• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
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  • 优先权
    • 专利摘要:
    1448316 Racemization of cyclopropane carboxylic acid halides SUMITOMO CHEMICAL CO Ltd 11 Nov 1974 [12 Nov 1973] 48643/74 Heading C2C Compounds of the formula where R 1 and R 2 are H or C 1 -C 4 alkyl or together with the carbon atom to which they are attached form a C 4 -C 6 cycloalkylidene group and X is halogen, are racemized by contact with a Lewis acid. The racemized acid halide may subsequently be converted to the free acid.
    公开号:SU722479A3
    申请号:SU742078312
    申请日:1974-11-11
    公开日:1980-03-15
    发明作者:Нагасе Цунеюки；Сузукамо Гоху
    申请人:Сумитомо Кемикал Компани Лимитед (Фирма)；
    IPC主号:
    专利说明:

    with a special basic catalyst when heated, the result is a trans-chrysanthemic acid, or heating of cis-pyrethrinic acid chloride at high temperature. However, using these methods, it is not possible to perform epimeriation at both asymmetric carbon atoms, and only the conversion of (-) - cis-chrysanthemic acid to (+) - trans-chrysanthemic acid or (4 -) - cis-chrysanthemic acid (-) -trans-chrysanthemum acid. This is because the methods are based on the higher thermodynamic stability of the trans-isomer as compared to the cis-isomero, therefore in such methods the conversion of the (-) - trans-isomer into (4 -) - isomer cannot be achieved. The latter can be carried out only as a result of a multistage process: the conversion of the (-) - t of the eans-isomer into the (-) - cis-isomer and the epimerization of the resulting isomer into the C position. A broad study was conducted of the possibilities of implementing the process of racemization, as a result of which several methods of racemization were developed. Thus, according to one method, the alkenyl group in the Cj position in {-) - trans-chrysant acid is converted to a ketospiritual group, and the acid group in the C - position is converted to an alkyl ester, which is then treated in an alkaline alkali metal solvent .According to another with soba (-) g-trans-chrysanthemum sour and its derivatives, they are subjected to ultraviolet irradiation with light in the presence of a photosensitizer. However, in the first case, the multistage interferes with industrial sales, and in the second, energy consumption is high. In order to simplify the process according to the invention, the optically active cyclopropanecarboxylic acid halide of the formula X is Cn-yn-cn-Cox; o X h / a C /, CH 3 i 4j -de RI and RJ have the indicated values X - a halogen atom, mainly chlorine, is subjected to racemization in the presence of Lewis acids. The acid halide can be obtained by a known method, for example, by the reaction of a carboxylic acid with a chlorinating agent; thionyl chloride, sulfuryl chloride, phosphorus pentachloride, phosphorus tre chloride as starting expedient to use Lewis acids chloride apkmlni aluminum bromide, iron chloride (II), tin chloride (IV), titanium chloride, boron trichloride, boron trifluoride, zinc chloride. Racemization does not depend on external pressure and proceeds without adverse effects on the reaction. When racemization is carried out, any of the four optical isomers can be used as starting compounds, taken both separately and in combination with others in arbitrary ratios, and independently of the optical purity of these isomers. Racemization can be carried out continuously or intermittently. Opti- Multiple active acid halide cyclopropanecarboxylic acid can be introduced into the reactor in full at the beginning of the process together with the catalyst. If desired, the acid halide can be introduced into the reactor sequentially or at intervals depending on the racemization. The reaction is expediently carried out in a solvent environment, which does not adversely affect the racemization. The solvent can be ether (diethyl ether, dioxane, ethylene glycol dimethyl ether), an aromatic hydrocarbon (benzene, toluene, xylene, chlorobenzene), an aliphatic hydrocarbon (hexane, heptane) or a halogen-substituted aliphatic hydrocarbon (chloroform, 1.1.2, 2-tetrachloroethane, trichlorethylene). The catalyst can be used in an amount of 0.0005-0.5 mol, a pre-respectfully 0.005-0.1 mol per 1 mole of the optically active cyclopropanecarboxylic acid anhydride. The reaction temperature is usually in the range of from 20 ° C to the boiling point of the reaction system, preferably 40-120 ° C. The reaction time is more or less related to the amount of catalyst and the reaction temperature. Usually, racemization takes place sufficiently from 10 minutes to 20 hours. After the completion of the reaction, the regeneration of the racemized product can be carried out using conventional separation techniques. For example, the reaction mixture is treated with an aqueous solution of alkali to hydrolyze, and then neutralized with a mineral acid, as a result, a pure racemized cyclopropaccarboxylic acid can be obtained. If desired, a racemized cyclohydride cyclopropanecarboxylic acid can be directly / directly, without hydrolysis, esterified with an alcohol (pyrethrolone or allerolone) in the presence of a hydrogen halide acceptor. Using the proposed method, it is easy to carry out the racemization of the (-) - isomer of the optically active hriEintemic acid. The racemized product thus obtained can be subjected to optical splitting to obtain the valuable (+) - isomer of chrysanthemic acid. For example, a 500 L flask equipped with a calcium chloride tube was charged with 40.0 g of {-) - trans-2,2-dimethyl-3-isobutenylcyclopropane-1-carboxylic acid chloride and 160 g of dioxane, then 0 was added to the flask. 86 g of anhydrous aluminum chloride. The col content was stirred at 70 ° C for 4 hours. A small amount of water was then added to the flask to deactivate the catalyst and the solvent was distilled off. The residue is hydrolyzed with an iodine solution of sodium hydroxide. The hydrolyzed product is acidified with 20% sulfuric acid and extracted with n-Hexane, the n-hexane extract is washed with water and dried. After distilling off the solvent, the residue is distilled to give 32.4 g of oil, which has a boiling point of. 110 ° C / O, 8 mm Hg and crystallizes quickly. Melting point 48-52 C. The IR spectrum of this product is identical to the spectrum of (±) - 2,2-dimethyl-3-isobutenyl cyclopropane-1-carboxylic acid. Such a product has the following composition (determined by gas chromatography): Optical Content, wt.% Isomer (+) - trans (-) - trans (+) - cis (-) - cis Example 2. 10 ml flask with a capacity of 50 ml 2 g of (+) - cis-2,2-dimethyl-3-isberbutenylcyclopropan-1-carboxylic acid chloride and 40 g of dioxane, then 0.43 g of anhydrous aluminum chloride are added. The contents of the flask are stirred at 67-70 ° C. During the reaction, part of the reaction mixture is taken from the flask and subjected to gas chromatographic analysis, the results of which are presented in Table 1.
    tion, min
    Starting material
    ten
    thirty
    60
    120
    After completion of the reaction, the reaction mixture was worked up as described in Example 1, and 7.4 g of (±) -2, 2-dimethyl-3-isobutylamine cyclopropan-1-carboxylic acid was obtained.
    Example 3. In a 1000 ml flask, 100 g of a mixture of levorotatory cis-and acid chlorides was charged. trans-2,2-dimethyl-3-isobutenylcyclopropam-. 1-carboxylic acid
    Table
    ABOUT
    ABOUT
    100
    40.9
    4.6 6.2 44.4
    Df c
    5.4 45.8
    4.8
    4.2
    4.4 45.45 4.5
    (composition, wt.%: (+) - trans 12.6;
    (-) - trans 67.8; (+) - cis 2.7; (-) - cis 16.9) and 400 g of dioxane, then 3.5 g of anhydrous aluminum chloride is added to the flask. The contents of the flask are stirred at 68-69 ° C. During the reaction, a part of the reaction mixture is selected and subjected to gas chromatographic analysis, as a result of which the results shown in Table 2 are obtained. After the completion of the reaction, the reaction mixture was worked up as described in Example 1, and 81.5 g of (+) -2, 2-dimethyl 3-iboutenyl polypropane - "1-carboxylic acid" was obtained. Example 4. As in the example | 3, racemization was carried out at 50 ° C. After 10 hours, the reaction was confirmed by gas chromatography analysis. The reaction mixture was worked up as in Example 3, and 80.1 g of (+) - -2,2-dimethyl-1-carboxylic acid was obtained. acid. Example5. In a 100 ml flask, 5.0 g of (-) -trans-2 2-dimethyl 3-isobutenylcyclopropanecarboxylic acid chloride and 45 g of dioxane are charged, 0.20 g of anhydrous alcine chloride is added. The contents of the flask are mixed at 80 ° C for 1 h. Then deactivate catalyst and
    After completion of the reaction, a small amount of water is added to deactivate the catalyst and the solvent is distilled off. The residue is hydrolyzed with an aqueous solution of sodium hydroxide. The hydrolyzed product is acidified with 20% sulfuric acid and extracted with toluene. The extract is pressed into water and distilled to dissolve. Table 2
    Table
    the ritor. During the distillation of the residue, 30.8 g of oil are obtained with bp. 103110 ° C / 0, 8 mm Hg, which quickly crystallizes, m.p. 48-52 C.
    Example 7. A 1000 ml flask was charged with 60.5 g of left-handed Rotary Cis- and transg. -2,2-dimethyl-e3-isobutenylcyclopropane &lig; carboxylic acid chlorine chlorine (composition, wt.% G the solvent was distilled off. The residue was distilled 4.4 g of racemized acid chloride 2, 2- "dimethyl-chr-isobutenyl cyclopropane-1-carboxylic acid, having a bp. 50-54 ° C / 0.6 mm Hg. Example 6.B A 1000 ml flask was charged with 42.0 g of cis-and trans-2, 2-dimethyl-3-isobutenylcyclopropane-1-carboxylic acid (4,2%; (+) - trans 14.0; (-) - trans 65.8; (+) -cis 2.9; (-) -dis 17.4) and 378 g of toluene, 1.85 g of ferric chloride (III) was added, the contents of the flask were stirred at 70 ° C. reactions take part of the reaction mixture and analyze it by gas chromatographic method.Get the results shown in table 3.
    (+) - trans 14.8; (-) trans 65.0; () -cis 2.9; (-) - cis 17.3) and toluene, and 2.2 g of C 5 N aqueous aluminum chloride are added. The contents of the flask were stirred at 68-70 ° C for 5 hours. The reaction mixture was worked up, kick in example b, and 43.2 g of (+) - 2, 2-dimethyl-3-isobutenylcyclopropane-1-carboxylic acid with bp were obtained. 127135 C / 4 mm Hg (composition, wt.%: (+) g-trans 43.2); (-) - trans 46 2 (+) - CIS 5.1; (-) - csn 5.7).
    Example 8. In a flask with a capacity of 200 ml load 8.6 g levorotatory Content of optical isomers,
    Reaction time, min
    i (+) trance
    After completion of the reaction, the reaction mixture was worked up as in Example 6, and 6.5 g of (t) -2,2-dimethylg-3-isobutenylcyclopropane-carboxylic acid was obtained.
    Example 9. In a flask with a capacity of 200 ml load 9.9 g of levogyrate the acid chloride and trans. -2,2-dimethyl-3-isobutenylcyclopropane. 1-carboxylic acid (composition, weight,% (+) -trans 14.0; (-) g-trax 65.8; (4 -) –CIS 2.8; (-) - cis 17.4) and 90 g of hexane, add 0.7 g of tin chloride (IV). The contents of the flask are stirred at 65-70 ° C for 5 hours. The reaction mixture is treated as in Example 6 and 6.7 g of (+) -2, 2-dimethyl are obtained -. g-3-isobutenylcyclopropane-1-carboxylic acid (composition, wt.%: (+): - trans 43.9; (-) g-trans 46.1; (+) -cis 4.4; (- (- cis 4.6).
    Example 10. In a flask with a capacity of 200 ml, 12.4 g of cis-, trans 2,2-dimethyl-3-isobutenylcyclopropane-L-carbonic acid trans-levogranide are loaded (composition, wt.%: (+) - trans 13.1; (-) -trans 67.2; () -cis 1.9; (-), -cis 17.9) and 109 g of 1,1,2,2-tetrachloroethane, 0.43 g of anhydrous aluminum chloride, chlorohydride and trans 2,2-dimethyl-3-isobutenylcyclopropane-1-carboxylic acid and 78 g of monochlorobenzene, 0.31 g of anhydrous aluminum chloride was added. The contents of the flask are stirred at 70 ° C. After the reaction time has elapsed, a portion of the reaction mixture is taken out and analyzed by gas chromatography.
    Table 4 gives the results obtained.
    Table wt.%
    (-)trance
    (-) cis
    (+) cis
    17.2
    13.9 6.5 31.3 6.2 36.3 6.3 39.3 6.0 41.1 6.0 42.7
    Nin The contents of the flask are stirred at 70-72 for 6 hours. The reaction mixture is treated as in Example 6, and 6.8 g of (+) -2, 2-dimethylht3-isobutenylcyclopropane-g1-carboxylic acid are obtained (composition, wt.%: ( +) - trans 42.1; (-) - trans 48.9; () -cis 4.3, (-) - cis 4.8).
    权利要求:
    Claims (1)
    [1]
    1. The method of recognition of the optically active halides of 2,2-di0, methyl-3- (1-alkenyl) -cyclopropane-1-carboxylic acids of the formula
    ".H
    j) C CH-cH-CH-COX
     with
    CHj CH
    where H | And the hydrogen atom or (C4) -alk.1L, or together with the carbon atom to which they are attached, represent a cycloalkylidene (C-Cg,) - group;
    X is a halogen atom, mainly chlorine,
    characterized in that, in order to simplify the process, the corresponding acid anhydride is in contact with a Lewis acid, 2, Method POP.1, characterized in that a metal halide selected from the group consisting of aluminum chloride, aluminium bromide, iron chlorine is used as the Lewis acid III), tin chloride (ly), titanium chloride, boron trichloride, boron trifluoride or zinc chloride. 3. Method according to PPL and 2.0 t and h and y and the fact that the original Lewis acid is taken in the amount of 0.0005-0.5 mol per 1 mol of acid halide. 4. A method according to claims 1.2 and 3, which is based on the fact that the process is carried out in an inert solvent such as ether, aliphatic hydrocarbon or halogen-substituted aliphatic hydrocarbon. 5. The method according to PP, 1-4, about tl and h ayusch and the fact that the process is carried out at a temperature not of the boiling point of the reaction system for 0.16-20 hours.
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    同族专利:
    公开号 | 公开日
    CA1025475A|1978-01-31|
    GB1448316A|1976-09-02|
    JPS5337858B2|1978-10-12|
    BE822046A|1975-05-12|
    NL7414766A|1975-05-14|
    CH615411A5|1980-01-31|
    DE2453639B2|1977-06-23|
    DE2453639A1|1975-05-15|
    FR2250728A1|1975-06-06|
    DK586374A|1975-07-14|
    US3989750A|1976-11-02|
    IT1024802B|1978-07-20|
    JPS5077346A|1975-06-24|
    FR2250728B1|1976-12-31|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    FR2038019A5|1969-03-22|1970-12-31|Sumitomo Chemical Co|US4206140A|1966-08-26|1980-06-03|Roussel Uclaf|Novel cyclopropanecarboxylic acids and esters|
    JPS618048B2|1976-05-24|1986-03-11|Sumitomo Chemical Co|
    US4473703A|1981-03-30|1984-09-25|Sumitomo Chemical Company, Limited|Method of epimerization of alkyl chrysanthemate|
    JPS6351136B2|1981-03-30|1988-10-13|Sumitomo Chemical Co|
    JPH0253429B2|1981-10-22|1990-11-16|Sumitomo Chemical Co|
    DE3565397D1|1984-02-22|1988-11-10|Sumitomo Chemical Co|Method for racemization of chrysanthemic acid or its ester|
    HU200310B|1984-06-15|1990-05-28|Sumitomo Chemical Co|Process for racemizing chrisanthemic acid and esters and for transforming raceme cys isomeres into raceme trans isomeres|
    JPH0586775B2|1986-02-27|1993-12-14|Sumitomo Chemical Co|
    EP0261824B1|1986-09-04|1990-05-09|Sumitomo Chemical Company, Limited|Method for racemization of optically active chrysanthemic acid or its ester|
    EP0282221B1|1987-03-09|1992-01-15|Sumitomo Chemical Company, Limited|Method for racemization of optically active chrysanthemic acid or its ester|
    HU203513B|1987-04-28|1991-08-28|Sumitomo Chemical Co|Process for racemizing and trans-isomerizing optically active chrisanthemic acid derivatives|
    JPH0688933B2|1987-07-17|1994-11-09|住友化学工業株式会社|Racemization Method for Optically Active Primary Chrysanthemic Acids|
    DE68905073T2|1988-05-19|1993-06-17|Sumitomo Chemical Co|METHOD FOR PRODUCING RACEMIC CYCLOPROPANCARBONIC ACID HALOGENIDES.|
    US5840958A|1996-10-17|1998-11-24|Fmc Corporation|1S to 1R Epimerizations of pyrethroid intermediates|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    JP12750273A|JPS5337858B2|1973-11-12|1973-11-12|
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