• 专利附录
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    • 专利摘要:
    This invention relates to the preparation of cyclopropane carboxylic acid ester derivatives, which are useful as pesticides. There is provided a process for preparing a 1:1 mixture of 1R cis S- and 1S cis R- isomers substantially free of 1S cis S- and 1R cis R- isomers of a compound of formula: <IMAGE> (I) wherein R1 and R2 are each independently selected from chlorine, bromine and methyl, which process comprises dissolving a mixture of 1S cis S- and 1R cis R- isomers of the compound of formula I, alone or in the presence of 1R cis S- and 1S cis R-isomers, in organic amine base containing from 5 to 7 carbon atoms and being a secondary amine containing two branched alkyl groups or a tertiary amine, and crystallizing out from the resulting solution of cis - isomers of formula I in the organic amine base a 1:1 mixture of the 1R cis S- and 1S cis R- isomers substantially free of 1S cis S- and 1R cis R- isomers. The process of the invention yields a product which contains substantially twice as much of the most active isomer of the compound of formula I as a racemic mixture of all four cis - isomers, and is a readily effected process which does not involve any asymmetric synthesis or optical resolution steps.
    公开号:SU1349697A3
    申请号:SU813275450
    申请日:1981-04-21
    公开日:1987-10-30
    发明作者:Фрэнк Мейзон Рональд；Александр Вуд Дерек
    申请人:Шелл Интернэшнл Рисерч Маатсхаппий Б.В. (Фирма)；
    IPC主号:
    专利说明:

    113496972
    The invention relates to a 94% process, the yield of which is to obtain a crystalline equivalent-81%,
    .Cool mixture of the pair (3) -cis-1E- and Example2. 106 g of cis- mixture. K-cis-18-isomers cyclopropanecarbono-j. -isomers of o-cyano (3 phenoxybenzyl) - acid of the formula.-3- (2,2-dichlorvinyl) -252-dimethylcyclic .f containing 1
    jjr weight,% 15-cis-5- and 1K-cis-8-isome. hc, ditch and 58% weight of% 1E-cis-3- and 18-cis-K / HFC Q isomers, dissolved in 212 ml three - / GPOC -fc y / ethylamine with stirring and heating .f, I / - vanes at. The solution is cooled ttr N - G
       mj - with stirring and at temperature
    30 ° C are added to it; a few crises are used as. 1K-cis-8- and IS-cis-, TS D of K-isomers of the α-cyano- (3-phenoxyben) The purpose of the invention is the increase in the yield of) -3- (2,2-diclorovinyl) -2,2-dimethyl- the course of the target product. cyclopropanecarboxylate. Mixing Example 1, 5.8 g of crystalline-so
    . Continuation continues after 38 hours to reach the racemic mixture of cis isomers niOr.
    ,,, „“ At a final temperature of 21 C, you are 1b-cyano-C3-phenoxybenzyl; -3-C2 .2-di
      ; -, oh, "fallen solid precipitated from chlorine; -2, 2-dimethylcyclopropane-,"
    , go. Filtered to dryness on a Büchcarboxylate funnel of formula I (tlsh, 58t- .o „h.pnera, then dried under vacuum at
    77 C) is dissolved in 10 ml of triethylamine-g o ,,
    -, 0 55 C, as a result receive
    on when heated to 70 C. Dissolve t,
    2572.9 g of crystalline product
    cooled to room temperature 82-84 ° C), which (as shown by stirring and entering into the results of liquid chromatography, several crystals of a 1: 1 mixture of 1R high resolution graphs) contains -cis-S- and 13- cis-E-isomers of oi-cya- 55 wtD of a 1: 1 mixture of Cx-cis-5- and 1S- but- (3-phenoxybenzyl) -3- (2,2-dichloro-cis-11-isomers.
    nyl) -2,2-dimethylcyclopropanecarboxy- - the filtrate is evaporated to 70 ml, nalata. The precipitate obtained as a result is heated to 70 ° C with stirring, crystallization, separated and dried, cooled and injected. Crystalline crystals — as a result of which 3.4 g are obtained without solid color crystals with t, pcs. 80-83 ° C, the material is similar to that described, in which (as shown by 35 u results, another 15.3 g liquid chromatography of a high crystalline product (mp. 82- resolution) contain 94 wtL mixtures containing 95 wt.% mixtures G: 1 1: 1 1R-3HC-S and 13-cis-E-isomers w-cis-3- and 1Z-cis-C-isomers. Compound of formula I. Filtrate obtained in the second
    After crystallization, the filtrate is evaporated to 25 ml, treated to half the volume and again, / p. stages, and crystallized, as a result of which an additional 7.7 g of crystals are obtained; in addition, colorless crystals of the product (mp. 83-84 ° C), crystals with mp. 82-84 ° C, which contain 95% by weight of a 1: 1 1R- mixture (as indicated by liquid 45 and 18-cis-K-isomers. High-resolution chromatography), by a three-stage method contain more than 94% by weight of a 1: 1 mixture A 1: 1 mixture of 1K-cis-1K-cis-8- and 18-cis-K-isomers is obtained by treatment ... g 1z-cis-K-isomers with a purity of 95%,
    The results of a similar analysis of which is 90%. trimethylamine solution, the remaining 50
    with after secondary crystallization. Example 3. 118.7 g of a mixture of cis- show that the ratio of the concentration of α-isomers of od-cyano- (3-phenoxybenzyl) - 15-cis-8- and 1K-cis K-isomers to 3- (2.2- The dichlorovinyl) -2,2-dimethylcyctic concentration of 1K-cis-8- and 18-cis-K-propanecarboxylate containing -) zomers is in the order of 16: 9. 55% by weight of the 13-cis-3- and 1K-cis-K-isomers and 31% by weight of the 1C-cis-3- and 18-cis-C. Thus, by two-stage isomers, dissolved in 236 ml of tri- A 1: 1 mixture of ethylamine is obtained in the treatment and the solution is treated as 1K-cis-8- and 18-cis-E-isomers with the number as in Example 2. 61.7 g are obtained.
    83 ° C) containing 95 wt.% 1: 1 mixture of 1K-cis-5- and 15-cis-K-isomers.
    The filtrate is evaporated to 70 ml and treated in the same way as in the second stage of Example 2, resulting in another 24.4 g of crystalline product (mp. 76-80 ° C) containing 90% by weight of a 1: 1 1 K mixture -cis-5- and 1S- -cis-K-isomers,
    Thus, by a two-stage treatment, a 1: 1 mixture of IR-cis-S- and 1Z-cis-K-isomers is obtained with a purity of more than 90%, the yield of which is 73%.
    PRI me R 4. 906 g of a mixture of cis-isomers of o-cyano- (5-phenoxybenzyl) -3- (2,2-dichlorovinyl) -2,2-dimethylcyclopropanecarboxylate containing
    42% by weight of 13-cis-3- and 1K-cis-K-isome- 20 Cis-K-isomers.
    58% by weight, 1K-cis-3- and 18-cis-11- Thus, the three-step o-isomers are dissolved in 1812 ml of trr-ethylamine by heating to 70 ° C. The resulting solution is filtered through a glass filter no. 3 and cooled, stirring with a stirrer, the blades of which are made of polytetrafluoroethylene. At 26. С ъ solution
    PRI me R 5. 100 g of a substance containing 91.5-g of a mixture of cis-isomers &amp; 1.-cyano- (3-phenoxybenzyl) -3- (2,2-dichloretenyl) -2.2 -dimethylcyclopropane carboxylate, consisting of 56.4% 30 13-cis-3- and 1K-cx-C-isomers and 38.6% 1C-cis-3- and 1Z-cis-C-isomers. dissolved in triethylamine at 70 ° C. Cooled to 10 ° C and stirred at this temperature for 24 hours. Several nucleating crystals of a mixture of 1: G are precipitated: 1C-cis-8- and 13-cis-K-isomers og, -cyano- (3-phenoxybenzyl) -3- - (2,2-dichlorovinyl) -2,2-dimethylcyclopropanecarboxylate. Stirring is continued for two days, the final solution temperature is 20 ° C. The tall glass is filtered off, the solid solid material is washed with a filter in 50 ml portions of pentane, dried, dried and sucked off on a vacuum overnight in air. A Kuum filter is obtained, and 67.0 g of the crystalline product is washed once (500 ml of 60-80% petroleum ether, 73%), which, according to chromatography at -10 ° C, is dried to constant weight until graphically analyzed. 89% sobbit in a vacuum cabinet at room temperature from a 1: 1 mixture of 1K-cis-3- and 1Z-cis-K-temperature, as a result of which -isomers are obtained.
    Example 6. The process is carried out under the conditions of example 5, but at high resolution temperature chromatography, when crystallization is about C. About 59.1 g is obtained. It is reduced to contain 94% by weight of crystalline product (1: 1 mixture yield: IR- cis-W- and 13-cis-R-iso- 65%), which according to the liquid.
    chromatography contains 92 wt.% a mixture of 1: 1 IR-cis-3- and 13-cis-R-isomers of the starting material.
    638 g of crystalline product
    t „il. 82-84 C. With liquid
    Merov.
    The filtrate is evaporated to a volume of 800 ml, heated to 60 ° C, cooled while being moved to 30 ° C and after reaching this temperature several crystals are introduced, 1: 1 mixture of IR-cis-3- and 13-cis-R- isomers about -cyano- (3-phenoxybenzyl) -3- (2,2-dichlorovinyl) -2,2-dimethylcyclopropanecarboxylate. Stirring is continued for three days, the final temperature of the solution is 23 C. The precipitated material is 50
    55
    Example 7. 200 g of a racemic mixture of cis-isomer E y-cyano- (3-phenoxybenzyl) -3- (2,2-dichloroethenyl) -2,2-. -dimethylcyclopropanecarboxylate is dissolved in 300 ml of triethylamino. The solution is stirred for 7Z hours at 14 ° C. The precipitate formed is filtered off and washed with cold triethnlamine.
    vacuum filter, washed once with 200 ml of triethylamine at -10 Cu once washed with 200 ml of 60-80% petroleum ether at
    , 0,
    -ten
    dried under the conditions described. and
    get more. 178 g of crystalline product (mp. 83-85 C), containing
    98 wt.% 1: 1 mixture of 1K-cis-5- and 15-cis -R-isomers.
    The filtrate obtained in the second stage is evaporated to a volume of 200 ml and treated in the same way, but
    stirring is continued for five days, as a result of which another 51 g of crystalline product (mp. 82–84 ° C) containing 92% by weight of a 1: 1 mixture of 1K-cis-5- and 1S is obtained
    a 1: 1 mixture of IR-cis-S- and 1Z-cis-K-isomerism with a purity of 94% and a yield of 95% are obtained.
    PRI me R 5. 100 g of a substance containing 91.5-g of a mixture of cis-isomers &amp; 1.-cyano- (3-phenoxybenzyl) -3- (2,2-dichloretenyl) -2.2 -dimethylcyclopropane carboxylate, consisting of 56.4% 13-cis-3- and 1K-cx-C-isomers and 38.6% 1C-cis-3- and 1Z-cis-C-isomers. dissolved in triethylamine at 70 ° C. Cooled to 10 ° C and stirred at this temperature for 24 hours. The precipitated crystals are filtered, washed with three 50 ml portions of pentane, and dried overnight in air. 67.0 g of crystalline product is obtained (yield 73%), which according to chromatographic analysis, is 89% combined from a 1: 1 mixture of 1K-cis-3- and 1Z-cis-K-isomers.
    50
    55
    Example 7. 200 g of a racemic mixture of cis-isomer E y-cyano- (3-phenoxybenzyl) -3- (2,2-dichloroethenyl) -2,2-. -dimethylcyclopropanecarboxylate is dissolved in 300 ml of triethylamino. The solution is stirred for 7Z hours at 14 ° C. The precipitate formed is filtered off and washed with cold triethnlamine.
    13496976
    air dried. Obtain As can be seen from the above examples, 142 g of crystals (71% yield), the product the proposed method allows to contain 95% of a 1: 1 mixture of 1K-cis-8- and the desired product can be read in 65-95% of 15-cis K-isomers. S (vs. 28-56% by attachment method).
    权利要求:
    Claims (2)
    [1]
    METHOD FOR PRODUCING CRYSTALLINE EQUIMOLECULAR MIXTURE OF A PAIR. Of enantiomers of (S) -ob-cyano- (3-phenoxybenzyl) -1R-cis-3- (2,2-dichloroethenyl) -2,2-dimethylcyclo-propanocarboxylate and (R) -ob-cyano- (3-phenoxy) -CIS-3- (2,2-DICHLORETHENYL) -2,2-DIMETHYL CYCLOPROPANOCARBOXYLATE by dissolving a mixture of the cis isomers of ob-cyano (3-phenoxybenzyl) -3- (2,2-dichloroethenyl) -2,2-dimethylcyclopropanecarboxylate in the presence of triethylamine with separation of the precipitated crystals of the target mixture from the mother liquor and removal of triethylamine, characterized in that, in order to increase the yield of the target product, racemic is used as the initial mixture a mixture of four isomers of ob-cyano- (3-phenoxybenzyl) -3- (2,2-dichloroethenyl) -2,2-dimethylcyclopropylcarboxylate or a mixture of (3) -cyano- (3-phenoxybenzyl) -1B-cis-3- ( 2,2-dichloroethenyl) - g
    [2]
    -2,2-dimethylcyclopropanecarboxylate and (E) -ob-cyano- (3-phenoxybenzyl) -1D-cis-3- (2,2-dichloroethenyl) -2,2-dimethylcyclopropanecarboxylate, which is dissolved in triethylamine used as a solvent , and incubated at 0-30 C.
    SU <. " 1349697 AZ
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    引用文献:
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    US4024163A|1972-05-25|1977-05-17|National Research Development Corporation|Insecticides|
    GB1413491A|1972-05-25|1975-11-12|Nat Res Dev|3-substituted-2,2-dimethyl-cyclopropane carboxylic acid esterstheir preparation and their use in pesticidal compositions|
    FR2348901B1|1976-04-23|1983-01-28|Roussel Uclaf|
    FR2375161B1|1976-04-23|1979-04-13|Roussel Uclaf|
    FR2383147B2|1977-03-09|1983-04-29|Roussel Uclaf|
    US4176195A|1978-07-20|1979-11-27|Sumitomo Chemical Company, Limited|Pesticidal α-cyanobenzyl ester enantiomer pair|
    US4261921A|1979-06-06|1981-04-14|Fmc Corporation|Process for preparation of a crystalline insecticidal pyrethroid enantiomer pair|
    CA1150301A|1979-11-27|1983-07-19|Michael J. Bull|Cyclopropane carboxylic acid esterderivatives|
    US4260633A|1980-04-21|1981-04-07|Zoecon Corporation|Pesticidal esters of amino acids|CA1206483A|1982-11-11|1986-06-24|Johannes Van Berkel|Process for preparing cyclopropane carboxylic acidester derivatives|
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    CA1275108A|1985-01-16|1990-10-09|Laszlo Pap|Insecticidal composition comprising more than oneactive ingredients|
    US4997970A|1987-06-15|1991-03-05|Fmc Corporation|Conversion of pyrethroid isomers to move active species|
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    GB9127355D0|1991-12-24|1992-02-19|Ici Plc|Isomerisation process|
    GB0229803D0|2002-12-20|2003-01-29|Syngenta Ltd|Chemical process|
    法律状态:
    优先权:
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