• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    A process for the preparation of a substituted vinyl-cyclopropanecarboxylic acid ester of the formula <IMAGE> in which R1 and R2 each independently is alkyl with 1-4 carbon atoms or halogen, R3 is halogen, phenoxy or phenoxy substituted by alkyl with 1-4 carbon atoms or by halogen, R4 is halogen or methyl, and n is 0, 1, 2, 3 or 4, comprising saponifying with alkali an ester of the formula <IMAGE> in which R5 is alkyl with 1-4 carbon atoms, thereby to replace R5 by an alkaline salt group, and directly reacting such salt without intermediate purification with a benzyl chloride of the formula <IMAGE> Advantageously the benzyl chloride is obtained by the gas-phase photochlorination of a compound of the formula <IMAGE> (IV), the chlorination proceeding to about 25 to 75%, and the chlorination mass being employed directly without isolation.
    公开号:SU725553A1
    申请号:SU2610503
    申请日:1978-05-04
    公开日:1980-03-30
    发明作者:Науманн Клаус；Шубарт Рюдигер；Шмидт Томас
    申请人:Байер Аг (Фирма)；
    IPC主号:
    专利说明:

    tse R - methyl, ethyl, ergüyt ŠYaYaNSH SRfiriirtCfcn, abbreviated to sodium Schröberkysi or kai; temperature t 50-1 with the subsequent interaction of the salt obtained in this at a temperature of 20 with a solution of a benyl derivative of the general formula. Cl-CHj dv R / R and n. Name indicated Enacho: and, -. : of the reaction process of gaseous loriation at the irradiation of the compound and formula, ... (Yu de R, R / and ri have the indicated meanings. It is advisable to carry out the solvent with a solvent, and to interact with the solution of the benzyl derivative of formula III with the salt in the catalytic solution. The gas of chlorination under the irradiation of the compound of formula IV is carried out at 200400 C and 1-6 and the ratio of the compound of formula IV and chlorine is 1: 0, 1-1. The starting compounds of formula II and III are known OR they can be obtained by known methods. Example 1. Preparation of 2- (3) phenoxybenzene ester 2, -dichlorovinyl) -3,3-dimethyl iklopropa karbokovy kiyloty. I. Alkaline saponification of a complex eff. 2- (2, 2-dichlorovinyl) -3, 3-dimethyl-cyPropropanecarboxylic acid methanol. dimethylcyclopropanecarboxylic acid and 1 mol of con at 0.5 mol of CH-jOH are boiled in the presence of 5 mol of water for 10 hours. Condensed in vacuum to obtain the soap mass of the potassium salt.. II. Alcohol saponification of methyl ester 2- (2,2-dichlorovinyl) -3, 3-dimethylcyclopropanecarboxylic sodium hydroxide in 3-fenok sitoluene. 0.2 mol of methyl 2- (2,2-dichlorovinyl) -3,3-dimethyl- (cyclopropanecarboxylic acid in 300 3-phenoxytoluene and 0.2 mol of porcine bw, NaOH is heated to 30 minutes NOL is distilled, PoPuch &amp; a suspension of sodium salt ...: III.Gasophasic chlorination of 3-phyrxitoluene .. In a round bottom flask with a 30 cm packed column, the upper part is connected to the reaction zone with a gas frit, zone and the refrigerator is heated to a boiling point of 0.75 mol of 3-phenoxytoluene. 0.25 mol of dry gaseous chlorine diluted with nitrogen in a ratio of 1 l is injected into the lamp by irradiation with a mercury lamp. According to the xpc analysis, the flask contains not only 3-phenoxytoluene, but also 3-phenoxy-benzylsolid with a purity of 95%. 3-Phenoxybaseyl chloride is almost quantitative. No distillation is obtained by distillation in vacuum. —N IV. Complicated 3- (2,2-dichlorovinyl) -3, 3-dimethylcyclopropanecarboxylic acid. Option A. Obtained in stage II sodium salt suspension 2- (2,2-dichlorovinyl) -3,3-dimeTylcyclopropane arbonovoy acid 3-fenoksitoluole is subjected to interaction with the reaction solution obtained in step III, in the presence of 10 g pentildietilentriamina at temperature for 5 hours. drained, washed and 3tfonoLsitoluolom first in vacuo. 0.1 Tfrr the components boiling up to a temperature of 150 ° C are distilled off. The high boiling point fraction is then fractionated. B.p. target product 190, 1 mm Hg The yield in terms of the methyl ester used is 88%, Option B. 3-Phenoxytoluene is chlorinated with 0.3 mol of CBg under the conditions indicated above. Get reactive. a solution containing 0.28 mol of 3-phenoxybenzyl .por11) :( a. 0.28 mol of ethyl 2- {2,2-dichlorovinyl) -3,3-dimethylcyclopropanecarboxylic acid and 0.28 mol of powdered NaOH are added, and also 0.01 mole of pentamethylene diethyl triamine and heat. The mixture is heated to 5 ° C for 5 hours, at first 0.28 mol of ethanol is distilled off. After processing in the manner described and distillation, the indicated benzyl ester is obtained with a yield of 89.5%, based on the ethyl ester used. Example 2. Example 1 is repeated, with the difference that the forearm saponification process is carried out at a temperature in the absence of a solvent, the reaction of a compound of formula II with a compound of formula III (according to option A) at a temperature of 20 ° C. No catalyst, and gas-phase chlorination at a temperature 200 C and molar ratio of 3-phenoxytoluoic and chlorine gas equal to 1: 1. The yield of benzyl ester is 81.5%, based on the starting methyl ester,
    权利要求:
    Claims (2)
    [1]
    1. · A method of producing benzyl esters of dichlorovinyl dimethylcyclopropane carboxylic acid of the General formula
    Yield,% {in terms of the ester of formula II) <i>
    R is halogen or phenoxy;
    R 4 is halogen;
    η - 0-4, using a benzyl derivative and isolating the target product by distillation, which is explained by the fact that, in order to increase the yield of the target product, the compound of the general formula is .91. 85 where they are subjected to saponification with an equimolar amount of potassium or sodium hydroxide at a temperature of 50-180 ° C, followed by interaction of the resulting salt at a temperature of 20-150 ° C with a solution of a benzyl derivative of the general formula "4" 2 "where R, R and η have ; indicated values, from the reaction of gas phaenogene chlorination upon irradiation of a compound of formula sn 3
    88.5 and η have the indicated ena
    The method according to claim 1, wherein the tea is prepared by the fact that saponification is carried out in a solvent environment.
    The method according to claim 1, with respect to the fact that the interaction
    TSNIIIPI Order 2134/60 Circulation 495 - ,,, Subscription
    Branch of PPP ’’ Patent * ’, g * Uzhhorod, st. Project 4, where R *, R * of reading.
    [2]
    ! ’2.
    u and Led:. h. the second solution of a benzyl derivative of the general formula III with a salt is carried out in the presence of a catalyst.
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    同族专利:
    公开号 | 公开日
    PL206644A1|1979-04-23|
    IL54665A|1981-07-31|
    GB1584526A|1981-02-11|
    PL110204B1|1980-07-31|
    IL54665D0|1978-07-31|
    SU725553A3|1980-03-30|
    CS198298B2|1980-05-30|
    BE866909A|1978-11-10|
    AT355005B|1980-02-11|
    DD138898A5|1979-11-28|
    NL7804910A|1978-11-14|
    IT7823198D0|1978-05-09|
    BR7802936A|1979-01-02|
    FR2390417A1|1978-12-08|
    HU175042B|1980-05-28|
    US4256907A|1981-03-17|
    JPS53141247A|1978-12-08|
    DK204878A|1978-11-12|
    DE2721185A1|1978-11-16|
    ATA336078A|1979-07-15|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    GB633435A|1946-06-22|1949-12-19|Monsanto Chemicals|Improvements in or relating to process for producing paraacetylbenzyl acetate, para- benzyl acetate and para- benzyl acetate|
    GB1102838A|1965-02-19|1968-02-14|Sumitomo Chemical Co|Cyclopropanecarboxylic acid esters, methods of making them and insecticidal compositions including them|
    US3850977A|1968-06-06|1974-11-26|Sumitomo Chemical Co|3-substituted-benzyl cyclopropane-carboxylates|
    USRE28110E|1968-12-09|1974-08-13|Chrysanthemic acid esters |
    US3666789A|1969-05-21|1972-05-30|Sumitomo Chemical Co|Cyclopropanecarboxylic acid esters|
    JPS4831891B1|1970-03-19|1973-10-02|
    JPS49489B1|1970-06-13|1974-01-08|
    US4024163A|1972-05-25|1977-05-17|National Research Development Corporation|Insecticides|
    GB1438129A|1973-12-21|1976-06-03|
    GB1533856A|1975-03-24|1978-11-29|Shell Int Research|Process for the preparation of meta-aryloxy benzyl bromides|
    GB1559799A|1975-11-12|1980-01-30|Shell Int Research|Process for preparing substituted benzylesters|DE2840992A1|1978-09-21|1980-05-29|Bayer Ag|AGENT AGAINST SOIL INSECTS|
    CA1150300A|1978-10-13|1983-07-19|Robert J.G. Searle|2,6-dihalobenzyl esters and their use aspesticides|
    DE2939913A1|1979-10-02|1981-04-30|Bayer Ag, 5090 Leverkusen|3--2,2-DIMETHYL-CYCLOPROPANCARBONIC ACID FLUOR-BENZYL ESTER, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE IN PEST CONTROL|
    GB2066810A|1979-12-21|1981-07-15|Ici Ltd|Fluorinated benzyl esters of cyclopropane carboxylic acids|
    US4370346A|1979-12-21|1983-01-25|Imperial Chemical Industries Plc|Halogenated esters|
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    US5238957A|1988-07-07|1993-08-24|Presidenza Del Consiglio Dei Ministri-Uffico Del Ministro Per Il Coordinamento Delle Iniziative Per La Ricerca Scientifica E Tecnologica|Esters of 2,2-dimethyl-cyclopropane-carboxylic acid|
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    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    DE19772721185|DE2721185A1|1977-05-11|1977-05-11|METHOD FOR MANUFACTURING SUBSTITUTED VINYLCYCLOPROPANCARBONIC ACID ENZYLESTERS|
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