• 专利附录
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    • 专利摘要:
    1. A method of producing tetronic acid using a basic agent, characterized in that, in order to simplify the process technology and increase the yield of the target product, sodium or potassium oenzylate or their mixture is used as the basic agent, which is reacted with the lower one. 4-chloroacetoacetic acid 4-benzyl ester with THF or DMSO or dioxane or dimethoxyethane followed by hydrogenolysis of the 4-benzyloxyacetoacetic acid ester obtained in the presence of palladium or platinum th or Reneynikelevogo 10-30s catalyst at a temperature and a pressure of 1-10 atm in the medium ethyl acetate or ethanol or isopropanol, whereupon the resulting ester 4-gidroksiatsetouksusnoy acid is treated with 10-35 / Snym or HC1 or CFjCOOH, or with acidic ionoobmenkikom. 2. A method of producing tetronic acid using a basic agent, characterized in that, in order to simplify the process and increase the yield of the target product, sodium benzylate is used as the basic agent, which is reacted with lower C-C4 alkyl ester 4 - chloroacetoacetic acid at. 40 ° C in THF followed by hydrogenolysis of the obtained 4-benzyloxy-acetoacetic acid ester in the presence of a platinum or palladium catalyst and HC1 from 10% to 20% with concentrated or from 10% to concentrated, or 20% CFjCOOH ethanol at a pressure of 1-10 atm and.
    公开号:SU1181536A3
    申请号:SU823450448
    申请日:1982-06-15
    公开日:1985-09-23
    发明作者:Миллер Раймунд；Тенуд Леандер
    申请人:Лонца Аг (Фирма)；
    IPC主号:
    专利说明:

    1 The invention relates to a method for producing tetronic acid, which is used as an accelerator for P1, as described in photographs. The purpose of the invention is to regulate the process technology and to increase the yield of the target product. Example 1. 7.56 g of 80% sodium hydride are freed from the vaseline of new oil by washing three times with 30 ml of petroleum ether (b.p. AO-bOc) and 160 m of tetrahydrofuran is added. Then, 14.28 g of benzyl alcohol was added in doses so that the reaction temperature was maintained at 40 ° C. After the formation was completed, a solution of 19.74 g (95.5% 0.11455 mol) was added dropwise over 1 hour. ) 4-chloroacetoacetic ethyl ester in a VO ml of tetrahydropha, and the temperature is. After stirring for 15 hours at room temperature, half of the tetrahydrofuran is evaporated in a vacuum rotary evaporator, and the liquid residue is poured in a thin stream into a mixture of 14.3 g of concentrated HCl in 150 g of ice water, and after the addition of pH / yiT is reached to 5 It is then extracted four times with ether and after washing and drying the ethers in a vacuum rotati; the ion evaporator is evaporated. The residue is distilled off. 22.52 g (83.2%) of 4-benzyloxy-acetoacetic ethyl ether (m.p. 126 ° C) are obtained, 21.24 t of this ether dissolved in ethyl acetate (100 ml are placed in a 200 ml steel autoclave equipped with a magnetic stirrer , and hydrogenated in the presence of 1.05 g of 5% palladium on carbon with a hydrogen pressure of 5 atm. After completion of the reaction, which lasts approximately 2 hours, and after additional reaction for 2 h, the catalyst is filtered off and the filtrate is evaporated, in vacuo on rotary evaporator at 35 ° C. The residue is dried under high vacuum to give 13.4 g 4-hydroxy acetoacetic ethyl ether as a yellowish oil. 4.43 g of this ether are dissolved in 10 ml of 18% HC1 and stirred for 6 hours at room temperature. Then HC1 is lowered in a vacuum rotary evaporator at 30 ° C, the crystalline residue is dissolved in a small amount of water and water are again lowered in a vacuum rotary evaporator under. This operation is repeated once more to obtain 3.0 g of tetronic acid with a purity of 95.8%, which corresponds to a yield of 95.8%, calculated on the benzyloxy firm. The overall yield, based on the 4-chlorether, is 79.7%. Example 2. 4-benzyloxy-acetoacetic ethyl ether is obtained as in Example 1. However, hydrogenolysis with palladium on carbon is carried out in the presence of ethanol as solvents and in the presence of concentrated 11C1. Tetronic acid is obtained directly with a yield of 79.1%. Example 3. As in Example 1, sodium benzylate in tetrahydrofuran is brought to reaction with 4-chloroacetoacetic acid isopropyl ester. Then, the resulting 4-benzyloxy-acetoacetic acid isopropyl ester is hydrogenolized. The isopropyl ester of 4-benzyloxy-acetoacetic acid thus formed is converted by treatment with 18% HCl at room temperature to tetronic acid. The total yield, based on isopropyl ester of 4-chloroacetoacetic acid, is 78%. Example 4. As in Example 1, sodium benzylate in tetrahydrofuran is brought to reaction with 4-chloroacetoacetic acid n-butyl ester. Then the resulting 4-benzyloxyacetoacetic acid n-butyl ester is hydrogenolized. The resulting 4-hydroxy acetoacetic acid n-butyl ester, thus formed, is converted by treatment with 18% HCt at room temperature to tetronic acid. The total yield, based on 4-chloroacetoacetic acid n-butyl ester, is 76.5%. Example 5. Analogously to Example 1, 17.17 g (0.132 mol) of sodium benzyl are subjected to interaction with 19.74 g (0.1145 mol) of 4-chloroacetoacetic acid ethyl ester in dimeterxyethane for 10 hours at a yield of 18.95 g (70 %) ethyl ester of 4-benzyloxyacetoacetic acid. Then it is analogous to Example 1, but in the presence of 5% platinum on coal at 10 atm, hydro3 is subjected to genolysis. 3.85 g of quantitatively obtained 4-hydroxyacetoacetic acid ethyl ester is converted by treatment with HCl (35%) and into tetronic acid. Yield: 2.45 g (93.0%); the total yield in terms of ethyl ester A-chloro acetoacetic acid is 65.0%. Example 6; Similarly to Example 1, 17.17 (0.132 mol) of sodium benzylate with 19.74 g (0.1145 mol) of ethyl ester of 4-chloroacetoacetic acid in DMSO is subjected to the reaction for 20 hours at room temperature with a yield of 20.30 g (75 %) ethyl ester 4-benzyloxyacetoacetic acid. It is then subjected to hydrogenolysis in the same way as in Example 1, but in the presence of a catalyst (platinum on coal at 1 atm), 4.12 g of quantitatively prepared 4-hydroxy acetoacetic acid ethyl ester is converted to tetratonic acid by treatment with IIC1 (10%) for 8 h at room temperature. Yield: 2.62 g (92.8%); the total yield in terms of ethyl ester of 4-chloroacetic acid 69.5%. Example 7. Similarly to Example 1, the interaction is subjected to 17.17 g (0.132 mol) of sodium benzyl with 19j74 g (0.1145 mol) of 4-chloroacetoacetic acid ethyl ester in THF for 25 hours with a yield at 20.60 g (76 %) in ethyl ester of 4-benzyloxyacetoacetic acid. The latter is then subjected to hydrogenolysis analogue to Example 1, but in the presence of 5% platinum on coal as a catalyst at 10 atm, 4.24 g of the obtained quantitative 4-hydroxyacetoacetic acid ethyl ester is converted to tetronic acid by treatment with sulfuric acid ( 30%) for 5 hours at room temperature. Yield: 2.74 g (4.4%); the total yield in terms of ethyl ester of 4-chloroacetoacetic acid is 71.7%. Example 8. Analogously to Example 1, 17.17 g (0.132 mol) of sodium beisylate with 19.74 g (0.1145 mol) of 4-chloroacetoacetic acid ethyl ester in alkaline hydrochloric acid at 30 h for 30 h is subjected to interaction with 19.62 g (72 , 5%) ethyl ester of 4-benoyloxyacetoacetic acid. The latter is then, in analogy with Example 36, subjected to hydrogenolysis, but in the presence of 5% palladium on carbon as a catalyst at 1 atm. 4.0 g of quantitatively obtained 4-hydroxy acetoacetic acid ethyl ester is converted to tetronic acid by treatment with an acidic ion exchanger (Nafion / H O) for 10 hours at room temperature. Yield: 2.55 g (93.1%); total yield based on ethyl ester of 4-chloroacetoacetic acid, 67.5%, Example 9, Analogously to Example 1, 17.17 g (0.132 mol) of sodium benzylate are reacted with 19.74 g (0.1145 mol) of 4-chloroacetoacetic ethyl ether . acids in dioxane for 20 hours at 20 ° C with a yield of 19.80 g (73%) of 4-benzyloxyacetoacetic acid methyl ester. The latter is then analogously to example 1 subjected to hydrogenolysis, but in the presence of 5% platinum on coal as a catalyst in ethanol at 10 ° C and a pressure of 5 atm. 4.01 g of quantitatively obtained 4-hydroxy acetoacetic acid ethyl zirfira by treating with HC1 (30%) for 8 hours at 30 ° C and converted into tetronic acid. Yield: 2.61 g (95.0%); total yield in terms of 4-chloroacetoacetic acid ester 69.4%, Example 10. Analogously to Example 1, 17.17 g (0.132 mol) of sodium benzylate are subjected to interaction with 19.74 g (0.1145 mol) of 4-chloroacetoacetic acid ethyl ester in dioxane for 20 hours, with a yield of 18.70 g of ethyl 4-benzyloxy-acetoacetic acid. The latter, as in Example 1, but in the presence of 5% palladium on carbon as a catalyst in isopropanol, is subjected to hydrogenolysis at 30 ° C and a pressure of 10 atm. 3.98 g of quantitatively obtained 4-hydroxy acetoacetic acid ethyl ester is converted to tetronic acid by treating with trifluoroacetic acid (35%) for 7 hours at. Yield: 2.55 g (93.5%); total output in terms of ethyl 4o-acetoacetic acid ester 64.6%,. Example 11. 19.48 g (68%) of 4-benzyloxy-acetoacetic acid isoprapyl ester is obtained as in Example 3. Using 7.8 g, the hydrogenolysis is carried out using 5% palladium on carbon as a catalyst, but in the presence of ethanol as a solvent. and in the presence of concentrated HC1 at a pressure of 10 atm and ZOC. Tetronic acid is obtained directly; yield: 2.85 g, 91.4%; the total yield in terms of 4-chloroacetoacetic acid ester is 62.2%.
    Example 12. Obtain 20.27 g (67%) of 4-benzyloxyacetoacetic acid n-butyl ester as in Example 1. Using 8.18 g, hydrogenolysis is carried out using 5% palladium on carbon as a catalyst, but in the presence of concentrated HC1 and in the presence of ethanol as a solvent at a pressure of 1 atm and 5s. Tetronic acid is obtained directly with a yield of 2.81 g (90.7%); the total yield in terms of 4-chloroacetoacetic acid ester is 60.8%.
    Example 13. Analogously to example 1, 19.49 g (72%) of 4-benzyloxyacetoacetic acid ethyl ester are obtained. Using 7.5 g, hydrogenolysis is carried out using 5% platinum on coal as a catalyst, but in the presence of ethanol as a solvent and in the presence of concentrated sulfuric acid at a pressure of 1 atm and. Tetronic acid is obtained directly with a yield of 2.91 g (91.6%); the total yield in terms of 4-chloroacetoacetic acid ester is 65.9%.
    Example 14. Analogously to Example 1, 19.62 g (72.5%) of 4-benzyloxyacetoacetic acid ethyl ester are obtained. With the use of 7.5 g, hydrogenolysis is carried out using 5% platinum on coal as a catalyst, but in the presence of ethanol as a solvent and in the presence of 20% triFluoroacetic acid at 1 atm. Tetronic acid is obtained directly with yield 2 , 8S g (90.7%), total yield in terms of 4-chloroacetoacetic acid ester 65.8%:
    Example 15. Analogously to example 1, but using 19.30 g (0.132 mol) of potassium benzylate, obtained from potassium hydride and benzyl alcohol, is obtained with the help of 19.74 g (0.1145 mol) of 4-chloroacetoacetic acid ethyl ester in dimethoxane for 15 hours with a yield of 20.30 g (75%) of 4-benzyloxyacetoacetic acid ethyl ester. Analogously to Example 1, it is reacted to obtain 4-hydroxyacetoacetic acid ethyl ester, after which 4.43 g of the latter are converted, as in Example 1, to tetronic acid.
    Yield 2.94 g (93.3%); the total yield in terms of 4-chloroacetoacetic acid ester is 70.4%.
    Example 16. Analogously to Example 1, however, using a mixture of 9.65 g (0.066 mol) of potassium benzylate and 8.50 g (0.066 mol) of sodium benzyl in a 1: 1 ratio, prepared using a mixture of sodium hydride and potassium with benzyl alcohol , 19.74 g (0.1145 mol) of 4-chloroacetoacetic acid ethyl ester in dimethoxyethane are obtained for 15 hours with a yield of 21.10 g (78%) of 4-hydroxyacetoacetic acid ethyl ester. Analogously to Example 1, the latter is converted to 4-hydroxy acetoacetic acid ethyl ester, 4.43 g of which is converted to tetronic acid as in Example 1.
    Yield: 2.89 g (92.3%); the total yield in terms of ethyl ester of 4-chloroacetoacetic acid is 72.0%.
    Example 17. Analogously to Example 1, however, using a mixture of 7.52 g (0.066 mol) of lithium benzylate and 8.58 g (0.066 mol) of sodium benzyl in a 1: 1 ratio, obtained from a mixture of lithium hydride and sodium hydride with benzyl alcohol , is obtained using 19.74 g (0.1145 mol) of 4-chloroacetoacetic acid ethyl ester in THF for 10 hours at 30 ° C with a yield of 17.60 g (65%) of 4-benzsyuxylacetoacetic acid ethyl ester. Analogously to example 1, it is converted to ethyl. 4-hydroxyacetoacetate; 4.43 g of the latter is converted analogously to example 1 in tetronic acid.
    Yield: 2.85 g (91.0%); the total output in terms of ethyl ester of 4-chloroacetoacetic acid 59,0%.
    Example 18. Analogously to Example 1, 20.00 g. (74%) of ethyl 71 A-benzoxooxyacetoacetic acid ester is obtained, which is then quantitatively converted into hydroxyacetoacetic ethyl ester as a catalyst, as in the case of Example 1. 4.43 g of the latter are converted analogously to example 1 to tetronic acid. Startup: 2.92 g (93.3%); total yield in terms of e (for 4-chloroacetoacetic acid 69, OZ. Example 19. As in Example 1, 18.6 g (73%) of 4-benzyloxy-acetoacetic acid methyl ester is obtained. Using 7.0 g of hydrogenolysis is carried out with 5% platinum on carbon, but in the presence of ethanol as a solvent and in the presence of 10% hydrochloric acid at a pressure of 368 1 atm and .Tetronic acid is obtained directly with a yield of 2.74 g (87.0%); the total yield in terms of 4-chloroacetoacetic acid ester is 63.5%. Example 20, as in Example 1, 19.5 g (72%) of ethyl eff. 4-benzyloxy-acetoacetic acid, using 7.5 g, hydrogenolysis is carried out using 5% platinum on carbon as a catalyst, but in the presence of ethanol as a solvent and in the presence of 10% sulfuric acid at a pressure of 1 atm and 20 s. directly tetronic acid with a yield of 2.85 g (89.8%), the total yield in terms of 4-chloroacetoacetic acid ester is 64.6%.
    权利要求:
    Claims (2)
    [1]
    1. A method of producing tetronoic acid using a basic agent, characterized in that, in order to simplify the process technology and increase the yield of the target product, sodium or potassium or lithium benzylate is used as the main agent, or a mixture thereof, which is reacted with a lower With 4-chloroacetoacetic acid 1- alkyl ester at 0-40 ° C in THF or DMSO or dioxane or dimethoxyethane followed by hydrogenolysis of the obtained 4-benzyloxyacetoacetic ester in the presence of palladium or platinum of the second, or Rheneynickel catalyst at a temperature of 10-30 ° C and a pressure of 1-10 atm in an environment of ethyl acetate or ethanol or isopropanol, after which the resulting 4-hydroxyacetoacetic acid ester is treated with a 10-35% solution of HCl or H ^ SO ^ or CFjCOOH , or acidic ion exchanger at 5-30 ° C.
    [2]
    2. A method of producing tetronic acid using a basic agent, characterized in that, in order to simplify the process technology and increase the yield of the whole product, sodium benzylate is used as the main agent, which is reacted with lower C 1 -C ^ -alkyl 4-chloroacetoacetic acid ester at. 40 ° C in THF, followed by hydrogenolysis of the obtained 4-benzyloxyacetoacetic acid ester in the presence of a platinum or palladium catalyst and HC1 from 10% to concentrated or H ^ S04 from 10% to concentrated or 20% CFjCOOH in ethanol at a pressure of 1-10 atm and 5-30 ° C.
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    法律状态:
    优先权:
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