• 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 present invention provides a novel method for the preparation of pyridine-2,3-dicarboxylic acids by the oxidation of 8-substituted quinolines.
    公开号:SU1690543A3
    申请号:SU874203342
    申请日:1987-09-11
    公开日:1991-11-07
    发明作者:Фредерик Райкер Вилльям；Алан Дэниелс Вилльям
    申请人:Американ Цианамид Компани (Фирма)；
    IPC主号:
    专利说明:

    The invention relates to improved. The method of producing pyridine-2,3-dicarboxylic acid derivatives of the general formula
    T @ S
    N
    soon soon
    where R is hydrogen or C1 C2-alkyl, or their N-oxides, which are intermediate products in the synthesis of imidazolinylnitotinic acids having a herbicidal action.
    The purpose of the invention is to increase the yield and simplify the process by oxidizing the corresponding 8-hydroxyquinoline derivative with hydrogen peroxide in an aqueous KOH solution.
    The oxidation is carried out when 4-7 mol of aqueous KOH concentration of 15-35 wt.% Is used per mole of the starting quinoline derivative. For complete oxidation, 8-20 mol of equivalents of H202 are added at 75-90 ° C to a mixture of the starting quinoline and at least 1 mol of aqueous KOH.
    EXAMPLE 1 Preparation of 5-ethylpyridine-2,3-dicarboxylic acid using hydrogen peroxide and potassium hydroxide KOH.
    To a stirred mixture of 25% potassium hydroxide (215.5 g, 0.96 mol) and 3-ethyl-8-hydroxyquinoline (30.28 g, 0.175 mol), at 90 ° C, 277.5 g of 30% - hydrogen peroxide (2.45 mol) for 3.25 hours, maintaining the temperature at 90 ° C for an additional 1-2 hours, during which the solution is analyzed for
    Yu
    about cl
    4 00

    00
    Hydrogen peroxide, and if present, is decomposed by potassium bisulfite. The reaction mixture is then distilled off in order to remove 243 g of water so that the mass of the reaction mixture is half of its initial mass. The solution is cooled to 45 ° C and sulfuric acid is injected until a pH of 3.5 is reached. The resulting suspension of potassium sulphate is cooled to 10 ° C, kept for 30 minutes, filtered and washed with 5 ml of cold water. Sulfuric acid is added to the filtrate until a pH of 1.8 is reached. The resulting suspension of 5-ethylpyridine dicarboxylic acid is kept at 10 ° C for 40 minutes, filtered and washed with 20 ml of cold water. Then the precipitate formed on the filter is dried at 55 ° C under reduced pressure for 3-8 hours, and 19.60 is obtained g (purity 97.6%) of the product as a solid with a color from light yellow to whitish. Using the described procedure with different substituted quinolines, with different amounts of different aqueous bases, taken in different concentrations, with different amounts of hydrogen peroxide of different concentrations, pyridine-2,3-dicarboxylic acids are obtained, under the conditions given in table (examples 2-11).
    EXAMPLE 12 Preparation of 5-methylpyridinedicarboxylic acid using potassium hydroxide and hydrogen peroxide.
    Hydrogen peroxide (30% by weight, 92.7 g, 0.818 mol) was introduced over 1.5 h into a stirred mixture of 26.4% potassium hydroxide (145.6 g, 0.665 mol) and chlorine hydrate-3-methyl-8-hydroxyquinoline (20.00 g, 0.102 mol) at 75-80 ° C with maintaining the temperature in the range of 75-80 ° C. The reaction solution is then maintained at 75-80 ° C for 2 hours and then heated at 90-95 ° C for 1 hour. The reaction mixture is cooled to 35 ° C and hydrochloric acid is added until pH 1 is reached. 8-1.6. The resulting suspension is stirred for 1 hour at 20 ° C, filtered, washed with 30 ml of water and dried in air for 12 hours. The result is 14.6 g (purity 96.1%) of the final product as a solid with color from whitish to light yellow.
    PRI me R 13. Production of pyridine-2.3-dicarboxylic acid N-oxide using potassium hydroxide and hydrogen peroxide.
    Hydrogen peroxide (30% by weight, 31.64 g, 279.1 mol) was introduced into the stirred mixture of 8-hydroxyquinoline-M-oxide (5.00 g, 31.06
    mol) and 7.95% aqueous solution of potassium hydroxide (43.99 g, 62.42 mol) at 90 ° C, maintaining this temperature. After the introduction of 5 ml of hydrogen peroxide, this addition is stopped, 10 ml of water are introduced, the pH is adjusted to 11.6 and maintained for 35 minutes. The peroxide feed is then continued for 83 minutes with maintenance. pH value of 11.6 by introducing 45% potassium hydroxide. After stirring the reaction mixture for 1 hour at 90 ° C, a 56% yield of pyridine-2,3-decarboxylic acid N-oxide is obtained.
    权利要求:
    Claims (3)
    [1]
    1. A process for the preparation of pyridine-2,3-dicarboxylic acid derivatives of the general formula
    UNC
    or their N-oxides, where R is H or C 1 -C 2 alkyl, by oxidation of the corresponding 8-hydroxyquinoline derivative, characterized in that, in order to increase the yield and simplify the process, the compound of the general form R
    and s he
    or its N-oxide, or its acid addition salt, where R has the indicated value, is oxidized with hydrogen peroxide with an aqueous solution of KOH.
    [2]
    2, the method according to claim 1, characterized in that 8-20 mol of equivalents of H20a are added to the mixture of the starting quinoline of general formula II and at least 1 mol of aqueous KOH.
    at 75-90 ° C.
    [3]
    3. The method according to claims 1 and 2, characterized in that 4-7 mol of aqueous KOH concentration of 15-35 wt.% Are used per mole of starting quinoline of general formula II.
    Compiled by I. Bocharova Tehred M. Morgenthal
    Corrector S.Cherni
    Editor N. Yatsola
    Order 3829 Circulation: Subscription
    VNIIPI State Committee for Inventions and Discoveries at the “NT USSR 113035, Moscow, Zh-35, 4/5 Raushsk nab.
    Corrector S.Cherni
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    同族专利:
    公开号 | 公开日
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    DK475387D0|1987-09-11|
    EP0259687B1|1991-07-03|
    HUT48211A|1989-05-29|
    BR8704717A|1988-05-03|
    IE872437L|1988-03-12|
    DK475387A|1988-03-13|
    CS270573B2|1990-07-12|
    CS652987A2|1989-11-14|
    EP0259687A3|1989-05-31|
    ES2028834T3|1992-07-16|
    AU7828287A|1988-03-17|
    DD262227A5|1988-11-23|
    ZA876838B|1988-03-15|
    JPS63119466A|1988-05-24|
    EP0259687A2|1988-03-16|
    GR3001297T3|1992-08-26|
    AU599698B2|1990-07-26|
    JPH07116153B2|1995-12-13|
    IL83795D0|1988-02-29|
    IE59547B1|1994-03-09|
    IL83795A|1992-06-21|
    CA1297112C|1992-03-10|
    AR245697A1|1994-02-28|
    DK169518B1|1994-11-21|
    DE3771153D1|1991-08-08|
    KR950011411B1|1995-10-04|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    JPS6347708B2|1980-02-25|1988-09-26|Yamamoto Kasei Kk|US5252538A|1984-05-21|1993-10-12|American Cyanamid Company| fused heteropyridine compounds, intermediates for the preparation of and use of said compounds as herbicidal agents|
    US5565412A|1984-05-21|1996-10-15|American Cyanamid Co.| fused heteropyridine compounds, intermediates for the preparation of and use of said compounds as herbicidal agents|
    IL89142A|1988-03-10|1993-04-04|American Cyanamid Co|Method for the sequential oxidation of substituted 8-hydroxyquinolines to produce substituted pyridine-2,3- dicarboxylic acids|
    ES2058625T3|1989-03-22|1994-11-01|American Cyanamid Co|METHOD FOR SEQUENTIAL OXIDATION OF SUBSTITUTED QUINOLINS TO PRODUCE SUBSTITUTED PIRIDIN-2,3-DICARBOXYLIC ACIDS.|
    TW232013B|1992-04-24|1994-10-11|Takeda Pharm Industry Co Ltd|
    NZ314904A|1996-06-10|1998-06-26|American Cyanamid Co|Preparation of a herbicidal [methyl]ammonium halide|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    US90671386A| true| 1986-09-12|1986-09-12|
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