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    • 专利摘要:
    1424170 Alkynyl cyclopropanecarboxylic acid esters SUMITOMO CHEMICAL CO Ltd 18 April 1974 [20 April 1973 24 May 1973 4 June 1973] 17127/74 Heading C2C The invention comprises compounds of the formula wherein R 1 is a hydrogen or halogen atom, or a C 1-5 alkyl, optionally substituted C 2-5 alkenyl, C 2-5 alkynyl, C 1-4 alkoxy-C 1-4 alkyl, C 1-4 alkylthio-C 1-4 alkyl, aryl, aryl-C 1-4 alkyl, aryloxy-C 1-4 alkyl or arylthio-C 1-4 alkyl group, an optionally substituted furyl group, an optionally substituted thienyl group, an optionally substituted furfuryl group, an optionally substituted thenyl group, an optionally substituted cyclo-C 3-6 alkyl group, or an optionally substituted cyclo-C 3-6 alkenyl group which said cyclo-C 3-6 alkyl and cyclo-C 3-6 alkenyl groups each optionally contain a hetero atom in the nucleus thereof; each of R 2 and R 3 is independently a hydrogen or halogen atom, or a C 1-5 alkyl, C 2-5 alkenyl, C 2-5 alkynyl, aryl, or aryl- C 1-4 alkyl group or R 2 and R 3 may together represent a carbon-carbon bond; or R 1 and R 3 may be joined to form a polymethylene chain optionally containing an oxygen or a sulphur atom in the chain, or R 1 and R 2 may be joined to form a polymethylene chain optionally containing an oxygen or a sulphur atom in the chain; R 4 is a hydrogen atom or a methyl group; R 5 is, when R 4 is a hydrogen atom, a hydrogen atom, or a methyl, vinyl, 1-propenyl-2-methyl- 1-propenyl, 2-methoxymethyl-1-propenyl, 2- methoxy - carbonyl - 1 - propenyl, 2,2 - dichlorovinyl, butadienyl, 2-methyl - butadienyl or cyclopentylidenemethyl, and R 5 represents methyl when R 4 is methyl; and R 6 and R 7 are hydrogen or methyl. The compounds are prepared by reacting a compound of the formula where A is hydroxy, halogen or arylsulphoxy with a compound of the formula or a reactive derivative thereof.
    公开号:SU1255048A3
    申请号:SU742021589
    申请日:1974-04-18
    公开日:1986-08-30
    发明作者:Китамура Сигейоси；Итайя Нобусиге；Окуно Иоситоси；Оно Нобуо；Мацуо Такаси；Хирано Масасика；Мицутани Тосио；Такеда Хисами
    申请人:Сумитомо Кемикал Компани Лимитед (Фирма)；
    IPC主号:
    专利说明:

    Priority signs: 20.04.73. R, - H, C, - C-alkyl, C,; - C4-alkenyl, C, - C-alkoxy-C - 64 alkyl; Rj is H, methyl;
    Rj is H, halo, C, -C5-alkyl; R and R; 2 form a polymethylene chain containing 4-5 carbon atoms;
    when R is hydrogen, R. is hydrogen, methyl, vinyl, 1-propyl, 2-methylpropenyl, 2-methoxymethyl-1-propenyl 2-methoxycarbonyl-1 propenyl or cyclopentylidenemethyl; if R is methyl; R methyl;
    "
    The invention relates to organic chemistry and relates, in particular, to a process for the preparation of new complexes of 1x alkynylcyctic propanecarboxylic esters, namely cyclopropanecarboxylates of the general formula
     ABOUT
    ss ,, - with s
    about RV
    .СНз Н5
    where R, is hydrogen, C4-alkyl, phenyl, phenyl, substituted with 1 or 2 groups of halogen. C, - C4-alkyl, C, - Cj-alkoxy or methylenedioxy, benzyl, furyl, thienyl, cyclo-kil, cyclo Cg-Cb-alkenyl containing 5-6 carbon atoms in the cycle, Cj-C-alkyn, C-alkoxy -C - C-alkyl, Gj-C-alkenyl; hydrogen or methyl; R is hydrogen, halogen, C, - CJ.-alkyl; R, and R-, and R2 together form a polymethylene chain containing 4-5 carbon atoms; R and R can form a carbon - carbon bond to form a triple bond; R4 is hydrogen or methyl; if R is hydrogen, then hydrogen, methyl, vinyl, 1-propenyl-2-methyl-1-propenyl, 2-methoxymethyl-1-propecyl, 2-methoxycarbonyl-1-pr6penyl, cyclopentylidenemethyl; Rg and R 55048
    Rg, Rj is hydrogen or methyl; 05/24/73. R (- phenyl, phenyl, substituted with 1 or 2 g1-upps of C, - alkyl, halo, C, - C-alkoxy or methylenedioxy, benzyl, furyl, thienyl;
    04.06.73.R ,, and RJ can form a carbon - carbon bond and become a triple bond as a whole:
    04.04.74.R, - cyclo C-alkyl, cyclo C - Cg - alk enyl;
    R and R, like R and R, form a polymethylene chain containing 4-5 aioMOB carbon.
    hydrogen or methyl if R is methyl; then Rg is methyl, which have an insecticidal effect.
    The purpose of the invention. is a highly novel cyclopropane carboxylate with a higher insecticidal effect.
    g The invention is illustrated by the following examples.
    Example 1. 0.05 mol of alcohol is dissolved in three times the volume of anhydrous benzene. 0.075 moles of pyridine was added to the solution. At the same time, 0.053 mol of carboxylic acid chloride is dissolved in a threefold volume of anhydrous benzene and added in one step to the described Mi solution, in connection with which an exothermic reaction occurs. After allowing the solution to stand overnight in a carefully sealed vessel, add a small amount of water to dissolve the precipitated pyridine hydrochloride. The aqueous layer is separated and the organic layer is then successively washed with 5% aqueous hydrochloric acid, saturated aqueous sodium bicarbonate solution and saturated aqueous sodium chloride solution. After the organic layer was dried over anhydrous sodium sulfate, the benzene solution was mixed with neutral alumina for 30 minutes to discolor.
    filtered, then the benzene is removed by distillation to obtain the final product.
    The following compounds were prepared using the privadan procedure.
    The data of elemental analysis are given in Table I.
    Example 2. A solution of 6.7 g
    20
    The NIN is added dropwise and the reaction mixture is left to stand overnight at room temperature and thereafter subjected to processing in the same way as Example 5 to form 10.9 g
    (0.0439 mol, yield 88%) 1-ethynyl-2-methyl-2-pentenyl 2,2,3,3-tetramethyl cyclopropanecarboxylate, which analytically corresponds to the compound (0.05 mol) of 1-ethynyl-2-methyl -3-progeny 21. pargylallyl alcohol in 50 ml of di- Example 5. To a solution of 8.6 g of chloromethane was added 11.9 g (0.15 mol) (0.05 mol) of 1-ethynyl-3-benzyllabsh10 - pyridine. The mixture is cooled to -20 ° C for 20 minutes with stirring and
    12.5 g (0.055 mol) (0.075 mol) of diethylaniline are added dropwise. To this acid chloride, 2,2-dimesh-1- 3- (2,2-di-mixture is dripped at room temperature - vinyl chloride) -cyclopropanecarboxylic acid. After completion of the addition, stirring is continued for another 20 minutes. The reaction mixture is brought to room temperature and treated according to Example 1 to form 14.5 g (0.0446 mol, yield 89%) of 1-ethynyl-2-methyl-3-propargyllallyl, 2.2-dimethyl-sodium temperature and subjected to after-3- (2,2-dichlorovinyl) -cyclopropane-subsequent processing according to the gtrimer of bauxyl, which analytically corresponds to 1 with the formation of 15.3 g (0.042 mol) corresponds to the compound 125.1-ethynyl-3-benzyl-lash-2.2-dimethyl 3. To a solution of 8.7 g of 3- (2,3-dichlorovinyl) -cyclopropane-car (0.05 mol) sb-ethynyl / E-meccine-30 boxylate, (84% of the extract), which is analogous to Peart in 100 ml of dry tetra- hydrofuran compound corresponds lytically added 11,9g 1P.
    (0.15 mol) pyridine. The mixture is boiled. Approx. In a solution of 6.8 g under reflux for (0.05 mol) 1-ethn-1-2-methyl-2.5-hexa-20 min and with stirring, dropwise 35 sadienyl alcohol in 50 ml of dimethyl; add a yutrast solution of 10.3 g (0.055 mol) of formamide; 5.9 g (0.075 mol) of chrysanthemoyl chloride in 20 ml of dry tetrahydrofuran are added. After completion of the addition, stirring is continued for another 10 minutes. The reaction was brought to room temperature for 20 at room temperature with a mixture of 20 cm. After twisting and processed according to example 1 to form 13.7 g (0.00425 mol), A-ethynyl- / 3 -methyl-. cinnamyl chrysanthemum yield 85%, the mixture obtained is subjected to the subsequent analytically corresponding to the processing according to example 1 with dilution 32. formation of W, 5 g (0.037 mol, Example 4. In a solution of 6.2 g, course 73%) 1 -ethynyl-2-methyl-2.5 / hexa- (0.02 mol) of 1-ethynyl-2-methyl-2-penny chrysanthemum, which was analyzed in 50 ml of n-butyl alcohol in 50 ml 29, acetate was added 15.2 g (0.15 mol). Example. In a solution of 6.2 g of triethylamine. The resulting mixture was cooled (0.05 mol) of 1-ethynyl-2-methyl-2-pentadehae, and 1.9 g was added dropwise to the 20 ml of n-heptane during 20 minutes while stirring. (0.15 mol) pyril solution of 8.8 g (0.055 mol) chlorine- $ 5 dyne. To the mixture was added 2.2,3,3-tetramethylcycloalkyl anhydride at 20 with a solution of 8.8 g of propancarboxylic acid in 20 ml (0.055 mol) of the hydrochloride 2,2,3,3-dry n-butyl acetate. After termination of tetramethylcyclopropanecarboxylic acid alcohol, 11.2 g are added to 50 ml of dry methyl isobutyl ketone.
    14.4 g of bromohydride (0.053 mol) of 2,2-dimethyl-3- / 2,2-dichlorovinyl cyclopropanecarboxylic acid, dissolved in dry methyl isobutyl ketone, are added in the course of 20 minutes. After completion of the dropping, the reaction mixture was allowed to stand overnight with compiridine. To this mixture is added dropwise 10.3 g (0.055 mol) of chrysanthemoyl chloride in 20 ml of toluene at
    dropping, the reaction mixture is left standing for yochi and then 100 ml of toluene is added to the mixture. By (0.0439 mol, 88% yield) of 1-ethynyl-2-methyl-2-pentenyl 2,2,3,3-tetramethyl cyclopropanecarboxylate, which analytically corresponds to compound 21. Example 5. A solution of 8.6 g (0.05 mol) 1-ethynyl-3-benzylllsh10-
    alcohol in 50 ml of dry methyl iso-butyl ketone was added 11.2 g
    (0.075 mol) diethylaniline. This mixture is dropped to the mixture at room temperature and subjected to further processing according to gtrimer 1 to form 15.3 g (0.042 mol) of 1-ethynyl-3-benzyl-lash-2.2-dimethylpere and add 14, 4 g of bromoanhydride (0.053 mol) of 2,2-dimethyl-3- / 2,2-dichlorovinyl cyclopropanecarboxylic acid, dissolved in dry methyl isobutyl ketone, with stirring for 20 minutes. After the completion of the dropping, the reaction mixture is allowed to stand overnight at a bed. Example. To a solution of 6.8 g (0.05 mol) of 1-ethins-1-2-methyl-2,5-hexadienyl alcohol in 50 ml of dimethylformamide is added 5 , 9 g (0.075 mol) at room temperature with stirring for 20. After the mixture is completed, it is subjected to further processing according to Example 1 to give III, 5 g (0.037 mol, pyridine. To this mixture is added dropwise to 10.3 g (0.055 mol) of chrysanthomoyl chloride in 20 ml of toluene at
     Example: In a solution of 6.8 g (0.05 mol) of 1-ethins-1-2-methyl-2,5-hexadienyl alcohol in 50 ml of dimethylformamide, 5.9 g (0.075 mol) are added at room temperature with stirring - for 20, After the finished mixture is subjected to further processing according to example 1 to form III, 5 g (0.037 mol, drop by drop, the reaction mixture is left standing for yochi and then 100 ml of toluene is added to the mixture. 20 ml of n heptane with stirring and for 20 minutes. After the completion of the dropping, the reaction mixture is incubated overnight at the same rate Routine and subjected to further processing according to example 1 and get 10.8 g (0.0435 mol) of 1-ethynyl-2-metsh1-2 - pentenyl-2,2,3,3-tetramethylcyclopropanecarboxylate yield 87%, which according to the analysis corresponds to compound 21,
    Example 8. To a solution of 6.2 g (0.05 mol) of 1-ethynyl-2-methi 1-2 pen syl alcohol in 50 ml of diisopropyl ether was added 15.2 g (0.15 mol) of triethylamine. . A solution of 10.3 g (0.055 mol) of chrysanthemic acid chloride in 20 ml of diisopropyl ether is added dropwise to the mixture at 20–30 ° C with stirring over 20 minutes. After the addition of the solution is complete, the reaction mixture is kept overnight at the same temperature and then subjected to the treatment as described in Example 1, and 12.2 g (0.045 mol) of 1-ethyl-2-methyl-2-methyl-2-penthyl ether of chrysanthemum is obtained. acid (yield 89%), which according to the analysis corresponds to compound 4.
    Example9. To a solution of 6.2 g (0.05 mol) of 1-ethyn. P-2-methyl-2-pentyl alcohol in 50 ml of a mixed solvent, toluene and tetrahydrofuran in a volume ratio of I: 1 is added 11.9 g (0.15 mol) pyridine. Then, a solution of 10.3 g (0.055 mol) of chryseitemic acid chloride in 20 ml of a mixed solvent from toluene and tetrahydrofuran in a volume ratio of 1: 1 is added dropwise at 20-30 ° C with stirring for 20 minutes. After the addition is complete, the reaction mixture is kept at night at the same temperature, and then subjected to a post-treatment as described in Example 1, and 12.3 g (0.045 mol) of 1-ethynyl-2-methyl-2-foam of phenyl chrysanthemic acid ester are obtained. (yield 89%), which analytically corresponds to compound 4.
    Example 10. In a solution of 6.2 g (0.05 mol) of 1-ethynyl-2-methyl-2-pentenyl alcohol in 50 ml of a mixed solvent consisting of methyl iso-butyl ketone and butyl acetate in a volume ratio of 1: 1, add
    11.9 g (0.15 mol) of pyridine. A solution of 13.3 g (0.055 mol) of chrysanthemic acid chloride in 20 MP of a mixed solvent consisting of methyl iso-butyl ketone and butyl acetate in a volume ratio of 1: 1 is added dropwise to this mixture at 20-30 ° C. , with stirring for 20 minutes. After the addition was complete, the reaction mixture was kept overnight at the same temperature, and then subjected to further processing as described in Example 1, and 2.0 g was obtained
    (0.044 mol) of 1-ethynyl-2-methyl-2-pen tylyl ester of chrysanthemic acid (yield 87%), which analytically corresponds to compound 4.
    Example 11. To a solution of 6.2 g
    (0.05 mol) -ethynyl-2-methyl-2-pentenyl alcohol in 50 ml of toluene was added 11.9 g (O, 15 mol) of pyridine. This mixture is refluxed and added to this mixture.
    drop by drop at the same temperature, a solution of 10.3 g (0.055 mol) of chrysanthemic acid chloride in 20 ml of toluene with stirring for 20 minutes. At the end of the addition, the reaction mixture was stirred for 10 minutes at the same temperature and subjected to further processing as described in Example 1 to obtain 10.7 g (0.039 mol)
    1-ghcnyl-2-methyl-2-pentenylchrismate, 78% yield, which analytically corresponds to compound 4.
    Specific examples of the cyclopropane carboxylates described by the formula
    (I) and refractive indices are given in table 2.
    An example of a test.
    A group of 20 flies is admitted into a glass chamber (70 cm).
    adult individuals. 1 g of each mosquito ring is set on fire at both ends and placed in the center of the bottom of the chamber. After that, the number of insects falling down is noted in order to calculate the time values during which 50% of insects die (CT), and
    get the results in the following table.3.
    50
    submitted
    0.6% coils for mosquito killing prepared from compounds 1, 2, 4, 6, 1 1, 12, 21, 63 and their isomers, 72, 74, 75, 76, 77 allets
    Rhina were tested in a glass chamber (70 ml) in northern mosquitoes of 20 adults per group and house flies (20 adults per group).
    The results of the experiments are given in table. 4 and 5,
    Compounds 1, 4, 5, 29, 60, 63, 87, 94, 96, 106-110, 121-123 and pyrethrin, respectively, were used for the preparation of oil preparations for spraying, each of which had a different concentration and was applied using the Campbell rotary table and camera doors opened for 20 seconds after spraying. Tests were conducted on a group of domestic flies consisting of approximately 100 adult flies.
    Repeat the test several times, Tables 6 and 7 show the values (lethal concentrations) required for half of the flies to be killed.
    550488
    The cyclopropanecarboxylic acid esters described by formula (I), examples of which are given compounds, have more than 5 high insecticidal effect and the ability to carry insects into an unconscious state than the known chrysanthemic esters. Dp to
     This was more obvious; a comparison was made between the efficacy of the typical compounds proposed by the invention and allethrin.
    It is especially important that these complex
    5 zfiry have low toxicity and harmless to mammals and, therefore, they can be easily applied to agricultural crops before harvest, on food and packaging materials, and creep when destroying insects harmful to stored grain and for home gardening and cultivation of various crops in greenhouses.
    Table 1
    20
    25
    15
    1255048
    16 Continuation of Table I.
     7125504818
    Continuation of table 1
    25
    1255048
    26 Continuation of table 1
    1-Ethynyl-2-cyclohexylidene-2, 2-dimethyl-3 - (2-methoxymethyl-1-propenyl) -cyclopropanecarboxylate 1.5081
    1-ethynyl-2-methyl-2-butenyl-2, 2, -3, 3 tetramethylcyclopropanecarboxylate1, 4765
    1-ethynyl-2-methyl-2-pentenyl-2, 2, 3-tri-methylcyclopropanecarboxclat1.4783
    1-ethnyl-2-methyl-2-butenyl-2, 2 dimetip3 - (1-propenyl) cyclopropanecarboxylate 1,4802
    one
    I
    291255048 30
    Continuation of table 2
    141-Ethynyl-2-methyl-2-butenyl-2, 2-dimethyl- -3 - (1,3-bydadienyl) -cyclopropancaparboxylate, 4844
    151-ETHINYL-1-1 (1-cyclopentenyl) -methyl-2, 2-dimethyl-3 - (2-methyl-1, 3-butadienyl-cyclopropanecarboxylate) 1.5024
    161-Ethynyl-2-methyl-2-butenyl-2, 2-dimethyl-3 - CyClopentylidenemethylcyclopropanecarboxylate, 5103
    171-Ethynyl-2-methyl-2-butenyl-G, 2,2,3,3-pen amethylcyclopropanecarboxylate1,4787
      ) /
    181-Ethynyl-2-methyl-2-butenyl-1, 2, 2-trime. Ttil-3 - (2-methyl-1-propenyl) cyclopropanecarboxylate1, 4866
    191- (1-propynyl) 2 methyl-2-butenylchrisantemate 1.4915
    201-Ethynyl-2-methyl-2-butenyl-2, 2-dimethyl- 3 - (2, 2-dichlorovinyl-cyclopropanecarboxylate) 1.4955
    211-Ethynyl-2-methyl-2pentenyl-2, 2, 3, 3-tetramethyl-cyclopropanecarboxylate1,4781
    221-Ethynyl-2-methyl-2-pentenyl-2, 2-dimethyl-1-3- (1-propenyl) cyclopropanecarboxylate, 4793
    231-ethynyl-2-methyl-2-pentenyl-2, 2 -dimethyl-3-vinylcyclopropanecarboxylate1.4788
    24 -Etinyl-2-methyl-2-pentenyl-2, 2-dimethyl3 - (l, 3 -butadienyl) -cyclopropanecarboxylt 1.4802
    251-ethynyl-2-methyl-2-pentenyl-2, 2-dimethyl-3- (2 methoxymethyl) -1-propenyl-cyclopropanecarboxylate1.4832
    261-Ethynyl-2-metsh1-2-pentyl-2, 2-dimethyl-z - - (2-methoxycarbonyl-1-propenyl) -cyclopropanecarboxylate1,4856
    271-Ethynyl-2-methyl-2-pentenyl-2, 2-dimethyl-cyclopropanecarboxylate1,4155
    281-Ethynyl-2-methyl-2-pentenyl. -2, 2-dimethyl-3-cyclopentylidenemethyl cyclopropanecarboxyllat, 5007
    291-Ethynyl-2-methyl-2,5-hexanediylchrisanthate 1.5036
    31
    301 Ethinyl-3-propargylallylhrisante1,5124
    31d-ethynyl cinnamyl chrysanthemum1,5323
    32d-ethynyl-beta-methylcinnamyl chrysanthemum 1.36565
    33d-ethynyl-beta-methyl-4-methylcinnamyl chrysanthemum 1, 5343
    34d-ethynyl-beta-methyl-2-chlorocinnamylxpantine1, 5410
    35d-ethynyl-beta-methyl-3, 4-methylenedioxycinnamyl chrysanthemum1,5441
    36d-ethynyl-beta-brominamine chrysanthemate 1,5606
    37d-ethynyl-beta-methyl-3, 4-dimethoxycinamyl-chrysantheme1,5390
    38d-ethnyl-beta-methylcinnamyl-1,2,3,3-tetramethylcyclopropanecarboxylate 1,5231
    39d-ethynyl-beta-methylcinnamyl-2,3-dimethyl-3-cyclopentylidenemethylcyclopropanecarboxylate1, 5350
    40d-ethynyl-beta-methylcinnamyl-2,3-dimethyl- -3- (2-methoxycarbonyl-1-propenyl) -cyclopropanecarboxylate1.5375
    41 -Etinyl-beta-4-ethyl-3-hydroxycinnamyl2, 2, 3-trimethylcyclopropanecarboksh1at1,5405
    42o4-ethynyl-beta-methyl-4-cyanocinnamyl-2, 2 - dimethyl-3 - (2-methyl-2, 3 5 -utadienyl) - cyclopropanecarboxylate1,5410
    43l-ethynyl-beta-methyl-4-isopropylcinnamyl-chrysanthemum. 1, 5290
    44 "-Ethynyl-beta-isopropylcinnamyl-2,2,3,3-tetramethylcyclopropanecarboxylate1.5211
    45os-Ethynyl-gamma-methylcinnamyl chrysanthemum1,5336
    46l-ethynyl-beta-methylcinnamyl-1,2,2-trimethyl-3- (2-methyl-1-propenyl) cyclopanecarboxylate1, 5344
    47oC-Ethynyl-beta-methyl-2-methylcinnamyl 1, 2, 3-trimethyl-3-cyclobenzyltilenemethyl-cyclopropanecarboxylate1.5366
    1255048
    32 Continuation of table 2
    one
    48OC-β-Ethynyl-beta-chlorocinnamyl-1,2,2,3,3-pentamethylcyclopropanecarboxylate1, 5340
    49ob-ethynyl-beta-methyl-3,4-methylenedioxycinnamyl-1, 2, 2-trimethyl-3 - (2-methoxy-carbonyl-1-propenyl) -cyclopropanecarboxylate1, 5431
    50ot- (1-propynyl) -beta-methylcinnamyl chrysanthemum 1, 5355
    5 th-Ethynyl-beta-methylcinnamyl-2,2-dimethyl3- (2,2-dichlorovinyl) cyclopropanecarboxylate1.5376
    52o-Etinil-gamma- (2-furyl) -allyl chrysanthemum 1,5355
    53ob-ethynyl-gamma (2-thienyl) -allyl chrysanthemum1,5331
    54ot-Ethynyl-gamma-benzylallylchristate1,5393
    55ob-Ethynyl-beta-ethylcinna nylchrysanthemate1,5303
    561-Ethynyl-2-butin-1-yl-chrysanthemum1.4822
    571-Ethynyl-2-pentin-1-yl chrysanthemum1,4901
    581-Etinsh1-2-hexin-1-yl-chrysanthemum1,4957
    591-Ethynyl-2-heptin-1-yl-chrysantheme1,5255
    601-Ethynyl-4-methoxy-2-butyn-1-yl-chrysanthemum 1, 5293
    611-Ethynyl-5-methoxy-2-pentin-1yl-chrysanthe. mat1,5421
    621-ethynyl-4-ethoxy-2-buGinyl-1-yl-chrysanthemum 1, 5572
    631-Ethynylhexa-2-yn-5-en-1-yl-chrysanthemum1.4965
    641-Ethynylhex-2,5-diin-1-yl-chrysanthemum 1.5061
    651-Etilingepta-2-in-6-en-1-yl-chrysanthema1,5032
    661-ethynylhepta-2,6-diin-1-yl-chrysanthemum 1.5021
    671-ethynyl-4-phenyl-2-butyl-1-yl-chrysanthemate1,512
    681-Ethynyl-3-phenyl-2-propyn-1-yl-chrysanthemum 1,5109
    691- (1-Propinyl) -hexa-2-yn-5-en-1-yl-chrysantheme1, 4978
    35
    T
    1-Ethynyl-2-hexin-1-yl-2, 2, 3,3-tetramethyl-cyclopropanecarboxylate
    1-ethynyl-2-heptin-1-yl-2, 2, 3,3-tetramethyl-cyclopropanecarboxylate

    1-ethynylhexa-2-yn-5-en-1-yl-2, 2, 3, 3 tetramethylcyclopropanecarboxylate
    1-Ethynyl-4-phenyl-2-butyn-1-yl-2, 2, 3, 3 - tetramethylcyclopropanecarboxylate
    1-Ethynylhexa-2-in-5-nn-1-yl-2, 2, 3-trimethylcyclopropanecarboxylate
    1-ethynylhexa-2-yn-5-en-1-yl-2, 2-dimethyl-3- (2-methyl-1, 3 butadienyl) - cyclo-opancarboxylate
    1-Ethynylhexa-2-yn-5-en-1-yl-2, 2-dimethyl-3 - (1-propenyl) -cyclopropanecarboxylate
    1-ethynylhexa-2-yn-5-en-yl-2, 2-dimethyl- 3 - (1, 3-butadienyl) cyclopropanecarboxylate
    1-Etishshgeksa-2-in-5-en-1-yl-2, 2-dimethyl- 3 -cyclopentelenmethylcyclopropanecarboxylate
    1-Ethylenehexa-2-in-5-en-1-yl-2, 2-dimethyl-cyclopropanecarboxylate
    1-Ethynylhexa-2-yn-5-en-1-yl-2, 2-dimetyu1- 3 - (2, 2-dichlorovinyl) -cyclopropanecarboxylate
    1-Ethynylhexa-2-in-5-en-1-yl-2, 2-dimethyl-3 - {2-methoxycarbonyl-1-propenyl) -cyclopropanecarboxylate
    1-Ethynylhex-2-yn-5-en-1-yl-2, 2-dimethyl-3- (2-methoxymethyl-1-propenyl) -cyclopropanecarboxylate
    1-Ztenilhexa-2-yn-5-en-1-yl-1, 2.2.
    f) 3, 3-pentamethyl cyclopropanecarboxylate
    1-Ethynylhexa-2-yn-5-nn-1-yl-1, 2, trimetnl-3 - (2-methyl-I-nponeHHn) -cyclopropanecarboxylate
    1-Ethynylhexa-2-yn-5-en-1-yl-1, 2, 2 - trimethyl-3-cyclopentylidenemethyl cyclopropanecarboxylate
    1255048
    36 Continuation of table 2
    1.5048 1.5055 1,5002 1,5118 1,5013
    1.4971 1.4953
    , 4968
    1.4922 1.5065 1.5077
    1.5081 1,4998
    1.4953 1.5063
    37125504838
    Continuation of table 2
    1-ethynyl-2-methyl-3- (2-cyclopentenyl) -allyl-2,2-dimethyl-3 - (1-propenyl) -cyclopro pan carboxylate 1.5019
    1-ethynyl-2-methyl-4- (1-cyclopentenyl) -2-butesh1p-2, 2-dimethyl-3-cyclopentilenide-methyl-cyclopropanacarboxylate 1.5206
    1-ethynyl-2-methyl-2-cyclohexylallyl-chrysanthemum 1, 4998
    1-Ethynyl-2-methyl-3- (3-cyclohexenyl) allyl chrysanthemum 1, 5079
    ),
    1-ethynyl-3- (3-cyclohexenyl) -allyl-2, 2 dimethyl-3 - (-propenyl) -cyclopropanecarboxylate., 1,5004
    1-ethynyl 3- (2-cyclohexenyl) -alls1-2, 2,
    3, 3-tetramethyl-cyclopropanecarboxylate 1.4911
    1-Ethynyl-4- (1-cyclohexenyl) -2-butenyl2, 2, 3-trimethylcyclopropanecarboxylate 1.4938
    102 1-Ethynyl-2-methyl-3- (3-cyclohexenyl) - allyl-2,2-dimethylcyclopropanecarboxylate1.4982
    39
    1 103
    104 105
    1-Ethynyl-2-methyl-4- (2-cyclohexenyl) -2-butenylchrisantemate1,5107
    1-Ethynyl-3- (3-cyclohexenyl) -allyl-2, 2 - dimethyl-3 - (2, 2-dichlorovinyl) -cyclopropanecarboxylate1.5263
    1-Etgp: tl-2-14gt1i1-3- (3-cpcpohexett) - allyl-2, 2 -dimethyl-3 -cyclopentylidene-methylcyclopropanecarboxylate -, 1.5239
    1061-Ethynyl-2-methyl-2-pentenyl-2, 2-dimethyl 3 - 2,2-dichloro-shcyclopropanecarboxylate 1.5307
    1071-Ethynyl-2 methyl-2,5-hexadien-1-yl-2, 2-dimethyl-3 (2, 2-dichlorovinyl) -cyclopropane carboxylate 1.5085
    1081-Ethynyl-2-methyl-2,6-heptadiene-1-yl-chrysanthema1, 4882
    1191 -Etinyl-gamma (2-furyl) -allyl-2, 2-dimethyl-3 - (2, 2-dichlorovinyl) -cyclopropane-carboxylate1.4975
    120e1-ethynyl-beta-ethyl-cinnamidallyl-2,2-dimethyl-3 - (2, 2-dichlorovinyl) -cyclopropanecarboxylate1, 4935
    1211-Ethynyl-4-methoxy-2-butyn-1-yl-2, 2-dn-methyl-3 (2,2-dichlorovinyl) -cyclopropanecarboxylate1.4955
    1221-ethynyl-4-vinyl-2-butyn-1-yl-2, 2-dimethyl-3 - (2, 2-dichlorovinyl) -cyclopropanecarboxylate1, 4943
    1231-Ethynyl-3-propargyl-allyl-2, 2-dimethyl3 - (2, 2 -dixJ opvinyl) -cyclopropanaparboxylate .1.5083
    1241-Ethynyl-2-methyl-3-propargyl-allyl-chrysanthemum, 5099
    1251-Ethynyl-2-methyl-3-propargyl-allyl-2, 2 - dimethyl-3 - (2,2-dichlorovinyl) -cyclopropane carboxylate 1.5045
    1261-Ethynyl-2-methyl-hepta-2-en-6-yn-1-yl-chrysanthemate1, 4988
    1271-Ethynyl-2-methyl-hepta-2-ext-6-yn-1-yl-2, 2 - dimethyl-3- (2, 2-dichlorovinyl) - cyclopropane carboxylate 1.4963
    125504840
    Continued tabl, 2
    128 1 -Etitt-hepta-2-en-6-yn-1 -yl-chrysanthemate
    1291-Ethynyl-2-methyl-3-benzylallyl-2, 2-dimethyl-3- (2, 2-dichlorovinyl) -cyclopropane carboxylate
    1301-Ethynyl-2-methyl-3-benzylallyl-chrysanthemate
    1311-Ethynyl-2,5-hexadienyl-chrysanthemum J32 l-Ethinyl-2,6-heptadienyl-xpisan hemat
    8 o
    t h 7 42
    1 ii
    8 33
    724
    9 5b
    847
    1103
    6 24 6 SG
    840
    b p
    7 0b
    . 8 15
    824
    1,4951
    1.5121
    1.5135 1.4899 1.4832
    Table 3
    10 02 1050 730 10 46
    814
    f
    "-And
    8 30
    1438
    957
    PCB
    1357
    sh zb
    822
    II 27
    45
    d-cis-transform ei-trans-form
    72
    74
    75
    76
    77
    12550А8-46
    TaOlica A
    Table 5;



    700
    4 48
    h
    554
    ) 5 06
    518,530
    524 500
    106 Alletrin
    Table 6
    Editor Y. Sereda
    Order 4732/59 Circulation 379 Subscription
    VNIIPI USSR State Committee
    for inventions and discoveries 113035, Moscow, Zh-35, Raushsk nab., d.A / 5
    Production and printing company, Uzhgorod, Projecto st., A.
    A 00
    D 18
    1730
    Table 7
    Compiled by S. Paul Kova
    Tehred I.Popovich Proofreader M.Sharoshi
    权利要求:
    Claims (1)
    [1]
    METHOD FOR PRODUCING CYCLOPRO-
    PANCARBOXYLATES of the general formula where R 4 is hydrogen, C, - C 4 ~ alkyl, phenyl, phenyl substituted with 1 or 2 groups of halogen, Cj - C 4 -alkyl, C 4 - C g apoxy or methylenedioxy, benzyl, furyl, thienyl , cyclo C f - C 6 -alkyl, cyclo Cj-C e ~ alkenyl containing 5-6 carbon atoms in the cycle, C 2 ~ C 4 -alkyl, C ( - C 4 -apoxy-C, - C 4 -alkyl C 2 ~ C 4 alkenyl;
    R 2 is hydrogen or methyl;
    R ^ is hydrogen, halogen, C, - C 5 -alkyl;
    R 4 and D 3 , R ( and R Together form a polymethylene chain containing 4-5 carbon atoms; R 4 and R 3 can form a carbon-carbon bond to give a triple bond;
    R 4 is hydrogen or methyl; if R 4 is hydrogen, then Rg is hydrogen, methyl, vinyl, 1-propenyl-2-methyl-1-propenyl, 2-methoxymethyl-1-propenyl, 2-methoxycarbonyl-1-propenyl, cyclopentylidenemethyl; R 6 and R are hydrogen or methyl, if R 4 is methyl; then R 5 is methyl, characterized in that the alcohol of the general formula
    B ^ <T C - R6 ^ C = C (B 3 ) -CH-0H
    Nya “where R ,, R 2 , R ^ and R 6 have the indicated meanings, are reacted with cyclopropanecarboxylic acid hapoid anhydride of the general formula where R 4 , R 5 , R have the indicated values;
    X is halogen, in the presence of a solvent selected from the group of hydrocarbon, halocarbon, ether or ester, ketone, amide, at a temperature of (-) 20 - (+) 110 ° C.
    SU <W 1255048 AZ
    Priority by signs:
    04/20/73. R ( - H, C, - C 4 -alkyl, C 2 - C 4 -alkenyl, C, - C 4 ~ alkoxy-C, C 4 -alkyl;
    R 2 is H, methyl;
    R 3 is H, halogen, C, C 5 ~ alkyl;
    R a and R 2 form a polymethylene chain containing 4-5 carbon atoms;
    if R 4 is hydrogen, R F is hydrogen, methyl, vinyl, 1-propenyl, 2-methyl-1propenyl, 2-methoxymethyl-1-propenyl, 2-methoxycarbonyl-1-propenyl or cyclopentylidenemethyl;
    if R 4 is methyl; R 5 is methyl;
    R 6 , R - hydrogen or methyl; 05.24.73. R ( is phenyl, phenyl substituted with 1 or 2 groups of C ( - C 4 alkyl, halogen, C f - C 7 alkoxy or methylenedioxy, benzyl, furyl, thienyl;
    06/04/73. R 2 and R 3 can form a carbon - carbon bond and become a triple bond as a whole: 04/18/74. R ( is cyclo C 5 ~ C e ~ alkyl, cyclo C - C 6 alkenyl;
    and R 3 , like R ^ and R 2 , form a polymethylene chain containing 4-5 carbon atoms.
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    同族专利:
    公开号 | 公开日
    US4003945A|1977-01-18|
    DE2418950B2|1977-12-15|
    IL44667D0|1974-06-30|
    AU6799474A|1975-10-23|
    CH611129A5|1979-05-31|
    IL44667A|1978-06-15|
    IT1049276B|1981-01-20|
    BR7403124D0|1974-11-26|
    DE2418950A1|1974-10-31|
    GB1424170A|1976-02-11|
    NL179202C|1986-08-01|
    FR2226383B1|1978-08-18|
    CS196253B2|1980-03-31|
    DK139212C|1979-06-18|
    CA1061351A|1979-08-28|
    HU171179B|1977-11-28|
    NL7405313A|1974-10-22|
    DE2418950C3|1978-09-07|
    DK139212B|1979-01-15|
    ES425399A1|1976-12-16|
    AR217225A1|1980-03-14|
    AU475303B2|1976-08-19|
    SE422051B|1982-02-15|
    PH11381A|1977-11-22|
    FR2226383A1|1974-11-15|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    DE2326077C2|1972-05-25|1985-12-12|National Research Development Corp., London|Unsaturated cyclopropanecarboxylic acids and their derivatives, their preparation and insecticides containing them|
    US3862174A|1972-06-26|1975-01-21|Sumitomo Chemical Co|Cyclopropanecarboxylates|US4118505A|1973-04-20|1978-10-03|Sumitomo Chemical Company, Limited|Novel cyclopropanecarboxylates|
    JPS5941966B2|1975-10-21|1984-10-11|Sumitomo Chemical Co|
    GB1594462A|1977-02-09|1981-07-30|Shell Int Research|Pesticidal composition|
    DE2819788A1|1978-05-05|1979-11-08|Bayer Ag|Benzyl esters with fluorine-substituted ether and / or thioether groups and their use as insecticides|
    US4225616A|1978-06-26|1980-09-30|Ciba-Geigy Corporation|Tetrahaloethylcyclopropane-carboxylic acid esters|
    US4322432A|1979-12-14|1982-03-30|Ciba-Geigy Corporation|Cyclopropanecarboxylic acid alkynyl esters, processes for producing them, and their use as pesticides|
    DE2951939A1|1979-12-22|1981-07-16|Degussa Ag, 6000 Frankfurt|CYCLOPROPANCARBONIC ACID ESTER, METHOD FOR THE PRODUCTION AND USE THEREOF|
    US6060076A|1981-10-26|2000-05-09|Battelle Memorial Institute|Method and apparatus for providing long term protection from intrusion by insects and other cold blooded animals|
    US6319511B1|1989-09-01|2001-11-20|Battelle Memorial Institute|Termite and boring insect barrier for the protection of wooden structures|
    US5856271A|1995-06-07|1999-01-05|Battelle Memorial Institute|Method of making controlled released devices|
    US6852328B1|1989-09-01|2005-02-08|Battelle Memorial Institute K1-53|Method and device for protection of wooden objects proximate soil from pest invasion|
    US6331308B1|1981-10-26|2001-12-18|Battelle Memorial Institute|Method and apparatus for providing long term protection from intrusion by insects and other cold blooded animals|
    US6572872B2|1989-09-01|2003-06-03|Battelle Memorial Institute|Method and apparatus for providing long term protection from intrusion by insects and other cold blooded animals|
    US6099850A|1981-10-26|2000-08-08|Battelle Memorial Institute|Termite and boring insect barrier for the protection of wooden structures|
    US5925368A|1981-10-26|1999-07-20|Battelle Memorial Institute|Protection of wooden objects in direct contact with soil from pest invasion|
    FR2547817B2|1982-12-15|1986-02-14|Roussel Uclaf|ESTERS OF CARBOXYLIC CYCLOPROPANE ACIDS AND UNSATURATED ALIPHATIC ALCOHOLS, PROCESS FOR THEIR PREPARATION AND PESTICIDE COMPOSITIONS CONTAINING THEM|
    FR2537973B1|1982-12-15|1985-11-08|Roussel Uclaf|ESTERS OF CARBOXYLIC CYCLOPROPANE ACIDS AND UNSATURATED ALIPHATIC ALCOHOLS, PROCESS FOR THEIR PREPARATION AND PESTICIDE COMPOSITIONS CONTAINING THEM|
    FR2570698B1|1984-09-26|1986-12-19|Roussel Uclaf|ESTERS OF CYCLOPROPANE CARBOXYLIC ACIDS AND DIACETYLENIC ALCOHOLS, THEIR PREPARATION PROCESS AND THEIR APPLICATION TO PEST CONTROL|
    PH21875A|1985-04-26|1988-03-25|Sumitomo Chemical Co|Novel carboxylic acid esters,their method of use and insecticides containing them as the active ingredient|
    DE3525624A1|1985-07-18|1987-01-22|Celamerck Gmbh & Co Kg|INSECTICIDALLY EFFECTIVE AGENT FOR CONTROLLING TEXTILE Pests|
    JP2546339B2|1988-06-03|1996-10-23|住友化学工業株式会社|Ester compounds and their use as insecticides and acaricides|
    US20060201053A1|2000-12-03|2006-09-14|Voris Peter V|Barrier preventing wood pest access to wooden structures|
    US5985304A|1998-02-25|1999-11-16|Battelle Memorial Institute|Barrier preventing wood pest access to wooden structures|
    US20020192259A1|1998-02-25|2002-12-19|Voris Peter Van|Barrier preventing wood pest access to wooden structures|
    RU2281280C2|2000-06-02|2006-08-10|Асахи Гласс Компани Лтд.|Method for preparing fluorinated derivatives of ethylene-unsaturated compounds|
    JP2001294504A|2000-04-13|2001-10-23|Fumakilla Ltd|Method for exterminating vermin by evaporation of agent|
    EP2114864A1|2007-02-21|2009-11-11|Yissum Research Development Company of the Hebrew University of Jerusalem Ltd|Alpha-halo- and alpha-alkyl-cyclopropylcarboxy compounds and uses thereof|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    JP4591573A|JPS5542045B2|1973-04-20|1973-04-20|
    JP5883073A|JPS5521009B2|1973-05-24|1973-05-24|
    JP48063118A|JPS5012232A|1973-06-04|1973-06-04|
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