• 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:
    Benzoyl cyanide is prepared by reacting benzoyl chloride and an alkali metal cyanide at elevated temperatures in an inert organic solvent in the presence of benzoic anhydride and/or substances which form benzoic anhydride with benzoyl chloride. The process produces pure, virtually dimer-free benzoyl cyanide in a surprisingly high yield of at least 90%.
    公开号:SU799652A3
    申请号:SU772490023
    申请日:1977-06-02
    公开日:1981-01-23
    发明作者:Кленк Херберт；Люсслинг Теодор；Майерхофер Альфред；Офферманнс Хериберт；Вагнер Ханс
    申请人:Дегусса (Фирма)；
    IPC主号:
    专利说明:

    The invention relates to organic chemistry, specifically to a method for producing beneoyl cyanide from benzoyl chloride and alkali metal cyanide.
    Benzoyl cyanide is of interest as an intermediate for the preparation of herbicides.
    A known method for producing benzoyl cyanide is interacted with an excess of copper cyanide at 80 ° C in acetonitrile or benzonitrile, or in ether with the addition of lithium chloride or lithium iodide. The yield of beneoyl cyanide 55% [1].
    The disadvantages of this method are the low yield of the target product and the difficulty of isolating it from the resulting mixture containing dimers and other aromatic derivatives.
    In addition, benzoyl cyanide is generally of low purity.
    Closest to the proposed technical essence is a method for producing beneoyl cyanide from benzoyl chloride and alkali metal cyanide <25 la - sodium cyanide - in a medium of methylene chloride in the presence of water and a quaternary ammonium salt - tetrabutylammonium bromide at 0 ° C. The yield of the target product 60% [2]
    However, in this method also a low yield of the target product with a low selectivity of the process. The formation of beneoyl cyanide dimers (35%), as well as benzoyloxyphenyl malonodinitrile, is observed, which reduces the purity of the target product. Benzoyl cyanide can be separated from its dimer only with significant difficulties and not completely.
    The purpose of the invention is to increase the yield of beneoyl cyanide.
    This goal is achieved by the method of producing benoeoyl cyanide by the interaction of benzoyl chloride and an alkali metal cyanide in an organic solvent medium with the isolation of the target products in which the process is conducted at 80-170 ° C in the presence of benzoic anhydride or substances forming benzoic anhydride with benzoyl chloride.
    Typically, xylene, chlorobenzene and naphtha are used as the organic solvent. The yield of the target product to 95%.
    Sodium or potassium cyanides are preferably used as alkali metal cyanide. Preferably, 1.05-2.0 equivalents of cyanide, in particular 1.05-1.5 equivalents of cyanide per mole of benzoyl chloride, are preferably used.
    The process is carried out in an organic solvent inert to the components of the exchange reaction. Preferably, at least 40 ml of solvent is used for each mole of benzoyl chloride. However, it is more preferable to use 70-2000 ml, in particular 100-350 ml of solvent for each mole of benzoyl chloride.
    The process is carried out in the presence of benzoic acid anhydride or substances that can convert benzoyl chloride to benzoic acid anhydride, for example water, benzoic acid and metal salts of benzoic acid, namely alkali metal salts of benzoic acid. In addition, you can use other carboxylic acids, mainly aliphatic, preferably saturated, for example lauric acid. Mixtures of these substances or mixtures of benzoic anhydride with these substances are also suitable.
    Benzoic anhydride and substances that can convert benzoyl chloride to benzoic anhydride can be used in stoichiometric or higher stoichiometric amounts with respect to benzoyl chloride. However, it is preferable to apply amounts below stoichiometric, namely 0.01-0.3 mol, in particular 0.03-0.1 mol per 1 mol of benzoyl chloride.
    The temperature of the exchange reaction depends on the type of solvent and other components of the exchange reaction, and it is maintained in the range from 80 to 170 ° C.
    Although the pressure can be arbitrarily selected, it is advisable not to deviate significantly from normal pressure. In some cases, due to the presence of volatile substances, it is advisable to work at elevated pressure, appropriate temperature.
    The invention is illustrated by examples, confirming, but not limiting it.
    Example 1. A mixture of 140.5 g (1.0 mol) of benzoyl chloride, 22.6 g (0; 1 mol) of benzoic acid anhydride, 7 3.5 g (1.5 mol) of sodium cyanide and 300 mp xylene are kept in for 8 hours at boiling point (140-145 s) in a vessel under reflux. Then the mixture is cooled and filtered. The precipitate, consisting mainly of sodium salts, is washed with xylene. The filtrate is subjected to fractional distillation. Obtain 119 g (91%) of beneoyl cyanide with T. boil.
    ; from 9 2 to 86 ° C at a pressure of '14, 5 mm RT, Art.
    Example 2. To a mixture of 294 g (6.0 mol) of sodium cyanide, 26 g (0.25 mol) of sodium benzoate and 500 ml of xylene, 702.5 g (5.0 mol) of benzoyl chloride are added dropwise. It is kept at 135 ° C for 8.5 hours. After cooling, the mixture is filtered off with suction. The filtrate is subjected to fractional distillation. Received benzoyl cyanide has so Kip. from 92 to 96 C at a pressure of 34 mm Hg yield 611 g, which corresponds to 94% with respect to the starting benzoyl chloride.
    Example 3. Similar to example 2. With 4.5 g (0.25 mol) of water instead of sodium benzoate, 598 g of benzoyl cyanide (^ 2%) are obtained with boiling point. from 115 to 117 C at a pressure of 34 mm Hg
    PRI me R 4. Similar to example 2, however, instead of sodium benzoate take 18 g (0.15 mol) of benzoic acid, and instead of xylene - 500 ml of chlorobenzene. yield 601 g (93% relative to the starting benzoyl chloride)
    Example 5. To a mixture of 19.5 g (0.3 mol) of potassium cyanide, 3 g (0.01 mol) of 4-chlorobenzoic acid anhydride and 80 ml of naphtha with T. boil. 110-140 ° C. 28, 1 g (O, 2 mol) of benzoyl chloride are added dropwise. During the time of formation of the mixture, and then another half hour, the mixture is kept at 125-135 ° C. After cooling, suction filtration and naphtha pumping are performed. The filtrate is evaporated at a pressure of 45 mbar until it reaches 117 C. 26 g of precipitate are obtained. According to the gas chromatogram, it contains,%: benzoyl cyanide 94, 4-chlorobenzoyl cyanide 3 and benzoic anhydride 3.
    Example 6. Similar to example 5, however, instead of 4-chlorobenzoic acid anhydride, 1.6 g (0.01 mol) of sodium salt of 4-methylbeneoic acid was taken. 26 g of benzoyl cyanide are obtained with a purity of 95% (1% of 4-methylbeneoyl cyanide and 4% of benzoic anhydride).
    PRI me R 7. Similar to example 5, however, instead of 4-chlorobenzoic acid anhydride, 2.0 g (0.01 mol) of lauric acid is used. Receive 23.2 g (89%) of benzoyl cyanide with T. boil. from 113 to 115 ° C at a pressure of 30.4 mm Hg
    权利要求:
    Claims (3)
    [1]
    (54) A METHOD FOR OBTAINING BENZOYL CYANIDE is preferably used 1.05-2.0 equivalents of cyanide, in particular 1.05-1.5 eq of VESENT of cyanide for each mole of benzoyl chloride. The process is carried out in an organic solvent inert with respect to the components of the exchange reaction. It is preferable to use for each mole of benzoyl chloride at least 40 4 L of solvent. However, it is more preferable to use 70-2000 m in particular 100-350 ml of solvent for each mole of benzoyl chloride. The process is carried out in the presence of benzoic acid anhydride or substances that can convert benzoyl chloride to benzoic acid anhydride, such as water, benzoic acid, and salts of benzoic acid metals, namely, alkali metal salts of benzoic acid. In addition, other carboxylic acids, preferably aliphatic, preferably saturated, for example lauric acid, can be used. Mixtures of these substances or a mixture of benzoic acid anhydride with these substances are also suitable. Benzoic anhydride and substances that can convert benzoyl chloride to benzoic anhydride can be used in stoichiometric or higher stoichiometric amounts relative to benzoyl chloride. However, it is preferable to use amounts below stoichiometric, i.e., 0.01-0.3 mol, in particular 0.03-0.1 mol per 1 mol of benzoyl chloride. The temperature of the exchange reaction depends on the type of solvent and other components of the exchange reaction, and is kept in the range of 80 to 170 ° Although the pressure can be chosen arbitrarily, however, it is advisable not to deviate significantly from the normal pressure. In some cases, due to the presence of volatile substances, it is advisable to work at an elevated pressure corresponding to temperature. The invention is illustrated by examples, confirming, but not limiting it. Example 1. A mixture of 140.5 g (1.0 mol) of benzoyl chloride, 22.6 g (mol) of benzoic anhydride, 7 3.5 g (1.5 mol) of natrn cyanide and 300 MP of xylene is incubated for 8 hours at boiling point (140-145 s) in a reflux vessel. The mixture is then cooled and filtered. The precipitate, consisting mainly of sodium salts, is washed with xylene. The filtrate is subjected to fractional distillation. Obtain 119 g (91%) of benzoyl cyanide with T. b.p. from 92 to at a pressure of 14, 5 eui Hg. st. Example 2 To a mixture of 294 g (6.0 mol) of sodium cyanide, 26 g (0.25 mol) of sodium benzoate and 500 ml of xylene, 702.5 g (5.0 mol) of benzoyl chloride were added dropwise. It is maintained at 135 ° C for 8.5 hours. After cooling, the mixture is filtered off with suction. The filtrate is subjected to fractional distillation. The resulting benzoyl cyanide has a bp. from 92 to 96 C at a pressure of 34 mm Hg. yield 611 g, which corresponds to 94% relative to the original benzoyl chloride. Froze Similar to the example
    [2]
    2. With 4.5 g (o, 25 mol) of water instead of sodium benzoate, 598 g of benzoyl cyanide (92%) are obtained with a boil. from 115 to 117 C at a pressure of 34 vCM Hg PRI me R 4. Similar to Example 2, however, instead of benzoate "atri, take 18 g (o, 15 mol) of benzoic acid, and instead of xylene, 500 ml of chlorobenzene. Yield 601 g (93% relative to the starting benzoyl chloride). Example5. To a mixture of 19.5 g (0.3 mol) of potassium cyanide, 3 g (0.01 mol) of 4-chlorobenzoic acid anhydride and 80 ml of ligroin with T. b.p. 110-140 ° C. 28.1 g (o, 2 mol) of benzoyl chloride are added dropwise. During the time of formation of the mixture, and then another half hour, the mixture is maintained at 125-135 ° C. After cooling, filtration is performed by suction and npoivfijBKy with ligroin. The filtrate is evaporated at a pressure of 45 mbar until it reaches 117 ° C. 26 g of precipitate are obtained. According to the gas chromatogram, it contains,%: benzoyl cyanide 94, 4-chlorobenzoyl cyanide 3 and benzoic anhydride
    [3]
    3. Example 6: Analogous to example 5, however, instead of 4-chlorobenzoic acid anhydride, 1.6 g (0.01 mol) of sodium salt of 4-methylbenzoic acid is taken. Obtain 26 g of benzoyl cyanide with a purity of 95% (1% 4-methylbenzoyl cyanide and 4% benzoic anhydride). Example 7: Similar to Example 5, however, instead of 4-chlorobenzoic anhydride, 2.0 g (0.01 mol) of lauric acid is used. 23.2 g (89%) of benzoyl cyanide are obtained with b.p. from 113 to 115 ° C at a pressure of 30.4 mm Hg Claims for obtaining benzoyl cyanide by reacting benzoyl chloride and alkali metal cyanide in an organic solvent, characterized in that with a view to increasing 5 7996526
    no yield of the target product, process sources of information,
    held at a temperature of 80 doprtye in charge during the examination
    170 C in the presence of benzo-l.Bull anhydride. Soc. Chlm. France, 1972,
    Acidic acid or substances forming 2402.
    with benzoyl chloride benzoic anhydride2. Tetrahedron letters, 1974, 26,
    acid.r. 2275 (prototype).
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    同族专利:
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    引用文献:
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    US2426014A|1944-02-03|1947-08-19|Du Pont|Preparation of acyl cyanides|
    FR1217929A|1958-03-03|1960-05-06|Ciba Geigy|Process for the preparation of 6-chloro-7-sulfamyl-3,4-dihydro-1,2,4-benzothiadiazine 1,1-dioxide and its salts|
    DE2528211C3|1975-06-25|1980-03-06|Bayer Ag, 5090 Leverkusen|Process for the production of acyl cyanides|
    DE2614240C3|1976-04-02|1980-03-06|Bayer Ag, 5090 Leverkusen|Process for the production of acyl cyanides|DE3015587A1|1980-04-23|1981-10-29|Bayer Ag, 5090 Leverkusen|METHOD FOR PRODUCING ACYLCYANIDES|
    DE3626411A1|1986-08-05|1988-02-11|Bayer Ag|METHOD FOR PRODUCING DIMERIC AROMATIC ACYLCYANIDES|
    FR2647109B1|1989-05-19|1991-07-26|Atochem|PROCESS FOR THE PREPARATION OF ACYLATE CYANIDES IN ANHYDROUS MEDIA|
    FR2647110B1|1989-05-19|1991-07-26|Atochem|PROCESS FOR THE SYNTHESIS OF ACYLATE CYANIDES|
    US5352826A|1989-05-19|1994-10-04|Atochem|Synthesis of acyl cyanides in an anhydrous reaction medium|
    US5352827A|1989-05-19|1994-10-04|Atochem|Synthesis of acyl cyanides in a hydrous reaction medium|
    EP0549531A1|1991-12-20|1993-06-30|Säurefabrik Schweizerhall|Process for preparing acid anhydrides|
    CN109651193A|2019-01-22|2019-04-19|江苏佳麦化工有限公司|A kind of synthetic method of benzoyl cyanide|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    DE19762642140|DE2642140C2|1976-09-20|1976-09-20|Process for the production of benzoyl cyanide|
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