• 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:
    Préparation d'intermédiaires pour herbicides de formule par réaction de phosphites organiques avec des benzoxazines de formule dans lesquelles - X est un substituant habituel des phénols - n est un entier de 0 à 4 - R' et R2 sont H ou tels que OR' et OR2 sont hydrolysables - Y est OM ou NR3R4 - M est H ou est tel que COOM est un sel ou ester - R3 et R4 sont H ou hydrocarbyle, l'une d'entre eux peuvent être R5-SO2- - R5 est un radicàl hydrocarboné éventuellement substitué. Produits ainsi obtenus et leur utilisation.
    公开号:SU1452482A3
    申请号:SU864027162
    申请日:1986-03-20
    公开日:1989-01-15
    发明作者:Корбе Жан-Пьер
    申请人:Рон-Пуленк Агрошими (Фирма)；
    IPC主号:
    专利说明:

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    This invention relates to the chemistry of organophosphorus compounds with a C — P bond, and specifically to a process for the preparation of new derivatives of aminomethyl-NHFSphonic acids of the general formula
    CH, -N-CH, CO-Y I
    Ш2 ОН
    (one)
    where R and R, - With, -C-alkyl;
    T OH, C, -C j-alkoxy or -N (CH h).
    The compounds of formula (I) can be used as intermediates for the preparation of a highly effective herbicide, phosphonomethylglycine.
    The purpose of the invention is to develop an affordable method for the preparation of aminomethylene phosphonic acid derivatives of formula (I), the use of which as intermediates simplifies the process for the preparation of N-phosphonomethylglycine.
    The compounds of formula (I) are obtained by reacting dialkyl phosphites with benzoxazine of the general formula
    0 --- N-CH CO-Y
    where Y - has the indicated values
    70-110 ° C.
    Example I. In a flask with a capacity of 50 cm, equipped with a magnetic stirrer, a thermometer, a branch tube, a condenser, and maintained in an argon atmosphere, 2.62 g (87.28 mmol) of paraformaldehyx1, a, 3.5 ml of methanol and 0.05- ml of solid potassium hydroxide. The contents are dissolved by heating, and then cooled. A solution of ethyl glycinate (4.50 g; 43.64 mmol) in methanol (1 cm) is introduced into the reaction solution at 20 ° C for 5 minutes. Then paracresol (4.71 rj 43.64 mmol) is added, after which it is heated to boiling for 20 minutes, then methanol is removed under reduced pressure of 0.2 atm and at 50 C.
    The residue is chromatographed on a silica column (eluant: hexane-ethyl acetate)
    After removal of the solvents under reduced pressure (0.2 atm) and extrusion, 3.65 g (15.5 mmol) of an oily substance of the formula: 5-methyl: -HrX-CH2, COOC4H5, where BZX - 0 is found, are obtained whose structure is convincing by IR spectroscopy (l 1750 cm-)
    3.5 g (14.8 mmol) of the resulting oil-5 substance and 2.07 g (14.8 mmol) of diethylphosphite are introduced into a 10-cm flask. The mixture is heated at 70 ° C for 55 minutes. Then 0.20 g (1.48 mmol) of diethylphosphite is added and the content Q is heated at 80 ° C for 35 minutes. Excess dimethyl phosphite is removed under reduced pressure (0.27 atm) and at. In the remainder receive
    25
    C HS0 P-CH2-N-CH, -CO-0-C2H5 CH2-SbNz - (- methyl-1-hydroxy
    .-Output 100%, IR spectrum (): 0: 1740 (C 0) i 1260-1200 (P 0).
    The phosphonate (1.0 G; 2.54 mmol) is dissolved in 5.05 ml of a 1.01 N methanol solution of sodium hydroxide (5.05 mmol). The mixture is heated at 80 ° C for 5 hours. The methanol is removed under reduced pressure (0.2 atm) and 40 ° C. The residue is dissolved in 3 cm of distilled water, after which the resulting aqueous phase is washed with methylene chloride. The aqueous phase is then acidified to pH 2 with HC1, and then extracted three times with 30 cm of methylene chloride. The combined organic textures are dried on magnesium sulphate. After separation by filtration and removal of methyl chloride under reduced pressure (0.2 atm), 550 mg (1.59 mmol) of substance are obtained in a solid white compound, melting at 102 ° C, having a purity of approximately 90% and meets the formula
    C, H
    2H5-9 0 P - CH2-N-CH2 CO-OH
     Hj-c Hj-lit-HeTHA-i-rHapoKCH)
    Yield 62.6%.
    Calculated%: C 57.64-, H 5.28 N 6.11,
    Found%: C 57.33j H 5.28; N 6,1
    IR spectra (VCM -): 3300 (OH), 2500-3000 (OH acid) J 1735 (C 0); 1205 (P 0); 1255 (C 0); 1030-1050; 980 (Р-О-С).
    This compound may be subjected to hydrogenolysis to compound
    (CjHyOj P-CH, 1 -Sh-CH, COOH I / O
    Example 2. In a flask with a capacity of 50 cm, 6.0 g (0.2 mol) of paraformaldehyde, 8 cm 3 of methanol and 0.1 g of solid potassium hydroxide are placed. The mixture is dissolved by heating, after which it is cooled.
    A solution of sodium glycinate obtained from glycine (7.50 rj 0.1 mol) of sodium hydroxide in the form of a powder (4.0 g; 0.1 mol) and methanol (30 cm) is then added dropwise to the above solution at 20 ° C and with stirring. Stirring is carried out for 20 minutes at. Then, 9.4 g (0.1 mol) of phenol is added and heated to 60 ° C. After 45 minutes, the mixture is cooled to 20 ° C and the precipitate is filtered off, after which it is washed three times with 10 cm of ethyl ether and dried.
    8.47 g of a white powder is obtained, which is purified at 60 ° C., while stirring it for 1 hour in 25 cm of netanol. There is an almost complete rast-40 of 0.317 g (1.062 mmol) of the obtained
    benzoxazine and 0.147 g (1.065 mmol diethylphosphite, as well as 1 cm-toluene.
    thief. The solution is allowed to recover at 20 ° C. The precipitate is filtered off, washed three times with 20 cm of ethyl ether, and then dried under reduced pressure (o, 27 6apj 20 C)
    Thus, 4.55 g (21.1 mmol) of benzoxazine with a purity of 90%, having the formula: BZX-CHi-COONa, are obtained.
    This benzoxazine can be treated with the phosphite referred to in Example 1 to obtain a compound having formula (I).
    Example 3.3 a 20 cm flask is placed 1.15 g (5 mmol) of benzoxazine, of the formula 4-CHj-BZX-CH COONa 5 cm of dry ethyl acetate, 0.11 g of tetra (n-butyl) ammonium chloride.
    the resulting suspension is cooled to. Ethyl chloroformate (0.48 cm -, 5 mmol) is then added, after which the reaction mixture is left until the temperature of the mixture rises to. Stirring is then carried out for 2 hours, after which the mixture is cooled to. A compound having the formula 4-methyl-BgX-CHCHCO-O-CO-O-C H is formed.
    Then N-methylmethanesulfonamide (0.59 g; 5.5 mmol) is added,
    then a 50% aqueous solution of caustic soda (0.44 G; 5.5 mmol) is added dropwise and the temperature is maintained. Upon expiration
    fj
    The mixture is diluted with 5 cm of water for 25 minutes.
    The organic phase is collected and the aqueous phase is extracted four times with 10 cm of ethyl acetate. The organic extracts are combined, washed with 10 cm of distilled water, and then dried on sodium sulfate. After separation by filtration and concentration under reduced pressure (0 atm) at 30 ° C, 1.25 g of an oily residue is obtained, which slowly crystallizes at a temperature approaching 4 ° C. Purification is carried out by recrystallization in a mixture of ethyl acetate and cyclohexane and get compound,
    melting pressure at 134 ° C and having the formula:
    .4-methyl-vgH-CH, -CO-S (CH3) -30.1-CH3 Into a flask with a capacity of 10 cm
    0.317 g (1.062 mmol) obtained
    benzoxazine and 0.147 g (1.065 mmol) diethylphosphite, as well as 1 cm-toluene.
    The mixture is heated to 80 ° C for 2 hours, then at boiling for 5 hours, after which toluene is removed under reduced pressure (CO, 2 atm) at 30 ° C.
    The residue (0.450 g) is chromatographed on silica (10 g), eluting with methylene chloride / meta-. NOL After removing the solvents under reduced pressure (0.2 atm) while drying under high vacuum (27 milliatm; 20 C) is carried out, a white solid is obtained, melting at 79 C (yield: 41.6%), having the formula
    CjHs-o
    0 P-CH -N-CH CO-NCCHjbSO-CH, C2H5-oCHj-CftH, - (i-CHj-l - HYDROXI)
    This compound can be hydrogenated, analogously as indicated in Example I.
    权利要求:
    Claims (1)
    [1]
    Invention Formula
    The method of obtaining derivatives of aminomethylene phosphonic acids of the general formula
    - N-CHoCO-Y R, Cr D
    ABOUT
    CH2
    L ™
    U52A826
    where R and Rj С - (.- allksh,
    Y is OH, C —C-alkoxnl or —N (CH3) -SO., ICHj,
    that dialkylphosphite of the general formula
    ten
    g de R, and R have the indicated meanings, are reacted with benchox - the general formula
    2 where Y has the specified value, 1e, when heated to 70-1 10 C.
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    同族专利:
    公开号 | 公开日
    ZA862048B|1986-11-26|
    EP0195734A3|1986-12-30|
    US4755614A|1988-07-05|
    ES8800579A1|1987-11-16|
    DK129486D0|1986-03-20|
    JPS61215399A|1986-09-25|
    EP0195734A2|1986-09-24|
    NO861053L|1986-09-22|
    HUT42078A|1987-06-29|
    FI861185A0|1986-03-20|
    AU5494286A|1986-09-25|
    PT82229B|1988-01-06|
    AU580660B2|1989-01-27|
    DK129486A|1986-09-22|
    IL78200D0|1986-07-31|
    FR2579210A1|1986-09-26|
    FR2579210B1|1987-09-11|
    FI861185A|1986-09-22|
    PT82229A|1986-04-01|
    DD249027A5|1987-08-26|
    ES553245A0|1987-11-16|
    BR8601236A|1986-12-02|
    HU198028B|1989-07-28|
    CN86101794A|1986-11-26|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US3082112A|1961-05-03|1963-03-19|Dow Chemical Co|Method for improving physical properties of clays and clay-containing soils and compositions resulting therefrom|
    ES8603901A1|1983-07-27|1986-01-01|Rhone Poulenc Agrochimie|Herbicides of the sulfon imide-type with an aminomethylphosphonic group.|
    FR2560198B1|1984-02-23|1987-05-07|Rhone Poulenc Agrochimie|ESTERS OF THE N-PHOSPHONOMETHYLGLYCIN FAMILY AND THEIR USE FOR THE PREPARATION OF KNOWN HERBICIDES|
    FR2575161B1|1984-12-26|1989-03-31|Rhone Poulenc Agrochimie|PREPARATION OF PHOSPHORUS INTERMEDIATES FOR HERBICIDE USES|
    FR2576024B1|1985-01-14|1988-01-08|Rhone Poulenc Agrochimie|TYPE N HERBICIDES - SULFONYLAMINES|FR2576024B1|1985-01-14|1988-01-08|Rhone Poulenc Agrochimie|TYPE N HERBICIDES -SULFONYLAMINES|
    FR2611204B1|1987-02-19|1989-05-05|Rhone Poulenc Agrochimie|INTERMEDIATE COMPOUNDS USEFUL FOR THE PREPARATION OF HERBICIDES|
    US5514200B1|1994-02-07|1997-07-08|Univ|Formulation of phosphorus fertilizer for plants|
    US6338860B1|1996-08-30|2002-01-15|Foliar Nutrients, Inc.|Compositions for plants containing phosphonate and phosphate salts, and derivatives thereof|
    US5800837A|1996-08-30|1998-09-01|Foliar Nutrients, Inc.|Plant fertilizer compositions containing phosphonate and phosphate salts and derivatives thereof|
    US5736164A|1996-08-30|1998-04-07|Taylor; John B.|Fungicidal compositions for plants containing phosphonate and phosphate salts, and derivatives thereof|
    FR2789991B1|1999-02-18|2002-02-22|Atochem Elf Sa|ALCOXYAMINES FROM NITROXIDE BETA-PHOSPHORUS, THEIR USE IN RADICAL POLYMERIZATION|
    JP4726172B2|2001-09-14|2011-07-20|四国化成工業株式会社|Thermosetting resin composition|
    US20060084573A1|2004-10-12|2006-04-20|Biagro Western Sales, Inc.|High calcium fertilizer composition|
    JP2008542170A|2005-05-23|2008-11-27|プラントプロテクタンツ，エルエルシー|Dithiocarbamate and phosphite formulations|
    EP2314579A1|2009-10-22|2011-04-27|Henkel AG & Co. KGaA|Fast-curing benzoxazine compounds|
    CN103965247A|2014-05-23|2014-08-06|厦门大学|Phosphor-containing nitrogen-containing structural type flame retardant polyhydric alcohol as well as preparation method and application thereof|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    FR8504433A|FR2579210B1|1985-03-21|1985-03-21|PREPARATION OF PHOSPHONATE GROUP HERBICIDES AND INTERMEDIATES FROM BENZOXAZINES|
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