• 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:
    Novel compounds are described which are substituted ben- in which m is 0 and n is 0 or m is 1 and n is 0 or 1; p is 0, or 3, x is 0 or 1; R1, R' and R7 are halogen, alkyl, haloalkyl, or alkoxy or Rand an adjacent R5 group together with the benzene to which they are attached for a naphthyl group; R2 and R' may be the same or different and are hydrogen, alkyl, acyl, an ester or thioester group, optionally substituted carbamoyl or optionally substituted thiocarbamoyl, or R2 and R' together with the nitrogen to which they are attached form a 5 to 7 membered ring which may optionally contain one or more heteroatoms; R3 is optionally substituted alkyl, alkenyl, N,N-dialkylamino, or phenyl optionally substituted by alkyl or halogen; with the proviso that when p is 0, R2 and R4 are not both hydrogen. They have pesticidal activity, especially against insects and acarids, and pesticidal compositions and methods are described. Methods of making the compounds, and novel intermediates, are also described.
    公开号:SU1223842A3
    申请号:SU792745703
    申请日:1979-02-28
    公开日:1986-04-07
    发明作者:Джордж Коппинг Леонард；Сесил Керри Джон；Исвел Ваткинс Томас；Джон Виллис Роберт；Харпер Палмер Брайан
    申请人:Дзе Бутс Компани Лимитед (Фирма)；
    IPC主号:
    专利说明:

    This invention relates to a process for the preparation of new benzophenone hydrazone derivatives of the formula
    -NMHR3
    xD- /
    where RI is halogen;
     methyl or trifluoromethyl;
    R is hydrogen, rpyraia, where
    U - unsubstituted
    or halogen-substituted alkyl with 1-4 carbon atoms, or rpjTina R, -CO-, where R5 is hydrogen or R / I,
    which exhibit insecticidal activity and can be used in agriculture.
    The aim of the invention is to develop a process for the preparation of new compounds from the class of benzophenone hydrazones, which would have a high insecticidal activity.
    Example 1. Explanation of Scheme 1. Phenol is reacted with p-chlorobenzoyl lower pressure, which gives an oil, which is extracted with chloroform. The extract is washed with water, water, sodium hydroxide solution and water, then dried for 5 mg of magnesium sulfate. The solvent is evaporated under reduced pressure, yielding 4-chloro-4-megylsulfonyloxybenzophen hydride, melting point TO-PO C (D),
    Example 3, Supplement to Scheme 3. JQ A solution of propionyl chloride (2 g) in ether (15 ml) is added dropwise while stirring to solution (D) of example 2 (2.62 g} in pyridine ( 20 ml) at 0 to 5 ° C for 30 minutes and then the mixture is stirred at room temperature for 1-1 / 2 h and subjected to rapid cooling with water (1 l). The solid is filtered off and washed with dilute hydrochloric acid and water , then dried in vacuum at 60 ° C for 1-1 / 2 h, which gives 4-chloro-4-mepsulphonyloxybenzophenone propionyl hydrazone, melting point 128-144 ° (C.).
    mentioned above and subsequently
    20
    thirty
    40
    -chloride according to the Friedel-Crafts reaction in Example 25, usually obtained in the presence of aluminum chloride, which gives 4-hpor-4-oxybenzophenone, 179-ISl C (A), To a solution of this compound (5 g) in pyridine (6 ml) methanesulfonyl chloride (2.5 g) is added at room temperature. The reactants are heated on a steam bath for 1-1 / 2 hours and the liquid reaction product is poured into dilute hydrochloric acid. The solid is precipitated and the solid is filtered off and dried in air. This solid is recrystallized from technical ethyl alcohol denatured with methanol, which gives 4-chloro-4-methylsulfonicloxybenzophenyl, melting point 120-121 ° C (B). A solution of 9.4 g of this product and ethyl carbazate (7.8 g) in glacial acetic acid (8 ml) and ethanol (200 ml) is heated under reflux for 48 hours, then evaporated to dryness in vacuo. The residue is extracted with methylene chloride (250 ml) and the extract is washed with water, an aqueous solution of sodium hydroxide (2.5 N) and water, followed by. dried and evaporated peszos. 4-β-chloro-4-methyl 1-sulfonyloxybenzophenone ethoxycarbonyl azidrazole is obtained, melting point 132.5-140 ° C (C),
    Example 2; Addition to Scheme 2; Hydrazine is added to a solution (B) of Example 1 (9.35 g) in ethanol (200 ml); hydrate (3 ml), then glacial acetic acid (1.5 ml). The mixture is heated under the action of a reflux condenser when the scientific research institute is peremogliv 17 h. The solvent is evaporated at
    mixtures of geometric isomers. The ratio between the two dimensions varies from one product to another.
    Example 4-41. The compounds shown in the table are prepared according to one of the schemes according to the proposed method. .
    Physical parameters (melting point in ° C, unless otherwise indicated) are given in column I of the desired target, final products. Accordingly, in the 35th K column the starting material is indicated, in the L column - intermediate product,
    When working under scheme 3, the starting material is lrodz kt in the previous example. The starting material (column K) of type A is used for schemes 1 or 2, the interstitial product (column L) of bgpa B is used for schemes 1 or 2. In the column entitled A, the type of acylation agent or hydrazine derivative is shown.
    Adating agents:
    M - Glyuidny acyl
    N - Acetic formic anhydride
    MS- Ethyl Fluoroacetate
    Hydrazine derivatives:
    S - Etklcarbazat
    T - methylcarbazate
     2,2,2. Trichloroethylcarbazate
    U-Sh, Sh-Heptafluorobutylcarbazate
    FOR - 2,2,2-Trifluoroethylcarbazate
    SD-2,2,3,3-Tetrafluoropropylcarbazate
    SE tert-butylcarbazate
    Similarly, reagentO is carried out, but ethanol is replaced by a group of solvents,
    45
    50
    55
    reduced pressure, which gives an oil that is extracted with chloroform. The extract is washed with water, water, sodium hydroxide solution and water, then dried over magnesium sulfate. The solvent is evaporated under reduced pressure, yielding 4-chloro-4-megylsulfonyloxybenzophen hydride, melting point TO-PO C (D),
    Example 3, Appendix to Scheme 3. A solution of propionyl chloride (2 g) in ether (15 ml) is added dropwise while stirring to solution (D) of example 2 (2.62 g) in pyridine (20 ml) at O to 5 ° C for 30 minutes Then the mixture is stirred at room temperature for 1-1 / 2 h and subjected to rapid cooling with water (1 l). The solid is filtered off, washed with dilute hydrochloric acid and water, then dried in vacuum at 60 ° C for 1-1 / 2 h, which gives 4-chloro-4-mepsulfenyloxybenzophenone propionyl hydrazone, melting point 128-144 ° C (WITH).
    mentioned above and subsequently,
     Our examples are usually obtained as
    mixtures of geometric isomers. The ratio between the two dimensions varies from one product to another.
    Example 4-41. The compounds shown in the table are prepared according to one of the schemes according to the inventive method. .
    Physical parameters (melting point in ° C, unless otherwise indicated) are given in column I of the desired target, final products. Accordingly, the starting material is indicated in the column K, and the intermediate product in the column L,
    When working under scheme 3, the starting material is lrodz kt in the previous example. The starting material (column K) of type A is used for schemes 1 or 2, the Span the product (column L) of bgpa B is used for schemes 1 or 2, In the column entitled A, the type of acylation agent or hydrazine derivative is shown.
    Adating agents:
    M - Glyuidny acyl
    N - Acetic formic anhydride
    MS- Ethyl Fluoroacetate
    Hydrazine derivatives:
    S - Etklcarbazat
    T - methylcarbazate
     2,2,2. Trichloroethylcarbazate
    U-Sh, Sh-Heptafluorobutylcarbazate
    FOR - 2,2,2-Trifluoroethylcarbazate
    SD-2,2,3,3-Tetrafluoropropylcarbazate
    SE tert-butylcarbazate
    Similarly, reagentO is carried out, but ethanol is replaced by a group of solvents,
    including toluene (boiling point with reflux condenser), xylene (boiling point), propane-2.ol (refluxing temperature 82 C) and butan-1-ol (refluxing temperature 117 C); acetic acid was replaced by a number of acidic
    J.
    CALIATORS, including p-toluenesulfide h - acid, pyrntine trifluoromethanesulfonate, and pyridine hydrochloride; the acylation reaction was carried out at OC and 100 C,, pyridine was replaced by a series of bases, including trimethylamine and triethylamine.
    权利要求:
    Claims (1)
    [1]
    METHOD FOR PRODUCING GENERAL FORMULA 1 DERIVATIVES OF BENZOPHENON HYDRAZONES
    NNHR 3 where R <is halogen;
    Ig is methyl or trifluoromethyl;
    Rj is hydrogen, the group R ^ OCO-, where Ri) is an unsubstituted or halogen-substituted alkyl with 1-4 carbon atoms, or the group Ry-СО-, where Rf is hydrogen or R ", characterized in that the benzophenone is of the general formula 11 where R , and Rj have the above meanings, are reacted with hydrazine of the general formula 111
    RjNH ΝΗ ΪΤ where R ^ has the above meanings, in a lower aliphatic alcohol or aromatic hydrocarbon such as toluene or xylene, in the presence of a catalytic amount of an acid catalyst such as acetic, p-toluenesulfo or S3 pyridine trifluoromethanesulfonic acid or pyridine hydrochloride, subsequent, if necessary, acylation of the obtained compound of formula 1, where R s is hydrogen, a compound of the general formula IV, V or VI, respectively
    R ^ OCOZ, R j -COZ or (Rj.-CO ^ O, where ΙΦ and Rj. Have the above meanings;
    Z is a halogen, or compounds of formula 1, where R ^ is CHO, with acetic anhydride in the presence of an organic base at 0-100 ° C.
    SU „„ 1223842 ϊ
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    同族专利:
    公开号 | 公开日
    PL120146B1|1982-02-27|
    GR66498B|1981-03-24|
    EP0003913A1|1979-09-05|
    JPS54122261A|1979-09-21|
    US4394387A|1983-07-19|
    MX5721E|1983-12-26|
    NZ189705A|1981-07-13|
    ES478212A1|1979-11-01|
    DE2966949D1|1984-06-07|
    SU1128833A3|1984-12-07|
    HU182463B|1984-01-30|
    AT367267B|1982-06-25|
    CA1093570A|1981-01-13|
    EP0003913B1|1984-05-02|
    ATA152979A|1981-11-15|
    RO76935A|1982-03-24|
    PL213790A1|1980-02-11|
    TR20169A|1980-09-29|
    BR7901261A|1979-10-09|
    AU526162B2|1982-12-23|
    OA06197A|1981-06-30|
    IL56721A|1984-03-30|
    US4344893A|1982-08-17|
    AU4456679A|1979-09-06|
    DD150422A5|1981-09-02|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US3732307A|1970-09-24|1973-05-08|Du Pont|Benzophenone hydrazones containing perfluoroalkyl,perfluoroalkoxy,and perfluoroalkylthio substituents|
    GB1488003A|1973-10-23|1977-10-05|Lilly Industries Ltd|1,2-benzisoxazole derivatives processes for their preparation and their use as pharmaceuticals|GB8503322D0|1985-02-08|1985-03-13|Fbc Ltd|Baits|
    US4895871A|1988-07-28|1990-01-23|Fmc Corporation|Benzoheterocyclyl ketone hydrazone insecticides|
    AU616041B2|1988-08-26|1991-10-17|Sumitomo Chemical Company, Limited|A hydrazone compound and production therefor, and an insecticidal composition containing the same|
    RU2067092C1|1988-12-27|1996-09-27|Е.И.Дюпон Де Немур Энд Компани|Semicarbazone derivatives, method of controlling arthropodes, and arthropocidal composition|
    US5268388A|1988-12-27|1993-12-07|E. I. Du Pont De Nemours And Company|Substituted semicarbazone arthropodicides|
    US5182303A|1988-12-27|1993-01-26|E. I. Du Pont De Nemours And Company|Substituted semicarbazone arthropodicides|
    US5112382A|1990-05-24|1992-05-12|Rohm And Haas Company|Halopropargyl compounds, compositions, uses and processes of preparation|
    EP0486937B1|1990-11-17|1995-03-22|Nihon Nohyaku Co., Ltd.|Hydrazone derivatives, processes for production thereof, and uses thereof|
    NZ241574A|1991-02-22|1993-08-26|Ishihara Sangyo Kaisha|Substituted phenyl derivatives of hydrazone and pesticidal compositions|
    IL105310D0|1992-04-16|1993-08-18|Ciba Geigy Ag|Benzophenone derivatives|
    TW268881B|1992-07-07|1996-01-21|Ciba Geigy Ag|
    IL111034D0|1993-10-06|1994-11-28|Sumitomo Chemical Co|Hydrazone compound and insecticide containing the same as active ingredient|
    ES2115190T3|1994-01-05|1998-06-16|Ciba Geigy Ag|HYDRAZONE DERIVATIVES AS PESTICIDES.|
    IL112265D0|1994-01-24|1995-03-30|Sumitomo Chemical Co|Hydrazone compound and insecticide containing said compound as active ingredient|
    JPH0841019A|1994-05-27|1996-02-13|Nippon Bayeragrochem Kk|Sulfamide derivative and insecticide|
    DE4439334A1|1994-11-04|1996-05-09|Bayer Ag|Butenyl dithiocarbazonate|
    DE69605353D1|1995-05-12|2000-01-05|Bayer Agrochem Kk|Benzophenone hydrazone derivatives as insecticides|
    TW479053B|1998-10-19|2002-03-11|Agro Kanesho Co Ltd|Hydrazineoxoacetamide derivatives and pesticides|
    DE10216568A1|2002-04-15|2003-10-23|Zahnradfabrik Friedrichshafen|Torque transmission device for brakes, clutches, etc. in motor vehicles has end plate to absorb axial loads to prevent it from tilting and reduce contact pressure, to increase service life|
    DE102010020882A1|2010-05-18|2011-11-24|Alzchem Trostberg Gmbh|Semicarbazone for curing epoxy resins|
    CN110128270A|2018-11-09|2019-08-16|郑州手性药物研究院有限公司|2,2- hexichol cyclopropyl class compound and its synthetic method|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    GB800378|1978-03-01|
    GB800278|1978-03-01|
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