• 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:
    A process for preparing a 2-R3-3-(cyanoimino)-3- (amino)propionitrile which comprises a. reacting a mineral acid addition salt of a 2-cyanoacetimidate of the formula with cyanamide in an organic solvent to form a N,2dicyanoacetimidate b. reacting a N,2-dicyanoacetimidate of the formula with an amine of the formula to form a 2-R3-3-(cyanoimino)propionitrile of the formula N,2-dicyanoacetimidate compounds are claimed as well.
    公开号:SU786889A3
    申请号:SU762386153
    申请日:1976-07-27
    公开日:1980-12-07
    发明作者:Майкл Мэккол Джон；Джон Урспрунг Джосеф
    申请人:Дзе Апджон Компани (Фирма)；
    IPC主号:
    专利说明:

    which can be applied lower aliphatic halohydrogen hydrogens: lower alcohols, cyclic ethers - tetrahydrofuran. The process can be carried out with the addition of water. The starting N-2-dicyanacetimidates and, accordingly, the target compounds can be in tautomeric form, namely: Y / NHCN, -КК if (J-CH2-C - Чк or ifC D "-CH, -L , "-T"; e The content of one form or another depends on the value of the radicals R, R ,, R The starting N-2-dicyanacetimidate is obtained by reacting the 2-cyanacetimidate mineral acid addition salt with cyanamide, preferably an anhydrous inert organic solvent at a temperature from About up to 100 ° C, the acid addition salt can be obtained i p 5 i tu. Example 1. 3- (Cyanimino) -3- iperidinpropionitrile a) Ethyl 2-cyanacetim hydrochloride date, Hydrogen chloride gas is boiled through a very cold solution of 33.0 g {0.50 mol) of malononitrile and 23.0 g (0.50 mol) of dry ethanol in 400 ml of dry ether for 1.5 h. The precipitate formed is filtered, washed with ether and dried at room temperature under vacuum and 72 g of product are obtained with a yield of 97%. b) Ethyl M-2-diiyanacetimidate. A mixture of 44.70 g (0.302 mol) of ethyl 2-cyanacetimidate hydrochloride and 13.29 g of cyanamide in 400 ml of benzene was stirred under nitrogen for 15 hours. The cyanamide was purified by extraction with ether and concentration of the soluble portion in vacuo. At the end of the reaction, the precipitated ammonium chloride is filtered off. The residue is washed twice with 50 ml of benzene. The combined extracts are concentrated in vacuo to give 41.36 g (100%) of a light yellow crystalline product. The resulting product is very pure, which is confirmed by thin layer chromatography and NMR analysis. The temperature of the melting of the crude crystalline material is 52-63 ° C. NMR Spectrum (COBS): sG4.43 (2H, d, -OCHd -); 3.93 (2H, S, CH.), 1.38 (3H t, CH). c) 3- (Cyanimino) -3-piperidinepropionitrile. Piperidine (25.67 g, 0.0302 mol) was added dropwise to a very strongly cooled solution of 41.36 g (0.0302 mol) of ethyl H-2-diacyanthium; 1 amidate in 60 ml of methanol. The reaction mixture from heterogeneous at the beginning of the process soon becomes homogeneous and yellow. Piperidine is added at a rate that provides a temperature reaction. After 50 minutes while standing, the reaction mixture is separated by. and aqueous saturated NaHCO. The organic phase is dried over and concentrated in vacuo to give 54 g of a yellow oil, which is a pure product according to thin layer chromatography. The NMR spectrum confirms the presence of the above product, EXAMPLE 2. 3- (Cyanimino) -3-morpholine propionitrile. Morpholine (2.54 g, 0.0292 mol) was added to a very strongly cooled solution of 4.00 g (0.0292 mol) of ethyl M-2-dicyanacetimidate in 80 ml of tetrahydrofuran. After 145 minutes at room temperature, the reaction mixture is concentrated, then filtered through 75 ml of silica gel. The latter is washed with a mixture of 4% NaOH-CH C E. After washing, the product is concentrated. The resulting crude product is subjected to chromatography (H PL C, 1 inch 40 30-50 µm silica gel, 2% NaOH / CH C Eg) to obtain the target is recrystallized from HIJ and 4.00 g of the first portion are obtained in the form of white needles (129-130 C) and 0.560 g of the second portion (128-130 ° C), which corresponds to a total yield of 84%. NMR, mass and IR spectra correspond to the target product. Found,%: C 53.77, H 5.66, 31.23. H, 5.66; C, 53.692; Calculated, N, 31.44. Froze 3- (Cyanimino) -3-pyrrolidinpropionitrile. Pyrrolidine (2.07 g, 0.0292 mol) is added to a very strongly cooled solution (4.00 g, 0.0292 mol) of ethyl M-2-dicyanacetimidate in 80 ml of tetrahydrofuran and stirred for 2 hours at room temperature. . The crude product is isolated and subjected to thin-layer chromatography as in Example 2. The pure crystalline product of thin-layer chromatography (4.80 g) is triturated with diethyl ether to obtain 4.00 g (84%) of the desired product, t, pl. NMR and IR spectra of it correspond to the above product. Found,%: C 58.51, H 6.33, N 33.67. % H
    权利要求:
    Claims (1)
    [1]
    Claim
    The method of obtaining derivatives of 3- (cyanimino) -3- (amino) -propionitrile of the General formula
    NCK hssn 2 - <k '"2 where R. ^ and R 2 are lower alkyl, allyl or flf, Rg together with the nitrogen atom with which they are bonded, represent a piperidino, methylpiperidino-morpholino-pyrrolidino group, about l and h βίο u and i with the fact that N-2-dicyanacetimidate of the formula
    COC
    OR gd g 'chzyl alkyl, is subjected to-amine with the formula
    Λ where R- and Rg have the above: values, at a temperature from 0 to 100 ° C in an inert organic solvent.
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    同族专利:
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    引用文献:
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    US3068274A|1960-08-18|1962-12-11|Eastman Kodak Co|thio-2-alkenamides|
    US3225077A|1963-03-05|1965-12-21|American Cyanamid Co|N-cyanoimidates and processes for preparing same|
    US3291827A|1963-03-05|1966-12-13|American Cyanamid Co|Process for preparing n, n'-dicyanoamidine salts|
    US3641103A|1969-06-03|1972-02-08|Grace W R & Co|Process for preparing amidine salts|
    US3910928A|1974-04-26|1975-10-07|Upjohn Co|3--propionitriles|
    US3948915A|1974-07-08|1976-04-06|Daiichi Seiyaku, Co., Ltd.|2-Halopyrimidine derivatives and a method for their preparation|JPS545608B2|1973-12-04|1979-03-19|
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    US4098791A|1977-07-29|1978-07-04|The Upjohn Company|Process for preparing 3--3-amino-propionitriles|
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    CH637153A5|1978-06-02|1983-07-15|Ciba Geigy Ag|AZO DYES AND METHOD FOR PRODUCING AZO DYES.|
    AR225772A1|1979-08-14|1982-04-30|Du Pont|NEW 3-AMINO-3-ALCOXI-N-CIANO-2-ALKYL PROPENIMIDATE AND PROCEDURES FOR ITS PREPARATION AND OF PYRIMIDINES STARTING FROM THOSE|
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    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    US05/599,912|US4032559A|1975-07-28|1975-07-28|N,2-dicyanoacetimidates|
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