• 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 a method for producing β-keto esters of the general formula (I) @ (II) @, used as intermediates in the synthesis of vitamin E. The purpose of the invention is to simplify the process technology. Fraction C 15 isoprene oligomers containing β-Farnesina formula @ (III), cyclic trimers of isoprene and linear trimers of formula @ (IV), is treated with a complex β-ketoester of the formula CH 3 CO COOR (Rvezde - CH 3, C 2 H 5) in the presence of a catalytic system, which consists of: a) three (metasulfophenyl) phosphine sodium salt; b) [RHCL (1,5-cyclooctadiene)] 2 ; c) NA 2 CO 3 The ratio of P 3+ / RH in the system is 4.67-7.9. The amount of RH in the solution is 8.25-10.3 mg-atom / 1 L, and the molar concentration of NA 2 CO 3 is 47.5-94.5 mmol. Upon completion of the reaction, compounds (I) and (II) are separated from unreacted cyclic trimers and linear trimers (IV) by distillation.
    公开号:SU1521280A3
    申请号:SU843703904
    申请日:1984-02-23
    公开日:1989-11-07
    发明作者:Морель Дидье
    申请人:Рон-Пуленк Санте (Фирма)；
    IPC主号:
    专利说明:

    31521280
    tylacetoacetate (92.8 mmol) and 6.7 / 4 g lots, then 100 CM pentafraction Cn containing 2.58 g pean is added. After stirring until decolorizing and dissolving pyridine in water, the reaction mixture is decanted. The organic layer is concentrated. Thus, 21.5 g of an organic layer is obtained, containing 5.24 g of toluene, 2.45 g of fraction C, n, 10.61 g of fraction containing 4.77 g of product of formula (I) and 3.20 g heavy products (as analyzed by gas phase chromatography).
    genes of formula (I) (12.65 mmol),
    2.7 g olefsyuv formula (II),
    (13.2 mmol) and 1.46 g of trimethylcyclododecatrienes.
    Heat at 80 ° C with stirring for 16 hours. After separating the aqueous phase containing the catalyst by decantation, 7.98 g of the organic phase, devoid of methyl acetylacetate and containing 0.26 g of the reagent of formula (O,
    2.7 g of olefins of the formula (II), 1.46 g of trimethyl cyclododecatriene, 3.57 g of an equimolar mixture of products a and a
    formulas
    , (, n, -, - ats-ss-ss-ss-ss ss
    SOOS.Z
    pine
    -СН -С СЫ-С11, .сн.
    sn
    sosk
    which corresponds to a conversion of 1 equal to 90%, methyl acetylacetate 12%, the selectivity in (a) + (a) is 98%.
    The obtained organic phase is subjected to distillation under reduced pressure (1.5 mm Hg; 0.2 kPa). Thus, 4.1 g of a mixture of reagents of the formula (1), which unreacted, from the olefin of the formula (II) and trimethylcyclododecatriene (BP. 93-), 3.35 g of a mixture of products a and a (BP. 150 C).
    Fraction C, 5 can be obtained as follows.
    In a flask with a capacity of 100 cm, previously purged with argon, is introduced 1.28 g of nickel acetylacetonate (5 mmol) as a 4% solution in toluene, 15.7 g of pyridine (0.2 mol)
    and 10 smesoprene (0,1-f.
    mole). After
    cooling to -10 ° C is slowly added; 15 mmol of triethaluminium 1L1 () ,, 3 are added as a solution in toluene. The solution, originally colored turquoise blue, becomes chestnut-colored, then red after warming to 20 ° C.
    This catalytic solution is introduced into a cylindrical reactor made of stainless steel with a capacity of 125 cm, containing 90 cm of isoprene (0.9 mol). The mixture is heated with stirring at 80 ° C for 8 hours.
    After cooling, the reaction mixture is poured into 100 cm 3 n. salty kitty
    lots, then add 100 CM penta
    0
    0
    five
    five
    five
    on . After stirring until decolorizing and dissolving pyridine in water, the reaction mixture is decanted. The organic layer is concentrated. Thus, 21.5 g of an organic layer is obtained, containing 5.24 g of toluene, 2.45 g of fraction C, n, 10.61 g of fraction containing 4.77 g of product of formula (I) and 3.20 g of t desired products (according to analysis by gas chromatography).
    By distillation, 6.74 g of the C fraction C, containing 2.58 g of the product of formula (I), is obtained.
    Example 2. Into a stainless steel autoclave, previously pro-argon, add 0.0408 g of RhCl (1,5-cyclooctadiene) 1 (0.165 mg-atom of rhodium), 0.613 g TPPTSNa (0.80 mg-atom of P ) 0.2 g (1.89 mmol), 15 cm of water and 5 cm of methanol.
    Then 11.08 g of methyl acetylacetate (95.5 mmol) and 14.46 g of fraction C., 5 containing 4.9 g of reagents of formula (I) (24 mmol), 6.66 g of olefins of formula (II) (32 , 6 mmol) and 2.6 g of trimethylcyclododecatrienes.
    Heat 14 hours with stirring at 80 ° C. After separation by decantation containing the aqueous phase catalyst, 16.6 g of the organic phase containing 0.78 g of the reagent of formula (I), 6.66 g of olefins of formula (II), 2.9 g of trimethyl cyclododecatriene, 6.26 g are recovered. an equimolar mixture of products a and a, which corresponds to a conversion of 1 equal to 84%, methyl acetylacetate 20.5%, selectivity in (a) + (a) is 75%.
    The organic phase is subjected to distillation under reduced pressure (1.5 mm Hg, 0.2 kPa) under the same conditions as in Example 1. In this way, 6.1 g of equimolar is obtained.
    0
    0
    0
    five
    mixtures of products aa aa (tk).
    Example 3. 0.0504 g of HhCl (1,5-cyclooctadiene) 32 (0.206 mg is a rhodium atom), 0.6 g of TPFTSIIa (o, 96) are successively introduced into a stainless steel reactor with central agitation, previously purged with argon. mg- atom P, 0.101 g ,, (0.95 mmol), 15 cm of water and 5 cm of methanol.
    Then, 6.29 g of methyl acetylacetate (140.43 mmol) and P are added, 84 g
    5, 1521280
    fractions C ,,) containing 1.47 g olefins, where R CH,
    C, jHN (isoprene dimers) and 4.14 g of olefins of formula (II), and trimethylcyclododocatrienes. Heated at 80 ° C with stirring for 16 hours.
    After separation by decantation of the aqueous phase containing the catalyst, 14.62 g of the concentrated organic phase containing 1.07 g of olefins C, with H, j, 1, 25 g of reagent of formula (I), 4.14 g of olefins of formula (II) are recovered "Trimethylcyclododecatrienes, 8.16 g of an equimolar mixture of products a and a, corresponding to a conversion degree of 1 equal to 80.7%, methyl acetate, 18.1%, selectivity in (a) + (a) is 95%.
    The organic phase is subjected to distillation under reduced pressure (1.5 mm Hg, 0.2 kPa). Thus, 7.95 g of equimopleculus p10 are obtained.
    20
    by interacting
    mules
    CH
    AND
    С 1 (3 Н - j СН
    with complex r-ketoph
    where R is indicated at a temperature of 80 n solvent, in an amount of 25 vol., the catalytic system is sodium salt three 15 phosphines, (1.5 and sodium carbonate, the effective medium is 8.25-10.3 mg and sodium carbonate in radios of 47.5-94.5 mm, which are produced by the technology of the new source technology - pharnesisation With oligomers, besides the pharm trimers and linear
    mixture of products 150 C).
    a and a- (t.kip.
    权利要求:
    Claims (1)
    [1]
    Invention Formula
    The method of producing complex -keto esters of the general formula
     COCHj
    С „К, т-С11.-С-СЫг-СН, -СЬЬ QQj, (I) and formulas
     Ssn,
    thirty
    where R has the indicated value, at a temperature in a water-methanol solvent containing methanol in an amount of 25 vol%, and in the presence of a catalytic system containing sodium salt three (metasulfophenyl) - 15 phosphine, (1,5-cyclooctadiene) and carbonate sodium, the ratio is 4.67-7.9, the reactive medium contains rhodium in the amount of 8.25-10.3 mg-atom / 1 l solution and sodium carbonate in a molar concentration of 47.5-94 , 5 mmol, characterized in that, in order to simplify the process technology, the C-oligome fraction C is used as the source of pharnesine. isoprene esors containing, in addition to α-farnesine, cyclic trimers and linear trimers of the formula
    I C 1, H, -, -CH J,
    (Iv)
    S1TS
    C, (, H 17 —CH, j — C CH — CH —CH
    COOR
    followed by separation by distillation of the desired products of formula (II) (I) and (II) from cyclic trimers and these linear trimers of formula (IV).
    by interacting p-farnesine for
    CH
    AND
    C 1 (3 H - j CH 2 C Cii Cn.-2.
    (Ill)
    with a complex p-ketoester formula
    CH COCH COGPv,
    where R has the indicated value, at a temperature in a water-methanol solvent containing methanol in an amount of 25 vol%, and in the presence of a catalytic system containing the sodium salt three (metasulfophenyl) phosphine, (1,5-cyclooctadiene) and carbonate sodium, this ratio is 4.67-7.9, the reaction medium contains rhodium in an amount of 8.25-10.3 mg-atom / 1 l of solution and sodium carbonate in a molar concentration of 47.5-94.5 mmol, characterized in that, in order to simplify the process technology, the C-olig fraction is used as the source of α-pharnesine isoprene omers containing, in addition to α-farnesin, cyclic trimers and linear trimers of the formula
    thirty
    I C 1, H, -, -CH J,
    (Iv)
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    同族专利:
    公开号 | 公开日
    EP0118354B1|1985-10-23|
    EP0118354A1|1984-09-12|
    CA1208662A|1986-07-29|
    DE3460008D1|1985-11-28|
    FR2541675B1|1985-06-14|
    JPS59163326A|1984-09-14|
    JPH0380130B2|1991-12-24|
    FR2541675A1|1984-08-31|
    US4621165A|1986-11-04|
    AT16175T|1985-11-15|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US2402954A|1943-04-30|1946-07-02|Socony Vacuum Oil Co Inc|Separation of isomeric paraffins|
    US2506289A|1948-10-05|1950-05-02|Standard Oil Dev Co|Process for the sepoaration of isomers|
    US3031515A|1959-12-18|1962-04-24|Scient Design Co|Process for purifying isoprenes|
    US3998872A|1970-10-05|1976-12-21|Universal Oil Products Company|Preparation of unsaturated carbonyl compounds|
    FR2486525B1|1980-07-10|1982-10-29|Rhone Poulenc Sante|
    DE3163383D1|1980-07-10|1984-06-07|Rhone Poulenc Sante|Process for the selective addition of a compound having an activated carbon atom to a substituted conjugated diene|FR2657871B1|1990-02-08|1993-02-05|Rhone Poulenc Sante|PROCESS FOR THE PREPARATION OF TERPENIC KETONES.|
    ES2764153T3|2014-04-30|2020-06-02|Basf Se|Procedure for the preparation of farnesilacetone|
    CN105859534A|2016-04-07|2016-08-17|能特科技有限公司|Method for synthesizing ketone compounds by continuous cyclic catalytic reaction|
    CN111032636A|2017-09-04|2020-04-17|帝斯曼知识产权资产管理有限公司|6-chromanol derivatives and synthesis thereof|
    WO2019121134A1|2017-12-20|2019-06-27|Dsm Ip Assets B.V.|Synthesis of alkyl 2-acetyl-5,9,13-trimethyltetradeca-4,8,12-trienoates and derivatives by a non-continuous production process|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    FR8303002A|FR2541675B1|1983-02-24|1983-02-24|CHEMICAL PROCESS OF PURIFYING A MIXTURE OF ISOPRENE TRIMERS|
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