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    • 专利摘要:
    The invention relates to keto esters, in particular, a method for producing a mixture of α-chloro-β-keto esters of the general formula (CH 3 ) 2 C = CH-CH 2 -CH 2 -C (CH 3 ) = CH-CH 2 -CCL [C (O) CH 3 ] -C (O) OR and (CH 3 ) C = CH-CH 2 -CH 2 -C (CH 2 ) -CH 2 -CH 2 -CCL [C (O) CH 3 ] -C (O) OR, where RC 1 -C 4 is alkyl, intermediates in the synthesis of pseudo-inino, which is used to produce vitamin A. The goal is to simplify the process. The latter is carried out by the reaction of a mixture of β - ketoesters of the general formula (CH 3 ) 2 C = CH — CH 2 —CH 2 —C (CH 3 ) = CH — CH 2 —CH [C (O) CH 3 ] - C (O) OR and (CH 3 ) 2 C = CH — CH 2 —CH 2 —C (═CH 2 ) —CH 2 —CH 2 —CH [C (O) CH 3 ] —C (O) OR, where R is cm. above, with sulphuryl chloride, N - chlorosuccinimide or hexachloroethane in dimethylformamide, tetrahydrofuran, acetone, acetonitrile, pentane, hexane, N - methylpyrrolidone, methyl tert-butyl ether, toluene, nitrobenzene or methanol at (-50) -1 ° if necessary in the presence of tetrabutylammonium hydrosulfate in methylene chloride. In this case, the initial mixture of β - keto esters must be pretreated with an anionization agent, such as a hydride, carbonate, hydroxide, amide compound, alkali metal alcoholate or 1,8-diazabicyclo [5,4,0] undec-7-ene, and the process must be carried out at a molar ratio of β-keto esters, halogenating agent and anionizing agent 1: (1-3) :( 1-6). The method allows to simplify the process by eliminating the filtration stage from the catalyst and represents a wide choice of halogenation agent and solvent. 2 tab.
    公开号:SU1493100A3
    申请号:SU853923556
    申请日:1985-07-11
    公开日:1989-07-07
    发明作者:Миньани Жерар；Морель Дидье
    申请人:Рон-Пуленк Санте (Фирма)；
    IPC主号:
    专利说明:

    This invention relates to a process for the preparation of a mixture of o-chloro-p-β-ketoesters of the general formula
    COCH3 C-C1 COOR
    AND
    SOCNs
     COOR
    where R is C, -C-alkyl, which are intermediate in the synthesis of pseudo-ionone, which is used to produce vitamin A.
    The purpose of the invention is to simplify the process.
    Example 1 Into a vessel with a capacity of 100 cm, under an atmosphere of argon, 20 cm of anhydrous dimethylformamide and 2.52 g (0.010 mol) of the mixture in the proportion 55/45 are introduced.

    cm
    (cnz) 7 (sn-cngS.H2-c (c11 -ciKcoocn h) cpcIs and
    (CH3) 2C CH-CH2 (: 112-С (С11з) CH-С112-СН (СООСЛ1з) ССОз,
    then 0.6 g (0.011 mol) of crushed potash and 2.5 g (0.011 mol O of hexachloroethane are added, stirred for 12 hours at 25 ° C. The reaction mixture is dissolved in 100 cm of water, extracted with ethyl ether (3-30 cmM The organic phases are combined and dried.
    (SIS) sS CH-CHECH2-C (CH (CHE), p CH-CH CH, -C (CH3)
    the KOTojiofi content is 81 / J. The yield of the individual products is 70%.
    P r and m about r
    In vessel capacity
    (SI) 2C CH-CH2CH, -C; (CH2) -CH2CH. (-CH (COOC11) COCl3 and (a1z) -, C CH-CH., C11, -C (CH3) CH-CH., - CH (SOOCHN) SUCLE,
    then 2.49 g (0.024 mol) of sodium carbonate and 5.24 g (0.022 mol) of hexachloroethane are added, the mixture is stirred at 25 ° C for 20 hours and the formation of a white precipitate is observed. After filtration, the reaction mixture is extracted into 150 cm of water, extracted with ethyl ether.
    (SIS) 2C SP-CH CH2-C (CH7) -CHN-CH2-CC1 (COOCH3) CCHH3 and (CH3) 2C CH-CHYaCI2-C (CH3) SPSNa-S.C1 (COOCH3) COSP.,.
    (3x50 cm). Organic and dried over sulphate. After filtration and evaporation of the 25 liter, 7.47 g of oil are obtained, representing 55/45.
    11 g. Measure 3. A 50 cm H-methio I1irrolidone and 4.8 g-g (0.019 mol) mixture in a 55/45 ratio are introduced into a 100-cm vessel.
    (CHj) 2 C CH-CH2 CHj-CH (CH.,) -CHj CHj -CHI (COOCHj) COCHj and (CH3) 2C CH-CHjCH2-C (CH.,) CH-CH2-CH (COOCHN) COCHz,
    Chromatography in the gas phase with an internal standard indicates that the conversion factor is 98% and the yield is 97%.
    then 1.10 g (0.020 mol) of the phases are added and dried over sulphated potash and 5 g (0.021 mol) with 40 fat sodium. After filtration and elongation of hexachloroethane, stirring for 40 minutes, the solvent is obtained, 8.2 g are obtained at 25 ° C. The reaction mixture is poured into yellowish oil, representing 100 cm of water, extracted with ethylic mixture in the proportion of 55/45 ether (3x50 cm). Organic (SPJ) 2C CH-SI 5SI 2-С (SP g) SI CH-CC1 (COOCH 3) COCH 3 and (P3) C CH-CH, CH.,-C (CH h) CH-CH j-CCl (Cope,) Coch 3.
    Chromatographic analysis of B gaseous Ex. In a vessel with a capacitance phase with an internal standard, it shows that the conversion ratio is 98-99%, and the yield is 90%.
    100 cm are introduced under an atmosphere of argon 15 cm of hexane, 5 cm of N-methylpyrrolidone, 0.56 g (0.010 mol) of potash, and then 2.52 g (0.010 mol) of the mixture in the proportion 55/45
    (CH) C CH-CHj-CH2-C (CHi) CH2 CHi-CH (COOCH3) COCH3 and (SI 3) 2 C CH-CH. (CH3) CH-CH2CH (COOCH e) COCH 3,
    then 2.36 g (0.01 mol) of hexachloroethane is added, stirred for 15 hours at 25 seconds. The reaction mixture is high
    over magnesium sulfate. After filtration and evaporation of the solvent, 3.75 g of a yellowish oil are obtained. By distillation under reduced pressure (0.1 mm Hg, 0.013 kPa) at 150 ° C, 2.5 g of the mixture is obtained in the proportion 55/43.
    2) CH. CHCH-CC1 (COOCHE) COCH J and CH-CH2-CC1 (COOCH3) COCH,
    100 cm are introduced under the atmosphere of argon 50 cm N-methylpyrrolidone and 5.5 g (0.022 mol) of the mixture in the proportion 55/45
    (3x50 cm). The organic phases are combined and dried over magnesium sulphate. After filtration and evaporation of the solvent, 7.47 g of a yellowish oil is obtained, which is a mixture in the proportion 55/45.
     Example4. In vessel capacity
    100 cm are introduced under an atmosphere of argon 15 cm of hexane, 5 cm of N-methylpyrrolidone, 0.56 g (0.010 mol) of potash, and then 2.52 g (0.010 mol) of the mixture in the proportion 55/45
    in the LLP, see water, extracted with ethyl ether (3x50 cm). The organic phases are combined and dried over magnesium sulfate 100g
    neither After filtration and evaporation of that oil, the precursor solvent gives 3.9 g of a yellow mixture in a ratio of 3 /.)
    I I (СНз) 2С СН-СН2СНг-С (СН2) -СН2-СН2-СС1 (СООСНз) ССН, and
    (СНз), С СН-СН2СН-С (СНз) -СН-СНг-СС1 (СООСНз) СОСНз.
    The output of a separate product after IrimerZ. A 100-cm distillation vessel is 100 cm injected under an argon atmosphere of 70%. 20 cm of N-methylpyrrolidone and 2.32 g.
    I10 (0.010 mol) of the mixture in the proportion of 35/45
    (CHj) jC CH-CH7CH4-C (CHj) CH, jCHj-CH (COOCH3) COCH, and (CH3), C CH-CH1CH, -C (CHE) CH-CH.r-CH (COOCH3) COCH,
    1.5 g (0.108 mol) of organic phases are then added; the organic phases are dried over potassium carbonate sulfate and 2.36 g (0.01 mol) of magnesium. After filtration and evaporation of hexachloroethane, the solvent is stirred for 24 hours and 3 g of yellow are obtained at 23 C. The reaction mixture is poured on wadded oil, which is 100 cm of water, extracted with ethyl ether in the proportion of 35/43 vial ether (3x30 cm) . United
    (СНз) 2С СН-СЛ, СН2-С (СНг) -СН-СНг-СС1 (СООСНз) СОСНз and (СНд), 1С СН-СН, СН, С (СНз) СН-СН4-СС1 (СООСНз) ССНз .
    The conversion factor is 80%, Example 6. In a vessel with a capacity and the yield of a separate product is „100 cm, it is introduced under an argon atmosphere of 73% .20 cm of tetrahydrofuran and 2.52 g.
    (0.010 mol) of the mixture in the proportion 55/45 I
    (CH3) C CH-CH5CHj-C (CH2) (COOCH3) COCH3 and (CH 3) 2 C CH-CH-gCH-C (CH g) CH-CH-CH (COOCH j) COCH,
    0.56 g (0.010 molar) phases are then dried over potash sulphate and 2.5 g (0.11 mol) of hexa-magnesium. After filtration and evaporation of chloroethane, stirred for 10 hours while the solvent is yellow, 25 ° C is obtained yellowish. The reaction mixture is poured into an oil, which is a mixture of
    100 cm of water, extracted with ethyl proportions 55/45 ether (3x50 cm), Combined organ (CH3), C CH-CHjCH, -C (CH2) -CH, CH2-CCl (COOCH3) COCHJ and (CH) j С CH- SNGN, -C (CH3) CH-CH-CC1 (COOCH3) COCH3.
    The yield of a separate product is 40–20 cm of methanol and in small portions it is 70%. , 0.23 g (0.010 g-atom) sodium. It is cooled to -50 ° C, after which it is added
    Example 7. A vessel with a capacity of 2.52 g (0.010 mol) of the mixture in a proportion of 100 cm is introduced under the atmosphere of argon 55/45
    (СНз), С СН-СН2СНа-С (СНг) СН5СНг-СН (СООСН ССНз) and (СНз) 2С СН-СНаСН-С (СНз) СН-СН2-СН (СООСН5) СС11
    and 1.33 g (0.010 mol) of the N-chlorosuccinium phase are dried over magnesium sulphate, mix and stir for 40 min at -50 ° C. After filtration and methanol extraction, the reactor is obtained after a single mixture is poured into 100 cm of water, distillation of 2.5 g of yellowish oil is extracted with ethyl ether (3x of the mixture in proportions x 3 cm). The combined organic 55/45.
    (CH3), CCH-CHiCHi-C (CHa) CH, CHt-CCl (COOCH3) COCH and (CH3), C CH-CH2CHj-C (CH,) CH-CHj-CCl (COOCH g) COCH3.
    The yield is 87% sodium amide. Cooled to 5 ° C and honey. The solution is capaciously added to the reactor for 1 h 40 min.
    1200 cm are introduced under the atmosphere of argon24.4 g (0.097 mol) of the mixture in the proportion of 500 cm of hexane and 4.04 g (0.103 mol) of cci 55/54
    1А93100 7о
    (CH3) 7C С | -CH2CH, -С (СНг) СН-, СН2-СН (СООСНэ) СОСНз and (СНз), С СН-СИСГСН, -С (СНд) С11-СН.г-СН (СООСНэ) ССНД
    in 100 cm of hexane. Stir 5h. and a white precipitate is observed.
    at 3 ° C (95% of theoretical 5 is released after filtration and evaporation of a plant amount of ammonia). Then the wither obtained 31.2 g of yellowish 45 minutes. Add a solution of 14.5 g of oil, which is a mixture (0.107 mol) of sulfuryl chloride in the proportion 55/45 in 50 cm of hexane, stirred for 1.5 hours
    (CH) 2C CH-CHiCHj-C (CH,) CH3CHj-CCl (COOCH3) COCHj and (CH3) C CH-CH -zCH 2-e (CHE) CH - SI i-CCl (COOCH h) COCH. .
    The chromatographic analysis in gas-250 cm is introduced under the atmosphere of argon.
    Howling phase with an internal standard until-80 cm of toluene and 0.76 g (0.019 mol)
    The conversion factor is sodium amide. Cooled to 5-10 ° C
    equal to 93.5%, and the yield equal to 90.2%, and a solution of 4.96 g (0.020 mol) is added
    Example9. To the reactor capacity of the mixture in the proportion of 55/45
    (СНз) 2С СН-СН2СН5-С (СН2) СН2 СН, -СН (СООСНэ) СОСНз and (СНз) С СН-СНГН-г-С (СНз) СНС-СН С-СНС
    in 20 cm of toluene. Leave for 2 hours at filtration and evaporation of the plant at 25 ° C, then a solution of 2.89 giteritel is added to obtain 5.63 g of yellowish
    (0.021 mol) sulfurium chloride oily liquid, representing
    in 10 cm of toluene. Stir 1 tsp with the mixture in the proportion 55/45
    (CH5) 2C CH-CH. | CH, -C (CH2) CHaCH2-CC1 (COOCH3) COCH3 and (CHD) 5C CH-CH2 CH2-C (CH3) CH-CH2-CC1 (COOCH3) COCH3.
    Chromatographic analysis in gas-20 cm of methanol and in small portions of the phase with an internal standard is shown to be 0.23 g (0.010 g-atom) of sodium. Cools that yield is 66.8%. give up, after which add
    Example 10. In a vessel with a capacity of 30, 2.52 g (0.010 mol) of the mixture in a proportion of 100 cm is introduced under the atmosphere of argon 55/45.
    (СНз) 2С СН-СН2СН2-С (СН7) СНгСНг-СН (СООСНз) СОСНз and (СНд), С СН-СН.гСН2-С (СНз) СНС) СНН „
    then at -50 ° C, 1.34 g of water is added, extracted with ethyl ether (0.010 mol) of sulfuryl chloride, (3x50 cm). The combined organic is stirred for 30 minutes at. The residual phases are dried over magnesium sulphate. The solution is kept until the temperature is left without filtration and extraction. dissolve to 20 ° C, after which the reactor receives 4.7 g of yellow oil, the mixture is poured into 100 cm, Q containing the mixture in the proportion 55/45.
    (CH3) C CH-CH2CHN-C (CH5) -CH CHG-CC1 (COOCH) COCH.3 and (CHD) C CH-CH2 CH-CH (CHE) CH-CH-CC1 (COOCH3) COCH3.
    The yield of a single product is 20 cm of methanol and 0.23 g (0.010 g — 65% .45 atom) of sodium. Cooled to 0 ° C, then
    Example 11. 2.52 g (0.010 mol) of a mixture of 100 cm is added to a vessel with a capacity of 55 cm under an argon atmosphere in the proportion 55/54.
    (CHj) 2C CH-CHjCH.j-C (CH) -CH2CH2-CH (COOCHj) COCH ,, and (CH3) 2C CH-CH2CH-C (CH3) CH-CH2-CH (COOCH3) SCOH
    SP 1
    and 1.33 g (0.01 mol) of N-chlorosuccinim-- filtering and evaporating the solvent
    yes, stirred 40 min at 0 ° C. Fe-2.3 g of yellow oil are obtained, the reaction mixture is poured into 100 according to chromatographic data.
    water, extracted with ethyl ether analysis in the gas phase contains 6.5%
    (3x50 cm). United organic source product and 41.6% of the mixture in
    the phases are dried over magnesium sulphate. After a 55/55 55
    (CH3), CH-CH, CHa-C (CH.g) -CHNCH2-CHC1-COOCH3 and (CH3) 2C CH-CH4CH7-C (CH3) CH-CH5-CHC1-COOCH,
    as well as 51.8% of the mixture in the proportion 55/45
    (CH3) j (Cil-CH ,,, - C (CH4) -CHjCH -CCl (COOCH.) SOSPi and (CH), C CH-CH.Sig-C (CHE) CH-CH2-CC1 (COOCH3) COCH) .,.
    Example 12. In a vessel with a container Washed (3x20 cm) with dry psnthan. 100 cm are added under an argon atmosphere. 20 cm of tetragon are added; fofura1; and 0.5 g (0.010 mol) of a 50% aqueous solution and 2.52 g (0.010 mol) of the mixture in sodium hydride in mineral oil. por1U1I 55/45
    (CH3) 2C CH-CH, (CH2) -CHNCH5-CH (COOCH3) COCl, and (CHd). C CH-CH CH ,, - C (CH,) CH-CH "Mr.-CH (COOCil,) COCH,
    then left for 5 hours at 25 ° C (x 50 cm). United Organic
    after which the plant phases are slowly added, dried over magnesium sulfate,
    thief 1, ZD g (0.010 mol) chloride After filtration and application of rastsulfuryl in 10 cm of tetrahydrofuran, the scavenger obtained 3.0 g of yellow mask over 3 h at 25 s. According to Dann-f chromatographic mixture poured into 100 cm of water, the gas phase analysis is extracted with ethyl ether (Zhzhit 62% of the mixture in the proportion 55/45
    (CI) .iC rH-CHjCHj-C (CH2) -CH2CH, -CCl (COOCH3) CCK: H, and (CPI h) 2 C C11-CH, CH-tC (SI3) CH-CH-CC1 (COOSP .) COCH
    According to the chromatographic ana-500 cm is introduced under the atmosphere of argon
    in the gas phase, the yield is 200 cm dimethylformag-: ida, 16.4 g
    75%. (0.118 mol) of potassium carbonate, 25.2 g
    Example 13. A vessel with a capacity (O, LLP mol) of the mixture in the proportion 55/45
    (CHj). C CH-CH, (CHl) -CP, CH -, - CH (COOCH) COCH3 and (CHE) C CH-SP ,, SP5-C (SP2) CH-CH, - CH (COO (: NC) COCH3
    and 14 g (0.104 mol) of the K-chloro-succinate phase is dried over sulfate: magnesium. Afterwards, leave for 16 h at. Reagently filtrates and evaporation of the mixture are injected in g, 100 cm of boiling water, 27 g of a yellow oil are obtained,
    dyes, extracted with ethyl ether-containing 75 / mixture in proportion
    (3x50 cm). United Organic 55/45
    (SP,) С СН-СН2СН, -С (СН2) -СНгСНг-СС1 (СООСНз) ССО11з and (СНз) С СП-СП, SPN-2 (СНз) СН-СИ2-СС1 (СООСНз) ССНз. PRI me R 14. In a vessel with a capacity (0,200 mol) carbonate kmtsi and
    500 cm are introduced under argon atmosphere 38 g (0.150 mol) of the mixture in proportion
    150 cm dimethylformade 1, 27.6 g55 / 45
    (CH3) C C1-SP2CH2-C (CH) -SP2CH-CH (COOSPe) COCH3 and (SIS) g C CH-CH CH2-C (CH) CH-CH-CH () COCl3,
    I is then added 42 g (0.177 mol). After filtration and evaporation of rasthexachloroethane, 15 choritel are stirred, 60 g of oil are obtained, which at 25 ° C, 200 cm of water are added and after distillation at 150 ° C and extracted with ethyl ether (1 mm Hg, 0.13 kPa) gives (3x50.cm). The organic compounds containing 94% of the mixture in the prophase are dried over magnesium sulfate. 55/45
    (СНз), С СН-СН2СНг-С (СНг) СН2 СН, g-СС1 (СООСНз) ССНз and (СИС) 2С СН-СНС СНС-С (СН,) СН-СНС-СНС.
    The yield of a single product is 20 cm of methylterbiobutylether, 1.5 g is 81%. (0.011 mol) of potassium carbonate and 2.52 g.
    Example 15. A vessel with a capacity (0.010 mol) of the mixture in a proportion of 200 cm is introduced under argon atmosphere 55/45
    (СНз) and С СН-СН, СН ,, - С (СН ,,) СН2СН2-СН (СООСНз) ССНз н (СНз) 2С СНН СНС СНН, then 1.33 g (0.010 mol) is added to extraction with ethyl ether.
    N-chlorosuccinimide, stirred for 15 hours (3x50 cm) .. Combined organic at 25 ° C, 100 cm of water is added and the phases are dried over magnesium sulfate.
    ,, 1493100
    1112
    filtered and evaporated the solvent containing 91% of the mixture in proportion
    l get 2, g of colorless oil, 55/45
    (СНз) 2С СН-СН2СН, -С (СН2) СН2СНг-СС1 (СООСНз) ССНз and (СНС) 2С СНН СНС - С (СНэ) СН-С and-CC1 (СООСН) СС1 С, С
    The yield of a separate product is 80 cm of acetone, 8.28 g of carbonate is 73%, LIA (0.060 mol) is 13.17 g of hexachlorophenyl ether 16. In a vessel with ethane capacity (0.056 mol) and 10.86 g 250 cm is introduced under argon atmosphere (0.043 mol) of the mixture in the proportion 55/45
    1 L
    (CH3) 2C CH-CH2CH2-C (CH2) -CH2 CH2-CH (COOCH g) COHCl and
    , (CH3) 2C SI-CH-gSN, g -C (CH3) - CH-CH2-CH (spo 3) COCH3,
    then stirred for 7 hours at a temperature; the organic phases are dried over sulfate
    re-ejection of the reaction mixture. Reaction-magnesium. After evaporation, the solvent mixture is poured into 100 cm of slightly 15 l and 15.45 g of yellow-acidified water is obtained, which is extracted with this orange-colored mixture containing lovine ether (3 x 50 cm). United
    (СНз), С СН-СНгСИ2-С (СН2) -СНГГСН2-СС1 (СООСНз) ССНН and (СНд) С СН-СНН СНН-СНН СНН СНН СНН СНН СНН СНН СНС-СНН.
    According to the chromatographic ana-100 cm, it is introduced under argon-lysis atmosphere in the gas phase with internal ethane-20 cm of dimethylformamide, 2.5 g w / w of the yield is 91.5% (0.011 mol), hexachloroethane and 2.52 g
    PRI me R 17. In a vessel with a capacity | (0.010 mol) of the mixture in the proportion 55/45
    (CH3) 2C CH-CH-CH2-C (CH2) CH2CH-CH (COOCH3) COCH3 and (CH3) 7 C C 1-CH2CH 2-e (CHD) CH-CH2-CI (SOOSP j) COCH 3,
    2 g (0.013 mol) are then added over magnesium sulfate. After the filter, 1,8-diazabicyclo 5,4,0j undec-7-eneation and evaporation of the solvent pslu (DBU), stirred for 4 hours at 25 s., 4.12 g of yellowish oil is poured, and the reaction mixture is poured into 100 cm swarm after a single distillation of water, extracted with ethyl ether, gives 2.41 g of a light yellow oil (3x50 cm 3). The organic phases are dried and containing the mixture in 55/45 proportions.
    (CH3) gC CH-CH2CH2-C (CH2) CH2CH-CC1 (cosense) COCHe and
    (cn e) 1 cn-dn gHs -c (enz). en, j-cei (pines h) pine h.
    The yield of a single product composition of 7.11 g (0.030 mol) of hexachloroethane,
    Let 73% .0.342 g (0.001 mol) of hydrogen-sulfon EXAMPLE 18. In a vessel of tetrabutylammo) 1i and 2.52 g
    100 cm are introduced under the atmosphere of argon (0.010 mol) of the mixture in the proportion 55/45
    (СНз) гС СН-СН2-еН2-С (СН.) - СНгСН2-СН (ССНз) -СООЕНз and (СНз) С СН-СНг-СН2-С (еНз) СН-СНг-СН (ССНЭ) -СООСз,
    dissolved in 50 cm of chloride I-After extraction of the reaction mixture
    Tilena. Then add 5 cm 50% -. According to the chromatographic aqueous solution of sodium, an energy analysis of 1, 2 g of the mixture in the preparation of
    mix and mix for 2 hours at 25 p.55 / 45
    (cnc) 2C sn-cn2en2-c (cn2) -sn2en-cc1 (coaxial) -cooenz and (cn3) .g cn cn – cnn1EN2-c (eH3) en-en2-cc1 (eosNz) -co.nz.
    The yield is 56.5% potassium carbonate and 0.34 g of hydrogen sulfate.
    Example 19. In the vessel capacitanceutrabutylammonium in 20 cm of chloride
    100 cm is added under argonamethylene atmosphere, then 2.52 g is added.
    3.08 g of hexachloroethane, 2.07 g of carbo- (0.10 mmol) mixture in the proportion 55/45
    (CH3) 2C CH-CH, gCH2-C (eH2) -CHNCH2-CH (COCH3) COOCH3 and
    (cN3) 2C sn-sn7CN2-c (cn3) en-cn, -cn (soEn3) eooo3.
    Heat the reaction mixture with about-at. With a yield of 20% get the mixture in
    Refrigerator 5 parts proportion 55/45
    . 1314931001
    (CH) j С СН-СН, СН ,, - С (СН2) -СН2 СН2-СС1 (ССНз) -СООСН and (СНз) 2С СН-СН2 СНЗ) СНС) СНС-СНЗ. Example 20: In a vessel with a capacity of ethane and 20 cm of acetonitrile, add 100 cm under an atmosphere of argon, 5.04 g (0.020 mol) of the mixture in about 11.04 g (0.080 mol) of calcium carbonate 55/45
    qi, 4.96 g (0.021 mol) hexachlor (CH 3) CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 SESN) SOOSNz,
    then the reaction mixture is heated from the phase, washed with water and dried over a reflux condenser for 3 hours. After magnesium sulfate. After filtering the cooling, the reaction mixture is quenched and the solvent evaporated is obtained in 100 cm of water, extracted with ethyl gas at a yield of 95% of the mixture with proportional ethyl ether (3 x 50 cm). Organic,. 55/45
    (СНз) гС СП-а СН2-С (СН2) СН2СН,) - СС1 (СОСНз) -СООСНз and (СНз) С СН-СИ, (CH д) СН-СI, 2-СС1 (СОСПз) -СООСНз
    in the form of an orange oil, calcium carbonate and 10 cm of nitrobenPro and measures 21, To a vessel with a capacity of zol, then add 1, 2fi g
    100 cm. 2.37 g (0.010 mol) of 20 (0.005 mol) of the mixture in the proportion of 55/45 hexachloroethane, 1.38 g (0.010 mol) are introduced.
    (СНз), С СН-СН2-С (СН2) -СИ2СНс -CH (ССНз) -СООСНз and (СНэ) 2 С СН-СН2-С (Нз) СН-СНСНз.
    The reaction mixture is stirred. After extraction, it is obtained at 5 h, with a course of 78% of the mixture in the proportion 55/45.
    (СНз) 2С СН-СНгСН2-С (СН2) -НН4СНг-СС-1 (СОСОз) -СООСНз and (СНз) 2С СН-СН, gСН2-С (СНз) СН-СН2-СС1 (ССНС) -СООСНз.
    In examples 1,4-7, 10,14,15,17,19ve the reference. The results are shown in
    the yield of the isolated product is receivable, 1 and 2,
    after distillation, and the starting product. Thus, the proposed composition consists of a mixture of products. The application is simpler to carry out (spark 18, the yield of the isolated product is the filtration stage from catalysis after chromatography, and others). in the examples, the yield is determined from the chromic agent. halogenation and solvtographic analysis of the starting material, product. The products in examples 1-21 have t, kip. 150 ° C. Formula of the invention
    43 Spectrum Mass Collection Method
    ., go (-chloro-keto-esters of the general formula
    C; -С1286 (СОСОСНз
    СООСНз Г С-С1
    -Sh xW-A oOR
    251
    i, aiu J J HOSPH
    (250). ro.o.N.
    - -69 COOR
    -m / xCCsHg) 1 (
    Mosnz) li-. L 4
     de R - C, -C-alkyl
    IR spectrum, sml l) p cc 3080, 1650, from a mixture of ketoesters of the general formula
    1605, 825, 895; , / COCH,
    .1, mt; i7; ;. / l1 (eo, 1735 1755, -.
    1 / I II vri
    Spectra PMR, Spectra register-XsjX v
    baths at 360 MHz in a solution of CCl4.COOR
    Chemical shifts are expressed in hours. / 3
    t x per million relative to hexame-ji I x
    tildisilane (HMDS), also as a quality: XX.X COOR

     de R - C, -C-alkyl
    where R has the indicated value using a halogenating agent in an organic solvent medium followed by treatment of the reaction shed with water and separation of the target product, characterized in that, in order to simplify the process, sulphuryl chloride, N-chlorosuccinimide or hexa chloroethane is used as the halogenating agent as an organic solvent - dimethylformamide, tetrahydrofuran, acetone, acetonitrile, pentane, hexane, N-methylpyrrolidone, methyl tertiary butyl ether, toluene, nit
    5СНп
    Table
    one
    СН2-СН -С-СН2-СЩ-СС1-СО-Ш5
     3 1 f. R"
    COO-CH
    SNO-SNg-C CH-CH2-CC1-CO-CH3
    -7 sk, 1

    soo-noo
    robenzene, methanol, while the initial mixture of / 3-keto esters is pretreated with an anionization agent selected from hydrides, carbonates, hydroxides, amide compounds, alkali metal alkali metal at 1,8-diazabicyclo C5,4, OJ undec-7-ene and halogenated, conducting the process at a temperature of (-50) -110 C and a molar ratio of US-keto esters, a halogenating agent and an anionizing agent, respectively, 1: 1-3si-6, if necessary in the presence of tetrabu-Thylammonium hydrosulfate in methylene chloride.
    Table 1
    one
    -CC1-CO-Sh5
    soo-noo
    权利要求:
    Claims (2)
    [1]
    1 6 where R has the indicated value using a halogenating agent in an organic solvent medium, followed by treating the reaction mixture with water and isolating the target product, characterized in that, in order to simplify the process, sulfuryl chloride, N-chlorosuccinimide or hexachloroethane is used as a halogenating agent, as an organic solvent, dimethylformamide, tetrahydrofuran, acetone, acetonitrile, pentane, hexane, N-methylpyrrolidone, methyl tert-butyl ether, toluene, nitrobenzene, methanol, with the outcome This mixture of 3-ketoesters is pretreated with an aionization agent selected from hydrides, carbonates, hydroxides, amide compounds, alkali metal alcoholates at 1,8-diazabicyclo C5,4, OJ undec-7-ene and halogenated by carrying out the process at a temperature ( -50) -110 ° C and the molar ratio of uzetoethers, halogenating agent and anionizing agent, respectively 1: 1-3: 1-6, if necessary in the presence of tetrabutylammonium hydrosulfates in methylene chloride.
    Chemical displacement, hours per 1 million —--------Signal type Integration 2.29 Singlet knowledge CH (1) 3.76 - n - knowledge sun 3(2) 2.05 Multiplet 2H sun 7(3) 22H sun 7(4) 4.70 Doublet 2H sun 7'(5) 2 Multiplet 4H SI (6 and 4.99 Triplet 1H cn (8) 1,54 Singlet ZN sun 3(9) 1,61ZN CH 3(10)
    ι table2
    Chemical Sig type Integration displacement nala hours per 1 million
    [2]
    2.27 Singlet knowledge sn e(1) 3.74knowledge CH 3(2) 2.781H sn r(3) 2.881H.5.06 Triplet 1H cn (4) 1.55 Singlet knowledge sun 3(5) 2 Multipip 4H CH 2(6 years 4.99 Triplet 1H cn (8) 1,54 Singlet ZN sun 3(9) 1, $ 1knowledge sun 3(YU
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    同族专利:
    公开号 | 公开日
    DE3560826D1|1987-12-03|
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    EP0171320A1|1986-02-12|
    FR2567512A1|1986-01-17|
    EP0171320B1|1987-10-28|
    CA1250313A|1989-02-21|
    JPS6136238A|1986-02-20|
    JPH0563456B2|1993-09-10|
    FR2567512B1|1986-11-14|
    AT30413T|1987-11-15|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US2481036A|1943-11-24|1949-09-06|Nopco Chem Co|Alpha-halogenated keto fatty compounds|
    US2788360A|1954-05-28|1957-04-09|Goodrich Co B F|Preparation of dicyano halo-ethane cyclic compounds|
    US3277147A|1963-06-05|1966-10-04|Olin Mathieson|Lower alkyl esters of beta-cyclocitrylidene fluoroacetic acid and beta-ionylidene fluoroacetic acid|
    FR2518538B1|1981-12-18|1984-09-21|Rhone Poulenc Sante|JPS63158595A|1986-12-22|1988-07-01|Nec Corp|Voice recognition equipment|
    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|
    US5132475A|1991-07-12|1992-07-21|E. I. Du Pont De Nemours And Company|Quaternary ammonium fluoride catalyzed halogenation of carbon acids|
    US5138107A|1991-07-12|1992-08-11|E. I. Du Pont De Nemours And Company|Phase transfer catalyzed halogenation of carbon acids|
    EP0673945B1|1994-03-23|2000-09-06|F. Hoffmann-La Roche Ag|Preparation of an ester salt of wittig|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    FR8411088A|FR2567512B1|1984-07-12|1984-07-12|PROCESS FOR THE PREPARATION OF UNSATURATED CHLORINE COMPOUNDS IN A OF TWO ELECTROATTRACTOR GROUPS IN POSITION B|
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