• 专利附录
  • 专利说明
  • 权利要求
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    • 专利摘要:
    1527967 Acyl cyanides DEUTSCHE GOLD - UND - SILBER SCHEIDEANSTALT 3 June 1977 [25 Feb 1977] 23667/77 Heading C2C Acyl cyanides of the formula wherein R is a substituted phenyl group or an optionally substituted C 1-18 alkyl, C 3-8 cycloalkyl, naphthyl or heterocyclyl group, are obtained by reacting acyl halides (R-CO-X wherein X is a chlorine or bromine atom) with alkali metal cyanides and cuprous salts, in the presence of inert carboxylic acid nitriles at 50‹ to 180‹ C., the weight ratio of alkali metal cyanide to cuprous salt being from 0À1 to 5 : 0À05 to 2.
    公开号:SU799653A3
    申请号:SU772491918
    申请日:1977-06-02
    公开日:1981-01-23
    发明作者:Кленк Херберт；Офферманнс Хериберт；Шварце Вернер
    申请人:Дегусса (Фирма)；
    IPC主号:
    专利说明:

    (54) METHOD FOR PRODUCING KETOKARBONIC ACID NITRILES
    In the environment of -organic inert solvent.
    The output of the product of the product to 95%. Along with a fairly simple implementation, the advantage of the proposed method is that it is not limited to the production of special keto acid nitriles and can be applied universally. According to the proposed method, still undescribed compounds have been obtained, for example (2,2-dichloro-1-methylcyclopropyl) -glycosylonitrile and 2,2-DICHLOR-1,3-dimethylcyclopropyl. When using nitriles of carboxylic acids, nitriles of simple monobasic carboxylic acids (propionitrile, benzonitrile and isobutyronitrile) are particularly suitable, however, it is preferable to use acetonitrile. Use (dx to interact with alkali metal cyanides are sodium and potassium cyanides. It is advisable to use at least stoichiometric amounts cyanide. As copper salts (1), you can use the cyanide chloride or methyl bromide copper (1) and tetracyanocuprate (1) potassium.
    The amounts of carboxylic acid nitriles used and the copper salt f1) depend on the type of carboxylic acid nitrile and copper salt (1) and on the reaction conditions (temperature and pressure), as well as on the type and amount of the additionally used solvent.
    It is advisable to use at least 0.05 mol of a carboxylic acid nitrile per 1 mol of the acid chloride. Nitrile can be used in multiple excess, but preferably a brother of not more than 1 mol of the carboxylic acid nitrile per 1 mol of the haployl anhydride.
    For example, cyclic ethers (dioxane), ethylene glycol ethers, or esters (butyl acetate) are used as organic inert solvents. Especially suitable are aromatic hydrocarbons (benzene, toluene, xylenes or tetralin) or aliphatic hydrocarbons (cyclohexane or ligroin) with boiling range from 90 to 140 ° C, or GShogenic, preferably chlorinated, aromatic or hyphatic hydrocarbons (trichlorethylene, and especially chlorobenzene, dichlorobenzenes and tetrachloroethane). Mixtures of these solvents can also be used. In addition, the organic solvent should be easily separated from the ketone acid nitrile formed.
    The reaction temperature can vary widely and is selected depending on the type of solvent and the components of the reaction. Takes into account temperatures from about 50 to 180 C, preferably / (} 130 C. Although the pressure can be used any, but preferably normal.
    The invention is illustrated by examples.
    Example. In the SMV reactor equipped with a refractory-freezer (1 cooler), 1 154.5 g (1.0 mol) of 4-methy, pbenzoic chloride with 59 g (1.2 mol) of sodium cyanistogch, 9 g (0.1 mol) of copper cyanide are fed (1), 50 ml of xylene and 12.3 g (0.3 mol) of acetonitrile. The mixture is heated with stirring to 130 s, incubated for 3 hours at this temperature, and then cooled to 20 ° C. The salts thus obtained (mainly sodium chloride) is filtered off and washed with 25 ml of xylene. The filtrate is subjected to fractional distillation under reduced pressure. 127 g of pure cyanide 4-methylbenzoyl is obtained, which corresponds to uet 88% yield according to the used otnssheniyu acid chloride. 4-methylbenzoyl cyanide has b.p.. 100-102 ° C / 5/15 mm Hg, p. Nitrile keto solidifies in the receiver and has T.GOG. 50 ° C,
    Example 2. Follow the procedure of example 1, however, instead of 4-methylbenzoyl chloride, 2-methylben: ohyl chloride is used, and instead of cyanic sodium 78 g (1.2 mol) of potassium cyanide. 135 g of cyanide 2-methylbe, n-zoyl, are obtained, corresponding to a yield of 93.5% with respect to the acid chloride used. Cyanic 2-methylbenzoyl has a Ti. Bp 107-110 ° C / / 15 mmHg, st.
    EXAMPLE 3 The procedure of Example 1 is followed. However, along with 154.5 g (1.0 mol) of 3-methylbenzoyl chloride, 74 g (1.5 gyul) of sodium cyanide, 30 g (0.3 mol) are used. ) copper chloride (1) 50 f, OT chlorobenzene and 20.5 g (0.5 mol) of acetonitrile. 1 4 g of cyanide 3-methylbenzoyl is obtained, which corresponds to a yield of 93% with respect to the acid chloride used. Cyanic 3-methylbenzoyl has T, KIPLOZ-108 ° C / 15 mm Hg,
    EXAMPLE 4 The procedure of Example 1 is followed; however, instead of 4-methylbenzoyl chloride, 130.5 g (1.0 mol) of furan-2-carboxylic acid chloride are used. Poluchyat 102 g of furyl-2-glyoksilonitrile, which corresponds to a yield of 85% relative to the used orahydride acid. Furyl-2-glyoxy-nitrile has a bp of 76 ° C / 12 mm Hg.
    Example 5. According to the procedure described in Example 4 using the corresponding starting materials, soy is obtained.
    Dineni formula G, -C
    values
    radicals in which the outputs and boiling points are presented in Table 1. Example In a reactor equipped with a reflux condenser, 157.0 g (2.0 mol) of acetyl chloride are mixed with 103 g (2.1 mol) of cyanide sodium, 90 rfl, 0 mol) of cyanic copper (I), 150 ml of ortho-iorbenzene and 49 g (1.2 mol) of acetonitrile. The mixture is slowly heated to 90 ° C with stirring, kept at this temperature for 4 hours, and then cooled to 15 ° C. The distilled salt is filtered off and washed with 100 ml of orthodichlorobenzene. The filtrate is subjected to fractional reflux under normal pressure. 192 g of the first fraction were recovered, which was distilled to a column top temperature of 100 ° C. This fraction, according to gas chromatography, consists of 58% pyruvic acid nitrile, which means 82% yield of nitrile pyruvic acid relative to the acetyl chloride used. Example 7. The procedure of Example 1 is followed, however, 120.5 g (1.0 mol) of trimethylacetyl chloride, 64 g (1.3 mol) of sodium cyanide, 9 g (0.1 mol) of copper cyanide (1) 50 ml 1 are used. , 2,3,4-tetrahydronaphthalene and 12.3 g (o, 3 mol) of acetonitrile. The mixture is heated with stirring for 4 hours at 110 ° C. After cooling to 15c, the precipitated salts are filtered off and washed with 30 ml of tetrahydronaphthalene. The filtrate is subjected to fractional distillation. 101 pure cyanic trimethylacetyl (nitrile trimethyl pyruvic acid) is obtained, which corresponds to a yield of 92% with respect to the chlorine used and trimethylacetyl. Cyanic trimethylacetyl has T.KKP.118-122 C at normal pressure. Example Follow the procedure of Example 7 to prepare compounds
    45
    Table 1 of the radicals in which, the yields and the boiling points are presented in table. 2. PRI me R 9. The procedure of Example 7 is followed; however, BMek.ro of trimethylacetyl chloride uses 146.6 g (1.0 mol) of cyclohexanecarboxylic acid chloride, and tetrachloroethylene is used instead of tetrahydronaphthalene. 105 g of cyclohexyl glyoxynonitrile are obtained, which corresponds to a yield of 77% with respect to the acid chloride used. Cyclohexyl-glyoxy-nitrile has a T. 85 87 C at 20 mm Hg. Example 10. The procedure of Example 9 is followed and compounds are obtained, the values of the radical in which, the yields and boiling points are presented in Table. 3. PRI me R 11. They act as in Example 9 to obtain compounds, the values of the radicals in which the yields and boiling points are presented in Table. four . Example 12. In the reactor under reflux, 199 g (1.0 mol) of 4-methylbenzoyl bromide is mixed with 59 g (1.2 mol) of sodium cyanide, 12.1 g (0.1 mol) of copper (1) rhodanide, 50 ml of xylene and 28 g (O, 4 mol) of isobutyronitrile. Next, they act as in Example 1. After distillation, 97 g of 4-methylbenzoyl cyanide are separated, which corresponds to a yield of 67%, counting on bromide. Example 13. The procedure was carried out as in Example 1, however, an additional 50 ppm of acetonitrile was added instead of xylene. After distillation, 4-methylbenzoylnitrile is isolated with a yield of 82% based on the acid chloride taken.
    ISO-0
    :) is114-116 / 18 120-125 / 12 85-87 / 14
    162/13 160 / 16,5
    118-122 / 15
    7996538
    Continued table. one
    CHilCHg) 72 62
    (cn) Invention Formula
    权利要求:
    Claims (2)
    [1]
    1. A method of producing nitriles of ketcarboxylic acids of general formula
     "XcN
    where R is unsubstituted or mono- or multiply substituted by phenyl, fluorine atom, chlorine, bromine linear silt branched alkyl C, -, unsubstituted or mono- or multiply substituted by alkyl C., chlorine atom, bromine, fluorine, phenyl, naphthyl, pendent heterocycle which can be interrupted by oxygen or sulfur atoms; substituted by yt of chlorine, fluorine, bromine, nitro, alkyl-, gshkoxygroup with C. - C, in alkyl private C, - C. cycloalkyl, by the interaction of the corresponding carboxylic acid halide with metal cyanide at elevated temperature in the presence of nitrile
    Table 4
    87 / 7.6 185-188 / 2.28
    carboxylic acid followed by isolation of the target product, characterized in that, in order to increase the yield of the target product and expand the range of the final product, alkali metal cyanide mixed with monovalent copper, taken in an amount of 0.1-5 and 0.05-2 molar equivalents, respectively, and the process is carried out at 50ISO C.
    [2]
    2. A method according to claim 1, characterized in that the process is conducted in an inert organic solvent medium.
    Sources of information taken into account in the examination 1. Edwards 0. E. et al. tJ.Amer, Chem. Soc. 1944, 2014
    2. oAmour Bull. Soc, Chem. France. 1972, 2402-2403 (prototype).
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    同族专利:
    公开号 | 公开日
    ATA392577A|1979-10-15|
    DE2708182B2|1978-12-21|
    DE2708182A1|1978-08-31|
    CH627442A5|1982-01-15|
    IL52237D0|1977-08-31|
    NL7706158A|1978-08-29|
    IT1143579B|1986-10-22|
    DE2708182C3|1979-08-30|
    FR2381748A1|1978-09-22|
    BE855254A|1977-11-30|
    US4108875A|1978-08-22|
    GB1527967A|1978-10-11|
    JPS6140659B2|1986-09-10|
    DD131015A5|1978-05-24|
    IL52237A|1981-02-27|
    FR2381748B1|1981-01-30|
    AT356643B|1980-05-12|
    JPS53105426A|1978-09-13|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    DE2528211C3|1975-06-25|1980-03-06|Bayer Ag, 5090 Leverkusen|Process for the production of acyl cyanides|DE2753656C2|1977-12-02|1982-11-25|Degussa Ag, 6000 Frankfurt|Process for the production of benzoyl cyanide|
    DE2753657C2|1977-12-02|1982-11-25|Degussa Ag, 6000 Frankfurt|Process for the production of benzoyl cyanide|
    US4209462A|1978-12-18|1980-06-24|Stauffer Chemical Company|Method for preparing acyl cyanides|
    NL8006594A|1979-12-21|1981-07-16|Ciba Geigy|ALFA-OXONITRILES, METHODS FOR PREPARING THEM AND THEIR USE|
    DE3011305A1|1980-03-24|1981-10-15|Degussa Ag, 6000 Frankfurt|METHOD FOR THE PRODUCTION OF CARBONIC ACID CYANIDES|
    DE3015587A1|1980-04-23|1981-10-29|Bayer Ag, 5090 Leverkusen|METHOD FOR PRODUCING ACYLCYANIDES|
    DE3045181A1|1980-12-01|1982-07-01|Bayer Ag, 5090 Leverkusen|METHOD FOR PRODUCING PIVALOYLCYANIDE|
    DE102005027149A1|2005-06-11|2006-12-14|Lanxess Deutschland Gmbh|Process for the preparation of substituted benzoyl cyanides|
    CN104387293B|2014-10-27|2017-02-22|河北诚信有限责任公司|Method for synthesizing trifloxystrobin intermediate methylbenzoyl cyanide|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    DE19772708182|DE2708182C3|1977-02-25|1977-02-25|Process for the production of acyl cyanides|
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