• 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 compounds containing phosphorus- carbon-nitrogen bond of the general formula I <IMAGE> wherein R1 and R2 are the same or different and stand for hydrogen or an organic radical, R3 and R4 are the same or different and stand for hydrogen, hydroxy or an organic radical. The compounds are prepared by reacting a phosphorus halide with ammonia, water soluble ammonium salts, primary or secondary amine in the presence of water and further with aldehyde or ketone. The product is recovered by reducing the reaction volume or by adding a water miscible organic solvent to the reaction mixture. The process is preferably suitable for the preparation of N-phosphono- methylglycine and derivatives thereof, which are significant in plant protection as herbicidally active compounds.
    公开号:SU776561A3
    申请号:SU782643651
    申请日:1978-08-03
    公开日:1980-10-30
    发明作者:Балинт Шандор；Колонич Золтан；Гаал Антал；Фаркаш Йожеф；Дуфек Ласло；Хорват Шандор；Карачоньи Бела
    申请人:Нитрокемиа Ипартелепек (Инопредприятие)；
    IPC主号:
    专利说明:

    (54) METHOD OF OBTAINING OI-AMINOPHOSPHONE COMPOUNDS The invention relates to the chemistry of organophosphorus compounds with a C-P bond, namely, a method for producing oi-iinophosphonic acids of the general formula RI-hydrogen) Ri-hydrogen or phenyl; identical or different and mean methyl, cyclohexyl, fdsfonomethyl, carboxymethyl or N, N-diphosphonomethylethylamino group. Compounds containing phosphorus, carbon and nitrogen are of great importance in the field of plant protection as a wide-spectrum herbicide. The method of preparation — phosphoronic acids by the interaction of dialkyl phosphites with aldehydes and amines when heated to 130-140 ° С in the presence of hydrochloric acid in a sealed ampoule til The disadvantages of this method include the need to use ACID dialkylphosphites, resulting in dialkylphosphonates, the separation of which and hydrolysis is a long process. The closest to the described invention by its technical essence and the achieved result is the synthesis of α-aminophosphonic acids, which consists in the fact that the amine is reacted with an aldehyde and a phosphorous acid at 100-150 ° C 2j. The disadvantage of this method is the need to use phosphorous acid, which is a hygroscopic reagent and leads to the formation of side products, which degrades the quality of the target products. The aim of the invention is to preach a process. This goal is achieved by the proposed method for the preparation of o-amiophosphonic acids, which consists in the fact that the amine is reacted with phosphorus trichloride in the presence of water while boiling the reaction mixture with. following its processing with formaldehyde or benzaldehyde.
    As amines can be used ammonia, or primary, or secondary amines, or their chlorine
    hydrogen chloride salts; --- - - --Distinguishing features of the method
    VYa; it is the use of Tpexit natural phosphorus as a phosphorus-containing reagent and carrying out the process in the presence of water during boiling of the reaction mixture with its subsequent
    Aldehyde treatment.
    The described method for the preparation of oL-amino-6-phosphonic acids eliminates undesirable side reactions, iric. which is the use of phosphorous acid, and also improves
    the quality of the target products, the output is 90-98% of theoretical.
    Rome 1. A flask equipped with a yoshapka contains 300 ml of water, 137 g of phosphorus trichloride is added to it with stirring, then 75 g of a 50% aqueous glycine solution is added to the heated ds1 solution. Constantly peremetdiva, heat the reaction mixture to a boil, then che. cut 30 minutes into the reaction mixture slowly from 200 g of 37% iodine formaldehyde. At the end of the reaction, the water is evaporated from the mixture. The resulting syrbic consistency liquid is dissolved in br-than ethanol. After cooling the ethanol solution, a Crys alliCool product containing N-difyfyiomethylglycine, purity 97% is recovered.
    tf 210 ° C. Yield 93%.
    Example 2. In a flask equipped with a thermometer, a stirrer and a reflux torbm, 125 MTSoSJiTTleipeMiuftiBajr was poured, cooled, 51.7 g of tpex chlorine phosphorus was added and the temperature was maintained at 40 ° C. At the end of the addition; trichloro-5bf6spho, 50 g of rmesymino-dyacetic cells are added and heated to boiling. The mixture is boiled using a dephlegmator and 119 g of 38% of the foot of formaldehyde water is added during 45 minutes. According to the windows. The addition of formaldehyde
      checkpoint 3 hours T, J. 2/3 of the mixture is distilled off, the solution is dispersed with ethanol and the residue is cooled. The precipitates are filtered, washed in ethanol and water, then dried. The resulting product is M-phosphonoylmethylaminoacetic acid.
    that Good purity, t. times l. 208 C. Yield 95%.
    From the N-phosphonomethylaminodiacetic acid obtained by the previous method, 114 g are poured into a flask equipped with a stirrer and 150 ml of water is added. After stirring the flp6aBnHioT v5jD g of concentrated sulfuric acid and, mixing, heated to 90 ° C. At this temperature, 260 1 of a 30% aqueous solution is added over 3 hours.
    776561
    hydrogen peroxide, while constantly maintaining a temperature of 60 ° C. After the peroxide was added, the mixture was left for 3 hours at 9000.
    After completion of the reaction, the rio is evaporated, after which the residue is mixed with ethanol and cooled. During cooling, N-phosphonomethylglycine is suspended in the form of crystals and dried after washing with water. Pure ... that product will be 98%; mp 230 ° C. Yield 95%. g
    Example 3: In a flask equipped with a stirrer and a deflating extinguisher (175 ml of water), and then stirring 69 g of trichloride are added.
    15 phosphorus and 44.5 g of methylglycine. After that, 188.4 g of a 38% aqueous formaldehyde solution are added. The reaction mixture is kept boiling. At the end
    Once added, the mixture is boiled for another 2 hours, evaporating it to half the volume. After the addition of ethyl alcohol, and cooling the mixture, the precipitate is washed. The present crystalline product in water
    5 then dried. The resulting product is N-fb.sup.on-glycine with 97% pure pure. Yield 90%.
    Example 4. To the flask equipped with the LECA and reflux condenser, add 525 ml of water and stirring, add 206 g. phosphorus trichloride
    so that the temperature was no more. 40 ° C. After that, 27 g of chloride is added, brought to a boil, and 565 g of a 38% aqueous formaldehyde solution are added and boiled for another 1 h after the reaction. The mixture is cooled to room temperature and the precipitated product is filtered off from a solution . The resulting product is N-trimethylphosphonic acid with a purity of 98%, mp 215 ° C. The yield of the product is 97%. . . .
    PRI me R 5. In the flask stocked. stirrer and reflux condenser, pour
     350 ml of water and 138 g of phosphorus trichloride are added with stirring, while maintaining the temperature around. After that, 62 g of cyclohexylamine hydrochloride,
    The Q mixture is heated to boiling and, after half an hour of boiling, 108 g of beisaldehyde are added. The mixture was boiled for 2 hours and cooled to room temperature. The resulting product was set by cyclhexylamine 5 benzidphosphonic acid with a purity of 97%. Exit 92% ....
    PRI me R 6. In a flask equipped with a stirrer and a reflux condenser, pour 350 ml of water and add: 1 dyut 138 g
    About phosphorus trichloride, while maintaining a temperature of about 40 ° C. Then 15 g of ethylenediamine are added and the reaction mixture is heated to boiling. After boiling for half an hour, 170 g of 38% aqueous
    formaldehyde solution, after which the mixture is cooled to room temperature. The resulting white crystalline product is ethylediamine tetramethylene phosphonic acid. The product is formed with p.98% yield and 98% purity; v.24fc
     the invention
    1, Method for preparing C-α-aminophosphonic acids of general formula
    BI
    (HObP-C-ll
    n o
    four
    at.
    hydrogen,
    hydrogen or phenyl; same or different and
    meaning methyl, cyclohexyl, phosphonomethyl, carboxymethyl, or N, N-diphosphonomethyl ethyl amino,
    interaction of the amine with the phosphorus-containing reagent when heated, so as to simplify the process, phosphorus trichloride is used as the phosphorus-containing reagent and the process is carried out in the presence of water while boiling the reaction mixture, followed by its treatment with formaldehyde or benzaldehyde.
    2. The method according to claim 1, characterized in that ammonia, or lervic, or secondary amines, or their hydrochloride salts are used as the amine.
    Information sources,
    5 taken into account in the examination
    1, K.A. Petrov et al. Synthesis of amyodiphosphonates and aminotriphosphonates of JOH, 1959, 29, p. 591-594.
    2. For the FRG 2337289, cl. C 07 F 9/38, published, 1973 (prototype). .
    权利要求:
    Claims (2)
    [1]
    Claim
    1. The method of obtaining SA-aminophosphonic acids of the General formula
    Ri
    II 1 about in g 'where R, is hydrogen',
    R t is hydrogen or phenyl;
    R ^ h R | are the same or different and mean methyl, cyclohexyl, phosphonomethyl, carboxymethyl or hl ', N'-diphosphonomethylethylamino group, the interaction of the amine with a phosphorus-containing reagent when heated, which are different in that, in order to simplify the process, as a phosphorus-containing phosphorus trichloride is used and the process is carried out in the presence of water while boiling the reaction mixture, followed by treatment with formaldehyde or benzaldehyde.
    "L 2. The method according to p" 1, characterized in that, as an amine, ammonia, or primary or secondary amines, or their hydrochloride salts are used.
    , Sources of information, '5 taken into account in the examination
    1. Petrov K.A. et al. Synthesis of aminodiphosphoates and aminotriphosphonates ZhOKh, 1959, 29, p. 591-594.
    [2]
    2. The application of Germany No. 2337289,
    20 cl. C 07 F 9/38, published, 1973 (prototype).
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    同族专利:
    公开号 | 公开日
    DK149473C|1986-12-01|
    NO791217L|1979-10-12|
    BR7900568A|1979-10-30|
    AT373602B|1984-02-10|
    YU85079A|1982-10-31|
    ATA263179A|1983-06-15|
    PL214793A1|1980-01-02|
    BG34334A3|1983-08-15|
    IL57008D0|1979-07-25|
    IN149779B|1982-04-10|
    AR227625A1|1982-11-30|
    CS239903B2|1986-01-16|
    DK149473B|1986-06-23|
    CH642666A5|1984-04-30|
    NO160373B|1989-01-02|
    BE875501A|1979-07-31|
    GR67713B|1981-09-14|
    DE2914294C2|1983-03-17|
    NL7902854A|1979-10-15|
    IT7967767D0|1979-04-11|
    CA1135279A|1982-11-09|
    NO160373C|1989-04-12|
    GB2021589A|1979-12-05|
    LU81126A1|1979-07-20|
    FR2422675A1|1979-11-09|
    DD142888A5|1980-07-16|
    DE2914294A1|1979-10-25|
    JPS554362A|1980-01-12|
    EG13622A|1982-03-31|
    IT1118553B|1986-03-03|
    DK148679A|1979-10-12|
    YU41154B|1986-12-31|
    PT69461A|1979-05-01|
    GB2021589B|1982-10-20|
    PL123998B1|1982-12-31|
    RO78631A|1982-03-24|
    TR20811A|1982-09-15|
    ES471960A1|1979-02-01|
    FR2422675B1|1986-03-21|
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    引用文献:
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    IL72142D0|1983-08-17|1984-10-31|Stauffer Chemical Co|Preparation of phosphonomethylated amino acids|
    GB2154588B|1984-02-20|1987-10-07|Sunlead Chemical Industry Co L|A process for preparation of n-phosphonomethyl glycine|
    JPH0130022Y2|1985-07-24|1989-09-13|
    HU205944B|1988-02-08|1992-07-28|Nitrokemia Ipartelepek|Process for producing n-phosphono-methyl-imino-diacetic acid|
    GB8825589D0|1988-11-02|1988-12-07|Albright & Wilson|Purification|
    HU203360B|1988-11-25|1991-07-29|Monsanto Co|Process for producing n-acylamino methylphosphonates|
    JP2525977B2|1991-10-17|1996-08-21|昭和電工株式会社|Process for producing N-acylaminomethylphosphonic acid|
    US5495042A|1993-11-04|1996-02-27|Cytogen Corporation|Non-alkaline purification of aminophosphonic acids|
    EP1353930B1|2001-01-12|2004-08-11|Basf Aktiengesellschaft|Method for producing n-phosphonomethyl iminodiacetic acid|
    CN100400543C|2006-09-08|2008-07-09|四川贝尔实业有限责任公司|Method for preparing Phosphonomethyl iminodiacetic acidthrough hydrolysis of imino diacetonitrile|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    HU78NI213A|HU177486B|1978-04-11|1978-04-11|Process for preparing phosphonic acid derivatives|
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