• 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:
    Halogeno-acetals of ethylenically unsaturated aldehydes are prepared by reaction of an ethylenically unsaturated ester with a halogen cation chosen from Cl+, Br+ and I+ and an alcohol. The products are useful, inter alia, for introducing an alpha , beta -ethylenically unsaturated aldehyde unit into a mono- or polyene radical.
    公开号:SU880250A3
    申请号:SU772455102
    申请日:1977-02-25
    公开日:1981-11-07
    发明作者:Декор Жан-Пьер
    申请人:Рон-Пуленк Эндюстри (Фирма)；
    IPC主号:
    专利说明:

    This invention relates to a process for the preparation of new ethylene aldehyde halides that can be used as intermediates in organic synthesis. They can be used to introduce an oL, p-ethylene aldehyde fragment into a mono- or polyene residue by reacting with a polyene sulfone in the presence of an alkaline agent. . As a result of the above transformations, using the proposed compounds, vitamin A aldehyde can be obtained. Similar halogen acetals are known in the literature, which were obtained by the action of haloalkoxylation agents, in particular M-halosuccinide, on 1-alkyl-oxides in alcohol. 1-Alkoxyloxy-1,3-1,3, in turn, is obtained by treating acetals of ci, p-yl p, TG-ethylenic acid and saturated aldehydes at 320-250 ° C in the presence of a catalyst. Halogen acetals are unstable under conditions of known spores. . It is obtained in the form of solid tal-containing non-saturated vinyl vinyl simple or complex emirs tlj. . The aim of the invention is to develop a new method for producing haloacetals not previously known. A method is proposed for the preparation of ethylene aldehyde halides of acetals of the general formula: where Y is chlorine or bromine; each of the radicals R represents a normal or isostatic alkyl. The C-Stimulantic feature of which is that the halogenating agent is reacted with 1 mol of the ester of the general formula SNg PES, where is normal or iso-alkyl at (-40 () C in the presence of an excess of primary or secondary alcohol of the general formula where R has the above As a halogenating agent, various types are preferably used, namely compounds in which a halogen is bonded by a covalent bond to a halogen atom or to a nitrogen or oxygen atom, compounds resulting from rice halogen to quaternary ammonium aliphatic halide, or complexes obtained by reacting molecular halogen with an aliphatic or cyclic amide. Typically used as this agent are compounds such as tert.-butanol hypochlorite, dimethylformamide complex with chlorine and bromine, or complex N -methylpyrrolidone with chlorine and bromine, or dimethylsulfoxide complex with chlorine, or N-halo-succinamide, or tetrachlorotetra-n-butylammonium iodide. To increase the reaction rate, it is preferable to conduct the process in the presence of a catalytic amount of a mineral or organic acid, known as an acetalization catalyst. The original products of the proposed method are relatively available. Target products are isolated in their individual state as a mixture of cis and trans isomers and are stable. Example 1. To a solution of 7.561 1-adetoxy-3-methylbutadiene-1,3 (95%, 5, 7-10 mole) in 50 cm of methanol, cooled to 15 ° C, pour 27.8 cm over 90 minutes 2.15 M pentane solution of tert-butyl hypochlorite. Upon completion, add a drop of concentrated hydrochloric acid and maintain the temperature at 15 ° C for 40 minutes. The reaction mixture is then slowly poured into 100 cm of water containing 7.56 g of sodium bicarbonate. After 15 minutes and at the end of the gas evolution, the methanol water solution is extracted 3 times with a total of 60 cm of pentane. The combined extracts are washed with 2 times with a total of 40 cm of water, dried over sodium sulfate and concentrated under reduced pressure (20 mm Hg), preventing temperature increase above 50 ° С. A residue (9.50 g) is obtained consisting of 74.3% of 1,1-dimethoxy-3-methyl-4-chloro-butane-2 and 9.5% of 1-acetoxy-1-methoxy-3-methyl- 4-chloro-butene-2, identified by NMR spectrum, which are separated from secondary products by distillation under reduced pressure (so kip. 38-39 0 / 0.2 mm Hg). . The resulting mixture is dissolved in 50 cm of methanol in the presence of a drop of concentrated hydrochloric acid and the solution is kept at 30 ° C for 1 hour. The reaction mixture is poured into 100 cm of water. After three extractions of a total of 60 cm pentane, drying over sodium sulphate, concentration to dryness and distillation, 7.107 g of 1,1-dimethoxy-3-methyl-4-chloro-butene-2 is obtained (mp. 38-38.5 ° C / 0.2 mmHg) containing 62% trans isomer and 18% cis isomer. Pentane solution of hypochlorite tert.-butyl can be obtained in the following way. To 780 cm of an aqueous solution of sodium hypochlorite containing 0.6 mol, is added at 2-4 ° C and within 7 minutes a mixture of 44.7 g (0.6 mol of tert-butanol and 40 g (.0666 mol of acetic acid After the addition is complete, the reaction mixture is kept for 8 minutes at 4 ° C, then extracted with 50 cm of pentane.The organic extract is washed with 50 cm of an aqueous saturated sodium bicarbonate solution, 50 cm of water, dried over calcium chloride and brought to a volume of 100 cm by adding pentane. a 100 cm 4.42 M tert-butyl hypochlorite solution pentane solution is obtained. Example 2. in a flask, 35.0 g (0.277 mol) of 1-acetic-3-methylbutadiene-1,3 and 277 cm of anhydrous dimethylformamide are preliminarily flushed with dry argon and charged with up to 19 g of chlorine gas to introduce 19, 66 g (0.277 mol) of chlorine for 90 minutes, then 277 cm of anhydrous methanol are added in 25 minutes. The temperature of the reaction mixture is maintained at -20 ° C for 30 minutes after the end of the addition of methanol, then the mixture is kept for raising the temperature to. After 2 hours at the end of the addition of methanol, the reaction mixture is poured into 700 cm of cooled water with 50.4 g of sodium bicarbonate, while carbon dioxide is released. When this process ceases, the organic phase is diluted with 100 cm of pentane, the aqueous phase is extracted 2 times with a total of 200 cm of pentane and the organic phases are combined, washed with 100 cm of a saturated aqueous sodium chloride solution and dried over sodium carbonate. After filtration and concentration, a residue weighing 41.094 g is obtained in which 25% cis-1,1-dimethoxy-3-methyl-4-chlorobutene-2 and 60% trans-1,1-dimethoxy-3-methyl are determined by NMR. 4-chlorobutene-2. The total yield of 1,1-dimethoxy-3-methyl-4-chlorobutene is 76.6% relative to the starting 1-acetoxy-3-methylbutadiene-1, 3., Example 3. In a flask previously purged with a dry rgon current , load 2,413 g (1,9-10 mol) of 1-acetoxy-3-methyLbutadiene-1,3 and 30 cm of anhydrous dimethylacetamide. Chlorine gas is drawn into the resulting solution, cooled to -20 ° C, carried with argon to introduce 1.36 g of chlorine over 1 hour, then 30 cm of anhydrous methanol is added over 5 minutes. The reaction mixture is kept at a temperature to raise the temperature to about 0 ° C. Two hours after the end of the addition of methanol, the reaction mixture is poured into 100 cm of water with 4.2 g of sodium bicarbonate, with carbon dioxide evolving. When this process is stopped, the organic phase is diluted with 25 cm of pentane, the aqueous phase is extracted 3 times with a total of 75 cm of pentane, and the organic phases are combined, washed with a 25% saturated sodium chloride solution and dried over sodium carbonate. After filtration and concentration under reduced pressure (20 mm Hg), a residue (2.806 g) is obtained, in which 7% of cis-1,1-dimethoxy-3-methyl-4-chlorobutene-2 and 63% trans-1, 1-dimethoxy-3-methyl-4-chloro-butene-2. The overall yield of 1,1-dimethoxy-3-methyl-4-chlorobutene-2 is 63% with respect to the starting 1-acetic hydroxy-3-methyl butadiene, 3. Example 4. In a flask previously blown by a stream of dry argon, 6.741 g (5.35-10 mol of 1-acetoxy-3-methylbutadiene-1.3 and 53 cm of anhydrous N-methylpyrrolidone are placed. Gaseous chlorine is passed into the resulting solution at A20c entrained with argon to enter 4.18 g of chlorine in 90 minutes, 53 cm of anhydrous methanol is added to the reaction mixture, cooled to -20 ° C, then held to increase the temperature to approximately 0 ° C over 90 The resulting homogeneous solution was poured into 115 s of 14.53 g of sodium bicarbonate, and carbon dioxide was released. this process is completed, 50 cm of pentane is added, the organic phase is separated and the aqueous phase is washed with 2 times overall 100 cm of pentane. The organic phases are combined, washed 3 times with a total of 45 cm aqueous saturated sodium bicarbonate solution, dried over sodium carbonate, filter and concentrate. An oily residue is thus obtained (7.323 in which, by NMR, 11.8% of cis-1,1-dimethoxy-3-methyl-4-chlorobutene-2 and 57.2% trans-1,1 dimethoxy-3-methyl-4-chlorobutene-2. The total yield of 1,1-dimetaxi-3-methyl-4-chlorobutene-2 is 61% with respect to the starting 1-acetoxy-3-methylbutadiene-1, 3. Example 5. 6.93 g (5.5-10 mol) of 1-acetoxy-3-- ethylbut scien-1, 3, and 50 cm of anhydrous dimethylformamide are charged into a flask pre-purged with cyxoi o nitrogen. To the resulting solution, cooled to -20 s, 8.789 g of bromine (5.5 mol) is added with stirring and within 2 hours and 15 minutes. Stirring of the reaction mixture is continued for 10 minutes after the end of the addition of bromine, then 50 cm of anhydrous methanol is added all the time at -20 ° C for 10 minutes. Stirring is continued for 90 minutes, allowing the temperature to rise to about 20 seconds. The reaction mixture is poured into 200 cm of cooled water to about 0 ° C. Water containing 12.6 g of sodium bicarbonate solution in 200 cm of water, with the release of carbon dioxide. When this process is stopped, 3 times a total of 150 cm of pentane is extracted, the organic extracts are combined and dried over sodium bicarbonate. After filtration and concentration, an oily residue (10.92 g) is obtained, in which 28% cis-1,1-dimethyxy-3-methyl-4-bromobutene-2 and 48% trans-1,1-dimethoxy are determined by the YaGP method. -3-methyl-4-bromobutene-2. The total yield of 1,1-dimethoxy-3-methyl-4-bromobutene-2 is 72.3% with respect to the starting 1-acetoxy-3-methyl butadiene-1,3. Example 6. In a flask previously blown with a stream of dry nitrogen, 6.457 g (5, 1-25-10 mol of 1-acetoxy-3-methylbutadiene-1,3 and 51.25 cm of anhydrous M-methylpyrrolidone are placed. To the resulting solution, cooled to -20 ° C, 8.2 g (5.125-10 mol) of bromine are added with stirring and within about 1 hour and 25 minutes. The reaction medium is stirred for approximately 15 minutes after the end of the addition of bromine, then all the time at -20 ° C, 51.25 cm 3 of anhydrous methanol was added over 20 g-ns. Stirring was continued at -20 ° C for 10 minutes, allowing the temperature to Punch out to about ot, and hold under agitation for 2.5 hours. The reaction mixture is poured into 85 cm of cooled water with 10.63 g of sodium bicarbonate, and carbon dioxide is released, and 50 cm of pentane is added, section The organic phase is extracted, the aqueous phase is extracted 3 times with a total of 150 cm of pentane, the organic phases are combined, washed with 3 times with a total of 45 cm of aqueous sodium bicarbonate solution and dried over sodium carbonate under argon. Filtration and concentration under reduced pressure (.15 mm Hg) and approximately 10.10 g of light are obtained, in which 22.5% of cis-1,1-dimethoxy-4-bromobutene-2 is determined by NMR. and 67.5% trans-1,1-dimethoxy-4-bromobutene-2. The total yield of 1,1-dimethoxy-4-broMbuten-2 is 84.81 with respect to the original 1-acetoxy-3-methylbutadiene-1,, Example 7. In a flask previously purged with dry nitrogen 5.46 g. {4, 33-KG mol) 1-ace toxio-Z-methylbutadiene-1,3 and 50 cm of methanol are placed. To the mixture cooled to 0 ° C and the stirring mixture is added one to one of concentrated sulfuric acid, then 11.35 g {2.22. ) iodis addition tetrachlorotetra-N-butylammonium for 4 h and while maintaining a temperature equal to approximately. Stirring is continued for 30 minutes after the end of the addition, the far-reaction mixture is poured into a cooled solution of 13.5 g of sodium bicarbonate in 200 cm of water, and carbon dioxide is released. When this process ceases, the mixture is extracted 3 times with a total of 150 cm of pentane and the combined extracts are dried over sodium bicarbonate, filtered and concentrated under low pressure. A residue (8.1 g) is obtained in which 11.5% of Cis-1,1-dimethoxy-3-methyl-4-chlorobutene-2 and 34.5% of trans-1, 1-dimethoxy-3 are determined by NMR. -methyl-4-chlorobutene-2. The total yield of 1,1-dimethoxy-3-methyl-4-chlorobutene-2 is 52.3% with respect to the starting 1-acetoxy-3-methyl butadiene-1, 3. Example 8. In a flask, pre-purged with a stream of dry argon, is placed 6.95 g of (5, 51) 1-acetoxy-3-methylbutadiene-1,3,, 50 cm of anhydrous methanol and 50 cm of anhydrous N-methylpyrrolidone. Chlorine gas is drawn into the resulting solution, cooled to, with a flow of argon to enter 4.31 g (b, 07-Humol) of chlorine for 1 hour and 35 minutes, then continue moving at -20 ° C for 25 minutes and, finally, the mixture is held to increase the temperature to approximately O9c for 30 minutes and kept stirring at this temperature for 2 hours. The reaction mixture is poured into 100 cm of cooled water with 12.6 g of sodium bicarbonate, and carbon dioxide is released. When this process is complete, 50 cm of pentane is added, the organic phase is separated, the aqueous phase is extracted 2 times with a total of 100 cm of pentane. The combined organic extracts are washed 3 times with a total of 45 cm of aqueous saturated pacTBdpa sodium bicarbonate. Pour water is extracted with 25 cm of pentane and the pentane extract is again washed with 3 times with a total of 9 cm of saturated aqueous sodium bicarbonate solution. The combined pentane extracts are combined, dried over sodium carbonate, filtered and concentrated under reduced pressure (mm Hg 7. The oily residue is obtained (8.72 g), in which 14.4% cis-1.1 is determined by NMR dimethoxy-3-glutyl-4-chlorobutene-2 and 67, trans-1,1-dimethoxy-3-methyl-4-chlorobutene-2. Total yield of 1,1-dimethoxy-3-methyl-4-chlorobutene-2 is 79.1% with respect to the starting 1-acetoxy-3-methylbutadiene-1, 3. Example 9. In a flask previously purged with a stream of dry nitrogen, 4.34 g of 97% is placed (3, 34–10 mol ) 1-acetoxy-3-methylbutadiene-1, 3 and 30 isopropanol cm. The mixture is cooled to -20 ° C and 0.03 cm of concentrated sulfuric acid is added to it. Then, continuing stirring all the time, 6.13 g (3.44-10 mol) are added at -20 ° C for 30 minutes K1-bromosuccinimide. After the addition is complete, stirring is continued for 30 minutes at -20 ° C, then the mixture is kept for temperature increase and stirring is continued for another 2 hours. The heterogeneous reaction mixture is poured into a cooled solution of 6.9 g of sodium bicarbonate in 100 cm of water, and the release of carbon dioxide. When this process is over, the mixture is extracted 3 times with a total of 75 cm of pentane. The organic extracts are combined, dried over sodium bicarbonate, filtered, and concentrated under reduced pressure. An oily residue is obtained (7.61 g, in which 17% cis-1,1-diisopropoxy-3-methyl-4-bromobutene-2 and 45.41 trans-1, 1-diisopropoxy-3-methyl -4-bromobutene-2. The total yield of 1,1-diisopropoxy-3-methyl-4-bromobutene-2 is 53.6% relative to the starting 1-acetoxy-3-methyL-butadiene-1, 3. Example 10. In a three-necked flask, purged with a stream of nitrogen, is placed 7.56 g (-6. lOTvionb) 1-acetoxy-3-methylbutadiene-1, 3 and 50 cm 3 of anhydrous methanol. The mixture is cooled to -20 ° C, then a drop of concentrated sulfuric acid is added (unit weight 1.83. To the mixture for 75 min d 10.68 g of N-bromo-succinimide mol), the mixture is held to raise the temperature to about 30 minutes, the reaction mixture is poured into 100 cm of cooled water with 7.65 g of sodium bicarbonate. After stirring for 10 minutes, spilling 50 cm water 80 cm of pentane, the organic phase is separated and the aqueous phase is extracted 3 times with a total of 90 cm of pentane. The organic phases are combined, washed with 50 cm of water, then 50 cm of an aqueous saturated sodium bicarbonate solution, dried over sodium carbonate and
    权利要求:
    Claims (2)
    [1]
    - The claims are ritually purified by a stream of dry argon, 7.71 g of 98% (6-10 ~ 2 mol) 1-acetoxy-3-methylbutadiene-1.3 th 50 methanol are charged. The mixture was cooled to -40 ° C and then 0.03 cm3 of concentrated sulfuric acid was added. The mixture was stirred while maintaining the temperature at -40 ° C, and 10.68 g (b-PG-mol) of N-bromosuccinimide were added to it over 2 hours. 20 each
    1. The method of obtaining haloacetals of ethylene aldehydes of the General formula
    At the end of the attachment, stirring was continued for 3.5 hours at -40 ° C. The heterogeneous mixture is poured into an ice solution of 7.56 g of sodium bicarbonate in 100 cm ^ of water. The mixture is stirred for 5 min and extracted a total of 150 cm3 of penta three times25 where X is chlorine or bromine) each of the radicals R represents a normal or isostructure alkyl СУ-С 6 , characterized in that the halogenating agent is reacted with 1 mol of an ester of the general formula on the. The collected organic extract is washed with 50 cm3 of water, then 50 cm3 of an aqueous saturated solution of bicar-SIS-, sodium bonate and finally dried over anhydrous sodium bicarbonate. After concentration under reduced pressure, a yellow liquid residue is obtained (10.065 g), in which 50.68% 1,1-diethoxy-3-methyl-4-bromobutene-2 and 10-, 1% 1-acetoxy- are determined by NMR 3-methylbutadiene-1,3 (non-converted). With respect to the starting 1-acetoxy-3-methylbutadiene, the yield of 1,1-diethoxy-3-methyl-4-bromobutene-2 is 41.7%.
    Example 12. Obtaining acetoxy-1-methyl-3-butadiene-1,3, starting from methyl-3-butene-2-al.
    To 80 g of acetate isoprenyl (0.8 mol) heated to 94 ° C, add 0.04 cm 3 of concentrated sulfuric acid, then 33.6 g of methyl 3-butene-2-al (0.4 mol) are added over 90 minutes while maintaining a temperature of 94-107 ° C (the acetone formed in this process is distilled). After cooling to 30 ° C., the reaction mixture was distilled under reduced pressure (14 mmHg). First of all, 28.3 g of dis- are collected. tillate formed by acetone and acetate isoprenyl, and then the second fraction in the amount of 83.95 g. Using spectral analysis, vapor phase chromatography and chemistry 30 where R 4 is normal or isostructure C4-C4 alkyl, at (~ 40 ° C) - ( + 30 ° C) in the presence of an excess of primary or secondary alcohol of the general formula ROH, where R has the above meanings.
    [2]
    2. The method according to claim 1, characterized in that tert-butanol hypochlorite or a complex of cimethylformamide with chlorine and bromine, or a complex of N-methylpyrrolidone with chlorine and bromine, or a complex of dimethyl sulfoxide with chlorine, or N-raloid succinamide are used as the halogenating agent. or tetrachlorotetra-N-butylammonium iodide.
    Featured Priority
    02/25/76 - halogenating agent hypochlorite of tert.-butanol, N-halosuccinamide.
    01/13/77 - a halogenating agent, a complex of N-methylpyrrolidone with chlorine and bromine or a complex of dimethylformamide with chlorine and bromine, or a complex of dimethyl sulfoxide with chlorine or tetrachlorotetra-β-butylammonium iodide.
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    同族专利:
    公开号 | 公开日
    CA1077952A|1980-05-20|
    DD128608A5|1977-11-30|
    IT1074317B|1985-04-20|
    NL7701702A|1977-08-29|
    JPS52102212A|1977-08-27|
    DE2708304C2|1982-07-01|
    NL176165B|1984-10-01|
    US4100201A|1978-07-11|
    GB1521234A|1978-08-16|
    SE7702068L|1977-08-26|
    DE2708304A1|1977-09-08|
    JPS5623411B2|1981-05-30|
    NL176165C|1985-03-01|
    SE436866B|1985-01-28|
    CH615897A5|1980-02-29|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US2330570A|1943-09-28|Halo acetal |FR2518534B1|1981-12-18|1984-03-09|Rhone Poulenc Sante|
    JPH0128416Y2|1983-10-31|1989-08-30|
    FR2620705B1|1987-09-22|1989-12-01|Rhone Poulenc Sante|NEW NONATRIENE-1,3,5 DERIVATIVES, THEIR PREPARATION AND THEIR USE|
    FR2655333B1|1989-12-01|1992-02-21|Rhone Poulenc Sante|PROCESS FOR THE PREPARATION OF HALOGENOACETALS FROM ENAMINES.|
    FR2655342A1|1989-12-01|1991-06-07|Rhone Poulenc Sante|NOVEL INTERMEDIATES, THEIR PREPARATION PROCESS AND THEIR USE FOR THE SYNTHESIS OF VITAMINS A AND E.|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    FR7605241A|FR2342265B1|1976-02-25|1976-02-25|
    FR7700854A|FR2377365B2|1977-01-13|1977-01-13|
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