和IV-2的反应条件来产生。

    Method for preparing 4-hydroxy-3-methyl-2-(2-propynyl)-2-cyclopentenolone
    4.
    发明授权
    Method for preparing 4-hydroxy-3-methyl-2-(2-propynyl)-2-cyclopentenolone 失效
    4-羟基-3-甲基-2-(2-丙炔基)-2-环戊烯醇的制备方法

    公开(公告)号:US4343953A

    公开(公告)日:1982-08-10

    申请号:US159497

    申请日:1980-06-16

    摘要: The present invention relates to a novel method for producing cyclopentenolone of the formula (I), ##STR1## which is a useful intermediate for producing agricultural chemicals, which comprises reacting an acetonedicarboxylic ester of the formula (VII), ##STR2## wherein R is a C.sub.1 -C.sub.6 alkyl group, with 2-propynyl chloride in the presence of magnesium alkoxide and in the presence of alkali iodide to obtain novel mono-(2-propynyl)-substituted acetonedicarboxylic ester of the formula (VI), ##STR3## wherein R is as defined above; hydrolyzing the mono-(2-propynyl)-substituted acetonedicarboxylic ester of the formula (VI) under alkaline conditions with an alkali and then reacting the hydrolyzed product with methylglyoxal of the formula, ##STR4## to obtain novel .gamma.-diketone of the formula (V), ##STR5## and ring-closing the .gamma.-diketone of the formula (V) under alkaline condition.

    摘要翻译: 本发明涉及一种制备式(I)的环戊烯醇酮的新方法,其是用于生产农药的有用的中间体,其包括使式(VII)的丙酮二羧酸酯, (Ⅶ)其中R是C 1 -C 6烷基,与2-丙炔基氯在烷氧基镁存在下,在碱金属碘化物的存在下,得到式(Ⅵ)的新型单 - (2-丙炔基) - 取代的丙酮二羧酸酯 ),其中R如上定义; 在碱性条件下用碱水解式(Ⅵ)的单 - (2-丙炔基) - 取代的丙二酸二羧酸酯,然后使水解产物与下式的甲基乙二醛反应,得到式(Ⅵ)的新的γ-二酮 V),(V)并在碱性条件下闭合式(V)的γ-二酮。

    Process for isomerization of a cyclopropanecarboxylic acid
    5.
    发明授权
    Process for isomerization of a cyclopropanecarboxylic acid 失效
    环丙烷羧酸异构化的方法

    公开(公告)号:US4008268A

    公开(公告)日:1977-02-15

    申请号:US585592

    申请日:1975-06-10

    CPC分类号: C07C51/353

    摘要: A process for isomerizing 2-(.beta.,.beta.-dichlorovinyl)-3,3-dimethylcyclopropanecarboxylic acid represented by the formula, ##STR1## which comprises heating the acid of the formula (I) in the presence of the anhydride of the acid or a reagent producing the acid anhydride in the reaction system.The ester resulting from 2-(.beta.,.beta.-dichlorovinyl)-3,3-dimethylcyclopropanecarboxylic acid and, for example, 3-phenoxybenzyl alcohol is a compound which has a very wide range of insecticidal spectrum and has a very high controlling effect as a low-toxicity insecticide not only for domestic use and public health but also against insects injurious to agriculture or forestry, and in the case of the 3-phenoxybenzyl ester or 5-benzyl-3-furylmethyl ester of the 2-(.beta.,.beta.-dichlorovinyl)-3,3-dimethylcyclopropanecarboxylic acid, the trans-isomer is lower than the cis-isomer in toxicity to warm-blooded animals.

    摘要翻译: 异构化由式(I)表示的2-(β,β-二氯乙烯基)-3,3-二甲基环丙烷甲酸的方法,其包括在存在下述的酸酐的情况下加热式(I)的酸 酸或在反应体系中产生酸酐的试剂。

    Novel cyclopropanecarboxylates
    6.
    发明授权
    Novel cyclopropanecarboxylates 失效
    新型环丙烷羧酸酯

    公开(公告)号:US4003945A

    公开(公告)日:1977-01-18

    申请号:US461029

    申请日:1974-04-15

    摘要: Novel alkynylcyclopropanecarboxylic acid esters represented by the formula, ##STR1## wherein R.sub.1 represents hydrogen, halogen, lower alkyl having up to 5 carbon atoms, lower alkenyl having up to 5 carbon atoms, lower alkynyl having up to 5 carbon atoms, C.sub.1 -C.sub.4 alkoxy C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 alkylthio C.sub.1 -C.sub.4 alkyl, aryl, aryl C.sub.1 -C.sub.4 alkyl, furyl, substituted furyl, thienyl, substituted thienyl, furfuryl, substituted furfuryl, thenyl, substituted thenyl, cyclo C.sub.3 -C.sub.6 alkyl, substituted cyclo C.sub.3 -C.sub.6 alkyl, cyclo C.sub.3 -C.sub.6 alkenyl or substituted cyclo C.sub.3 -C.sub.6 alkenyl; R.sub.2 and R.sub.3 individually represent hydrogen, halogen, lower alkyl having up to 5 carbon atoms, lower alkenyl having up to 5 carbon atoms, lower alkynyl having up to 5 carbon atoms, aryl, aryl C.sub.1 -C.sub.4 alkyl or may form a carbon-carbon bond; or R.sub.1 and R.sub.3 are bonded to each other at the ends to form a polymethylene chain containing or not containing an oxygen or a sulfur atom, or R.sub.1 and R.sub.2 are bonded to each other at the ends to form a polymethylene chain containing or not containing an oxygen or a sulfur atom; R.sub.4 represents hydrogen or methyl; R.sub.5 represents hydrogen, methyl, vinyl, 1-propenyl, 2-methyl-1-propenyl, 2-methoxymethyl-1-propenyl, 2-methoxycarbonyl-1-propenyl, 2,2-dichlorovinyl or cyclopentyl-idenemethyl when R.sub.4 is hydrogen, and R.sub.5 represents methyl when R.sub.4 is methyl; and R.sub.6 and R.sub.7 represent hydrogen or methyl. These novel esters are produced by reacting an alcohol or its halide or arylsulfonate of the formula, ##STR2## wherein R.sub.1, R.sub.2, R.sub.3 and R.sub.6 are defined above, and A is hydroxy, halogen or arylsulfoxy, with a cyclopropane-carboxylic acid of the formula, ##STR3## wherein R.sub.4, R.sub.5 and R.sub.7 are as defined above, or its reactive derivative. These esters are useful as an insecticide harmless to mammals.

    摘要翻译: 由式表示的新型炔基环丙烷羧酸酯,其中R 1表示氢,卤素,具有至多5个碳原子的低级烷基,具有至多5个碳原子的低级链烯基,低至5个碳原子的低级炔基,C1-C4烷氧基 C 1 -C 4烷基,C 1 -C 4烷硫基C 1 -C 4烷基,芳基,芳基C 1 -C 4烷基,呋喃基,取代的呋喃基,噻吩基,取代的噻吩基,糠基,取代的糠基,噻吩基,取代的芳基,环C 3 -C 6烷基,取代的环 C 3 -C 6烷基,环C 3 -C 6烯基或取代的环C 3 -C 6烯基; R 2和R 3各自表示氢,卤素,具有至多5个碳原子的低级烷基,具有至多5个碳原子的低级链烯基,具有至多5个碳原子的低级炔基,芳基,芳基C 1 -C 4烷基或可形成碳 - 碳 键; 或者R 1和R 3在末端彼此键合以形成含有或不含有氧原子或硫原子的多亚甲基链,或者R 1和R 2在末端彼此结合形成含有或不含有 氧或硫原子; R4代表氢或甲基; 当R4为氢时,R5代表氢,甲基,乙烯基,1-丙烯基,2-甲基-1-丙烯基,2-甲氧基甲基-1-丙烯基,2-甲氧基羰基-1-丙烯基,2,2-二氯乙烯基或环戊基 - 当R 4为甲基时,R 5表示甲基; 并且R 6和R 7表示氢或甲基。 这些新型酯通过使下式的醇或其卤化物或芳基磺酸盐与其中R1,R2,R3和R6定义如上,A是羟基,卤素或芳基磺酰基的醇或其卤化物或芳基磺酸酯与 式,其中R 4,R 5和R 7如上所定义,或其反应性衍生物。 这些酯可用作对哺乳动物无害的杀虫剂。