• 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:
    The invention relates to carboxylic acid esters, in particular to the preparation of Δ-2-dihydromuconic acid methyl ester, which is used in the production of adipic acid. The goal is to simplify the process technology. The preparation is carried out by catalytic dimerization of methyl acrylate in the medium of an organic solvent at 50-190 ° C in the presence of a catalyst. As the latter, a catalytic system consisting of dibenzylidene acetonate PD (II) or dibenzylideneacetonate PD (III) or their mixture, or acetylacetonate PD (II), or PO acetate (II) acetate and tributylphosphonium with tetrafluoroboric acid, or hydrotributylphosphonatetrapteraser is used. tetrafluoroboric acid. The process is carried out at a molar ratio of P: PD = 1: 1 ÷ 4 at a molar ratio of ion H: ion PD = 1: 1 ÷ 10, while the catalytic system is dissolved in diethyl ether. The duration of the process is reduced from 10-30 hours to 1-5 hours. 3 table.
    公开号:SU1574168A3
    申请号:SU874202277
    申请日:1987-03-26
    公开日:1990-06-23
    发明作者:Гренуйе Пьер；Нейбекер Дени；Ткаченко Игорь
    申请人:Рон Пуленк Шими (Фирма)；
    IPC主号:
    专利说明:

    This invention relates to an improved process for the preparation of u-2-dihydromuconic acid methyl ester, which is a valuable intermediate for the preparation of adipic acid derivatives.
    The aim of the invention is to simplify the process technology.
    Examples 1-17. These examples illustrate the dimerization of methyl acrylate when operating according to the following procedure.
    Into a Schlenk tube, equipped with a magnetic stirrer and a device for
    purge argon, successively injected: the equivalent of 0.2 mmol palladium in a mixture of 1: 3 complexes of palladium (II) dibenzylideneacetonate and palladium (III) dibenzylideneacetonate complexes Pd (dba) 2 and Pds (dba) 3, degassed methyl acrylate; tributylphosphine- (RVi) h distilled in argon; solution, in tetrafluoroboric acid diethyl ether, the titer of which is predetermined. The tube is closed, its contents are stirred at 80 ° C for the required time. The temperature is then lowered to room temperature and neutralized.
    O5 00
     ABOUT
    the reaction mixture by adding 0.5 g of sodium bicarbonate. Distillate under reduced pressure (3 Torr) and collect the liquid fraction.
    The distillate obtained in this way is analyzed on a gas chromatograph using methyl malonate as a internal standard, column 2X1 / 8 m, Carbovax 20 M (10%) on PAW 60-809 Chromosorb, Injector temperature 250 ° C, furnace temperature 150 ° C, flame temperature 250 ° C ionization detector; nitrogen is used as carrier gas (25 ml / min).
    Specific conditions and the results are shown in Table. one.
    As can be seen from the table. 1, in the absence of palladium, only a polymer is formed (example 13) j in the absence of a phosphorus compound (III) no conversion of the acrylate is observed (example 14); in the absence of a phosphorus (III) compound and in the presence of an increasing amount of hydrogen acid, no conversion of the acrylate is observed (Example 15); in the absence of hydrogen acid, no conversion of the acrylate is observed (Example 16); the presence of only hydrogen acid is not enough to ensure any conversion of acrylate (example 17).
    Example 19. These examples show the pre-salt formation (HPBu) of BF4.
    A Schlenk tube, equipped with a magnetic stirrer and an argon purge device, is sequentially loaded: the equivalent of 0.2 mmol palladium in the mixture specified in examples 1-1 of the complexes; degassed methylacry lat; hydrogentributylphosphonium tetrafluoroborate obtained by the interaction of equivalent amounts of tributylphosphine and tetrafluoroboric acid in a solution of diethyl ether and, in some cases, tetrafluoroboric acid in a solution of diethyl ether. The Slanka tube is closed, then its contents are mixed at 80 ° C for 20 hours. Processing the reaction mixtures according to the methods described above leads to the results given in Table. 2
    Example 20. A Schlenk tube equipped with a magnetic stirrer and an argon supply is sequentially charged (H47Pd 4): the equivalent of 0.1 milliatom-gram of palladium in a mixture of degassed methyl acrylate (13.8 ml, 153 mmol) in examples 1-17; tributyl phosphine (PBu) j (40 mg, 0.2 mmol); tetrafluoroboric acid in the form of 9.3 n. solution in diethyl ether (0.05 ml or 0.4 mmol. The Schlenk tube is closed, then stirred at 80 ° C for 20 hours. Processing the reaction mixture according to the described procedure leads to the conversion of 41% methyl acrylate. The following products are obtained: A2- dihydromuconic acid methyl ester (more than 95%); 2-methylene glutaric acid methyl ester (1%); dihydromuconic acid methyl ester (traces), unidentified dimers (3%).
    Example21. This example illustrates the use of palladium acetate for the dimerization of methyl acrylate.
    In a Schlenk tube, equipped with a magnetic stirrer and purging with argon, are sequentially loaded (H); palladium acetate (22.5 mg, 0.1 mmol); degassed methyl acrylate (13.8 ml, 153 mmol); tributylphosphine (60 mg, 0.3 mmol), tetrafluoroboric acid as 9, .3 n. diethyl ether solution (0.075 ml, 0.6 mmol).
    i The Slang tube is closed, then stirred at 80 ° C for 5 hours. Processing the reaction mixture according to the described procedure results in a conversion of 52% methyl acrylate (rotation frequency 76 hours). Selectivity & - dihydromuconic acid methyl ester is above 95%,
    PRI me R 22. This example illustrates the use of palladium acetylacetonate in the dimerization of methyl acrylate.
    A Schlenk tube, equipped with a magnetic stirrer and argon purge, is successively loaded with: palladium acetyl acetonate (30.5 mg, 0.1 mmol degassed methyl acrylate (14 ml, 155 mmol); tributylphosphine (40 mg, 0.2 mmol); tetrafluoroboronic acid in the form of 9.3 n, solution in ethyl ether (0.125 ml, 1 mmol).
    The Slang tube is closed, then stirred at 80 ° C for 5 hours. Treatment of the reaction mixture according to the described procedure leads to the conversion of 67% methyl acrylate (rotation frequency 88 h). The selectivity of D4-methyl
    five
    dihydromuconic acid ester above 95%.
    Example 23. A palladium acetylacetonate (II) acetylacetonate, dissolved in distilled methyl acrylate in an amount of 0.6 mmol palladium per mole acrylate, was successively introduced into a stainless steel reactor, purged with argon, in a stainless steel reactor. hydrogen tetrafluoroborate in the amount of 6 mmol per mole acrylate (); and tetrafluoroboric acid, which forms a complex with ethyl ether in a cat. 2.5 mmol per mole of acrylate (). I
    After closing the reactor and stirring, the temperature of the reaction medium is adjusted to 110 ° C.
    The progress of the reaction is monitored by sampling during the gas chromatographic analysis.
    The following results were obtained.
    After 55 min of reaction, the degree of conversion of the acrylate is 22% and the selectivity of dihydromuconic acid methyl ester is above 98%. After 4 hours and 25 minutes of reaction, the degree of conversion of acrylate is 79% and the selectivity of dihydromuconic acid methyl ester is above 95%.
    Examples 24-33. The process is carried out as in Example 23. The process conditions are given in Table. 3
    86
    In all cases, the desired product is obtained with a selectivity of 95% and higher. The proposed method significantly simplifies the process technology in comparison with the known method by using an available catalytic system and shortens the process time from 10-30 hours to 1-5 hours.
    权利要求:
    Claims (1)
    [1]
    Invention Formula
    The method of producing u-2-dihydromuconic acid methyl ester by catalytic dimerization of methyl acrylate in an organic solvent medium at 50-190 ° С in the presence of a palladium-containing catalyst, which is used in order to simplify the process technology, consisting of palladium (II) dibenzylidene acetonate or palladium (III) dibenzylidene and tonate palladium (III), or a mixture thereof, or palladium (II) acetylacetonate, or palladium (II) acetate and tributyl phosphonium with tetrafluoroboric acid, or hydrotributyl phosphono dimes of the fluorofibrate, if necessary with the addition of tetrafluoroboric acid, and the process is carried out at a molar ratio of osfor: palladium of 1: 1-4 and at a molar ratio of hydrogen ion: palladium ion of 1: 1-10, while the catalytic system is dissolved in diethyl furi,
    v
    Table 1
    94 95 95 94 95 94 95 96 96 95 95 96
    4574168
    Example
    Table H J 00 P / Pd
    8 Continuation of table 1
    Spreadsheets
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    同族专利:
    公开号 | 公开日
    JPH0548218B2|1993-07-20|
    JPS6317845A|1988-01-25|
    EP0243281A3|1989-03-29|
    DE3776387D1|1992-03-12|
    FR2596390A1|1987-10-02|
    US4889949A|1989-12-26|
    AT72225T|1992-02-15|
    FR2596390B1|1989-02-17|
    ES2028121T3|1992-07-01|
    EP0243281B1|1992-01-29|
    EP0243281A2|1987-10-28|
    US4786623A|1988-11-22|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    DE2104626C2|1970-02-09|1982-07-29|Mitsubishi Chemical Industries, Ltd., Tokyo|Process for the preparation of an addition product of a conjugated diene and a compound having a terminal vinyl group|
    US4243829A|1976-10-04|1981-01-06|Charles U. Pittman, Jr.|Production of 1,7-octadiene from butadiene|
    US4318860A|1979-09-28|1982-03-09|Atlantic Richfield Company|Preparation of unsaturated monester precursor for pelargonic acid|
    US4501822A|1982-01-26|1985-02-26|Celanese Corporation|Hydroesterification of 1-alkene|
    FR2524341B1|1982-03-31|1984-10-12|Centre Nat Rech Scient|
    US4519954A|1982-12-29|1985-05-28|The Standard Oil Company|Leach resistant catalyst useful for the dimerization of acrylic compounds|
    US4451665A|1982-12-30|1984-05-29|E. I. Du Pont De Nemours And Company|Process for dimerizing acrylates and methacrylates|
    DE3336691A1|1983-10-08|1985-04-25|Studiengesellschaft Kohle mbH, 4330 Mülheim|METHOD FOR THE CATALYTIC DIMERISATION OF ACRYLIC ACID DERIVATIVES AND USE OF THE DIMERS RECEIVED|
    GB8428347D0|1984-11-09|1984-12-19|Shell Int Research|Dimerization of olefins|FR2619564B1|1987-08-19|1989-12-08|Rhone Poulenc Chimie|IMPROVEMENT IN THE CATALYTIC DIMERIZATION PROCESS OF AN ALKYL ACRYLATE|
    FR2652514A1|1989-06-22|1991-04-05|Rhone Poulenc Sante|NEW PALLADIUM-BASED CATALYST AND ITS USE.|
    US5099048A|1990-09-11|1992-03-24|The University Of North Carolina At Chapel Hill|Rhodium-catalyzed olefin dimerization|
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    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    FR8604644A|FR2596390B1|1986-03-27|1986-03-27|CATALYTIC DIMERIZATION PROCESS OF A LOWER ALKYL ACRYLATE AND CATALYTIC COMPOSITION|
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