Novel process for preparing semi-caronic aldehydes
    4.
    发明授权
    Novel process for preparing semi-caronic aldehydes 失效
    制备半碳醛的新方法

    公开(公告)号:US5004840A

    公开(公告)日:1991-04-02

    申请号:US282382

    申请日:1988-12-09

    CPC分类号: C07D317/30 C07C62/16

    摘要: A novel process for the preparation of compounds of the formula ##STR1## with cis or trans structure in racemic or optically active form wherein R is selected from the group consisting of hydrogen, alkyl of 1 to 4 carbon atoms and aryl of 6 to 12 carbon atoms comprising reacting an optically active isomer, or racemate of the formula ##STR2## wherein R has the above definition and the way line indicates Z or E geometry with a gem-dimethyl cyclopropanation agent if there is Z geometry to obtain a compound of the formula ##STR3## or if the geometry is E with a gem-dimethyl cyclopropanation agent other than isopropylidene triphenyl phosphorane to obtain a compound of the formula ##STR4## wherein R has the above definition and the cyclopropane ring has the trans configuration and either hydrolyzing the compound of formula III or IIIa to obtain a compound of the formula ##STR5## and then cleaving the 4,5 bond to obtain the corresponding compound of formula I or simultaneously cleaving the 4,5 bond and hydrolyzing the dioxolane group to obtain the corresponding compound of formula I and novel intermediates.

    摘要翻译: 用于制备具有外消旋或旋光活性形式的顺式或反式结构的式I化合物的新方法,其中R选自氢,1至4个碳原子的烷基和6至12个芳基 包括使光学活性异构体或其中R具有上述定义的光学活性异构体或外消旋物,如果存在Z几何形式,则使用偕二甲基环丙烷化剂代替Z或E几何形式,以获得化合物 或者如果几何形状是具有除异亚丙基三苯基膦之外的偕二甲基环丙烷化剂的E,以获得式IIIa的化合物,其中R具有上述定义,并且环丙烷环具有反式构型,并且 水解式III或IIIa的化合物以获得式IV的化合物,然后切割4,5键以获得相应的式I化合物或同时进行 研制4,5键并水解二氧戊环,得到相应的式Ⅰ化合物和新型中间体。

    Process for preparing cis or trans, optically active monoalkyl esters of
cyclopropane-1,3-dicarboxylic acids
    5.
    发明授权
    Process for preparing cis or trans, optically active monoalkyl esters of cyclopropane-1,3-dicarboxylic acids 失效
    制备环丙烷-1,3-二羧酸的顺式或反式光学活性单烷基酯的方法

    公开(公告)号:US4487955A

    公开(公告)日:1984-12-11

    申请号:US511506

    申请日:1983-07-06

    申请人: Alain Krief

    发明人: Alain Krief

    IPC分类号: A01N53/00 C07C69/74

    CPC分类号: A01N53/00

    摘要: A novel process for the preparation of esters of 2,2-dimethyl-cyclopropane-1,3-dicarboxylic acids in their optically active forms having a cis or trans configuration I comprising salifying the monomethyl ester of (1RS,3SR) cis 2,2-dimethyl-cyclopropane-1,3-dicarboxylic acid with d or l .alpha.-methyl-benzylamine, recovering the crystallized salt formed, dissolving the said salt in water, treating the solution with a mineral base and then with an acid to obtain either the monomethyl ester of (1R,3S) cis 2,2-dimethyl-cyclopropane-1,3-dicarboxylic acid I or its (1S,3R) cis isomer depending on whether d or l .alpha.-methyl-benzylamine, respectively was used, if desired, reacting the latter cis compound with a strong base to isomerize the monomethyl ester to the monomethyl ester of (1S,3S) trans 2,2-dimethyl-cyclopropane-1,3-dicarboxylic acid I or (1R,3R) trans isomer, respectively, or reacting the latter cis compound with a tert-butyl esterification agent to obtain a compound of (1S,3R) configuration of the formula ##STR1## or a compound of (1R,3S) configuration of the formula ##STR2## subjecting the said compound to selective hydrolysis to remove the methyl ester group to form a compound of the formula ##STR3## of (1S,3R) cis or (1R,3S) cis configuration, respectively and optionally subjecting the compound of formula I.sub.A to a strong isomerization base to obtain a compound of the formula ##STR4## of (1R,3R) trans or (1S,3S) trans configuration which is a useful intermediate for the preparation of pesticidal compositions.

    摘要翻译: 一种以其旋光活性形式制备2,2-二甲基 - 环丙烷-1,3-二羧酸的酯的新方法,其具有顺式或反式构型I,其包括使(1RS,3SR)顺式2,2 - 二甲基 - 环丙烷-1,3-二羧酸与d或lα-甲基 - 苄胺反应,回收形成的结晶盐,将所述盐溶解在水中,用矿物碱然后用酸处理溶液,得到 (1R,3S)顺式2,2-二甲基 - 环丙烷-1,3-二羧酸I或其(1S,3R)顺式异构体的单甲酯分别使用d或lα-甲基 - 苄胺,如果 (1S,3S)反式2,2-二甲基 - 环丙烷-1,3-二羧酸I或(1R,3R)反式异构体的单甲酯使单甲基酯异构化 或使后一顺式化合物与叔丁基酯化反应,得到(1S,3R)配合物的化合物 式(III)化合物或下式的化合物(1R,3S)构型IIIB使所述化合物进行选择性水解以除去甲基酯基团以形成下式的化合物: (1S,3R)顺式或(1R,3S)顺式构型,并任选地使式IA化合物进行强异构化碱,得到(1R,3R)反式或(1S ,3S)反式构型,其是制备杀虫组合物的有用中间体。

    Methyl cyclopropane-1,3-dicarboxylate
    6.
    发明授权
    Methyl cyclopropane-1,3-dicarboxylate 失效
    环丙烷-1,3-二羧酸甲酯

    公开(公告)号:US4408066A

    公开(公告)日:1983-10-04

    申请号:US308026

    申请日:1981-10-02

    申请人: Alain Krief

    发明人: Alain Krief

    CPC分类号: A01N53/00

    摘要: Novel methyl esters of cis or trans configuration in their optically active form of the formual ##STR1## which are useful as intermediates for the preparation of pesticidal compounds and a process for their preparation and intermediates.

    摘要翻译: 新颖的顺式或反式构型的甲基酯以其光学活性形式的形式可用作制备杀虫化合物的中间体及其制备方法和中间体。

    Process for preparation of trans-chrysanthemates
    10.
    发明授权
    Process for preparation of trans-chrysanthemates 失效
    过菊酯的制备方法

    公开(公告)号:US4048215A

    公开(公告)日:1977-09-13

    申请号:US673458

    申请日:1976-04-05

    IPC分类号: C07C69/743 C07C67/30

    CPC分类号: C07C69/743

    摘要: A novel process for the preparation of alkyl esters of dl-trans chrysanthemic acid of the formula ##STR1## wherein R is alkyl of 1 to 6 carbon atoms comprising reacting in the presence of a strong base an alkyl 4-oxo-2E-butenoate of the formula ##STR2## with at least about 2 molar equivalents of a triphenyl isopropyl phosphonium halide which uses easily accessible starting materials.

    摘要翻译: 用于制备式I的dl-反式菊酸的烷基酯的新方法,其中R是1至6个碳原子的烷基,包括在强碱存在下,将4-氧代-2E-丁烯酸烷基酯 具有至少约2摩尔当量的使用容易获得的起始原料的三苯基异丙基鏻卤化物的式II“IMAGE”。