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    • 专利摘要:

    公开号:SU942592A3
    申请号:SU792847570
    申请日:1979-12-04
    公开日:1982-07-07
    发明作者:Штайнер Эгинхард；Мартин Пьер；Беллус Даниэль
    申请人:Циба-Гейги Аг (Фирма)；
    IPC主号:
    专利说明:

    solvent and the desired product is isolated.
    Preferably, the interaction of trichloroacetate Pudehyde and acrylonitrile is carried out in a closed system at a pressure of 70-140 ° C.
    The catalyst for the addition of trichloroacetaldehyde to acryloiitrile is taken in an amount of 0.1-5 mol per acrylonitrile.
    The addition of trichloroacetaldehyde to acrylonitrile is carried out in the presence of an inert organic solvent.
    As the organic solvent, nitrile of alkanecarboxylic acid with 2-5 atoms, carbon, 3 alkoxypropionitrile with 1-2 carbon atoms in the alkyl group or in excess of acrylonitrile is used.
    The cyclization of 2, +, -trichloro-4-formylbutyronitrile is carried out in the presence of hydrogen chloride or hydrogen bromide, aluminum chloride or phosphorus pentachloride.
    The cyclization of 2, A, -trihlop-4-formylbutyronyl is carried out at 80200 ° C in an environment of chloroform, dialkyl ethers with 1-A carbon atoms in alkyl groups or in dimethylformamide. About
    This goal is achieved by the same method of producing 2,3. Trichloropyridine, which implies that trichloroacetaldehyde is reacted with acrylonitrile at 150–200 ° C in the presence of a catalyst C, CIC (|), dichloro-tris-triphenylphosphine ruth (II) in the amount of 0.1-5 mol. in the calculation of acrylonitrile in an inert organic solvent.
    Preferably, the reaction is conducted in a closed system at a pressure corresponding to the reaction temperature.
    Nitrile of alkane carboxylic acid with 2-5 carbon atoms or 3 alkoxypropionitrile with 1-2 carbon atoms in the alkyl group is used as an inert organic solvent.
    The reaction is best carried out in acetoiitrile, butyronitrile or Zmethoxypropionitrile.
    A method of producing A-trichloro-4-formylbutyronitrile is also proposed. It is concluded that trichloroacetaldehyde is reacted with acrylonitrile in the presence of a catalyst Cu, CyCe (1), copper bronze in amounts. ve 0.01-10 MOL.1 based on acrylonitrile and the desired product is isolated.
    Variants of the method for producing 2,3,5-trichloropyridine are different in that, according to the first embodiment, the intermediate obtained as a result of the interaction of trichloroacetaldehyde and acrylonitrile 2.4, trichloro-4-formylbutyronitrile is subjected to cyclization; the intermediate product is carried out in a single step.
    The goal is also achieved by the method of obtaining 2,., 4-trichloro formylbutyronitrile of the formula
    „Ci ce I I
    / -C-CH2-CH- (N "Ci
    which is a new intermediate for the synthesis of 2,3,5-trichloropyridine and consists in the fact that trichloroacetaldehyde is reacted with ecrylonitrile at
    70-YO C in the presence of a catalyst Cu, CuCE (|), copper bronze in an amount of 0.01-10 MOL.1 calculated on acrylonitrile, and the target product is isolated.
    Preferably, the reaction is carried out in a closed system at a pressure corresponding to C, the catalyst is taken in an amount of 0.1-5 mol. based on acrylonitrile.
    Preferably, the reaction is carried out in the presence of an inert organic solvent, such as alkanecarboxylic acid nitrile, with 2-5 carbon atoms, Zelkoxypropionitrile
    with 1-2 carbon atoms in the alkyl group or in excess of acrylonitrile.
    Example 1 a. Preparation of 2,4,4-trichloro-4-formylbutyronitrile.
    22.0 g of trichloroacetaldehyde, 5.3 g
    权利要求:
    Claims (3)
    [1]
    Acrylonitrile and 0.5 g of copper (I) chloride, together with 30 ml of acetonitrile, are heated in an enameled autoclave for 20 hours at 115 ° C. After cooling, the solvent is distilled off in vacuum at a temperature of about 40-50 ° C, the residue is mixed with 50 ml of diethyl ether and the copper chloride (|) obtained as a precipitate is filtered off. After the distillation of diethyl ether, the residue is subjected to fractional distillation in vacuum, and the fraction boiling at 64–65 ° C and the residual pressure of TSOO mm Hg is taken off. 13.6 g (60% of theory) of 2.4, -trichloro-4-formylbutyronitrile in the form of a colorless oil are obtained. Infrared spectrum (CHCCj) in cm 2250 {CN), 1750 (CO). Calculated D: C 29.96; H 2.01; N 6.99; C 53.06 (molecular weight 200.4. Found; C 29.89; H 2.13; N 6.95; se 52.67. Example 16. Preparation of 2,3, -trichlorpyridine. 13.6 g 2 , 4, t-trichloro-4-formylbutyronitrile, prepared according to example 1a, with the addition of 1, Og of trichloride aluminum is heated in an enamel autoclave for 1 hour at a time. Then the crude product is distilled with water vapor and 2.3, 5 trichloropyridine is separated in the form of white crystals.The yield is 9.1 g (83% of theory) 2,3,5 trichloropyridine, having a mp of 49-50 seconds Example 2a 1.7 g trichloroacetaldehyde, 5.3 acrylonitrile and 0.5 g of copper (I) chloride are heated, in a medium of cho, ml of 3-methoxypr opionitrile at 30–85 ° C. During the reaction, the boiling point of the mixture rises and, about 30 hours later, reaches 125 130 ° C. After cooling, the dark color in the flask is extracted with diethyl ether. After the distillation of diethyl ether, the brown oil that remains is heated in a vacuum created by a water jet under pressure. The residue is subjected to fractional distillation under high vacuum. 10.2 g (5C from theory) of a colorless oil are obtained, which is identical to the product obtained in Example 1a. Example 26. Obtained according to Example 2 a 2 ,, 4-tpichloroprophenyl-nitrophenyl is converted to 2,3.5 trichloropyridine (yield 805G, from theory), heating for 3 hours at 130 ° C followed by distillation with water vapor. Froze 20 g of 2, ", 4-trichloro-C-formylbutyronitrile, prepared in Example 1a, is dissolved in 20 ml of diethyl ether and treated at 025 ° C for 5 hours with a stream of gaseous hydrogen bromide. The diethyl ether is then distilled off in vacuo and the residue is purified by steam distillation. 13.6 g (60% of theory) of 2-bromo 3, 5 dichloropyridine are obtained in the form of white crystals with m.p. 2 ° C A good yield is also obtained with the same preparation procedure, using chloroform instead of diethyl ether as a solvent. Example k a. Getting 2 ,, -trichloro-β-formylbutanol. , 7 g of trichloroacetaldehyde, 13.2 acrylonitrile, and 0.63 g of porous activated copper are heated for 12 hours at 10 ° C in a reactor to operate at elevated pressure. Then, excess acrylonitrile is distilled off at LO-50 ° C in a vacuum created by a water-jet pump. 18.2 g of a dark oil are obtained, which, according to gas chromatographic analysis, consists of 85.4% of 2,4,4-trichloro-formylbutyronitrile, which corresponds to a yield of 77 from the theory. Example 46. Preparation of 2,3,5-trichloropyridine. 18.2 g of 2.4, -trichlor - + - formylburonitrile obtained in Example 4a are added dropwise over a period of 15 minutes to a vertically positioned column 0 cm long and 2.5 cm in diameter filled with half Raschig rings and equipped with jacket heated with hot oil at 175. At the same time, a weak stream of gaseous hydrogen chloride countercurrent with respect to the movement of the reaction mixture is passed through the bottom of the column. The dark, resinous mass flowing out of the reactor is distilled with steam. 11.5 g (851 from the theory) of 2,3,5-trichloropyridine are obtained in the form of white crystals, m.p. 9-5fl c. Pr them. 5 a. Preparation of 2, k, k-trichloro-4-formylbutyronitrile. The mixture, 7 g of trichloroacetaldehyde, 13.2 g of acrlonitrile and 0.63 g of activated copper bronze are heated for 48 hours with reflux. Then, an excess amount of acrylonitrile is distilled off from nff 40-50 ° C in a vacuum created by a water-jet pump. 17.3 g of dark oil is obtained, which, according to gas chromatographic analysis, consists of 88.5% of 2,4,47-trichloro-formylbutyronitrile, which corresponds to a yield of 76.5 from the theory of Example 56. Preparation of 2,3, -trichloropyridine . 17.3 g of 2, A-trichlo-β-phthalylbutyronyl obtained in example 5a, while passing the weak perspiration of hydrogen chloride gas, heated the hydrogen for 2k h at 80–85 s. The entire reaction mixture is then distilled with steam. Obtain 10.0 g (72 from theory) 2,3,5 trichloropyridine in the form of white crystals with so pl. 9 Example 6. Preparation of 2,3,5-trichloropyridine. In a solution of 25.0 g (0.125 mol) 2, 4, A-trichloro-β-formylbutyronitrile in 50 ml of M, M-dimethylformamide, hydrogen chloride gas is passed in at a rate such that the temperature of the reaction mixture does not exceed 120 ° C. Upon completion of the reaction, the mixture is poured into ice water. The beige precipitate is filtered off and dried. In this way, 15.1 g (from theory) of 2,3, 5-trichloropyridium with m.p. 48-50 ° C. PRI me R 7- Preparation of 2,3,5-trichloropyridine. 10.3 g of phosphorus pentachloride are added separately by chi mi at a temperature not exceeding 60 ° C in 0.0 g of dimethylformamide. After this, the resulting solution is saturated with hydrogen chloride, and. After the temperature rises to the reaction mass, 50,4-trichloro-formylbutyronitrile obtained in Example 1a is added dropwise to cooling 50 ° C, so that the temperature does not exceed 75 ° C. After adding 2, + , -trichloro-formylbutyronitrile mixture is heated for 1 hour at. Then the reaction mixture with a temperature of 60 ° C was poured onto ice, the precipitated 2,3,5 trichloropyridine was filtered off, dried, and 16.2 g (8% of theory) were obtained with a mp of 951С. Example 8. 17.7 g of trichloroacetaldehyde, 5.3 g of acrylonitrile and 0.5 g of copper chloride (1) are heated with 40 ml of acetonitrile in an enameled h at. autoclave for 1 After cooling, the solvent is distilled off at about + 0-50 ° C in vacuum 2 created by a water-jet pump. 2,3,5-trichloropyridine in the form of white crystals with m.p. 49-50 seconds Yield 11.1 g (theory). 2,3,5-trichloropyridine with an equally good yield is obtained in case of replacing copper (I) chloride 0.5 g of copper bronze or 0.5 g of anhydrous ferric chloride (ill), and the rest is received as described., Example 9-17.7 g of trichloroacetaldehyde, 5.3 g of acrylonitrile, 0.3 g of dichloro-tris-triphenylphosphine ruthenium (M) and 30 ml of 3-methoxypropionitrile are heated in an enameled autoclave for 2 hours. After treatment, similar to example 1, receive 10.5 g (58 from theory) 2,3,5-trichloropyridine. 2,3,5-tr.ichloropyridine is obtained with a good yield and in the case of replacing 3-methoxypropionitrile with butyronitrile. Example 10. 17.7 g of trichloroacetaldehyde, 5.3 g of acrylonitrile and 0.5 g of copper chloride (|) together with tO ml of acetonitrile are heated in an enameled autoclave for 1/2 hour at 190 C. After cooling, the solvent is distilled off at about C. vacuum created by a water jet pump. The residue is distilled with steam. From the product of distillation 2,3,5-trichloropyridine precipitates as white crystals with m.p. 49-50 ° C. Yield 11.3 g (from theory). 2,3,5-trichloropyridine is obtained with a good yield if, all other things being equal, the synthesis temperature is maintained at 2 hours at 6 hours or at 15 ° C. The proposed method of producing 2,3,5-trichloropyridine (and its variant) allows to obtain the target product in one or two stages of the available starting materials with good yields (60-90), high purity. The proposed method of obtaining 2, 4, | -trichloro-4-formylbutyronitrile allows to obtain a new intermediate product for the synthesis of 2,3,5-trichloropyridine from the available starting reagents. Claim 1. Method for producing 2,3,5-trichloropyridine, characterized in that, in order to simplify the process, trichloroacetaldehyde is reacted with acrylonitrile at yO-TiO C in the presence of a catalyst Cu, Cu (|), copper bronze in the amount of 0 , 01-10 mol per acrylonitrile, and the resulting 2, k, -trichloro-formylbutyronitrile of the formula ". 1 (-C-CH, -CH-CN ii 1 | is subjected to cyclization at a temperature of 20-220 ° C, if necessary in the presence of an organic solvent, and the target product is isolated. 2, The method according to claim 1, characterized in that the interaction of trichloroacetaldehyde and acrylonitrile is carried out in a closed system at a pressure corresponding to 70-IlO C. 3. The method according to claim 1, aphid aryl and that the catalyst for the connection of trichloroacetaldehyde to acrylonitrile is taken in the amount 0, 5 mol / d based on acrylonitrile. K. The method according to claim 1, in which the addition of trichloroacetaldehyde to a The nitrile is carried out in the presence of an inert organic solvent, 5- Method 1 and 4, characterized in that trichloroacetaldehyde is added to acrylonitrile in an alkanecarboxylic acid nitrile with 2-5 carbon atoms, 3-alkoxypropionitrile with 1-2 carbon atoms in the alkyl group or in an excess of acrylonitrile as an inert organic solvent. 6. The method of claim 1, about 1 tl and -, due to the fact that the cyclization of 2, 4, trichloro-formylbutyronitrile is carried out in the presence of chlorine or hydrogen bromide, chloride a Yuminov or phosphorus pentachloride. . 7. The method according to claim 1, characterized by the fact that the cyclization of 2.4, - trichloro - "- formylbutyronitrile, is carried out at 80-200 ° C. 8. The method according to claim 1, distinguishing between CI and CI in that the cyclization of 2, -t rhloro-j-formylbutyronone is carried out in chloroform, dialkyl ethers with carbon atoms 210 in alkyl groups or in dimethylformamide. 9. A method of producing 2,3,5 trichloropyridine, differing from 1S to the fact that, in order to simplify the process technology, trichloroacetaldehyde is reacted with acrylonitrile at 150-200 ° C in the presence of a catalyst Cu, SiCb (|), dichloro-tri-trifenilphosphinuthenium (11 ) in the amount of 0.1-5 mol per acrylonitrile in an inert organic solvent. 10. The method according to claim 9, wherein the reaction is carried out in a closed system at a pressure corresponding to the reaction temperature. 11. Method according to paragraphs. 9 and 10, in that, as an inert organic solvent, nitride of an alkane carboxylic acid with 2-5 carbon atoms or 3-alkoxypropionitrile with 1-2 carbon atoms in an alkyl group is used. 12. Method according to paragraphs. 9-11, which is based on the fact that the reaction is carried out in acetonitrile, butyronitrile or 3-methoxy-nitrile. 13. Method for preparing 2, 4-trichloro - + - formylbutyronitrile of the formula p 1 1 I CC-CH, -CH-CN " ii characterized in that trichloroacetaldehyde is reacted with acrylonitrile in the presence of Uu, CuCE (I), copper Bronze in an amount of 0.01-10 mol% based on acrylonitrile, and the desired product is recovered. 1A. The method according to claim 13, characterized in that the reaction is carried out in a closed system at a pressure corresponding to a temperature of 70-11 ° C. 15- The method according to claim 13, characterized in that the catalyst is taken in an amount of 0.1-5 mol.% Based on acrylonitrile. 16. The method according to claim 13, wherein the reaction is carried out in the presence of an inert organic solvent. 17.. Method according to paragraphs. 13 and 16, about the fact that the reaction is 11 9 + 259212
    ration is carried out in the nitrile alkancarbo-Sources of information,
    New acid with 2-5 carbon atoms are taken into account in the examination
    yes, 3-alkoxypropionitrile with 1-2
    carbon atoms in the alkyl group in
     . UK patent
    or 8 excess acri onitrile as ir-i-io
    ve inert organic anic-dissolve-1978 213/61,
    tel.
    Priority points
    [2]
    2. M. Shinji et al. Accession
    12/5/78 by pp. 1.3, "6, 9-13, trichloroacetic acid ethyl ester 5 17. . “Olot to olefins. -
    [3]
    3. Org Chem
    23.10.79pp. 2,5,7,8, lit, 17.196, 29, № 7, 210.
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    US3592817A|1968-05-17|1971-07-13|Dow Chemical Co|Preparation of perchloropyridine and perchlorocyanopyridine compounds by vapor phase chlorination of aliphatic nitriles|
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    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    CH1239478|1978-12-05|
    CH1239578|1978-12-05|
    CH948979|1979-10-23|
    CH948879|1979-10-23|
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