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    • 专利摘要:
    Process for the preparation of di-n-propyl acetonitrile of the formula : whereby, in a single step, sodium n-propylate in n-propanol medium is added to a reaction medium which is formed of a cyanacetate of general formula : in which R represents an alkyl radical having from l to 4 carbon atoms, and n-propyl bromide or iodide, the alkylation reaction taking place under reflux, the crude ester obtained is saponified with a 10 to 20 % solution of sodium hydroxide or potassium hydroxide, the resulting salt is acidified with a strong acid, to give crude di-n-propyl cyanacetic acid, which is decarboxylated by heating at a temperature between 140.degree.C and 190.degree.C, so as to obtain the di-n-propyl acetonitrile.
    公开号:SU715017A3
    申请号:SU772490024
    申请日:1977-06-06
    公开日:1980-02-05
    发明作者:Шиньяк Мишель；Грэн Клод；Пижероль Шарль
    申请人:Лябаз С.А. (Фирма)；
    IPC主号:
    专利说明:

    (54) METHOD FOR RECEIVING DIH-PGOPILACETONITRILE
    sodium in the amount of moles per 1 mol of crude ester at 30-70 ° C, the resulting salt of da-n-hydroxy acetic acid is acidified at 35-40 ° C, and the resulting crude di-n-propylacetic acid is heated at 175-190 ° C. Yield target product 80%. The proposed method is based on the use of completely dosage starting materials and is not associated with the use of extremely toxic products.
    Usually, saponification is carried out with a solution of potassium hydroxide soda in the presence of 0.005OD mole of trimethylammonium bromide per 1 mole of di-n-1-propyl hydroxyacetate acid.
    For the addition of the salt of di-n-propyl cyanoacetic acid, it is better to use a 36% solution of hydrochloric acid. In addition, the decarboxylate may be carried out by the continuous supply of di-n-propyl cyanoacetic. acid and removal of di-n-propyl acetonitrile.
    Example 1. In a 0.5 l flask equipped with a dropping funnel, mechanical stirrer, thermometer and a calcium chloride tube condenser, 16.95 g (0.141 mol) of cyanoacetic acid ethyl ester and 40.69 g (0.33 mol) of methyl bromide are added. -propyl, heated to 45 ° C, is gradually added while stirring, preliminarily prepared from 7.42 g of sodium and 180 ml of anhydrous propanol, a solution of n-goshshata sodium, maintaining the temperature at 50-55 ° C.
    After the introduction of propyl, the sodium is heated to boiling for 30 minutes and boiled for 3 hours; Then, n-propanol is distilled off to 115 ° C.
    The crude crude ester is treated with a solution of 7.5 g sodium hydroxide in 67.5 ml of water 3 250 g flask equipped with a refrigerator, gradually heated to 60-70 ° C and pulled for 3 hours, cooled to 50 ° C and the ethanol formed and the residue n propanol is removed in vacuo (70 mm Hg). The resulting solution is cooled to 20 ° C and acidified with stirring, 26.25 g of a 36% aqueous solution of hydrochloric acid at a temperature below 40 ° C. Recycled for 30 min., Settle for 30 minutes. The oily n-propyl cyanoacetic acid layer is decanted, the aqueous phase is extracted with 35 ml of toluene. The extract is added to the decanted da-n-propyl cyanoacetic acid, prepared using a separatory funnel with a solution of 1.5 g of sodium chloride in 14 ml of water, decanted, and toluene is distilled off at atmospheric pressure.
     25 g of di-c-propyl cyanoacetic acid.
    In a 100 No. 1 flask equipped with a thermometer and a cooler, 25 g of di-n-propyl cyanoacetic acid are introduced and heated in an oil bath.
    Decarboxylation begins at 40 ° C. The mixture is heated to boiling point (160 ° C) and then to 190 ° C for 2 hours. This temperature is maintained until the end of gas evolution (2 hours). The resulting di-n-propyl acetonitrile is slowly dispersed and a fraction of 165-175 ° C, which is distilled a second time, is collected.
    14.7 g of di-n-propylaptenitrile, T.KIP are obtained. 170 ° C.
    Example 2. A solution of sodium n-propyl is prepared from 50 g of sodium and 804 g (1000 ml) of anhydrous propanol, heating to
    50-55 ° C for 60-90 minutes
    In a 2-liter flask, 99.1 g (1 mol) of cyanoacetic acid methyl ester and 270.6 g (2.2 mol) of n-propyl bromide are placed, heated to 45-50 ° C with stirring and introduced
    sodium n-propyl solution in propanol for 60-70 minutes.
    The resulting mixture was cooled under reflux for 3 hours, n-propanol was distilled off to 120-125 ° C, the crude ester was treated
    500 g of a 10% sodium hydroxide solution and 0.36 g of cetyltrimethylammonium bromide are heated to boiling for 1 h, cooled to 50 ° C and the remaining alcohols are removed in BaKjfyMe (50-100 mm Hg).
    The resulting solution is cooled, acidified with 175 g of a 36% hydrochloric acid solution, the temperature is maintained at no higher than 40 ° C, it is kept for 30 minutes, the di-n-propyldian acetic acid is decanted, the aqueous phase is extracted with 250 g
    toluene, the organic phases are mixed, washed with 100 g of distilled water and the solvent is distilled off in vacuo to obtain 154.5 g of crude di-n-propyl cyanoacetic acid. Crude di-n-propyl cyanoacetic acid
    in a 250 ml flask, it is gradually brought to a boil, removing traces of toluene in a DinaStark nozzle until the temperature of the mass reaches 175-180 ° C. Decarboxylation begins at 140 ° C, and the reaction is almost complete after 1 hour. Then heated for 2 hours under reflux. In the first few mints, the temperature of the mixture reaches 205-210 ° C, and then decreases again and is maintained at 185 ° C. The mixture is accelerated
    at atmospheric pressure.
    102.5 g of di-n-propyl acetonitrile are obtained. The yield is 92% based on the cyanoacetic acid methyl ester.
    The yield of pure product is 80%.
    Example 3. In a 50-liter enamelled vessel is placed 30 kg of di-n-propyl cyanoacetic acid. The mixture is heated with stirring at reflux to 185-190 ° C and this temperature is maintained for 15 minutes. 57 The resulting di-n-propylacetonitrile is distilled with simultaneous continuous feeding of 69.4 kg of di-n-propyl cyanoacetic acid. The feed rate is controlled depending on the rate of distillation of the nitrile, while the temperature of the mixture is maintained at 185-190 ° C. The feed is continued for 4.5 hours during this time, 40.9 kg of crude di-n-propyl acetonitrile are obtained. The distillation is continued by gradually increasing the temperature of the mixture to 206 ° C (6 h). This gives 16350 kg and then an additional 8.980 kg of crude di-n-proshacetonitrile. In a vacuum (100 mm Hg), another 1.640 kg of the nitrile is distilled off. A total of 67.87 kg of crude di-n-proshcetonitrile are obtained. Example 4. A solution of sodium n-propyl is prepared from 50 g of sodium and 804 g (1000 ml) of anhydrous n-propanol by heating to 5055 ° C for 60-90 minutes. 99.1 g (1 mol) of cyanoacetic acid methyl ester and 270.6 g (2.2 mol) of n-propyl bromide were introduced into a 2-l flask, heated to 45-50 ° C with stirring, and nocTeneifflO was introduced at this temperature A solution of sodium n-propyl in n-propanol for 60-75 minutes is heated for 3 hours under reflux and up to 120-125 ° C the n-pro panol is distilled off. The resulting ester is treated with 500 g of a 10% sodium hydroxide solution and 0.36 g of trimethyl bromide, heated for 1 hour under reflux, cooled to 50 ° C and the remaining alcohols removed in vacuo (50-100 mm PT.CT.). The resulting solution is cooled, acidified with a 36% hydrochloric acid solution, maintaining the temperature not higher than 40 ° C, allowed to stand for 30 minutes, decanted di-npropylacetic acid, the aqueous phase is extracted with 250 ml of toluene. The organic phases are combined, one time 100 g of distilled water are removed, and the solvent is distilled off in vacuo. In three experiments, 165.3, 158.4 and 154.5 g of crude di-n-propyl cyanoacetic acid were obtained, respectively. Crude di-n-propyl cyanoacetic acid. The first test was transferred to the reactor and 331.6 g of an 85% potassium hydroxide solution was added to it. The temperature of the reaction mixture is gradually increased. Distillation starts at 190 ° C and is cooled at 360 ° C. Distillate consists of two phases, separated in the ether. The aqueous phase is removed, the organic is washed, dried and dispersed. 13.4 g of di-n-propyl acetonitrile are obtained. Yield 11% based on methyl cyanacetic acid ester. The crude di-n-propyl cyanoacetic acid obtained in the second experiment is transferred to the reactor and 316.8 granulated sodium hydroxide is added to it. The temperature of the reaction mixture is gradually increased until the end of distillation (2.25 h), then the temperature is raised to 370 ° C. Distributed with ammonia smelt, decanted and extracted with ether. The organic phase is dried over sodium sulfate. 443 g of crude di-n-propyl acetonitrile with a purity of 94.1% are obtained. The yield of the product is 40.7%, the yield of pure di-n-propyl acetonitrile is 383%, calculated on the metal ester of vdanacetic acid. The crude di-n-propylcyl acetic acid obtained in the third runner is placed in a reactor and 2.4 g of copper powder is added per 1 mole of acid. The temperature of the reaction mixture is gradually increased. The release of CO starts at 150-160 ° C, becomes significant at 160-170 ° C and lasts for 10 minutes at 170 ° C. At 180 ° C, the release of CO2 is completely stopped. Thereafter, the mixture is distilled. The output of DK-n-Progosha acetonitrile 50% in the calculation of the di-n-Past anuxic acid and 45.7% in the calculation of the methyl ester 1-1 chasoic acid. Example 5. The order of addition of the reagents for half-methyl-di-n-propylate cylate is the same as in 3, and further, as in the proposed method. Prepare a solution of sodium n-proshchat from 50 g of sodium and 804 g (1000 ml) of anhydrous n-propanol while nlgrevanii to 50-55 ° C for 60-90 minutes, 99.1 g (1 mol) are added over a period of 20 minutes methyl ester of tsnanususnuyu slots and extracts 30 minutes at 50 ° C, a white precipitate is observed. At 4050 ° C, 270.6 g (2.2 mol) of methyl and blunt bromide are introduced in the course of 30 minutes, boiled for 4 hours with a reflux condenser (91-92 ° C). Up to 1,20125 ° C, the n-propanol is distilled off. The crawled crude ester is treated with 500 g of a 10% sodium hydroxide solution and 036 g of trimethyl acetylammonium bromide, heated under reflux for 1 hour, cooled to 50 ° C and the alcohols removed in vacuo (50100 mm Hg). The resulting solution is cooled, acidified with 175 g of a 36% hydrochloric acid solution at hempeff-pef at 40 ° C, kept 30 m-l and decanted di-n-propyl cyanoacetic acid. the phase is extracted with ether, the organic phases are combined, washed with water and the solvent in vacuo to give 155.75 g of crude di-n-propyl cyanoacetic acid. The resulting acid is placed in a 250 ml flask, boiled under reflux with a gradual increase in temperature to 175-180 ° C, removing traces in a Dean-Stark trap. Decarboxylation begins at 140 ° C, the reaction is almost complete within 1 hour. It is heated under reflux for 2 hours. The temperature of the reaction
    the mixture reaches 205-210 ° C in the first few minutes after the start of boiling, after which it gradually falls and stabilizes at about 185 ° C. The reacton mixture is dispersed at atmospheric pressure. 99.2 g of crude n-propylacetonitrile are obtained, yield 793% based on methyl ester of cyaciacetic acid. The product contains 94.8% di-n-propyl acetonitrile, 3.6% vitrile nitrile, 1.0, and 0.6% two other unknown impurities (GLC). The yield of pure di-n-nropyl acetonitrile is 75.2% based on cyanoacetic acid methyl ester.
    The di-n-0-propylacetonitrile obtained in Example 2–3 contains 98.2% di-n-propyl acetonitrile, 0.3% vitrile nitrile, and 0.6 and 0.8% two other unknown substances (DKX) .
    Example 6. Preparing a solution of patriot n-propyl solution from 50 g of sodium and 804 g (1000 ml) of anhydrous n-propigol when heated to 5055 ° C during 60-90. 99.1 g (I mol) of dianoacetic acid methane ester and 270.6 g (2.2 mol) of n-propl bromide are placed in a 2-L flask, heated at 45-50 ° C with stirring, and the solution is introduced at this temperature i-propyl nahri in n-propanol in 60-75 min. The reaction mixture was refluxed for 3 hours and the mixture was distilled to 120-125 seconds. In the first and second experiments, 174.1 g and 172.3 g of crude meth1-1I-di-n-propyl cyanoate cooTBOTCTBeifflb are obtained.
    The crude methyl-d, n-propyl, acetate obtained in the first experiment is transferred to a reactor equipped with. a cooler, and 348.2 g of granulated sodium hydroxide was added. The temperature of the reaction mixture is gradually increased until the end of the distillation (2.25 h). At the end of the distillation, the temperature of the reaction mixture is 380 ° C. 59.9 g of crude di-n-propyl acetonitrile are obtained, yield 58.8% based on methyl di-n-propyl cyanoacetate. The yield, in the main, is D1 -n-prog1G1-acetosh trilum, 44.4%, based on methyl di-propane acetate and 42.1%, calculated on the methyl ester of cyanic acid.
    The crude methyl di-n-proshlciasch acetate obtained in the second experiment is transferred to a reactor equipped with a condenser and 344.6 g of fused potassium hydroxide are added. The temperature of the reaction mixture is gradually increased until the end of the distillation. Get 40.6 g of raw di-n-prop-lacetonitrile, yield 40.44% based on methyl di-n-shch1 1 anadate. The yield of the pure product is 28.4% based on methyl, di-n-nronyl acetate and 26.7% based on methyl ester of cyanoacetic acid.
    Pr and Ie p 7. Get di-n-proglademonitr from methyl cyanoacetic acid ester in accordance with 3, and then proceed, as in the proposed method.
    A solution of sodium ethylate is prepared from 23.5 g of sodium in 200 g (250 ml) of absolute ethanol at reflux, and at 45-50 ° C 99.1 g (1 mol) of cyano acetic acid methyl ester are added, precipitation is observed sodium salt. 1353 g (1.1 mol) of n-added methyl bromide are added and heated under reflux for 3 hours, sodium is added to 280 g (350 ml) of absolute ethanol while maintaining the temperature at 50 ° C, 1353 g (1.1 mol) are added methyl bromide and heated for 3 hours under reflux. The mixture is cooled to room temperature and stirred for 12 hours, 2.5 g of sodium 1 in 40 g (50 ml) of absolute ethanol and 24.6 g (0.2 mol) of n-propyl bromide are added successively, the mixture is heated for 2 hours under reflux. the solvent is distilled off in vacuo. The residue is taken up in water and extracted with ether-benzene (50:50). The organic phase is washed with 100 MP of a 15% potassium hydroxide solution, 100 ml of water saturated with sodium chloride, dried over sodium sulfate and evaporated. 180.7 g of crude methyl di-n-propyl cyanoacetate. The crude ester is transferred to the reactor and 50 ml of pure ethanol and 630 g of a 35% potassium hydroxide solution are added, the mixture is heated under reflux for 26 hours, and the alcohol is distilled off. The residue is diluted with water and acidified with a 36% hydrochloric acid solution to a pH of 1. The mixture is extracted with ether, washed, sweetened and evaporated. 140 g (853%) of crude di-n-propyl cyanoacetic acid are obtained. According to GLC, the methyl ester of the indicated acid contains 32-34.4% of the product, which is identified as di-n-propylformagta dadetate. The resulting di-n-propyl cyanoacetic acid is transferred to the reactor with 0.97 g of copper powder, and the mixture is kept under reflux. Decarboxylation begins at 130 ° C, boiling becomes intense at 142-145 ° C. After that, the mixture is distilled; the first fraction is collected at 130-184 ° C, the second at 200-250 ° C. The first fraction contains 91.6% di-n-propyl acetonitrile, 5.4% di-n-nropylacetic acid and 1.7% di-n-propylacetamide, and the second 55.9% di-n-propyl acetonitrile, 22.4% di-n-propylacetic acid and 20.5% of di-n-pronyl acetamide (GLC). 48 g of di-n-propylacetamide. Yield 40% based on cyanoacetic acid methyl ester. The main by-products are di-n-propylacetic acid (10%) and di-n-propylacetamide (5%).
    Example 8. The original methyl di-n-propyl cyanate get, as indicated in 4,
    further, the experiment was carried out in accordance with 5.
    A solution of sodium methoxide is prepared from 46 g of sodium and 790 g (1000 ml) of methanol at reflux, 99.1 g (1 mol) of methyl cyanacetic acid in 395 g (500 ml) of methanol are added, maintaining the temperature at 45 -50 ° C, maintained at 55 for 15 minutes until completely dissolved, 307.5 g (2.5 mol) is added
    methyl n-propyl and heated for 36 hours under reflux. The reaction mixture is dispersed at atmospheric pressure and about 1300 ml of distillate are collected. After cooling, the distress is diluted with water and extracted with 3 :: X 150 Mil ether. The organic phases are combined, smashed, dried over sodium sulfate and the solvent is removed. 162.2 g (883%) are obtained by using me-di-n-shshtcyanate. The resulting ester was heated under reflux in 463 ml of a 35% potassium hydroxide solution and 51.5 ml of ethanol. The alcohol is aggravated and the residue is acidified with 36% -H1m hydrochloric acid solution to pH 1. The resulting oil is decanted, cooled, washed, washed over sodium sulfate and evaporated to dryness. Obtain 142.1 g of crude da-n-proshchishanacetic acid, containing 60.9% of di-n-shshischuacetic acid and 25.2% of diH-11roshshform1 | Sdatatat. The yield of pure di-n-propane} of acetic acid is 53% based on the cyanoacetic acid methyl ester.
    权利要求:
    Claims (5)
    [1]
    Invention Formula
    The method of producing di-n-propyl acetonitrile, differing from the fact that, in order to simplify the process and improve the raw material base, cyanacetic acid esters of the general formula CA-CH2-COOB, where R is alkyl Ci-jC4, is treated with sodium propyl in n-propanol medium in the presence of n-propyl bromide or iodide at 45-55 ° C, the resulting crude ester of di-n-2-6 acetic acetic acid is washed with a 10-20% solution of potassium sodium hydroxide in an amount of 1.25-2 moles per 1 mole of crude ether 30-70 ° C, the semi-saturated salt of da-n-propane cyanoacetic acid is acidified at 35-40 ° C and obtained Crude di-n-proshshtsianuksusvuyu acid is heated at 175-190 ° C.
    [2]
    2. The method according to item 1, about tl and h and y and the fact that the saponification is carried out with a solution of sodium hydroxide potassium in the presence of 0, 1 mole of trimethyl acetylmolem bromide per 1 mol of di-n-propyl cyanoacetic acid ester.
    Sources of information that are included in the examination
    1.M.S. Newan at a1. Atkitation of nitriles; ketenimine formation. JACS, 82, 873875. 1960
    2.W.Keil. Zur Kenntnis der Fette aus Fettsauren mit ungerader Kohlenstoffoatomzahl, J.Physieal. Oieml. 282. 137-141, 1947 (prototype) ..
    [3]
    3.M.S. Newan etal. JACS, 80, 6350-6355, 1958.
    [4]
    4.JACS, 43, 205-208, 1921.
    [5]
    5.Marschal et a1. J. Chem. Soc., 2754-2761 1930.
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    同族专利:
    公开号 | 公开日
    DK158038B|1990-03-19|
    IE45345L|1978-09-15|
    IE45345B1|1982-08-11|
    AU2626377A|1979-01-04|
    USRE31260E|1983-05-31|
    JPS53112813A|1978-10-02|
    MX4779E|1982-09-15|
    BE854486A|1977-11-14|
    HU175110B|1980-05-28|
    NO771576L|1978-09-18|
    FI771781A|1978-09-16|
    ES467125A1|1978-11-01|
    CS196365B2|1980-03-31|
    DK195877A|1978-09-16|
    ATA423077A|1978-12-15|
    CA1068302A|1979-12-18|
    DD129904A5|1978-02-15|
    IL52021A|1980-07-31|
    IN145220B|1978-09-09|
    ZA773779B|1978-05-30|
    OA05696A|1981-05-31|
    GR60808B|1978-08-30|
    DK158038C|1990-08-13|
    DE2721265A1|1978-09-21|
    NL7705562A|1978-09-19|
    IL52021D0|1977-07-31|
    SE7705257L|1978-09-16|
    YU40674B|1986-04-30|
    SE441596B|1985-10-21|
    DE2721265C2|1982-05-19|
    GB1522450A|1978-08-23|
    FI65232C|1984-04-10|
    FR2383920B1|1980-12-05|
    PT66542B|1978-10-18|
    AT351012B|1979-07-10|
    PL198559A1|1978-10-09|
    AU504487B2|1979-10-18|
    NZ184326A|1979-03-16|
    FR2383920A1|1978-10-13|
    FI65232B|1983-12-30|
    NL173747B|1983-10-03|
    JPS5735868B2|1982-07-31|
    AR212999A1|1978-11-30|
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    LU77305A1|1977-08-24|
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    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    FR7707587A|FR2383920B1|1977-03-15|1977-03-15|
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