• 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:
    The invention relates to derivatives of difluorocyclopropane, in particular, compounds of the general f-ly @ where R 1 and R 3 (identical or different) are H, halogen, C 1 , C 4 is alkoxy, substituted by fluorine, C 1 -C 4 -alkoxy, C 1 -C 4 -alkyl or CF 3 R 2 - H or F with insecticidal activity that can be used in agriculture against spider mites, moths of cabbage, spinous worms, Mexican kernels. The goal is to create new, more active substances of the specified class. Synthesis is carried out by the reaction of difluorocarbon with the corresponding methylene-substituted pentane. The starting carbon is obtained by IN SITU by thermal decomposition of sodium chlorodifluoroacetate in a polar solvent. New substances in a concentration of 0.1% destroy almost 100% of insects. 3 tab.
    公开号:SU1500152A3
    申请号:SU864027264
    申请日:1986-04-08
    公开日:1989-08-07
    发明作者:Франке Хайнрих；Йоппиен Хартмут；Франке Хельга
    申请人:Шеринг Аг (Фирма)；
    IPC主号:
    专利说明:

    The invention relates to a process for the preparation of new derivatives of difluorocyclopropane of the general formula
    where R and Rj
    identical or different and denote hydrogen or halogen, C-Cf-alkoxy, substituted by fluorine, C-C-alkoxy,.-alkyl or trifluoromethyl, R is a hydrogen or fluorine atom,
    which possess insecticidal activity.
    The purpose of the invention is the search for new derivatives of cyclopropane, which have a higher activity compared with analogues in the structure of the same purpose.
    Example 1. 1- (4-Chlorophenyl) -2,2-DIFTOR-1- 3- (4-fluoro-3-phenoxy-phenyl) -propyl 1-cyclopropane,
    SP GO

    cm
    3.0 g (20 mmol) of sodium chlorofluoroacetate, dissolved in 15 ml of di-glyme, are added dropwise over 60 minutes to the boil 1 solution (bath temperature 200 ° C) 2.76 (7.5%). mmol of 2- (4-chlorophenyl) -5- (4-fluoro-3-phenoxyphenyl) -pentene- (1) in 15 ml of diglyme and the mixture is boiled for another 30 minutes. After cooling, it is poured into water three times extract with ether, wash the ether extracts with water and dry over magnesium sulfate. The residue after evaporation is subjected to chromatography on 100 g of silica gel using a mixture of ether and hexane as a mobile phase in the ratio 1: 9. After evaporation, 2.8 g of the title compound remain. Yield: 90% of theory, p 1.559
    The original compound was prepared as follows.
    1. 2- (4-Chlorophenyl) -5- (4-fluoro-3-phenoxyphenyl) -valeronitrile.
    To a mixture of 30.6 g (0.2 mol) of 4-chlorobenzyldianide, 50 ml of 50% sodium hydroxide and O, 5 g of methyl bromide, tetrabutyl ammonium are added dropwise with vigorous stirring 23.2 g (6.075 mol) 1 bromo-3- (4-fluoro-3-phenoxyphenyl) propane .. Cool the mixture slightly, keep its temperature at 30 ° C. After stirring for three hours, it is extracted into ice water twice and extracted with ether, the ether extracts are washed water, dried with magnesium sulfate and evaporated. Excess benzyl cyanide is distilled off using a spherical tube at 150 ° C and a pressure of 0.1 Torr. The residue is subjected to chromatography on silica gel. The output of 27.0 g (.95% of theoretical), p 1,5752.
    2. 1- (4-Chlorophenyl) -4- (4-fluoro-3-phenoxyphenyl) -butan-1-one.
    They vigorously mix, pass air over it, a mixture of 27.0 g (0.071 mol) of the nitrile obtained at the previous stage, 220 ml of toluene, 220 ml of 50% sodium hydroxide and 1.5 g of benzyltriethylammonium chloride. room temperature After 2.5 hours, the reaction is complete. The mixture is poured into ice water, extracted three times with ether, washed with water and dried. The residue after evaporation, which is an individual compound without additional chromatography
    50
    5 0 5 0

    0
    thorough purification is used for synthesis. The output of 18.9 g (72% of theoretical).
    3. 2- (4-Chlorophenyl) -5- (4-fluoro-3-phenoxyphenyl) -pentene- (1).
    4.2 g (0.095 mol) of a 55% dispersion of sodium hydride are cleaned from oil by repeated washing with toluene, and then mixed with 150 ml of dimethyl sulfoxide. The mixture is heated to 80 ° C until the sodium hydride is completely dissolved (approximately within 30 minutes). To the resulting solution, 36.5 g (0.09 mol) of methyl triphenylphosphonium iodide are added at room temperature and the mixture is stirred until it is completely dissolved. Thereafter, 18.8 g (0.051 mol) of ketone dissolved in 50 ml of dimethyl sulfoxide is added dropwise and the mixture is stirred at room temperature for 12 hours. Then it is poured into ice water, extracted three times with ether, the organic phase is washed with water and dried with magnesium sulfate. The residue after evaporation is subjected to silica gel chromatography. The output of 12.6 g (68% of theoretical), p 1,5898.
    The compounds shown in Table 1 are prepared in a similar manner, elemental analysis and yield are given in Table 2.
    Example 28. Effect on the larvae (L3) of the Mexican bean weevil (Epilachna varivestis).
    The compounds are used in the form of aqueous emulsions with an active substance concentration of 0.0064%. In these preparations of the active substance, plants of haricot bean curd (Phaseolus. Bulgaris) are immersed at the stage of the appearance of their first leaves. In each experiment, two stems with four primary leaves are placed in water-filled glass vases and placed in plexiglass cylinders. After that, 5 larvae of Mexican grain bobs (Epilachna varivestis) are placed in glass cylinders in the third stage of development and they are held there for three days. For the criterion of the effectiveness of the tested compounds take the percentage of death of the larvae after three days.
    It was found that the proposed compounds in accordance with examples
    five
    1-12, 14-18 and 20-22 have a 100% effect (100% death of the larvae), while 2,2-dichloro-1- (4-dichlorophenyl) -1-3- (3-phenoxyfeiyl ) -propyl-cyclopropane analogue in structure and action has only a 90% effect.
    Example 29. Effect on young larvae of the cabbage moth (Plute 1a xylostella).
    The compounds are applied in the form of aqueous emulsions with a concentration of the active substance of 0.0064%, which are sprinkled on the leaves of cauliflower in a polystyrene petri dish. The flow rate of the preparation is 4 mg / cm. After the liquid dries, a crawler moth (Plutella xylostella) is placed in each back of Peter's cups and kept in closed cups with the feed in the described manner for 2 days. As a criterion of the effectiveness of compounds using the percentage of death of caterpillars after 2 days.
    It was established that the proposed sodinis in accordance with examples 1,2,4-7, 9-11, 15, 16, 18 and 19 have a 100% effect (100% of the death of the caterpillars), while the above analogue of The structure has only a 20% effect.
    Example 30. Effect on larvae (L) of spinous worms (Spodoptera littoralis).
    The proposed compounds are used in the form of aqueous emulsions with a concentration of the active substance of 0.0064%, which in each experiment are sprayed on a pair of complex leaves of beans (Vicia faba) and 10 masks of spinous worms (Spodoptera littoralis) at the stage of development of L 2. Spraying is carried out in cups Petri from polystyrene. The drug consumption is 4 mg / cm. After processing, closed Petri dishes are held in the laboratory under conditions of a long day for 2 days. As a criterion of the effectiveness of compounds using the percentage of death of the larvae after 2 days.



    0
    five
    0
    five

    the compound has no effect (0%).
    PRI me R 31. Effect on all mobile stages of development and spider mite eggs (Tetrahychus urticae).
    The proposed compounds are used in the form of aqueous emulsions with a concentration of the active substance of 0.1%. which are sprayed before the appearance of droplets of the common bush plant bean (Pháseolus vulgaris) planted in pots at the stage of the appearance of their primary leaves, artificially-infested klep (spider web (Tetra nychus urtical), and kept in the laboratory for 7 days. After this period, the number of dead insects at all stages of development and the individual number of dead eggs in percent are determined using a magnifying loupe.
    The results are presented in table 3.
    权利要求:
    Claims (1)
    [1]
    Invention Formula
    The method of obtaining the derivatives of difluorocyclopropane of the general formula
    CM2)
    where r and r
    J may be the same or different and means hydrogen, or halogen, C, -C-alkoxy group substituted by fluorine, C-C4 alkoxy group, C-C-alkyl or trifluoromethyl, R ,, is hydrogen or fluorine,
    y u and with the fact that
    about tl and h
    compound of general formula
    50
    RI
    It was found that the proposed compounds in accordance with examples 1-5, 7-9, 11-13, 15 and 17-19 have a 100% effect (100% death of the larvae), while the known
    where they have the indicated meanings, they are reacted with difluorocbene obtained in situ during the thermal decomposition of sodium chlorofluorr acetate in a polar solvent.
    Table 1
    one
     i
    2,2-Difluoro-1- 4- (2-fluoroethoxy) -3-fluorophenyl -1-fЗ- (4-fluoro-3-phenoxy-syphenyl) -pOII II-cyclopropane
    2,2-Difluoro-1-fenyl-1- 3- (3- -phenoxyphenyl) -propyl -cyclopropane
    2,2-Difluoro-1- (4-ethylphenyl) (3-phenoxyphenyl) -propyl-cyclopro150015210
    Continuation of table 1
     i :::::
    1,5D09 1,5643
    T a D l and c a 2
    92
    88
    90
    91
    53
    78
    67
    52
    80
    78
    82
    91
    88
    88
    93
    89
    85
    74
    87
    72
    Continued table. 2
    13
    150015214
    Continuation of table 3
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    同族专利:
    公开号 | 公开日
    AT40349T|1989-02-15|
    DE3661908D1|1989-03-02|
    ES553826A0|1987-03-16|
    ES8703832A1|1987-03-16|
    CN86102369A|1986-11-19|
    PH21941A|1988-04-15|
    JPS61275238A|1986-12-05|
    KR860008114A|1986-11-12|
    EP0198791A1|1986-10-22|
    DE3513041A1|1986-10-16|
    US4701563A|1987-10-20|
    AU5559286A|1986-10-16|
    EP0198791B1|1989-01-25|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US4562213A|1982-05-12|1985-12-31|Sumitomo Chemical Company, Limited|Certain phenoxy-benzyloxy ether derivatives and an insecticidal and/or acaricidal composition containing the same and methods of use|
    JPS58201737A|1982-05-18|1983-11-24|Mitsui Toatsu Chem Inc|Novel aromatic alkane derivative, its preparation and insecticide and acaricide containing the same as active constituent|
    IL69796A|1982-09-24|1986-10-31|Commw Scient Ind Res Org|Phenylcycloalkylalkane derivatives,their preparation and arthropodicidal compositions containing them|
    EP0125204A1|1983-04-12|1984-11-14|Ciba-Geigy Ag|3-Phenoxybenzyl ethers, process for their preparation and their use as pesticides|
    DK181683A|1983-04-25|1984-10-26|Cheminova As|ARYLCYCLOALKYLETHER DERIVATIVES, THEIR USE AND PREPARATION|
    DE3333239A1|1983-09-12|1985-03-28|Schering AG, 1000 Berlin und 4709 Bergkamen|ARYL METHYL ETHER DERIVATIVES, PEST CONTROLLING AGENTS CONTAINING THESE COMPOUNDS AND METHOD FOR THE PRODUCTION THEREOF|US5248834A|1984-04-09|1993-09-28|British Technology Group Limited|Pesticides|
    EP0390228A3|1986-03-04|1991-03-13|Imperial Chemical Industries Plc|Chemical intermediates|
    DE3812967A1|1987-06-24|1989-01-05|Bayer Ag|AZOLYL METHYL CYCLOPROPYL DERIVATIVES|
    GB9219612D0|1992-09-16|1992-10-28|Khambay Bhupinder P S|Pesticidal fluoroolefins|
    DE4342601A1|1993-08-13|1995-02-16|Solvay Fluor & Derivate|Process for the preparation of poly- and perfluorocarboxylic acid chlorides|
    EP0659729B1|1993-12-23|1998-06-24|Solvay Fluor und Derivate GmbH|Process for preparing chlorides of polyfluorochloro- and perfluoro carboxylic acids in the presence of chlorine|
    CN108191737B|2018-01-17|2020-04-21|温州大学|Process for producing N-isoindole-1, 3-dione compound|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    DE19853513041|DE3513041A1|1985-04-09|1985-04-09|DIFLUORCYCLOPROPANDERIVATES, PEST CONTROL, CONTAINING THESE COMPOUNDS AND METHOD FOR THE PRODUCTION THEREOF|
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