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    • 专利摘要:
    The invention relates to carbonyl compounds, in particular to the preparation of an ethylene carbonyl compound in the form of R 1 R 2 C = CH-CHO, where R 1 and R 2 are methyl, which are used as starting monomers for the synthesis of polymeric materials. The purpose of the invention is to increase the yield of the target product. The preparation is carried out by isomerization of an alcohol in the form of alcohol R 1 R 2 (OH) CC = CH, where R 1 and R 2 are as indicated above at 130 ° in the presence of a catalytic system formed by a derivative of titanium. The process is conducted in the liquid phase in the presence of acid at a molar ratio of acetylene alcohol and acid (5.80-27.18): 1, an organic solvent and a catalytic system formed by a derivative of titanium, at a molar ratio of acetylene alcohol and a derivative of titanium (46, 07-141.36): 1 and copper (1+) chloride at a molar ratio of acetylene alcohol and copper chloride (1+) (46.27-137.11): 1. 1 tab.
    公开号:SU1567121A3
    申请号:SU4202262
    申请日:1987-04-02
    公开日:1990-05-23
    发明作者:Шабард Пьер
    申请人:Рон Пуленк Санте (Фирма)；
    IPC主号:
    专利说明:

    The invention relates to methods for producing ethylene carbonyl compounds of the general formula
     sn-sno
    Kjf
    (one)
    where R and RЈ is methyl.
    The compounds of general formula (1) are used as starting monomers for the synthesis of polymeric materials,
    The purpose of the invention is to increase the yield of non-product.
    Example 1. In a 50 cm3 three-neck flask equipped with a condenser, argon feed, a sample separator and a magnetic stirrer, under an atmosphere of argon, 12.8 g (152.2 mmol) of methylbutynol, 3.6 g (26.4 mmol) of 4-methylbenzoic acid, 19.6 g of dichlorobeneol, 5.3 g of dicyclohexyl (internal standard for chromatography), 0.75 g (2.20 mmol) of butyl titanate and O, H of g (3, 03 mmol) of copper chloride. The flask is heated in an oil bath, the temperature of which is regulated to 130 ° H. In 12 minutes, the temperature of the reaction mixture rises from 50 to 126 ° C and a yellow saliva is formed. Measure i 15 min.
    CM
    The temperature rises to 137 ° C, then stabilizes at 125-126 ° C. After 1 hour of stirring at this temperature, the reaction mixture is cooled to a temperature of about 20 ° C.
    The analysis of the crude product by vapor phase chromatography shows that the conversion rate of methylbutynol is 96.6%, the yield of prenal of the general formula (1) relative to the converted methylbutol is 90%.
    The crude reaction product, which is non-uniform, is subjected to distillation under reduced pressure (15 mm Hg; 2 kPa), heating to a maximum temperature of 72 ° C. In this way, 13.2 g of a colorless distillate are obtained, the analysis of which shows that the conversion rate of methylbutynol is 96.3% and that the prenal yield is 86% relative to the converted methylbutolol; 28.8 g of residue, the analysis of which shows that it contains 1% prenal.
    To the obtained residue (28.8 g) was added 12.8 g of methylbutolol, then heated for 1 hour 30 minutes in an oil bath, the temperature of which was regulated to 130 C.
    Analysis of the crude product of the reaction by vapor phase chromatography shows that the conversion rate of methylbutynol is 94%, the yield of prenal in relation to the converted methylbutolol is 90%.
    The crude reaction product is subjected to distillation under reduced pressure (15 mm Hg; 2 kPa), heating to a maximum temperature of 73 C. In this way, 13.9 g of a colorless distillate are obtained, an analysis of which shows that the conversion degree of methylbutolol is 94 % and that the prenal yield is 89% with respect to the methylbutynol converted; 27.35 g of residue, the analysis of which shows that it contains 1.1% prenal.
    8 g of methylbutinol and 2.9 g of dichlorobenzene are added to the residue (27.35 g), then heated for 2 hours on an oil bath, the temperature of which is regulated to 130 ° C.
    Analysis of the crude product by vapor phase chromatography shows that the conversion of methylbutynol is 88% and that the prenal yield is 91% relative to the terminated methylbutynol,
    The crude reaction product is subjected to distillation under reduced pressure (20 mm Hg; 2.7 kPa), heating to a maximum temperature of 12 ° C. In this way, 12.4 g of a colorless distillate is obtained, the analysis of which shows that the conversion degree of methylbutanol is 87% and that the prenal yield is 82% relative to the converted methylbutol.
    Analysis of the three colorless distillates combined shows that the average conversion is 92% and that the average prenual yield of the general formula (1) is 85.4% relative to the methylbutynol converted.
    The average prenual yield for the three operations is 78.6% relative to the methylbutnol used.
    Example 2. In a three-neck flask with a volume of 25 cm3, equipped with a condenser, argon feed, a reflux for sampling, and a magnetic stirrer, were injected into the inert gas of 4.34 g (51.6 mmol), methylbutol, 4.5 g (51 , 1 mmol) of ethyl acetate and 0.5 g (1.46 mmol) of butyl titanate. Heat for 4 hours to 80-90 ° C. Analysis by vapor phase chromatography shows no prenal formation. Then 0.5 g of copper chloride (5.05 mmol) is added. After 2 hours of heating to 90 ° C, a vapor chromatography study on the surface indicates that the conversion rate of methylbutynol is approximately 80% and that the prenal yield is 65% relative to the converted methylbutolol.
    Example 3 (comparative). Carried out as in example 2, but in the absence of butyl titanate. After 1 hour 30 minutes of heating to 90 ° C, methylbutynol is recovered without change.
    Example 4. Orvmen method according to example 2, but using 4, t g (51.6 mmol) methylbutynol, 5.43 g (39.8 mmol) methylbenzogm l and 0.25 g (0.73 mmol) butyltitlnate. After 3 hours of heating to 130 ° C, no prenal formation was observed. 0.1 g of chalk chloride was added to this (1.01 mmol was then heated to 130 ° C for 7 hours.
    Analysis by vapor chromatography on the surface shows that the degree of conversion of methylbutol is about 100% and that the prenal yield is 58%.
    Example 5 "Carried out as in example 4, but using 4.34 g (51.6 mmol methylbutynol, 4.9 g (18.4 mmol)) of tributyl phosphate, 0.25 g (0.73 mmol) of butyl titanate and 0.1 g (1.01 mmol) copper chloride.
    After 2 hours of heating to 130 ° C, chromatographic analysis indicates that the conversion of methylbutynol is about 100% and that the prenal yield is about 60%.
    Example 6 (comparative). Carried out as in example 5, but in the absence of copper chloride. After 2 hours of heating to 140 ° C, the formation of prenal of general formula (1) 0 is not observed.
    Example 7. Carried out as in Example 2, but using 4.34 g (51.6 mmol) of methylbutynol, 0.5 g (3.68 mmol) of methylbenzoate, 1.75 g of dicyclohexyl (internal standard for chromatography), 26 g of dichlorobenzo la, 0.25 g (0.75 mmol) butyl titanate and 0.1 g (1.01 mmol) of copper chloride. Heated for 2 hours before).
    The conversion of methylbutol is 98.5% and the prenal yield is 62% with respect to the converted methylbutol.
    Example 8. Carried out as in Example 2, but using 4.34 g (51.6 mmol) of methylbutynol, 0.3 g (3.05 mmol) of 2-acetoxypropene, 1.76 g of dicyclohexyl (internal standard for chromatography), 0 , 25 g (0.73 mmol) of butyl titanate and 0.1 g (1.01 mmol) of copper chloride. Heated for 4 hours 30 minutes to 110 C.
    The conversion of methylbutol is 98.5% and the prenal yield is 55% with respect to the converted methylbutol.
    Example 9. Carried out according to Example 2, but using 4.34 g (51.6 mmol) of methylbutynol, 4.38 g (37.7 mmol) of butyl acetate, 0.41 g (5.5 mmol) of butanol, 1.74 g of dicyclohexyl (internal standard for chromatography), 0.25 g (0.73 mmol) of butyl titanate and 0.1 g (1.01 mmol) of copper chloride. Heat for 2 h 30 min to 120 ° C.
    five
    0
    five
    0
    The degree of conversion of methylbutol. is 98.5% and the prenal yield is 61% with respect to the methylbutanol converted.
    Example 10. Carried out according to example 2, but using 4.36 g (51.9 mmol) of methylbutanol, 5.44 g (40 mmol) of methyl benzoate, 0.43 g (1.55 mmol) of triphenylsilanol, 1.76 g of dicyclohexyl (internal standard for chromatography), 0.29 g (0.86 mmol) of butyl titanate and 0.11 g (1.1 mmol) of copper chloride. Heat-for 2 h 30 min to 130 ° C.
    The conversion of methylbutol is 96% and the prenal yield is 60% with respect to the converted methylbutol.
    Example 11. Carried out as in Example 2, but using 4.35 g (51.8 mmol) of methylbutynol, 0.51 g (4.04 mmol) of methylbutynol acetate, 1.75 g of dicyclohexyl (internal 5 standard for chromatography), 13, 10 g of dichlorobenzene, 0.25 g (0.75 mmol) of butyl titanate and 0, 101 g (1.02 mmol) of copper chloride. Heat for 1 h 30 min to 130 ° C.
    0 The conversion of methylbutol is 97% and the prenal yield is 61% with respect to the converted methylbutol.
    Example 12. Carried out according to example 2, but using 4.34 g
    (51.6 mmol) of methylbutynol, 5.42 g (39.8 mmol) of methyl benzoate, 0.525 g (8.74 mmol) of acetic acid, 1.73 g of dicyclohexyl (internal standard 0 For chromatography), 0.25 g ( 0.73 mmol) butyl titanate and 0.1 g (1.01 mmol) of copper chloride. Heat for 2 hours to 180 ° C.
    The degree of conversion of methylbutol is 99% and the prenal yield is 67% with respect to the converted methylbutynol3
    Example 13. Carried out as in Example 2, but using 4.34 g (51.6 mmol) of methylbutynol, 0.525 g. (8.74 mmol) of acetic acid, 1.728 g of dicyclohexyl (internal standard for chromatography), 6.55 g of dichlorobenzene and 0.25 g (0.73 mmol) of butyl titanate, After 2 hours of heating to 130 ° C, no prenal formation is observed . Then 0.1 g of copper chloride (1.01 mmol) is added, heated to 130 ° C for 1 h 30 min.
    0
    five
    The conversion of methylbutol is 92% and the prenal yield is 78% with respect to the converted methylbutol.
    Example 14 (comparative). Carried out as in example 13, but in the absence of butyl titanate. After 2 hours of heating to 130 ° C, no prenalEo formation is observed.
    Example 15. Carried out as in Example 2, but using 4.34 g (51.6 mmol) of methylbutanol, 0.324 g (3.17 mmol) of acetic anhydride, 6.55 g of dichlorobenzene, 1.73 g of dicyclohexyl (internal standard for chromatography), 0.25 g (0.73 mmol) of butyl titanate, 0.1 g (1.01 mmol) of copper chloride ,. After 30 minutes of heating to 130 ° C, the degree of conversion of methylbutynol is 88% and the prenal yield is 80% with respect to the converted methylbutol. After 1 hour 30 minutes of heating to 130 ° C, the degree of conversion of methylbutinol is about 100% and the prenal yield is 66% relative to the converted methylbutinol.
    Example 16. Carried out according to Example 2, but using 4.34 g (51.6 mmol) of methylbutynol, 1 g (8.19 mmol) of benzoic acid, 1.73 g of dicyclohexyl (internal standard for chromatography), 6.55 g dichlorobenzene, 0.25 g (0.73 mmol) of butyl titanate and 0.1 g (1.01 mmol) of copper chloride. After 1 hour 30 minutes of heating to 130 ° C, the degree of conversion of methyl butynol is 95% and the prenal yield is 79% with respect to the converted methyl butynut.
    Example 17. Carried out as in Example 2, but using 4.34 g (51.6 mmol) of methylbutynol, 0.8 g (4.81 mmol) of terephthalic acid, 1.73 g of dicyclohexyl (internal standard for chromatography), 6, 55 g of dichlorobenzene, 0.25 g (0.73 mmol) of butyl titanate. and 0.1 g (1.01 mmol) of copper chloride. After 1 hour of heating to 130 ° C, the conversion rate of methylbutynol is 98% and the prenal yield is 76% with respect to the converted methylbutol.
    Example 18. Carried out as in example 2, but using 4.34 g (51.6 mmol) of methylbutanol, 1.2 (8.81 mmol) of 4-methylbenzoic acid
    5 Q 5
    0 0
    5 Q
    five
    You, 1.73 g of dicyclohexyl (internal standard for chromatography), 6.55 g of dichlorobenzene, 0.25 g (0.73 mmol) of butyl titanate, and 0.1 g (1.01 mmol) of copper chloride. Molar ratios are: acetylene alcohol and titanium derivative 70.68; acetylene alcohol and copper derivative 51.09; acetylene alcohol and acid 5.85.
    The mixture is heated to 130 ° C and the reaction mixture is monitored by vapor phase chromatography: after 30 minutes, the conversion of methylbutanol is 94% and the prenal yield is 91% relative to the converted methylbutol; after 1 h, the degree of conversion of methylbutol is 97% and the prenal yield is 89% relative to the converted methylbutol; after 1 h 30 min, the conversion of methylbutol is 98% and the prenal yield is 86% with respect to the converted methylbutol.
    Example 19 Carried out as in example 2, but using 4.34 g (51.6 mmol) of methylbutanol, 1.02 g (8.78 mmol) of caproic acid, 1.73 g of dicyclohexyl (internal standard for chromatography), 6, 55 g of dichlorobenzene, 0.25 g (0.73 mmol) of butyl titanate and 0.1 g (1.01 mmol) of copper chloride. The molar ratios are: acetylene alcohol and titanium derivative 70.68; acetylene alcohol and copper derivative 51.09; acetylene alcohol and acid 5.87.
    The mixture is heated to 130 ° C and the reaction mixture is monitored by vapor phase chromatography: after 30 min, the conversion of methylbutynol is 87% and the prenal yield is 91% with respect to the converted methylbutol; after 1 h, the degree of conversion of methylbutol is 95% and the prenal yield is 86% with respect to the converted methylbutol; after 1 h 30 min, the degree of conversion of methylbutol is 97% and the prenal yield is 84% with respect to the converted methylbutol.
    Example 20. Carried out according to Example 2, but using 4.34 g (51.6 mmol) of methylbutynol, 0.65 g (4.45 mmol) of adipic acid, 1.73 g of dicyclohexyl (internal standard), 6.55 g Lichlorobenzene, 0.25 g
    (0.73 mmol) of butyl titanate and 0.1 g (1.01 mmol) of copper chloride. After heating to 130 ° C, the degree of conversion of methylbutynol is 82% and the prenal yield is 74% with respect to the converted methylbutinol.
    Example 21. Carried out according to example 2, but using 4.34 g (51.6 mmol) of methylbutanol, 6.55 g of dichlorobenzene, 1.73 g of dicyclohexyl (internal standard), 0.25 g (0.73 mmol) of butyl titanate and 0.10 g (1.01 mmol) of copper chloride. After 1 hour and 30 minutes of heating to 130 ° C, the degree of conversion of methyl butynol is 99% and the prenal yield is 60% with respect to the converted methyl butynol.
    Example 21. Carried out according to Example 2, but using 4.34 g (51.6 mmol) of methylbutynol, 1.2 g (8.81 mmol) of 4-methylbenzoic acid, 3.46 g of dicyclohexyl (internal standard), 13.1 g of dichlorobenzene, 0.3 g (0.72 mmol) of titanium indibutoxy-bis-acetylacetonate and 0.10 g (1.01 mmol) of copper chloride0 The molar ratios are: acetylene alcohol and titanium derivative 71.66; acetylene alcohol and copper derivative 51.09; acetylene alcohol and acid 5.85.
    Example 22. Carried out according to Example 2, but using 4.34 g (51.6 mmol) of methylbutynol, 1.2 g (8.81 mmol) of 4-methylbenzoic acid, 3.46 g of dicyclohexyl (internal standard), 13, 1 g of dichlorobenzene, 0.3 g (0.72 mmol) of titanedibutoxy-bis-acetylacetonate and 0.10 g (1.01 mmol) of copper chloride. The molar ratios are: acetylene alcohol and titanium derivative 71.66; acetylene alcohol and copper derivative 51.09; acetylene alcohol and acid 5.85.
    After 2 hours of heating to 130 ° C, the degree of conversion of methylbutol is 98% and the prenal yield is 88% relative to the converted methylbutol.
    Example 23: Carried out as in example 2, but using 4.34 g (51.6 mmol) of methylbutanol, 1.2 g (8.81 mmol) of 4-methylbenzoic acid, 1.73 g of dicyclohexyl (internal
    S 15 20
    5 30
    40 d5
    about
    five
    standard), 6.55 g of dichlorobenzene, 0.25 g (0.73 mmol) of butyl titanate and 0.15 g (1.12 mmol) of copper chloride. After 1 hour 30 minutes of heating to 130 ° C, the degree of conversion of methylbutol is 97% and the prenal yield is 77% with respect to the converted methylbutol.
    Example 24. Carried out according to Example 2, but using 4.34 g (51.6 mmol) of methylbutynol, 1.2 g (8.81 mmol) of 4-methylbenzoic acid, 1.73 g of dicyclohexyl (internal standard), 6.55 dichlorobenzene, 0.25 g (0.73 mmol) of butyl titanate and 0.22 g (1.0 mmol) of silver tfluoroacetate. After 2 hours of heating to 130 ° C, the conversion rate of methylbutynol is 61% and the prenal yield is 82% with respect to the converted methylbutol.
    Example 25. Carried out as in example 2, but using 8.68 g (103.2 mmol) of methylbutanol, 2.4 g (17.6 mmol) of 4-methylbenzoic acid, 13.1 g of dichlorobenzene, 3.46 g of dicyclohexyl ( internal standard), 0.4 g (1.53 mmol) of titanium acetylacetonate and 0.2 g (2.02 mmol) of copper chloride3 The molar ratios are: acetylene alcohol and titanium derivative 67.45; acetylene alcohol and copper derivative 51.09; acetylene alcohol and acid 5.85.
    After 1 hour 30 minutes of heating to 130 ° C, the degree of conversion of methylbutol is 99% and the prenal yield is 85% with respect to the converted methylbutol.
    Example 26. Carried out according to Example 2, but using 8.68 g (103.2 mmol) of methylbutanol, 13.1 g of dichlorobenzene, 3.46 g of dicyclohexyl (internal standard), 2.4 g (17.6 mmol) 4 -methylbenzoic acid, 0.38 g (1.53 mmol) of titanocene dichloride and 0.2 g (2.02 mmol) of copper chloride. The molar ratios of the reactants are as in Example 25.
    After 2 hours of heating to 130 ° C, the conversion of methylbutynol is 99% and the prenal yield is 82% with respect to the converted methylbutol.
    Example 27 In a 100 cm3 flask, under an atmosphere of argon, 2.4 g (17.6 mmol) of 4-methylbenoic acid, 5.25 g of acetic acid are introduced,
    50 cm3 of dichloroethane and 2.76 g (2.24 mmol of titanium trichloride (in 15% aqueous solution.
    Heater is heated to 85 ° C and an aeotropic mixture of dichloroethane and water is subjected to distillation. The reaction mixture (initially lilac and heterogeneous) changes color to purple-black and becomes homogeneous.
    Then 10 cm3 of dichlorobenol and 0.3 g (2.23 mmol) of anhydrous copper chloride are added. The molar ratios of the reagents are: acetylenic alcohol and titanium derivative 46.07; acetyl alcohol and copper derivative 46.27; acetylene alcohol and acid 5.85.
    Heated under reflux, removing the residual dichloroethane by distillation. The temperature of the reaction mixture reaches 120 ° C. The reaction mixture gradually fades, goes from purple-black to brown, to green, to yellow, then to white. Sediment formation is observed. After cooling, 3.46 g of dicyclohexyl (internal standard) and 8.68 g (103.2 mmol) of methylbutynol o are added. The mixture is heated. The white precipitate dissolves. The reflux temperature is set at 115 ° C, and the light yellow reaction mixture becomes homogeneous. Then the temperature is quickly brought to 130 ° C and heated at this temperature.
    within 1 h 30 min
    The conversion of methylbutol is 98% and the prenal yield is 84% with respect to the converted methylbutol.
    Example 28. Carried out according to Example 2, but using 4.34 g (51.6 mmol) of methylbutynol, 5.0 g of benzonitrile, 1.73 g of dicyclohexyl (internal standard), 1.2 g (8.81 mmol of ) 4-methylbenzoic acid, 0.25 g (0.73 mmol) of butyl titanium and 0.073 g (0.74 mmol) of copper chloride. The molar ratios are: acetylene alcohol and titanium derivative 70.68; acetylene alcohol and a derivative of copper 69,72; acetylene alcohol and acid 5.85.
    After 1 hour and 30 minutes of heating to 130 ° C, the degree of conversion of methylbutol is 98% and the prenal yield is 81% with respect to the converted methylbutol.
    Example 29. Carried out according to Example 2, but using 8.68.
    Q
    five
    0 5 0
    five
    0 5 Q
    five
    (103 mmol) methylbutynol, 10 cm3 of dichlrrbenzene, 4 cm3 of dicyclohexyl (internal standard), 2.7 g (17.76 mmol) of 4-methoxybenzoic acid, 0.56 g (1.67 mmol) of butyl titanate and 0.2 g (2.02 mmol) of copper chloride. The molar ratios are: acetylene alcohol and titanium derivative 61.67; acetylene alcohol and copper derivative 51.00; acetylene alcohol and acid 5.80.
    After 50 min of heating at 130 ° C, the conversion rate of methylbutynol is 96.4% and the prenal yield is 85; 8% relative to the converted methylbutol.
    Example 30. Carried out as in Example 2, but using 8.68 g (103 mmol) of methylbutynol, 10 cm3 of dichlorobeneol, 4 cm3 of dicyclohexyl (internal standard), 3.8 g (17.76 mmol) of 4-phenoxybenzoic acid, 0, 56 g (1.67 mmol) of butyl titanate and 0.2 g (2.02 mmol) of copper chloride 0 Molar ratios of the reagents are the same as in Example 29.
    After 1 hour and 30 minutes of heating to 130 ° C, the degree of conversion of methylbutol is 93.8% and the prenal yield is 82.3% relative to the converted methylbutol.
    Example 31. Carried out as in Example 2, but using 0.1 mol of methylbutynol, 25.4 g of dichlorobeneol, 0.0037 mmol of caprylic acid, 0.00073 mmol of butyl titanate and 0.00081 mol of copper chloride. The molar ratios of the reagents are: acetylene alcohol and titanium derivative 137.00; acetylene alcohol and copper derivative 123,45; acetylene alcohol and acid 27,02.
    After 3 hours of heating to 130 ° C, the degree of conversion of methylbutol is 97% and the prenal yield is 80% with respect to the converted methylbutol.
    Example 32. Carried out as in Example 2, but using 0.1 mol of methylbutynol, 25.4 g of dichlorobenzene, 0.0037 mol of phenylacetic acid, 0.00073 mol of butyl titanate and 0.00081 mol of copper chloride. The molar ratios of the reagents are similar to Example 31.
    After 3 hours of heating to 130 ° C, the conversion rate of methylbutynol is 85% and the prenal yield is 82% with respect to the converted methylbutol.
    Example 33. The procedure was carried out as described in Example 2, but using 0.1 mol of methyl butynol j 25.4 g of dichlorobenzene, 0.0074 mol of 2-ethylcaproic acid, 0.00073 mol of butyl titanate and 0.00081 mol of copper chloride. The molar ratio of acetylene alcohol and acid is 13.51. The remaining relationships are similar to example 31 "
    After 3 hours of heating to 130 ° C, the degree of conversion of methylbutol is 95% and the prenal yield is 79% with respect to the converted methylbutol.
    Example 34. Carried out as in example 2, but using 0.1 mol of methylbutynol, 25.4 g of dichlorobenzene, 0.0074 mol of enanthic acid, 0.00073 mol of butyl titanium and 0.00081 mol of copper chloride. The molar ratios of the reagents are similar to Example 33.
    After 2 hours 30 minutes of heating to 130 ° C, the degree of conversion of methylbutol is 96% and the prenal yield is 85% with respect to the converted methylbutol.
    Example 35 Carried out as in example 2, but using 8.4 g (99, 86 mmol) of methyl butynol, 17.9 g of methyl benzoate, 4 g of dicyclohexyl (internal standard), 0.96 g (7.37 mmol) of enanthic acid, 0.21 g (0.75 mmol) of isopropyl titanate and 0.08 g (0.81 mmol) of copper chloride. The molar ratios of the reagents are: acetylene alcohol and titanium derivative 133,14; acetylene alcohol and copper derivative 123.28; acetylene alcohol and acid 13,54.
    After 3 hours of heating to 130 ° C, the degree of conversion of methylbutol is 94% and the prenal yield is 86% relative to the converted methylbutol.
    Example 36 ° Carried out as described in Example 2, but using 8.4 g (99.86 mmol) of methyl butynol, 15 g of anisole, 4 g of dicyclohexyl (internal standard), 0.96 g (7.37 mmol) of enanthic acid, 0.21 g (0.75 mmol) of isopropyl titanate and 0.08 g (0.81 mmol) of copper chloride. The molar ratios of the reagents are similar to example 35.
    0
    five
    0
    five
    0
    five
    0
    five
    0
    five
    After 3 hours of heating to 130 ° C, the conversion rate of methylbutynol is 97% and the prenal yield is 87% relative to the converted butynol.
    Example 37. Carried out as in example 2, but using 8.4 g (99.86 mmol) of methyl butynol, 15 g of phenetol, 4 g of dicyclohexyl (internal standard), 0.96 g (7.37 mmol) of enanthic acid, 0, 21 g (0.75 mmol) of isopropyl titanate and 0.08 g (0.81 mmol) of copper chloride. The molar ratios of the reagents are similar to example 35.
    After 3 hours of heating to 130 ° C, the conversion rate of methylbutynol is 96% and the prenal yield is 87% with respect to the converted methylbutol.
    Example 38. Carried out as in example 2, but using 8.4 g (99.86 mmol) of methylbutynol, 12.4 g of dicyclohexyl (solvent), 4 g of tetradecane (internal standard), 0.96 g (7.37 mmol) enanthic acid, 0.21 g (0.75 mmol) of isopropyl titanate and 0.08 g (0.81 mmol) of copper chloride. The molar ratios of the reagents are similar to example 35.
    After 4 hours and 45 minutes of heating to 130 ° C, the degree of conversion of methylbutol is 77% and the prenal yield is 95% relative to the converted methylbutol.
    Example 39. In a glass tube (Carius tubes) with a volume of 34 cm3, 21 cm3 of a mixture consisting of 5.6 g (66.6 mmol) of methylbutanol, 14.25 g of dichlorobenzene, 2.66 g of dicyclohexyl (internal standard ), 2.45 mmol of 4-methylbenzoic acid, 0.49 mmol of isopropyl titanate and 0.54 mmol of copper chloride. The tubes are sealed in an inert atmosphere, then heated in an oven to 130 ° C.
    After 2 hours 30 minutes of heating, the degree of conversion of methylbutol is 98% and the prenal yield is 90% relative to the converted methylbutol.
    Example 40. Carried out as in Example 2, but using 8.68 g (103.2 mmol) of methylbutanol, 13.1 g of dichlorobenzene, 3.46 g of dicyclohexyl (internal standard), 2.4 g
    (17.68 mmol) of 4-methylbenzoic acid, 0.5 g (1.47 mmol) of butyl titanate and 0.15 g (1.52 mmol) of copper chloride. After 1 hour of heating to 130 ° C, the degree of conversion of methylbutynol is 97% and the prenal yield is 85% relative to the converted methylbutol.
    Example 41. Carried out according to Example 2, but using 8.68 g (103.2 mmol) of methylbutanol, 26.2 g of dichlorobenzene, 3.46 g of dicyclohexyl (internal standard), 0.6 g (4.41 mmol of 4- methyl benzoic acid, 0.25 g (0.73 mmol) of butyl titanate and 0.08 g (0.81 mmol) of copper chloride. After 2 hours and 30 minutes of heating to 130 ° C, the conversion of methylbutol is 98% and the prenal yield is em 89% relative to the converted methylbutinol.
    Example 42. Carried out as in example 2, but using 4.4 g (52.31 mmol) of methylbutynol, 6.5 g of dichlorobenzene, 1.72 g of dicyclohexyl (internal standard), 1.2 g (8.81 mmol) 4 -methylbenzoic acid, 0.25 g (0.73 mmol) of butyl titanate and 0.12 g (0.75 mmol) of hemihydrate oxalate of copper.
    After 5 hours of heating to 130 ° C, the conversion rate of methylbutynol is 91% and the prenal yield is 85% with respect to the converted methylbutol.
    Copper oxalate is obtained in an aqueous medium by the addition of the main copper carbone to oxalic acid. The blue precipitate that forms is filtered off.
    Example 43. In a flask equipped with a vertical condenser, in an inert atmosphere, 19.5 g of dichlorobenzene, 1.8 g (13.2 mmol) of 4-methanol, benzoic acid, 0.37 g (1, 09 mmol) of titanium are introduced. Heat for 15 minutes to 130 ° C. The liberated butanol is condensed in a refrigerator. Butanol is subjected to distillation under reduced pressure (T 32 ° C, P 13 mm Hg, 1.43 kPa), heating the flask to 64 C. Then a mixture of butanol (90% of theory) and dichlorobenzene (2 cm3 ) 0 2 cm3 of dichlorobenzene, 12.8 g (152.2 mmol) of methylbutanol, 5.3 g of dicyclohexyl (internal standard) and 0.11 g (1.11 mmol) of copper chloride are introduced into the flask. After 2 h of heating to
    0
    0
    ,
    five
    -
    0
    130 ° C, the conversion of methypotinol is 977 and the prenalum yield is 88% with respect to the converted methylbutinol.
    Example 44. Carried out as in example 2, but using 8.4 g (99.86 mmol) of methyl butynol, 16.2 g of methyl benzoate, 4 g of dicyclohexyl (internal standard), 0.4 g (4.65 mmol) of crotonic acid, 0.21 g (0.75 mmol) of isopropyl titanate and 0.08 g (0.81 mmol) of copper chloride. After 1 hour of heating to 130 ° C, the conversion degree of methylbutynol is 96% and the prenal yield is 93% with respect to the converted methylbutolol.
    Example 45. Carried out as described in Example 2, but using 8.4 g (99.86 mmol) of methyl butynol, 17.8 g of nitrobenzene, 4 g of dicyclohexyl (internal standard), 0.96 g (7.37 mmol) of enanthic acid, 0.21 g (0.75 mmol) of isopropyl titanate and 0.08 g (0.81 mmol) of copper chloride.
    After 2 hours of heating to 130 ° C, the degree of conversion of methylbutynol is 94% and the prenal yield is 86% with respect to the converted methylbutol.
    Example 46. Carried out as in example 2, but using 8.4 g (99.86 mmol) of methylbutanol, 15.3 g of M-methylpyrrolidone, 4 g of dicyclohexyl (internal standard), 0.96 g (7.37 mmol) of enanth acids, 0.21 g (0.75 mmol) of isopropyl titanate and 0.08 g (0.81 mmol) of copper chloride. After 2 hours of heating to 130 ° C, the conversion rate of methylbutynol is 81% and the prenal yield is 65% with respect to the converted methylbutol.
    Example 47. Carried out as in Example 2, but using 8.4 g (99.86 mmol) of methylbutynol, 14 g of cyclohexanone, 4 g of dicyclohexyl (internal standard), 0.96 g (7.37 mmol) of enanthic acid, 0, 21 g (0.75 mmol) of isopropyl titanate and 0.08 g (0.81 mmol) of copper chloride. After 2 hours of heating to 130 ° C, the degree of conversion of methylbutol is 51% and the prenal yield is 63% relative to the converted methylbutynol.
    The ratios of the reagents in examples 39-45 are shown in the table.
    Thus, the proposed method allows to increase the yield of the target product up to 98% against 87% by a known method.
    权利要求:
    Claims (1)
    [1]
    Invention Formula
    e ni
    Method for preparing ethylene carbonyl compound of general formula JQ
    sn-sno
    where R (and Rz is methyl,
    by isomerization of acetylene alcohol of the general formula
    K-C-CESN
     - I HE
    2
    where R4 and Kr have the indicated value 7 at an elevated temperature in the presence of a catalyst in the liquid phase, characterized in that, in order to increase the yield of the target product, the process is carried out at a rate Q
    0
    five
    130 ° C in the presence of an acid selected from the group of acetic, hexane, heptanoic, 2-ethylhexanoic, octanoic, crotonic, 4-methylbenzoic, 4-methoxybenzoic, 4-phenoxybenzoic or phenylacetic acid at a molar ratio of acetylene alcohol: acid 5.80-27.18: 1 in the presence of an organic solvent selected from the group of dichlorobenzene, benzonitrile, methane isoate, anisole, phenetol or dicyclohexyl, kata is used as a catalyst. lytic system formed by a derivative of titanium selected from etiltitanata group izopropiltitanata, butyl titanate, titanium trichloride, titanium tetrachloride, titanium dibutoxy-bis-acetylacetonate, titanium acetylacetonate or titanotsenhlorida at a molar ratio of acetylene alcohol: 141 46,07- titanium derivative, 36: 1 and copper (I) chloride at a molar ratio of acetylene alcohol to copper (I) chloride 46.27-137.11: 1.
    Editor N. Yatsola
    Compiled by N. Kulikova Tehred L. Serdyukova
    Order 1231
    Circulation 337
    VNIIPI State Committee for Inventions and Discoveries at the State Committee on Science and Technology of the USSR 113035, Moscow, Zh-35, Raushsk nab. 4/5
    Corrector I. Muska
    Subscription
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    同族专利:
    公开号 | 公开日
    JPH07116091B2|1995-12-13|
    FR2596755A1|1987-10-09|
    CA1265816A|1990-02-13|
    EP0240431B1|1991-11-27|
    EP0240431A2|1987-10-07|
    AT69795T|1991-12-15|
    FR2596755B1|1988-05-27|
    BR8702013A|1988-02-02|
    EP0240431A3|1989-04-05|
    US4749814A|1988-06-07|
    DE3774742D1|1992-01-09|
    JPS62238228A|1987-10-19|
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    EP0952139B1|1998-04-20|2004-02-04|Givaudan SA|Preparation of unsaturated aldehydes from propargyl alcohol and conjugated diolefins|
    CN110028392B|2019-04-29|2021-04-13|山东新和成药业有限公司|Method for isomerizing and synthesizing isopropenal by using methylbutynol|
    CN111167471B|2020-01-17|2020-10-02|浙江新和成股份有限公司|Metal oxide coated ceramic corrugated plate catalyst, preparation and application thereof in preparation of citral key intermediate|
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    法律状态:
    2005-01-10| REG| Reference to a code of a succession state|Ref country code: RU Ref legal event code: MM4A Effective date: 20030403 |
    优先权:
    申请号 | 申请日 | 专利标题
    FR8604769A|FR2596755B1|1986-04-03|1986-04-03|PROCESS FOR THE PREPARATION OF ETHYLENIC CARBONYL COMPOUNDS|
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