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    • 专利摘要:
    The invention relates to chlorine-containing compounds, in particular new chlorine-containing α-ketoesters of the general formula (I): R20 (0) C Cl-C-CH2. -CH (ROC-CH3 HzCo) with U -CH2-CH2 (where R is methyl or 4-mets-1 -3-pentenenyl; Rj-C, alkyl, which are new intermediates in the synthesis of pseudo-ionone, which is used to produce vitamin A. Compound (I) is obtained by c: credits of compounds of the general formula (II): H3C (0) C) CH — CH2. (RiVCH3. i O) t {20 (0) C 1L SNCHY. / CH-CH2-CH2CIR. R OCOlC where R, and R2 is as defined above, with CuCl j in the presence of LiCl at their molar co 1: 2.35-20: 1-4, respectively, in dimethylformamide or N-methylpyrrlidone at 20 C. The degree of conversion of the starting mixture is 95%, the selectivity over the target mixture of ketoesters is 100%. o; o) UD eo CN
    公开号:SU1299498A3
    申请号:SU823521251
    申请日:1982-12-17
    公开日:1987-03-23
    发明作者:Морель Дидье
    申请人:Рон-Пуленк Санте (Фирма)；
    IPC主号:
    专利说明:

    11299498
    The invention relates to organic synthesis, specifically to a method for producing a mixture of new chlorine-containing p-keto ester, which are intermediate in the synthesis of pseudo-ionone, which 5 is used for the production of vitamin A.
    The purpose of the invention is the creation of new intermediates in the synthesis of pseudoionone mixtures of chlorine-containing p-ketoesters, which allow to increase its yield (Na,) and (Hb,).
    Example. Chlorination of compounds of the formulas
    CH. SNL
    , С. СНССНз
    sn

    sn
    SNG
    /
    / h
    sn.
    SOOSNz
    pine,
    : oosnz
    with .sn,.
     // СН СНг С-С1 I 1V
    ,
    CH-i CH-j
    (Ib.) 55%
    bp at 0.027 kPa (mixture) the content in the mixture of chlorine is 12.4%; the degree of conversion of the mixture (But,) and (Hb,) is 95%; 100% selectivity.
    The structure of the compounds (1,) and (Ib,) is confirmed by the data of mass, NMR and IR spectra.
    NMR spectrum (in CDCl4, with hexamethyl disilane as ethanol). The numbers indicate chemical shifts in ppm. corresponding atoms
    / nf
    sn
    SOCNs
     SOOCH-:
    JC. Sn, COCH
     / vf X
    SN sn C-HSE
    SNG.SOOSNz
    T: HI CHi
    (la,) 45%
    . (Ila.) 48%
    SN-CH-i
    v

    (JH CH2, C
    CH2 CH; i
    (lib,) 52%
    to a mixture of 32.3 g of divalent copper chloride (0.24 mol) and 5.1 g of lithium chloride (0.12 mol), 24.66 g of a mixture of compounds (Ha,) and (lib,) (0.102 mol). The reaction mixture was incubated for 91 h at 20 ° C. The reaction mixture is then diluted with 600 cm of water. The precipitated cupric chloride was separated by filtration, after which the reaction mixture was extracted twice with 50 cm of pentane. After drying the organic portion on the sulfate and concentrating under reduced pressure, 28.39 g of a mixture of compounds (1a,) and (Ib,) are obtained, the purity of which is close to 95% and which has the following characteristics:
    CHj CHj
    2.27
    5.02
    2.29
    40
    35
    COCH3 C1
    - SOOSNz
    45
    - g, 70 3.76 A mixture of the starting compounds (Ha,) and (Hb,) is obtained as follows.
    Into a stainless steel reactor, preliminarily purged with argon, 40.8 mg of KHB 01 (1.5–1C1Cloooctadienes) ,, (0.165 gatom rodi), 2.2 g of compound
    (or TPRT SNa)
    50
    55
    (3 „256 gatom P), 78.2 mg sodium carbonate (0.68 mmol), 15 cm of water and 5 cm of methanol. Then, 15.92 g of myrcene (0.117 mol) and 13.9 g of methyl acetylacetate (0.120 mol) are introduced.
    Heating is carried out with stirring at 90 ° C for 1 hour.
    After treatment of the reaction mixture, 12.488 g of a mixture of compounds is obtained.
    31299498
    If heating is carried out at 100 ° C for 5 hours, the yield is increased to 72.7%. Example 2. Hporyirovanie mixture of compounds (Ia,) and (lib,)
    S W SOSNz W W CH Sho .N
     v
    Ш2 СН
    (On.) 45%
    Shz CHj
    V III, COCHN CH Pcs. CH
    CH / C COOCzHs
    I7.SH7.
    (Pb) 55%
    To a mixture of 120 g of divalent copper chloride (0.89 mol) and 17 g of lithium chloride (0.4 mol) in 300 cm of N-methylpyrrolidone was added 107 g of a mixture of compounds (Ia) and (Ilb) (0.102 mol). the mixture was kept at 20 ° C for 90 hours. Then the reaction mixture was diluted with two liters of cold water. The precipitated bivalent copper chloride is separated by filtration, after which the reaction mixture is extracted twice with 200 cm of pentane. After drying the organic phase on sodium sulfate and concentrating under reduced pressure, 119 g of a mixture of compounds (iQz) and (Ib) is obtained, the purity of which is close to 92% and which has the following characteristics:

    ,
    oj
    i / GOCHj C-Cl
    (IQ) 45%
    five
    0
    0
    Shz Sh
     , / COCH3 W SNO C-C1
    I I
    t / s
    CHT, CH-i
    (Ib,) 55%
    boiling point at 0.027 kPa (mixture) 129. ° С, chlorine content (mixture) 11.8%.
    The Ct eneHb conversion of the mixture of compounds (IIa, j) and (Ilbj) is 91%, the selectivity for compounds (IQ) and (Xb) is 100%.
    A mixture of compounds (Er,) and (B) is prepared as follows
    In a reactor made of stainless steel, previously purged with argon, 100 mg of RhCl (1,5-cycloooctadiene) (0.41 g of rhodium mat), 0.78 g of TPa SNa (1.15 g of mat , 0.156 g of sodium carbonate (1.5 mat) and 30 cm of water. Then 8.8 g of myrcene (64.7 mmol) and 16.5 g of ethyl acetylacetate (127 mmol) are added. With stirring, the mixture is heated to 100 ° C within 6 hours. After treatment of the reaction mixture, 12.66 g of a mixture of compounds (llQj) and (II bj) are obtained.
    Example 3. Chlorination of a mixture of compounds (Na,) and (Ilbj)
    0
    W u
    sleep
    :BUT
    I
    С02СНз
    Shz
    Sn / O
    g ii
    % n
    SOG
    45 I
    (Ilq,) 40%
    (lib,) 60%
    to a mixture of 32.3 g of bivalent copper chloride (0.24 mol) and 5.1 g of chloride
    50 lithium (0.12 mol) in 100 cm of N-methyl-pyrrolidone added 18.87 g of a mixture of the compounds (Ha,) and (Ilb) (0.102 mol). Maintain the reaction mixture at 20 ° C for 27 hours. After treatment
    55 of the reaction mixture, as in Example 1, 21.57 g of a mixture of compounds (loj) and (Ib,) are obtained, the purity of which is close to 88%, having the following characteristics:.

    sn
    CIS
    /
    sn,
    about
    II
    with
    X
    BUT
    about

    ccf
    (IP) 40%
    Shz
    SNT, with /
    CC1 CH3
    SOG
    (Ib,) 60%
    bp at 0 „067 kPa (mixture) the chlorine content (mixture) is 16.2%.
    The degree of conversion of the mixture of the compounds of 5 II (Na,) and (II bO is 88%, the selectivity of the compounds (1a,) and (I b) is 100%, the yield of crude product is 96.8%, and the pure product is 5.1% .20
    Compound mass spectrum
    five
    Sh
    SOSNg P1
    sooss
    ttz-
    IR spectrum: С CH 3080 С О: 1735
    WITH
     CH2 890 cm
    1755 cm
    A mixture of compounds (On,) And (Hb,) can be obtained as follows. I
    U) A stainless steel reactor, previously purged with argon, is injected with 20.8 mg of Rh C1 (1.5–1 ohccooctadiene) .2 (0.085 g of mother-water), 0.24 g of sodium carbonate (2.2 mmol) ,, 1,128 g of TPa SNa (1.7 g) F / and 15 cm of water. Then 10,, 2 g of isoprene (150 mmol) and 21.6 g of methyl acetylacetate (186 mmol) are introduced. The reaction mixture is heated with stirring and at 100. C for 1 hour. After treating the reaction mixture, 15.85 g of a mixture of compounds (Ha,) and (HbE) are obtained. Yield 58.37%.
    Example 4. Chlorination of the mixture
    - 5 20
    2994986
    20 ° C for 70 hours. After processing the reaction mixture in Example 1, 5.26 g of a mixture of compounds having the formulas (IQ) and (Ib,) purity, which is close to 60% and which has the following characteristics: (1a,) 45%; (IbJ 55%.
    The degree of conversion of the mixture of compounds (Na) and (lib) is 62%. The j selectivity of the compounds (Iq) and (1b) is 100%. The characteristics of the product are given in Example 1. The yield to the initial mixture is 91.7% (crude product) or 55.1% (pure product).
    Example 5. K1g chloride ShШ
    25
    Ti (0.0235 mol) in 10 cm of N-methylpyrrolidone and 0.18 g of water (0.010 mol) added 2.56 g of a mixture of compounds having the formula (1 °) and (Ib,) obtained in Example 1 (8.5 mmol). The mixture was kept in an inert atmosphere of argon, after which it was heated to 100 ° C for 45 minutes while being transferred. Thus, it happens).
    thirty
    dits complete decarboxylation. Heating is then continued for 17 hours at the same temperature. After treating the reaction mixture by adding 30 cm of water, extracting the compounds with 20 cm of pentane and removing pentane under reduced pressure, 1.83 g of a mixture containing, according to chromatographic analysis carried out in the gas phase, 35.559 g (yield 34.25%) of pseudo-ionone are obtained, 0.34 g of a mixture of compounds having the formulas (I, IIa) and (I, IIb), in which R is 4-methyl-3-pentenyl, and 0.6 g of the heavy compounds not eluted by chromatography. .Kip. pseudo-ionone 124-126 C (4 mm Hg). NMR spectrum of proton pseudo-ionone 1.62
    7.36 "
    2.22 6.01
    40
    45
    1,1) it
    5.00
    50
    NMR spectrum of proton deacylated compound
    (On.) And (HL,). RPPGN
    To a mixture of 5,, 38 g bivalent chloride- (CHILDREN. S
    Copper (0.40 mol) and 0.87 g of lithium hydrogen chloride (0.020 mol) in 20 cm of dimethylformamide were added 5.1 g of a mixture of compounds (Ha,) and (HbJ (example 1) (0.020 mol) The mixture is kept at
    55
    C1
    SOOSNz)
    C1
    55
    C1
    SOOSNz)
    C1
    1.62
    1.53 2.68 g,
      2.57
    11th,
    1 3.71 1.57
    OSSN
    2
    3.73
    Example 6. KO, 46 g of lithium chloride (0.0108 mol) in 5 cm of S-methyl-pyrrolidone and 0.3 g of water (0.0166 mol) were added 3.14 g of a mixture of compounds (IQ) and (1b ,), obtained in example 1 (0.011 mol). The mixture is heated at 105 ° C for AO minutes. In this way
    Example 7. KO, 5 g of lithium chloride 5 (11.7 mmol) in 5 cm of N-methyl-pyrrolidone, containing 0.49 g of hydrochloric acid (13.4 mmol), was added 2.64 g of a mixture of compounds (1a ,) and (1b) obtained in Example 1 (9.2 mmol). 20 The mixture is heated to t. 105 ° C for 2 h 30 min. After treatment of the reaction mixture, 1.025 g of a mixture of compounds (Illa) and (111b), (4.5 mmol) is obtained (yield 48.91%). Watching education
    the reaction mixture contains 1.87 g
    ,, „/ -tttt N 25 of the degradation compound, the degree of deaci (0.0082 mol) of the mixture of the compound (Ilia)„ „“ 1 ...%
    and (SH). The yield is 74.5%.
    Li is close to 5%.
    Example 8. KO, 5 g of lithium chloride (11.7 mmol) in 5 cm of N-methyl-pyrrolidone, containing 0.13 g of salt III

    sn
    / sn
    SNS1-Susn, Sn Sn
    (llla) 45%
    with Sin SNG SNSO-SNz
    I I / s
    CH2 CHi
    (Illb) 55Wo
    .kip. at 0.054 kPa (mixture) 93 ° C. The degree of deacylation is close to 25%. NMR spectrum of proton g
    : A 1. month
    (with
    2.2} U
    , 99
    2.26
    Example 7. KO, 5 g of lithium chloride (11.7 mmol) in 5 cm of N-methylpyrrolidone, containing 0.49 g of hydrochloric acid (13.4 mmol), was added 2.64 g of a mixture of compounds (1a, ) and (1b) obtained in Example 1 (9.2 mmol). The mixture is heated to t. 105 ° C for 2 h 30 min. After treatment of the reaction mixture, 1.025 g of a mixture of compounds (Illa) and (111b), (4.5 mmol) is obtained (yield 48.91%). Watching education
    "" "one...%
    Li is close to 5%.
    Example 8. KO, 5 g of lithium chloride (11.7 mmol) in 5 cm of N-methylpyrrolidone, containing 0.13 g of hydrochloric acid (3.6 mmol), was added 2.6 t g of a mixture of compounds (1a ,) and (1b (), obtained in Example 1, (9.2 millimole). The mixture is heated to 130 ° C with stirring for 2 hours. Observation 5 K) T is complete decarboxylation for 15 minutes. After treatment, the reaction mixture is obtained at a yield of 40.5%, 0.716 g of pseudo-ionone (so kip. 124-126 ° C / 4 mm Hg). The stump of the deacylation is about 5%. About 28% of heavy compounds not eluted at BHC were formed.
    The pseudo-ionone selectivity is 57.4% with the degree of dehydrochlorination,
    5 equal to 70.6%.
    Example9. K5.0g lithium chloride (11.7 mmol) in 5 cm of N-methyl-pyrrolidone, containing 0.19 g of hydrochloric acid (5.7 mmol), is added
    0 2.22 g of a mixture of compounds (Iq) and (1b) obtained in Example 1 (9.5 mmol). The mixture was held under argon atmosphere, then heated to 140 ° C for 1 hour with stirring. A total decarboxylation is observed for 15 minutes.
    After treating the reaction mixture, a yield of 40% is obtained, 0.734 g of pseudo-ionone (so kip. 1241299498
    126 ° court mm of mercury.). The degree of deagglomeration is close to 5%. About 18% of heavy compounds of non-eluted at BHC were formed.
    ABOUT
    The pseudoionone selectivity is 75.5% with a dehydrochlorination degree of 92.4%.
    Example 13. K Oh, 5 g of chloride
    The selectivity of a pseudo-ionone compound is lithium (11.7 mmol) in 20 cm of N-methyl 60 j6% with a degree of dehydrohalogenation of 66%.
    Example 10. KO, 5 g of chloride
    pyrrolidone containing 0.45 g of hydrochloric acid (12.3 mmol) was added g of the mixture of compounds (la) and (Ib) obtained in Example 1 (9.4 mmol).
    pyrrolidone containing 0.44 g of salt -) 0 Then the mixture is heated to 150 seconds in teic acid (12 mmol) for 2 hours and 30 minutes with stirring.
    lithium (11.7 mmol) in 5 cm N-methylate 1.27 g of 2,4,6-trimethylpyridine (10.5 mmol) and 2.58 g of a mixture of compounds having the formulas (iQ,) and (Ib,), obtained in example 1 (9 mmol). The mixture is then heated to 130 ° C. for 4 hours with stirring. Full decarboxylation is observed for 15 minutes. After treatment, the reaction mixture is obtained at a yield equal to 52.5%, 0.909 g of pseudoionone (t, bale 124-126 ° C / 4 mm Hg). The degree of deadylation is less than 1%. 06
    About 2.5% of the yellow compound formed in Example 13, however, the addition of 5 1.26 g of 2,4,6-trimethylpyridine (10.5 mmol) and 2.55 g of a mixture of compounds (Ict | ) and (1b) obtained in Example 1 (8.9 mmol). Obtained with a yield of 71.2% 1.218 g pseudoionone
    Research institutes not eluted at BHH.
    The pseudo-ionone selectivity is 90% with a dehydrochlorination degree of 58.1%.
    Example 11. To 0., 5 g of chloride 30 (BP. 124-126 ° C). lithium (11.7 mmol) in 10 cm of N-methyl The degree of deacylation is less than 1%. pyrrolidone, containing 0.46 g of salt - About 11% of heavy compounds were formed. hydrochloric acid (12.6 millimoles), applications not eluted by BHH. Bavly 1.26 g of 2,456-trimethylpyridine Selectivity of a pseudo-ionone is (10.5 mmol) and 2.70 g of a mixture of 35.3% with a degree of hydrochlorination (1a) and (1b,) e obtained in 97.2%. measure 1 (9.4 mmol). The mixture is then heated to 130 ° C. for 8 hours with stirring. Full decarboc was observed. Example 15 Repeat the procedure of Example 13, however 2.83 g of 2,4,6-trimetramylpyridine are added.
    Example 15. Repeat the procedure of example 13, however, 2.83 g of 2,4,6-trimethylpyridine are added.
    xylation for 15 min. After 40 (23.3 millimoles) and 2.66 g of the mixture to co-process the reaction mixture, yields having the formula (Id,) are obtained, and at a yield of 59.7%, 1.069 g of pseudoionone (bp 124-1 26 ° C / 4 mm Hg).
    The degree of deacidation is less than 1%.
    (j.b,), obtained in example 1 (9.3 millimoles). A yield of 76.2% yields 1.366 g of pseudo-ionone (t, kip. About 12% of heavy compounds of 4.5 24-126 ° C / 4 mm Hg, Art.) Are formed by non-eluted research institutes (according to BHH). The degree of deacylation is less than 1%.
    The selectivity of pseidononon is equal to 62.5% with a degree of dehydrochlorinated. About 12.5% of heavy compounds not eluted by BHC are formed.
    The pseudo-ionone selectivity is equal to 797, with the degree of dehydrochlorination, indicated in Example 11, however, 96 5%,
    use 20 cm of N-MeTminHppoj fflOHa, Example 16, Repeat:
    According to Example 13, however, 4.25 g of ethyldicyclohexa-55 silamine (22.7 mmol) and 2.66 g of a mixture of compounds having the formulas (Iq,) and (1b,) obtained in Example 1 are added. (9.3 mmol).
    nor equal to 95.50%.
    Example 12. Repeat
    When the yield is 69.7%, 1.274 g of pseudo-ionone (t, kip. 124–126 C / 4 mm Hg).
    The degree of deacylation is less than 1%. About 9% of non-eluted heavy compounds (BHH) are formed,
    ABOUT
    The pseudoionone selectivity is 75.5% with a dehydrochlorination degree of 92.4%.
    Example 13. K Oh, 5 g of chloride
    Full decarboxylation is observed for 10 minutes. After treatment, the reaction mixture gives, at a yield of 28.2%, 0.509 g of pseudo-ionone (bp 124–12b).
    The degree of deacylation is less than 1%. About 10.5% of heavy compounds not eluted by BHC are formed,
    The pseudo-ionone selectivity is 29.3% with a dehydrochlorination degree of 96.2%.
    Example 14. Repeat dei (bp. 124-126 ° C). The degree of deacylation is less than 1%. About 11% of heavy compounds not eluted by BHC were formed. The pseudo-ionone selectivity is 3.2% with a dehydrochlorination degree of 97.2%.
    Example 15. Repeat the procedure of example 13, however, 2.83 g of 2,4,6-trimethylpyridine are added.
    (23.3 millimoles) and 2.66 g of a mixture of compounds having the formula (Id,) and
    one
    With a yield of 77 4%, 1.385 g of pseudo-ionone is obtained (boiling point 12A-126 ° C / 4 mm Hg).
    The degree of deacylation is less than 1%. About 1% of heavy compounds not eluted by BHC are formed.
    The pseudo-ionone selectivity is 85.7% with a dehydrochlorination degree equal to 90.4%.
    Example
    17. To 0.5 g
    chloride
    1.29 g of 2,4,6-trimethylpyridine (10.6 mmol) and 1.94 g of a mixture of compounds having the formulas (lllo) and ( IIIb) obtained in example 6 (8.5 mmol). The mixture is heated to 150 ° C. 1.44 g of pseudo-ionone is obtained at 88% yield (boiling point 124-126 ° C / 4 mm Hg)
    About 6.5% of heavy non-eluted TIZH compounds are formed.
    The selectivity of pseudo-ionon is 94.6% with a dehydrochlorination degree of 93%.
    Example 18. The procedure of Example 13 is repeated, however, 4.82 g of ethyldicyclohexylamine (23 mtoma) and 2.70 g of a mixture of compounds having formula (la) and (Ib) obtained in example 2 (9 mmol) are added. .
    When the output 79,9% 1,377 g of pseudo-ionone.
    The degree of deacylation is less than 1%. About 2% of heavy compounds not eluted by BHC are formed.
    The selectivity of the formation of pseudonon is 90.2% with a dehydrochlorination degree equal to 88.6%.
    Example 19. To 0.5 g of lithium chloride (11.7 mmol) in 20 cm of tetramethyl urea containing 0.5 g of hydrochloric acid (13.7 mmol), 2.72 g of a mixture of compounds having the formula (Id, ) and (1b |), obtained in example 1 (9.5 mmol). The mixture is then heated under stirring for 2 hours and 30 minutes. Full decarboxylation is observed in 15 minutes. After treatment, the reaction mixture is obtained at a yield of 55.9%, 1.0 g of pseudo-ionone (so kip. 124-126 C / 4 mm Hg)
    The degree of deacylation is less than 1%. About 5% of heavy compounds not eluted by BHC were formed.
    Pseudo-ionone selectivity is 80% with a dehydrochlorination degree of 68.4%.
    Example 20. KB, 45 g of lithium chloride (0.15 mol) in 250 cm N-me
    1299498
    12

    of tilpyrrolidone containing 5.77 g of hydrochloric acid (0.16 mol), 64.52 g of ethyldicyclohexylamine (0.31 mol) and 32.77 g of a mixture of the scientific research institute (IQ) and (1B) obtained in Example 3 (o, 15 mol). The mixture is then heated to 150 ° C. for 3 hours 30 minutes with stirring. See complete decarboxylation in 10 min. After treating the reaction mixture, 75.5% yield 14.237 g of methylheptadiene of formula (IVa)



    sleep
     And jn j:
    Sn
    The degree of deacylation is less than 1%. About 7% of heavy non-capped compounds were formed during BHH.
    The selectivity of methylheptadiene (IVa) is 79% with a dehydrochlorination degree of 95.6%.
    Example 21 KO, 5 g of chloride lithium (11.7 mmol) in 20 cm of dimethylformamide containing 0.42 g of hydrochloric acid (11.5 mmol) were added 4.18 g of ethyldicyclohexylamine (20 mmol) and 2 , 72 g of a mixture of compounds having the formulas (1a,) and (1b,) obtained in Example 1 (9.5 mmol). Then the mixture is heated at a temperature of 15 ° C for 2 hours and 30 minutes with stirring. Full decarboxylation is observed in 15 minutes. After treatment, the reaction mixture is obtained at a yield equal to 59.3%, 1.079 g of doionone (bp 125-126 C / 4 mm Hg).
    The degree of deacylation is less than 1%. About 6.5% of the heavy compounds not eluted at BHC are formed.
    The selectivity of pseudo-ionone is 80% with a dehydrochlorination degree of 74.1%.
    权利要求:
    Claims (1)
    [1]
    Invention Formula
    The method of obtaining a mixture of chlorine containing -ketoesters of the general formula
    R.
    / pine
    COOR.
    131299498 14
    / SOSSCH pH / pine
    II U,
    U f C-ClnL COOR, L
    R, OOR. ".- -
    GDH Cd and R have the indicated values
    where K is methyl or 4-metsh1-3-pentenyl, is reacted with e CuCl in
    R - c. - C.4 - alkyl, in the presence of LiCl at their molar cobalt and with the fact that the ratio is 1 ;; 2.35-20: 1-4. the corresponding mixture of compounds of the general form is young, in dimethylformamide or N-melytilpyrrolidone at 20 C.
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    同族专利:
    公开号 | 公开日
    FR2518538A1|1983-06-24|
    AT12487T|1985-04-15|
    CA1203247A|1986-04-15|
    FR2518538B1|1984-09-21|
    EP0082781A1|1983-06-29|
    JPS58110542A|1983-07-01|
    US4906414A|1990-03-06|
    JPH0379333B2|1991-12-18|
    JPH03184938A|1991-08-12|
    US4837365A|1989-06-06|
    DE3262905D1|1985-05-09|
    EP0082781B1|1985-04-03|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US3277147A|1963-06-05|1966-10-04|Olin Mathieson|Lower alkyl esters of beta-cyclocitrylidene fluoroacetic acid and beta-ionylidene fluoroacetic acid|FR2567512B1|1984-07-12|1986-11-14|Rhone Poulenc Sante|PROCESS FOR THE PREPARATION OF UNSATURATED CHLORINE COMPOUNDS IN A OF TWO ELECTROATTRACTOR GROUPS IN POSITION B|
    FR2567511B1|1984-07-12|1986-11-14|Rhone Poulenc Sante|PROCESS FOR THE PREPARATION OF HALOGENATED COMPOUNDS INTO AN ELECTROATTRACTOR GROUP|
    US5202460A|1989-06-22|1993-04-13|Rhone Poulenc Sante|Terpene derivatives, their preparation and their use|
    FR2648813B1|1989-06-22|1992-01-17|Rhone Poulenc Sante|NEW TERPENIC DERIVATIVES, THEIR PREPARATION AND THEIR USE|
    US5274178A|1989-06-22|1993-12-28|Rhone-Poulenc Sante|Terpene derivatives, their preparation and their use|
    FR2648811B1|1989-06-22|1991-11-22|Rhone Poulenc Sante|PROCESS FOR THE PREPARATION OF PSEUDO-IONONE|
    CN1036457C|1991-10-01|1997-11-19|武田药品工业株式会社|Method of producing lower alkyl 2-keto-L-ketogulonic acid ester|
    US6191321B1|1998-09-30|2001-02-20|Shell Oil Company|Process for preparing 1,3-propanediol from methyl 3-hydroxypropionate|
    EP2927207A4|2012-11-27|2016-07-13|Kureha Corp|Production method for carbonyl compound|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    FR8123684A|FR2518538B1|1981-12-18|1981-12-18|
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