• 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:
    Aliphatic and cycloaliphatic alpha -ketocarboxylic acids of the formula I are prepared by hydrolysing (saponifying) acyl cyanides of the formula II to carboxamides of the formula III, the substituents R, R1 and R2 being as defined in Claim 1. The hydrolysis is carried out in an organic solvent or solvent mixture that is liquid and inert under the reaction conditions and using gaseous hydrogen chloride in a first stage and water at from -70 to +70 DEG C in a second stage. The resulting carboxamides of the formula III are converted into the alpha -ketocarboxylic acids of the formula I by acid or alkaline hydrolysis. The process gives a good yield and makes it possible for example to prepare (2,2-dichloro-1-methylcyclopropyl)- and (2,2-dichloro-1,3-dimethylcyclopropyl)-glyoxylic acid. <IMAGE>
    公开号:SU793376A3
    申请号:SU772489000
    申请日:1977-06-02
    公开日:1980-12-30
    发明作者:Клееманн Аксель；Кленк Херберт；Шварце Вернер
    申请人:Дегусса (Фирма)；
    IPC主号:
    专利说明:

    : 54) METHOD OF OBTAINING ci.-KETOKAPBOHOBOR ACID
    The invention relates to the field of organic synthesis, specifically, to a method for producing o1-ketocarboxylic acids used in the synthesis of herbicides. Methods are known for producing oL-ketocarboxylic acids by saponifying the corresponding nitriles with concentrated hydrochloric acid. The disadvantages of these methods are the low yield of the target product. The closest in technical and achievable results is a method of obtaining, for example, o-ketolic acid by reacting propionylnitrile with concentrated acid and the product obtained is treated with diluted hydrochloric acid when heated. in a water bath. The yield of the target product is 40%. A disadvantage of the known method is the low yield of the target product. The purpose of the invention is to increase the yield of the target product. This goal is achieved by the described method of obtaining o-ketocarboxylic acid of the general L015mulki RCC-COOH, where R. (is alkyl containing.,;, R2-H; alkyl containing or R2 and R form a ring that can be noticed by chlorine, alkyl containing R-N; by treating the corresponding nitrile at a temperature of from -30 to + 35 ° C first with gaseous hydrogen chloride in an inert organic solvent, usually ethylene glycol dimethyl, diethyl, isopropyl ether, methylene chloride, toluene, and then water, using the ratios of the initial reagent nitrile - HCl - water 1: 0.6 - 8: 1-11, followed by hydrolysis of the amide formed. The yield of the desired product is 75%. Distinctive features of the process are acidic hydrolysis by passing gaseous hydrogen chloride through the nitrile, dissolved in an inert organic solvent at a temperature of from -30 to + 35 ° C, followed by treatment with water at this temperature of the reaction mass, and the hydrolysis is carried out at a ratio of nitrile to HC1 - water of 1: 0.6 to 8: 1 to 11, which allows increase target output product. The starting nitrile is obtained by reacting the corresponding carboxylic acid halides with CuCN in a mixture of 1-10 weight, h. inert nitrile of carboxylic acid and 0.5 to 20 weight.h. inert organic solvent at a temperature of 50-180 °. This interaction is also possible in the presence of a mixture of 0.1-5 parts by weight. alkali metal cyanide and 0.05 2 weight.h. copper salts (1) instead of CuCN. Hydrocarbons like toluene, chlorinated hydrocarbons like dichloromethane and ketones like acetone can be used as inert organic solvents. Ethers like diethyl ether, diisopropyl ether, ethylene glycol ether, and also cyclic ethers like dioxane are particularly suitable. Mixtures of these solvents are also used. Example 1. 97.1 g (1.0 mol) of isopropyl glyoxynonitrile and 250 ml of dimethyl ether ethylene glycol are added to the apparatus, which is protected from moisture and equipped with a tube for introducing gas. Then a strong current of gaseous HC1 is supplied until 146 g; (4.0 mol) are passed. After that, within 10 minutes, 21.6 g (1.2 mol) of water are added dropwise, while the temperature rises to 0 ° C with stirring for 2 hours. Then a strong stream of nitrogen is passed through and excess hydrogen chloride is removed. The solution is evaporated at 40 ° C in a vacuum water jet pump, with a yellowish mixture of crystals and mother liquor remaining. The residue is mixed with 1 l of 2N HC1 solution and heated for one hour with stirring at 100 ° C. After cooling, the aqueous phase is extracted three times with 100 ml of ethyl acetate each and the combined organic phases are subjected to fractional distillation. 94 g of ci-OK of seisovaleric acid are recovered, which corresponds to a yield of 81% with respect to the keto acid nitrile used. 75-7b With pr 20 mbar. When cooled, it solidifies to form a solid, m.p. which is 30-31 C. Mol. weight 116. Calculated,%: C 51.7; H 6.9. .CgHgOj. Found,%: C 51.4j H 6.8. Example 2. The procedure of Example 1 is followed, but instead of isopropylglyoxynonitrile, 111.1 g (1.0 mol) of the nitrile of oxone: juicaproic acid, diethyl ether as the solvent are used. The combined organic phases after extraction are also subjected to fractional distillation. 125 g of;, - hydroxyisocaproic acid is obtained, which corresponds to a yield of 96% with respect to the keto acid nitrile used. Ketoacid has so pl. 84-85 ° C at 20 mbar. They say ,, weight 130. Calculated,%: C 55.4; -N 7.8. b SO-Н Found,%; C 55.5; H 7.7. Example 3. The procedure of Example 1 is followed; however, instead of the initial isopropylglyoxynonitrile, 111.1 g (1.0 mol) of 0.1-1-oxo-2-methylvaleric acid nitrile is used, and a mixture of 100, ml of toluene and 200 is used as solvent. ml of diisopropyl ether. For fractional distillation, 109 g of D, 1-3-methyl-2-oxo-valeric acid are obtained, which corresponds to a yield of 83.7% with respect to the keto-acid nitrile used. Ketoacid has t. Kip. 83 ° C at 19 mbar. Mol. Weight 130. Calculated,%: C 55.4; H 7.7. , Found,%: C 55.45; H 7.9. Example 4. While stirring, 95 g (1.0 mol) of cyclopropylglyoxynonitrile in 400 ml of diethyl ether are placed in the apparatus and 182.5 g (5.0 mol) of gaseous HC1 are introduced at -20 ° C. Then, while stirring, 19.6 g (1.1 mol) of water are added dropwise at -20 ° C and then the solution is slowly heated to for 4 hours. After the temperature reaches a preheat temperature, a dilute NaOH solution is added dropwise to the solution at 010 ° C until the pH of the aqueous phase reaches 8. Then the organic phase is separated and evaporated in vacuo. The white residue is crystallized from water and dried in vacuum at 40 ° C. 97.5 g of cyclopropylglyoxide acid amide are isolated in the form of white crystals; m.p. 111-112 C. This means a yield of 87.5% with respect to the keto acid nitrile used. (molecular weight 113). Calculated,%: C 53.1; H 6.34; N 12.39. Found,%: C 52.7; H 6.4; N 12.25. The amide obtained is boiled under reflux in 1 liter of 2N KOH solution, with an intensive release of ammonia. At the end of the release of ammonia, the pH of the solution is cooled, with cooling, adjusted to 1 with semi-concentrated HC1. Then three: cdl are extracted each with 100 ml of methylene chloride. The combined ol 1111 (the. Phases are evaporated and the residue is imitated by fractional vacuum nej-xi gonko. 95 g of cyclopropyl 1; 1ioxybic acid is recovered, which gives a yield of 82.4%, with respect to the keto acid nitrile and 94% with respect to used amide. The keto acid has a boil of 88c at 23 mbar. Example 5. The procedure described in Example 4 is followed, but 178 g (1.0 mol) of nitrile (2,2-dichloro-1-methylcyclopropyl) are used instead of cyclopropylglyoxynonitrile -glyoxylic acid. After crystallization from ethyl acetate, 168 (85.7% of theory) amide (2,2-dich op-1-methylcyclopropyl) -glyce of strength acid; mp 92-93 C. C / HCl; M02 (molecular weight 196): C, 36.72; H, 3.6; N, 7.15; C1 36.2. Found: C, 36.92; H, 3.7; N, 7.2; C1, 35.9. The amide obtained is then sieved as described in Example 4. During fractional distillation, 136.5 g (2 , 2-dichloro-1-methylcyclopropyl) -glyoxylic acid, which corresponds to yield 81 with respect to the amide used. 52-54 ° C (molecular weight 197). Calculated,%: C 36, 5; H 3.65; C1 36.0. Found,%: C 36.8; H 3.6; C1 35, Example 6. Following the procedure of Example 4, however, nitrile- (2,2-dichloro-1,3-dimethylcyclopropyl) -glyoxylic acid is used as the nitrile. 72% keto acids are obtained, with respect to the nitrile- (2,2-dichloro-1, 1,3-dimethylcyclopropyl) -glyoxylic acid has a t. Bale. 115 ° C at 1 mbar. Mol weight 211. Calculated,%: C 39.8; H 3.79; C1 33.65. . Found,%: C 40.1; H 3.85; C1 33.27. Example 7. The experiment was carried out as described in Example 1, however, instead of isobutyric acid cyanide, 90.5 g (0.5 mol) of capric acid cyanide was used. 64 Gs of α-coundecanoic acid was recovered, which corresponds to a yield of 64%, considering the cyanide acid Keto acid recrystallized from gasoline had m.p. 55 ° C. Mol weight 200. Calculated,%: C 65.95; H 10.07. С-) 1 2.о г Found,%: С 65.75; H 9.90. Example 8. The experiment was carried out as described in Example 4, however, instead of cyclopropanecarboxylic acid cyanide, 137 g (1.0 mol) of cyclohexylcarboxylic acid cyanide was used. The cyclohexylglyoxylic acid amide, isolated as an intermediate product, had an mp. . 117 g of cyclohexylglyoxylic acid was recovered, which corresponds to a yield of 75%, counting on the introduced cyanide acid, the keto acid had t. Bale. at 5 mbar. Mol weight 156. Calculated,%: C 61.53; H 7.69. Found,%: C 61.53; H 7.71. Example 9. By analogy with example 4, the following keto acids were obtained. The table shows the values of C (.-Keto acid (R-CO-COOH) from acyl cyanides. Example 10. In a mixture consisting of 89 g (0.5 mol) of the nitrile (2,2-dichloro-1-methylcyclopropyl) glyoxy . Pipic acid and 300 ml of diiopropyl ether, which is held under stirring at 30-35 ° C, pass a strong stream of gaseous HC1. After the mixture is saturated with HC1, (73 g, 2.0 mol) are introduced at the same temperature and with a slight further improvement in HC), 20 ml of water are added dropwise and stirred for a further 2 hours. The solution is immediately evaporated on a rotary evaporator and the solid residue is recrystallized from ethyl acetate. Get 66 g (67% of theory) of the amide (2,2-dichloro-1-methylcyclopropyl) -glyoxylic acid; m.p. 92-93 ° C. Saponification is carried out similarly to that described in Example 5. CHd, (- CH C1-CHO-CH-CH, Example 11. A solution of 11.1 g (1.0 mol) of isovalerianic acid cyanide in 350 ml of methylene chloride is cooled to -20 ° C and then at 22 g (0.6 mol) of gaseous hydrogen chloride are added to the solution in this solution. Then 20 ml (1.1 mol) of water are added dropwise with gentle stirring. From the organic phase
     ..
    .
    :, "7
    793376
    At the same time, the mixture is notched up to -5 ° C in the form of ice, while stirring the mixture, and a spontaneous reaction occurs and the ice melts. The solution is evaporated. 221 g of crude amide of oxoisocaproic acid remain, which corresponds to a yield of 94% of theory, based on cyanide acid. Amid has so pl. 76-78 ° C. The subsequent saponification is carried out as described in Example 5.
    Example 12. The experiment was carried out in Example 10, however, instead of 20 ml of water, only 10 ml of water (0.55 mol) was used. After evaporation, 65.1 g of the amide of the acid remain, which corresponds to a yield of 52%, calculated on cyanide, or 94.5%, on water. The washing is carried out analogously to example 5.
    Example 13. B11.1g (0.1 mol) of isovaleric acid cyanide in 25 ml of ethylene glycol dimethyl ether with stirring at from -15 to inject 10.5 g of gaseous hydrogen chloride. At the end of the introduction of hydrogen chloride, 20 ml of water (1.1 mol) is added dropwise at the same temperature, partly crystallization occurs. Immediately after this, the mixture is poured into 100 g of crushed ice and the crystals formed are sucked off after a short standing. The crystals are dried. Remaining with 10.3 g of amide (-oxo-isococaproic acid, which corresponds to a yield of 80% based on used cyanide acid. Subsequent saponification is carried out as in Example 5.
    Example 14. The experiment was carried out as described in Example 1, however, instead of isobutyric acid cyanide, 83 g of propionyl cyanide was used. 76.5 g of ct-ketoacute were isolated.
    eight
    acids that COOT :, -vr C1 pu.T in-, 1xC-) Lu 75% with respect to the use of cyanide acid.
    权利要求:
    Claims (2)
    [1]
    1. The method of obtaining X-ketocarboxylic acid of General Formula
    , R.O
    And and
    R-C-C-COOH,
    where R is alkyl containing J alkyl containing, or R 2 and R. form a ring which may be substituted by chlorine, alkyl containing R — H by acid hydrolysis of the corresponding nitrile and subsequent additional hydrolysis of the resulting product, characterized in that To increase the yield of the target product, acidic 1 idrolysis is carried out by passing gaseous hydrogen chloride through a nitrile dissolved in an inert organic solvent at a temperature of from -30 to + 35 ° C, followed by treatment with water at this rate ture of the reaction mass and the hydrolysis is carried out at a ratio of nitrile - HC1 - water 1: 0.6 - 8: 1 - 11.
    [2]
    2. A method according to claim 1, characterized in that ethylene glycol dimethyl or distil ether or isopropyl ether or toluene is used as an organic solvent.
    Sources of information taken into account in the examination
    1. L. Claisen, E. Moritz.Ber dtsch chem. ges 1880, 13, 2121-2122 (prototype).
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    同族专利:
    公开号 | 公开日
    JPS53105423A|1978-09-13|
    DD131013A5|1978-05-24|
    GB1533818A|1978-11-29|
    ATA392777A|1981-10-15|
    IL52239D0|1977-08-31|
    DE2708185B2|1978-11-30|
    FR2381735B1|1980-01-18|
    IL52239A|1980-11-30|
    IT1143581B|1986-10-22|
    DE2708185C3|1981-06-04|
    NL7706161A|1978-08-29|
    FR2381735A1|1978-09-22|
    DE2708185A1|1978-08-31|
    JPS6055497B2|1985-12-05|
    AT367014B|1982-05-25|
    BE855257A|1977-11-30|
    CH627430A5|1982-01-15|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US4234739A|1978-12-05|1980-11-18|Stauffer Chemical Company|Method for preparing glyoxylic acids and derivatives thereof|
    DE3003541A1|1980-01-31|1981-08-06|Bayer Ag, 5090 Leverkusen|METHOD FOR PRODUCING 4-AMINO-6-TERT.-BUTYL-3-METHYLTHIO-1,2,4-TRIAZINE-5-ON|
    DE3009043A1|1980-03-08|1981-09-24|Bayer Ag, 5090 Leverkusen|METHOD FOR PRODUCING 4-AMINO-6-TERT.-BUTYL-3-METHYLTHIO-1,2,4-TRIAZINE-5-ON|
    DE3134230A1|1981-08-29|1983-03-10|Bayer Ag, 5090 Leverkusen|METHOD FOR PRODUCING 4-METHYL-5-OXO-3-THIOXO-TETRAHYDRO-1,2,4--TRIAZINES|
    AT25843T|1983-11-15|1987-03-15|Ethyl Corp|METHOD FOR THE PRODUCTION OF CYCLIC KETOAIDS.|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    DE19772708185|DE2708185C3|1977-02-25|1977-02-25|Process for the preparation of α-ketocarboxylic acids|
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