• 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:
    Benzoylureas are prepared from a benzamide, an alkyllithium, a phenyl chloroformate, and an amine. Two reaction sequences are described. The benzoylureas obtained by the process are useful as insecticides.
    公开号:SU799662A3
    申请号:SU782628947
    申请日:1978-06-21
    公开日:1981-01-23
    发明作者:Луис Мизел Джон；Фазал Абдулла Риаз；Генри Терандо Норман
    申请人:Эли Лилли Энд Компани (Фирма)；
    IPC主号:
    专利说明:

    This invention relates to a process for the preparation of new benzoylurea derivatives having insecticidal properties that may be used in agriculture. The benzamide is known to react with alkyl lithium and feiyl chloroformate in an inert solvent at (-30) (-40) 1 s to form urethane and its interaction with the amine in the solvent at (-80) - (-40) C and slowly raising the temperature to 50-100 ° C, resulting k benzoylurea fl. The purpose of the invention is a method of obtaining new derivatives of ben uureas having insecticidal properties. The aim is achieved based on a known reaction method of obtaining benzoyl urea derivatives of the general formula 1 -CNCNR v-; // II I o n o w e A and B - the same or different chlorine, bromine, fluorine, methyl or trifluoromethyl; R - group / R. or cT. radical hydrogen, methyl or ethyl, RJ-halogen, haloalkyl with 1-4 carbon atoms or alkyl with 1-6 carbon atoms, X - halo, trifluoromethyl or alkyl with 1-4 carbon atoms, p. - 0.1 or 2, p -0 or 1; t-0, 1, 2 and 3. The method consists in the fact that the benmide of the general formula e A and B have the indicated meanings, interact with lithium alkyl, where alkyl with 1-7 carbon atoms, and phenyl chlorothirate in an inert solvent at (-80 ) - (-40) C followed by treatment of the resulting urethane with an amine of the general formula
    RNH, where R has the indicated values in an inert solvent at (-80) - (-40) C and slowly raising the temperature to 50-100 C.
    Unsubstituted phenyl chloroformate and 4-nitrophenyl chloroformate are usually used, however, 2,4-Dinitrophenyl chloroformate and 4-trifluoromethylphenyl chloroformate can also be used.
    As an inert solvent at this stage, those that remain liquid at (-80) - (-40) s, for example tetrahydrofuran and diethyl ether, can be used.
    It is preferable to carry out this first stage of the process at (-75) - (-65) C.
    As lithium alkyl it is preferable to use p-butyl lithium.
    The addition of the amine in an inert solvent, such as tetrahydrofuran, diethyl ether or toluene, is carried out at (-80) - (-40) C (j and then the mixture is heated to 50-100 ° C, preferably to 50-65 ° C.
    The method is carried out as follows.
    Alkyl-lithium is added to benamide in a solvent at (-80) - (-40) C for 10-15 minutes and the mixture is stirred at this temperature for 30 minutes. Phenyl chloroformate in the indicated solvents is then added over a period of 15 to 20 minutes and re-cold 2-6 hours.
    In the second part of the reaction, amine in an inert solvent is added for 15-20 minutes at (-80) - (-40) C and allowed to rise in the temperature of the reaction mixture and then heated to 50100 C, preferably 50-65 for 4-24 hours
    Example. 1- (2,6-Dichlorobenzoyl) -3- b-methyl-5- (4-bromophenyl) -2-pyrazinnol urea.
    A solution of 304 mg of 2.6-dichlorobenzamide in 25 ml of dry tetrahydrofuran is placed in a 3-necked 50 ml round-bottomed flask. While stirring under nitrogen atmosphere, the solution is cooled to -72 ° C (dry ice / acetone). To the STdfeiy solution was added 0.6 ml of i-butyl lithium within 5 minutes. After completion of the addition, the mixture is stirred at -72 ° C for 30 minutes. A solution of 0.268 ml of 4-nitrophenyl chloroformate in 8 ml of dry tetrahydrofuran is added dropwise over 1520 minutes. A light yellow solution is obtained. After that, the mixture is stirred at -72 ° C for 30 minutes until a colorless solution is obtained. The temperature was raised to (-40) - (-30) C and stirring was continued for 3 hours. The mixture was cooled again to -72 C and a solution of 351 mg of 2-amino-5- (4-bromophenyl) - 6-methylpyrazine in 6 ml of dry tetrahydrofuran. The cooling bath is removed and the mixture is allowed to warm to room temperature. The mixture is then heated at 50 ° for about 16 hours. The solvent is removed in vacuo and the residue is taken up in ethyl acetate.
     The ethyl acetate solution is washed 5 times with an aqueous solution of sodium carbonate and twice with sodium chloride solution. The solvent is again evaporated and the residue is dissolved in 2 ml of tetra5 hydrofuran and it is chromatographed on silica gel using benzene / tetrahydrofuran in a 4: 1 ratio. The product isolated by chromatography is dissolved in tetrahydrofuran and
    0 the solution is evaporated in vacuo to an oil. Ether is added and the solution is cooled until precipitate forms, 240 mg of product is obtained. Recrystallization from tetrahydrofuran / ether 5 mg of product. M.p.
    225-227 C. Additionally, 69 mg of the product from the filtrate is obtained by chromatography on a thin layer.
    Example 2. 1- (2,6-Dichlorobenzoyl) -3-5- (4-chlorophenyl) -2 pyrazinyl} -urea.
    In the same manner as in Example 1, using 273.5 mg of 2-amino-5- (4-chlorophenyl) pyrazine, 222 mg of the expected product with m.p. 245-249 ° C.
    5 Example. 1- (2,6-Dichlorobenzoyl) -3-5- (3-triftoletylphenyl) -6-methyl-2-pyrazinyl urea.
    Analogously to Example 1, using 336.8 mg of 2-amino-5- (3-trifluoromethyl-phenyl) -6-methylpyrazine, a product is obtained which is chromatographed first on a column of silica gel and then 3 thin layer to give a viscous oil,: when standing
    5 crystallizes. The solid is triturated, stirred with cooled ether and then filtered. Obtain 62 mg of the product, Tp, 182-185 C. The filtrate concentrates the RUOZ in a hood and produces a yellow oil. Crystallization of the oil from ether gives an additional 102 mg of a white solid; a total of 164 mg of product is obtained.
    e Example4. 1- (2,6-Dichlorobenzoyl) -3- (6-trifluoromethyl-2-pyrazinyl) urea.
    Similarly, Pr. 1, using 217 mg of 2-amino-6-trifluoromethylpyrazine, a product is obtained which is chromatographed as in Example 3. The oil obtained by chromatography in a thin layer crystallizes on standing at room temperature. The crude solid is mixed into powder with ether, filtered, get
    权利要求:
    Claims (3)
    [1]
    Claim
    A method for producing benzoylurea derivatives of the general formula 1 wherein A and B are the same or different and are chlorine, bromine, fluorine, methyl or trifluoromethyl)
    Rj is the radical ; r is hydrogen, methyl or ethyl;
    R 3 is halogen, haloalkyl with 1-4 carbon atoms or alkyl with 1-6 carbon atoms) X is halogen, trifluoromethyl or alkyl with 1-4 carbon atoms, p-0, 1 or 2; p-0 or 1) t-0.1,
    [2]
    2 or 3, characterized in that the benzamide of the General formula And / And about in
    where A and B have the indicated meanings, they are reacted with lithium alkyl, where is alkyl with 1-7 carbon atoms and feyl chloroformate in an inert solvent at a temperature of (-80) - (-40) ° C, followed by treatment of the resulting urethane with an amine of the general formula RNH where R has the indicated meanings, in an inert solvent at a temperature of (-80) (-40 / С and a slow temperature increase to 50-100 ° C.
    2. The method according to claim 1, different from the fact that the interaction of benzamide with alkyl lithium is carried out at (-75) - (-65) ° C and the treatment of urethane with an amine at 50-65 C.
    [3]
    3. The method according to claim 1, is thin with the fact that η-butyllithium is used as lithium alkyl.
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    同族专利:
    公开号 | 公开日
    US4133956A|1979-01-09|
    PL115711B1|1981-04-30|
    CS198106B2|1980-05-30|
    IE47001B1|1983-11-30|
    ES471879A1|1979-02-01|
    PL207831A1|1979-11-19|
    NZ187621A|1980-11-28|
    IL54928A|1982-02-28|
    HU180726B|1983-04-29|
    CS198105B2|1980-05-30|
    IE781242L|1979-01-27|
    CA1103251A|1981-06-16|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    NL160809C|1970-05-15|1979-12-17|Duphar Int Res|METHOD FOR PREPARING BENZOYLURUM COMPOUNDS, AND METHOD FOR PREPARING INSECTICIDE PREPARATIONS BASED ON BENZOYLURUM COMPOUNDS.|US4399152A|1980-04-03|1983-08-16|Duphar International B.V.|Substituted benzoyl ureas as insecticides|
    US4425343A|1980-10-24|1984-01-10|Nissan Chemical Industries, Ltd.|Benzoazine ether or thioether linkage containing urea compounds, process for producing same and insecticides containing said compounds|
    US4405552A|1981-03-03|1983-09-20|Eli Lilly And Company|1-Benzoyl-3-urea compounds|
    US4366155A|1981-03-30|1982-12-28|Eli Lilly And Company|1-Benzoyl-3-ureas, compositions, and insecticidal method|
    US5135953A|1984-12-28|1992-08-04|Ciba-Geigy|Use of acyl urea compounds for controlling endoparasites and ectoparasites of warm-blooded animals|
    AR029489A1|2000-03-10|2003-07-02|Euro Celtique Sa|PIRIDINES, PYRIMIDINES, PIRAZINAS, TRIAZINES REPLACED BY ARILO, PHARMACEUTICAL COMPOSITIONS AND THE USE OF THE SAME FOR THE MANUFACTURE OF A MEDICINAL PRODUCT|
    EP1292580A1|2000-05-17|2003-03-19|Universite Catholique De Louvain|Pyrazine and imidazopyrazine derivatives as antioxidants|
    AR037233A1|2001-09-07|2004-11-03|Euro Celtique Sa|PIRIDINAS ARIL REPLACED, PHARMACEUTICAL COMPOSITIONS AND THE USE OF SUCH COMPOUNDS FOR THE PREPARATION OF A MEDICINAL PRODUCT|
    AR036873A1|2001-09-07|2004-10-13|Euro Celtique Sa|PIRIDINAS ARIL REPLACED A, PHARMACEUTICAL COMPOSITIONS AND THE USE OF THE SAME FOR THE PREPARATION OF A MEDICINAL PRODUCT|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    US05/819,639|US4133956A|1977-07-27|1977-07-27|Preparation of benzoylureas|
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