• 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 monocyclic amines, in particular to derivatives of acrylic acid, f-ly @, where R 1 is nitrile, the group is COOR 2, where R 2 is methyl or ethyl X-CL or F X 1-H or F X 2 is CL or F, which are intermediate products for the synthesis of antibacterial drugs. The goal is to simplify the process and increase the yield of the target product. The preparation is carried out by reacting the benzoyl halide with the carboxylic acid derivative in an inert solvent and an acid acceptor, followed by treating the resulting compound with cyclopropylamine in an inert solvent.
    公开号:SU1590039A3
    申请号:SU864028029
    申请日:1986-08-27
    公开日:1990-08-30
    发明作者:Грохе Клаус
    申请人:Байер Аг (Фирма)；
    IPC主号:
    专利说明:

    while stirring, 14.3 g of fc and 20 ° C are added dropwise, while stirring, a drop of the addition of 3-dimethylaminoacryloxy ether of ethyl 3-dimethylaminoacrylo. 14.3. g of ethyl 3-dimethyl ether. acids and 10.5 g of N-methylpiperidine. Stir for 3 hours at room temperature, heat in amino-acrylic acid and 8.5 g of pyridine. Stir for 3 hours at room temperature, heat
    and 20 ° C, adding 14.3 g of ethyl 3-dimethyl ester with stirring.
    tylaminoacrylic acid and 8.5 g of pyridine. Stir for 3 hours at room temperature, heat
    71
    for 2 hours at 40-50 ° C, the solvent is distilled off in a vacuum and the residue is taken up in methylene chloride - water. The phases are separated and the aqueous solution is further extracted with methylene chloride. The methylene chloride npoi-ibi solution is water, dried with sodium sulfate and the solvent is removed in eaxyyi i. The crystalline residue is recrystallized from cyclohexane, a light gasoline. 3-di-methylamino 2- (2,4-dichlor-5-fluoro-benzoyl) -acrylic acid ethyl ester is obtained with T.itn. 94-. Bypass 90.8% of theory.
    Found,%: C 50.4; H 4.2; F 5.5; N 4.1.
    Cjj H CljFNOj (334.2)
    Calculated,%: C H 4.22; F 5.68; N 4.19.
    Example 8. Step I of Example 2 is repeated with the difference that to a solution of 22.75 g of 2,4-dichloro-5-fluoro-ben

    To a solution of 22.25 g of 2,3,4,5-tetrafluoro-benzoyl chloride in 75 ml of anhydrous toluene, cooled with ice and stirred
    zoyl chloride in 100 ml of anhydrous ethyl acetate, ice-cooled and stirring, 25 gels, 9.7 g added in drops, 3-dimethyl g-dimethyl-thylamino-acrylonitrile and 8.5 g are added dropwise. pyridine-acrylonitrile and 8.5 g of pyridine. Stir for 1 hour at room temperature and then heat at 90-100 ° C for 4 hours.
    The solvent is then distilled off in vacuo and the residue is taken up in methylene chloride-water. The methylene chloride phase is washed with water and dried with sulphate.
    sodium and concentrated in vacuo. Crist; 1Ls current recrystallized from ethanol; recrystallized ethanol residue; 3-dimethylamino-2-nitrile is obtained from ethanol.
    Get the nitrile of 3-dimethylamino-2- - (2,4-dichloro-5-fluorobenzoyl) -acrylic
    on. Stir for 1 hour at room temperature and then boil for 5 hours under reflux. 30 The solvent is then distilled off in vacuo and the residue is taken up in methylene chloride-water. The methylene chloride phase of the washings) t. water7 is dried with sodium sulfate and concentrated in vacuo. Crystalline osta- (2,3,4,5-tetrafluorobenzoyl) -acrylic acid with so pl. 149-15l c. Yield 91% theory.
    eight
    0
    de. The methylene chloride phase is washed with water, dried over sodium sulfate and concentrated in vacuo. The crystalline residue is recrystallized from ethanol.
    3-dimethylamino-2- - (2,4-dichloro-5-fluorobenzoyl) -acrylic acid nitrile is obtained with m.p. 138-139 C. Output 92.2% of theory.
    Found,%: C 50.3; H 3.1; C1 24.6; N 9.8.
    C HpClj.FNjO (287.1)
    Calculated,%: C 50, .9; H 3.15; 5 C1 24.70; N 9.75.
    Example 10. Nitrile 3-cyclopropylamino-2- (2,3,4,5-tetrafluoro-benzoyl) -acrylic acid.
    Stage I. Nitrile 3 Dimethyl-2- - (2,3,4,5-tetrafluoro-benzoyl) -acrylic acid.
    To a solution of 22.25 g of 2,3,4,5-tetrafluoro-benzoyl chloride in 75 ml of anhydrous toluene, cooled with ice and stirred
    0
    5, 9.7 g of 3-dimethylamino-acrylonitrile and 8.5 g of pyridium are added dropwise.
    9.7 g of 3-dimethylamino-acrylonitrile and 8.5 g of pyridium are added dropwise.
    on. Stir for 1 hour at room temperature and then boil for 5 hours under reflux. The solvent is then distilled off in vacuo and the residue is taken up in methylene chloride-water. The methylene chloride phase of the washings) t. water7 is dried with sodium sulfate and concentrated in vacuo. The crystalline residue is recrystallized from ethanol. 3-dimethylamino-2- nitrile is obtained.
    - (2,3,4,5-tetrafluorobenzoyl) -acrylic acid with m.p. 149-15l c. Yield 91% theory.
    acids with so pl. 138-139 C. Output 91.5% of theory.
    C, HgF4NO (258.2) Calculated,%: C 55.81; H 3.12; F -29.43; N 5.42.
    HaitoeHo,%: C 50.3; H 3.1; C1 24.6; N 9.8.
    C, H (287.1) 45
    Calculated,%: C 50.9; H 3.15; Stage II. Nitrile 3-hschclopropylCl2 24.70; N 9.75. Amino-2- (2,3,4,5-tetrafluoro-benzosh1) Example 9. Repeat the α-acrylic acid step.
    I of example 2 with the difference that stage II of example 2 was repeated with a range of 22.75 g of 2.4 dichloro-5- |) tor-ben-CQ the difference that the interaction with zoyl chloride in 100 ml of anhydrous toluene - cyclopropylamine - subject the product ol, chilling with ice and stirring, add 9.6 g of 3-dimethyl: ino-acrylonitrile and 8.5 g of pyridine dropwise. Stir for 1 h at room temperature - so pl. 125-127 C. The yield of 93.8% of theory, temperature and then within 6 h ki (284.2). pt t with reflux condenser. The solvent is then distilled off in vacuo and the residue is taken up in methylene chloride -
    of stage I. In this case, 3-cyclopropylamino-2- (2,3,4,5-tetrafluorobenzosh1) -acrylic acid nitrile with
    Thus, the yield of the desired product is 785%, based on the starting compound of formula (II).
    Found,%: C 55.9; H 3.1; F29.3; N 5.3.
    C, HgF4NO (258.2) Calculated,%: C 55.81; H 3.12; F -29.43; N 5.42.
     Stage II of Example 2 is repeated with the difference that the product is subjected to interaction with cyclopropylamine; 125-127 C. The output of 93.8% of theory, (284.2).
    of stage I. In this case, 3-cyclopropylamino-2- (2,3,4,5-tetrafluorobenzosh1) -acrylic acid nitrile with
     Stage II of Example 2 is repeated with the difference that the product is subjected to interaction with cyclopropylamine; 125-127 C. The output of 93.8% of theory, (284.2).
    Thus, the yield of the desired product is 785%, based on the starting compound of formula (II).
    )
    Example 11, methyl ester of 3-cyclopropylamino-2- (2,4-dichlor 5-fluoropropyl benzoyl) -acrylic acid.
    Stage I. 3-ST-PIR methyl ester; rolidinyl) -2- (2,4-dichlor 5 т fluor benzoyl) acrylic acid.
    To a solution of 22.75 g of 2,4-dichloro-5- -h | a-tor-benzoyl chloride in 100 ml of anhydrous dioxane, cooled with ice and solution; stirring, add a solution of 15.5 g of methyl ester 3- (1-pyrrolidinyl) -acrylic acid in 25 ml of dioxane and then 10.5 g of tetraethylamine. Stir for 1 hour at room temperature, boil for 2 hours, distill off the solvent in vacuo and absorb the residue in methylene chloride - water. The phases are separated and the aqueous solution is further extracted with methylene chloride. The methylene chloride solution is washed with water, dried over sodium sulfate, and the solvent is removed in vacuo. The crystalline residue is recrystallized from cyclohexane.
    The methyl ester of 3- (1-pyrrolidinyl) -2- (2,4-DICHLOR-5- -fluoro-benzoyl) -acrylic acid is obtained. Mp. 74-76 ° C.
    Found,%: C 52.1; H 4.0; N 4,2
    15
    , 5-H,%:
    (346.2)
    C 52.03; H 4.07;
    Calculated N 4.04.
    Stage II. 3-cyclopropylamino-2- (2,4-dichloro-5-α-fluoro-benzoyl) -acrylic acid methyl ester.
    A mixture of 3.5 g of the product of stage 1, i.e. 3- (G- -pyrupolidinyl) -2- (2,4-dichlorop-5-fluorophen-benzoyl) -acrylic acid methyl ester, and 0.8 g of cyclopropylamine in 50 ml of toluene boil for 1 h after which gas evolution ceases. Toluene is distilled off in vacuo and the solid residue is crystallized from acetonitrile. Methyl ester of 3-cyclopropylamino-2- (2,4-dichloro-5-fluoro-benzoyl) -acrylic acid is obtained. Mp. 150-151 C. Output 94.2% of theory. C HjjCljFNOj (331.2).
    Thus, the yield of the desired product is 85%, calculated on the starting compound of formula (II).
    Example 12. Methyl ester of 3-cyclopropylamino-2- (2,4-dichloro-5-fluoro-benzoyl) -acrylic acid.
    ten

    - - | j t -25
    20
    35
    40
    d - cn
    -with
    59003910
    Stage I. Methyl ester of 3- (1-morpholinyl) -2- (2,4-dichl-5-fluorobenzyl) -acrylic acid.
    To a solution of 4.5 g of 2,4-dichloro-5-fluoro-benzoyl chloride in 40 ml of anhydrous dioxane at a temperature between 10 and 20 ° C, 3.4 g of methyl 3- (1-morpholi) ether is added dropwise while stirring. - Nile) -acrylic acid and 2.5 g of triethylamine. Stir for 3 hours at room temperature, heat for 2 hours at 70-80 ° C, and distill off. the solvent in vacuo and absorb the residue in methylene chloride - water. The phases are separated and the aqueous solution is further extracted with methylene chloride. The methylene chloride solution is washed with water, dried over sodium sulfate, and the solvent is removed in vacuo. The crystalline residue is recrystallized from methanol. 6.6 g (92% of theory) of 3- (1-morpholinyl) -2- (2,4-dichloro-5-fluoro-benzoyl) -α-acrylic acid methyl ester are obtained, m.p. 120-12I C. C, 5-11 „CljFNO (362.2).
    Stage II. 3-Cyclo-propylamino-2- (2,4-dichloro-5-fluoro-benzo-yl-yl) -acrylic acid methyl ester.
    Stage II of Example 11 is repeated with the difference that methyl 3- (1-morpholinyl) -2- (2,4-dihpor-5-fluoro-benzoyl) -acrylic acid methyl ester is reacted with cyclopropylamine. This gives 3-cyclopropylamino-2- (2, 4-di chloro-5-fluoro-benzoyl) -acrylic acid methyl ester with mp. 150-15l C. Yield 91.8% of theory.
    Thus, the yield of the desired product is 85% based on the starting compound of formula (II).
    Example (comparative).
    Stage I. 2,4-Dichloro-5-fluoro-benzoyl-maleic acid complex diethyl ester of the formula.
    24.3 g of magnesium chips are suspended in 650 ml of anhydrous ethanol. 5 ml of carbon tetrachloride are added and, after the start of the reaction, 160 g of malonic acid diethyl ester, 100 ml of absolute ethanol and 400 ml of anhydrous ether are added dropwise. There is intense reflux. After completion of the reaction, they are heated under reflux for an additional 2 hours, cooled to (-5) - (-10) C with the aid of dry ice and acetone, and at this temperature the solution is added dropwise to a honey blend.
    thirty
    227 g of 2J4-dichlor-5-fluoropenzoyl chloride in 100 ml of absolute ether. Stir at (0) - (-5) C for .t h, warm the mixture to room temperature overnight and then add 400 ml of ice-cold water and 25 ml of concentrated sulfuric acid to the phases and separate with ice cooling. times extracted with ether. The combined ethereal extracts are washed with complete sodium chloride solution, dried over sodium sulfate and the solvent is distilled off in vacuo. 349.5 g of 2,4-dichloro-5-fluorobenzoyl-malonoic acid diethyl ester are obtained.
    Stage II, 2,4-dichloro-5-fluoro-benzo-l-acetic acid diethyl ester.
    An emulsion of 349.5 g of crude ester of stage I in 500 ml of water is mixed with 1.5 g of p-toluenesulfonic acid. At intensive mixing, it is heated under reflux for 3 hours, cooled. The emulsion is extracted five times with methylene chloride, the combined phases of methylene chloride are washed with a saturated solution of sporious sodium,; dried over sodium sulphate and the solvent is distilled off in a vacuum; 142 ° C.
    Stage III. Complex, diethyl ester of 2- (2,4-dichloro-5-fluoro-benzoyl) -3-ethoxyacrylic acid.
    A mixture of 218 g of the desired product of stage II, 172 g of ethyl ester of 0-formic acid and 192 g of acetic anhydride is heated at 150 ° C for 2 hours. The volatile components of g are subsequently distilled off in a vacuum created by a water jet pump and medium vacuum at bath temperature. 260.4 g of crude 2-- (2,4-dichloro-5-fluoro-benzoyl) -3-ethoxy-acrylic acid ethyl ester are obtained as a residue.
    Stage IV. 2- (2,4-Dichlor-5-fluoro-benzoyl) -3-cyclopropylaminoacrylic acid ethyl ester.
    To a solution of 260.4 g of the desired product of stage II c. 750 ml of ethanol
    45 g of cyclopropylamine are added dropwise with ice-cooling and stirring. After completion of the exothermic reaction, it is stirred for another 1 hour at room temperature, the solvent is distilled off in vacuo, and the residue is recrystallized from a mixture of cyclohexane and petroleum ether. 239.5 g of ethyl 2- (2,4-dichloro-5-fluoro-benzoyl) -3-cyclopropylaminoacrylic acid ethyl ester are obtained with a mp. 89-90 S.
    Thus, the yield of the desired product, based on the starting 2,4-dichloro-5-fluoro-benzoyl chloride, is 69.16%. In addition, the proposed method is simpler by reducing the number of stages.
    权利要求:
    Claims (1)
    [1]
    Invention Formula
    The method of obtaining derivatives of acrylic acid of the General formula
    ABOUT
    where R is nitrile, the group is SOOE, where
    R, y
    X, X - -
    methyl or ethyl; chlorine or fluorine; hydrogen or fluorine; chlorine or fluorine.
    40
    the interaction of the benzoylhalogenide formula
    ABOUT
    X
    f Y e-Hai
    X,
    h
    with a carboxylic acid derivative in an inert solvent and an acid acceptor, followed by treating the resulting compound with cyclopropylamine in an inert solvent, characterized in that, in order to simplify the process and increase the yield of the target product, a compound of the general formula
    1315900391
    H RI, where X, X ,,, Xj, R, EZ, and R have indicated values,
    Crumble cyclopropylamine.
    KG "4,
    where R has the indicated value j 5 Priority by features
    RJ and R are the same and mean me on 09/29/84 at R, is a nitrile, a thyl group, together with nitrogen, with which is COORj, where Rj is methyl or ethyl; X eye they are bound, form pyrrolidine, chlorine or fluorine; X, is hydrogen or fluorine;
    and the resulting compound ob- - chlorine or fluorine; Rj and R are the same.
    common formula Oi means methyl, ethyl.
    30.01.85 with Rj and R, together with the nitrogen to which they are bound, form pyrrolidine. 15
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    同族专利:
    公开号 | 公开日
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    AT45565T|1989-09-15|
    PT81214B|1988-01-22|
    DK438885D0|1985-09-27|
    FI87765C|1993-02-25|
    EP0176846B1|1989-08-16|
    ES547253A0|1987-04-16|
    KR870001999B1|1987-11-30|
    FI87765B|1992-11-13|
    EP0176846A2|1986-04-09|
    HU193346B|1987-09-28|
    UA8023A1|1995-12-26|
    DK170638B1|1995-11-20|
    PT81214A|1985-10-01|
    HUT39148A|1986-08-28|
    DE3502935A1|1986-04-10|
    US4699992A|1987-10-13|
    NO170150C|1992-09-16|
    EP0176846A3|1987-06-03|
    IL76521D0|1986-01-31|
    CA1255678A|1989-06-13|
    IL76521A|1988-10-31|
    GR852344B|1986-01-27|
    KR860002453A|1986-04-26|
    ES8705098A1|1987-04-16|
    NO170150B|1992-06-09|
    FI853717L|1986-03-30|
    DK438885A|1986-03-30|
    NO853604L|1986-04-01|
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    DE3142854A1|1981-10-29|1983-05-11|Bayer Ag, 5090 Leverkusen|1-CYCLOPROPYL-6-FLUOR-1,4-DIHYDRO-4-OXO-7-PIPERAZINO-CHINOLINE-3-CARBONIC ACIDS, METHOD FOR THE PRODUCTION THEREOF AND THEIR CONTAINING ANTIBACTERIAL AGENTS|
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    法律状态:
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    DE3435930|1984-09-29|
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