• 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:
    2,5-Dimethyl-2,4-hexadiene is reacted with a diazo acetate of the formula N2CHCOOR (V> in the presence of a catalyst. The catalyst used is a copper complex of a chiral Schiff base of the formula: <IMAGE> In the formulae, R, R<1>, R<2>, X<1>, X<2> and C<*> have the meanings given in Patent Claim 1. The optically active alkyl chrysanthemates thus prepared can be hydrolysed to give the corresponding optical isomers of chrysanthemic acid. These isomers can be used for the preparation of synthetic, insecticidally active pyrethroids.
    公开号:SU719491A3
    申请号:SU762387252
    申请日:1976-07-30
    公开日:1980-02-29
    发明作者:Аратани Тадатоси；Ениеси Юкио；Фудзита Фумио；Нагасе Цунеюки
    申请人:Сумитомо Кемикал Компани Лимитед (Фирма)；
    IPC主号:
    专利说明:

    (54) A METHOD FOR OBTAINING AN OPTICALLY ACTIVE ALKYL CHRISANTEMATOR with substituents with a total number of carbon atoms of 7-30; Xi and Xg - hydrogen, alkyl Ci-Xu, phenyl, alkoxy, halogen or nitro group; Xi and X2 together form a beisogroup 2. However, but this method produces a mixture of all possible isomers, as a result of which the yield of each is not high enough. The purpose of the invention is to increase the selectivity of the process and increase the yield of the target products and optical purity. The goal is achieved by a method, the distinctive feature of which is that a diazoacetate of the formula CgCH-COOR is used as the initial medium, 11 where R is menthyl, neomentyl, 1-adamantyl, a, a-dimethyl-p- (mentoxy) - ethyl; 2,3-dnmethyl-2-butyl; 2,3,4-trimethyl-3-pentyl, bornyl, cyclohexyl, treg-butyl, a, a-dnmethylbenzyl. Preferably, the process is carried out at a molyb ratio of copper complex and dnazoacetate 0.001-0.1. When the Schiff base forms a complex with a divalent copper ion, three types of chelates are possible. One of the following: it has the following dimeric structure (P A), in which the Schiff base acts as a triadentate Lingand. C-C-C C-C I / I (PA) where Ri and Ro have the indicated meanings. The other type has the following monomeric structures (II B) or (IW), in which Schiff's oiovannena conducts itself as a badeitate or tri-cate ligoid, respectively, C - NC HC-OH, / g tf) 0-Cu-O Rj L where Hb R2 and X have the indicated values, and L is a neutral myoadentate ligand. Diazoacetates of general formula II can have both achiral and chiral structures. In the latter case, any form of enantiomers or racemic modification can be used in this reaction. In the case when the alkyl chrysanthemum formed by this reaction exhibits some insecticidal activity, it can be used as an insecticide. Among the chiral copper complexes used as catalysts for the proposed method, specific examples of copper complexes II A, II B and P B are complexes of the following chiral Schiff bases: N-salicylidene-2-amio-1,1-day- (2 -methoxyphenyl) -3-phenyl-1-propanol; N-salicylidene-2-amino-1,1-di- (2-isopropoxyphenyl) -3-phenyl-1-propanol; N-salicylidene-2-amio-1,1-di- (5-tregbutyl-2-isopropoxyphenyl) -3-phenyl-1-propaiol; N-salicylidene-2-amino-1,1-di- (2-butoxy-3-greg-butylphenyl) -3-phenyl-1-iropanol; N-salicylicide-2-amino-1,1-di- (5-tert-butyl-2-heptyloxyphenyl) -3-phenyl-1-propanol; N-salicylidene-2-amino-1,1-di- (5-terbuty-2-isoproxyphenyl) -l-propanol; N-calicyliden-2-amino - 1,1-di- (2-butoxy-5-gret-butylphenyl) -1-propanol; N-salicyliden-2-amino-1,1-di- (5-tregbutyl-2-octyloxyphenyl) -1-iropanol; N- (3-methoxysalicylidene) -2-amino-1,1di- (5-gret-butyl-2-oxyloxyphenyl) propanol; N- (3,5-dibromocalycylidene) -2-amino-1,1di- (2-isopropoxyphenyl) -3-phenyl-1-propyl; N- (3-ethoxysalicylidene) -2-amino-1,1di- (2-isopropoxyphenyl) -3-phenyl-1-propaiol; N- (2-OKCH-1-naphthylmethylene) -2-amino1, 1-day- (2-isopyropoxyphenyl) -3-feiyl-1-propanol; N-salicylidene-2-amino-1,1-di- (4-butoxybiphenyl-3-yl) -3-phenyl-1-propanol; N-salicylidene-2-amino-1,1-di- (2,5-dibutythoxyphenyl) -3-phenyl-1-propanol; N-salicylidene-2-amino-1,1-di- (2-butoxyphenyl) -3-methyl-1-, butanol or N-malicylidei-2-amio-1,1-di- (2-benzyloxn-5greg- butylphenyl) -4-methyl-1-menthol. As copper complexes of an optically active Schiff base, the effective complexes of these common PA, P B and II B forums are effective, but it is preferable to use comilex having a dimeric structure of formula II A. The process can be carried out as in the case of a chiral copper catalyst in the reaction system , and toga, when it is not soluble in it. The catalyst can be isolated and purified by reuse. The preferred molar ratio of edible comilex and alkyl diazoacetate is in the range of 0.001-0.1. The process is carried out at a temperature of from -50 to 150 ° C. In specific cases,
    the reaction temperature is below the melting point of 2,5-dimethyl-2, 4-hexadiene (15 ° C), and an appropriate solvent can be added to the reaction mixture. Suitable solvents in such cases are aromatic hydrocarbons, for example benzene, toluene or xylene.
    Example 1. 0.3 g (0.2 mmol) of the dimeric copper complex (K) -M-salicylidene-2-amino-1, 1-di- (5-gret-butyl-2 - octyloxy) propanol corresponding to the formula A, where RI is methyl, K2-5-7ret-butyl-2-octyloxyphenyl; X1 X2 hydrogen) is dissolved in 17.6 g (160 mmol) of 2,5-dimethylhexadiene2,4. To this solution is added dropwise a mixture of 4.4 g (40 mmol) of the indicated diene and 4.5 g (20 mmol) of α-phenyldiazoacetate, with stirring over 7 hours. At the beginning of the dropping, the catalyst solution is heated to 75 ° C to initiate decomposition of the diazo acetate, after which the mixture is kept at 40 ° C. At the end of the addition, a substantially quantitative amount of nitrogen gas is released.
    The reaction mixture is distilled to release an unreacted diene (m.p. 45 ° C / 20 mmHg) in vacuo to give 4.7 g / -mentylchristatemate as an oil with m.p. 123 ° C / 0.2 mmHg Art. Its yield is 76% based on the diazo compound.
    A-Mentil ether is analyzed by gas chromatography using a glass capillary column (liquid
    QF-1 phase) to determine the composition of the optical isomers of chrysanthemum.
    d-trans form 89.9%, / -grance form 2.7%.
    The total amount of d-cis- and 1-transform (separation is impossible) is 7.4%.
    It is calculated that the percentage content of the grams isomer in the ether is 93%, and the optical purity of the grams isomers is 92%.
    A mixture of 4.2 g / -mento ether, 1.8 g of potassium hydroxide, 1.5 ml of water and 11 ml of ethanol is heated while being transferred at 100 ° C for 7.5 hours. After the ethanol is distilled off from the reaction mixture, the residue is diluted with water and extracted with ether. The aqueous alkaline solution is acidified with dilute sulfuric acid and extracted with toluene. After the organic layer was washed with water and precipitates, the toluene was distilled off in vacuo to give chrysanthemic acid (2.4 g; yield 90%).
    Chrysanthemic acid is reacted with -2-octanol, the resulting diastereoisomers are analyzed by gas chromatography to determine the composition (%) of the optical isomers of chrysanthemic acid.
    uf-gras-form 90,4; / -trans-form 4,7; d-g is-form 3,6; / -r {y-form 1,3.
    The calculation shows that the optical purity of the trans isomers is 90%, and that of the cis isomers is 50%.
    Examples 2-6. The experiments were carried out as in example 1, using dimeric copper complexes, as shown in Table 1. 1, and Imentildiazoacetate.
    The results are shown in Table. one.
    Table I
    The content of the isomer of the / -mentilchrisantemate is determined by gas chromatography. The optical purity of chrysanthemic acid, obtained after hydrolysis, is determined by gas chromatography analysis of the corresponding (R) / -mentylheptyl ester.
    It should be noted that when the catalyst of the (R) -configuration is used, preferably the right rotational
    chrysitemic acid; when used as a catalyst of the S-configuration, levorotating chrysanthemic acid is preferably obtained.
    Example (comparative).
    Copper powder is used as a catalyst for the reaction of α-amino-diazoacetate and 2,5-dimethylhexanedien2, 4 instead of chiral copper complex.
    The results are presented in table. one.
    Examples 7-16. Under conditions similar to those given in Example 1, the process is carried out using the diazo acetates shown in Table 1. 2, and a chiral copper complex of the formula P A, where the configuration (R), where RI is methyl, R2 - 5t; et-butyl-2-oxyloxyphenyl.
    The results are presented in Table. 2
    The content of the tra c-isomer in alkyl chrysanthemates is estimated by gas chromatography. The optical purity of chrysanthemic acid obtained by hydrolysis of the corresponding esters is assessed by gas chromatography analysis of the corresponding (5) -1-menthyl-1-heptyl ether.
    Example (comparative).
    The reaction between ethyldiazoacetate and 2,5-dimethylhexadiene-2, 4 is carried out in the presence of the same copper catalyst as in Examples 7-16.
    The results are presented in Table. 2
    table 2
    权利要求:
    Claims (1)
    [1]
    Claim
    A process for producing an optically active alkilhrizantemata reacting 2,4-2,5dimetilgeksadiena with diazoacetate in the presence of a copper complex coordinatively bound Schiff base of formula I C = N .N-CH-C it with a chiral base / Ri ^ · ρ 1 OH wherein C * - asymmetric carbon atom;
    Ri is alkyl C] —Ci; aralkyl unsubstituted or substituted by alkoxyl with a total number of carbon atoms of 7-20;
    R 2 is aryl substituted with alkoxyl with a total number of carbon atoms of 7-30, and aryl may have one or more of these substituents, at a temperature of from -50 to 150 ° C in an aromatic solvent, characterized in that, in order to increase selectivity the process, increasing the yield and optical purity of the target product, as diazoacetate use compounds of the General formula
    N 2 CH — COOR, where R is mental, neo-methyl; 1-adamantyl; a, a-dimethyl-p- (mentoxy) ethyl, 2,3-dimethyl-2-butyl; 2,3,4-trimethyl-3-pentyl; bornyl, cyclohexyl; tert-butyl, α, α-dimethylbenzyl.
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    同族专利:
    公开号 | 公开日
    CH621767A5|1981-02-27|
    DE2634663C3|1980-01-17|
    DE2634663A1|1977-03-17|
    DK142765B|1981-01-19|
    IL50100D0|1976-09-30|
    IT1070323B|1985-03-29|
    NL7608508A|1977-02-03|
    GB1499094A|1978-01-25|
    BE844631A|1976-11-16|
    CA1121813A|1982-04-13|
    FR2319623B1|1979-09-28|
    IL50100A|1982-02-28|
    JPS5910336B2|1984-03-08|
    DE2634663B2|1979-05-31|
    FR2319623A1|1977-02-25|
    DK345276A|1977-02-02|
    DK142765C|1981-08-17|
    JPS5217448A|1977-02-09|
    引用文献:
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    JP4576642B2|1998-01-29|2010-11-10|住友化学株式会社|Process for producing optically active chrysanthemic acid|
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    CN103789789B|2014-02-11|2016-06-29|华东师范大学|Electrochemical synthesis has the method for optically active Styrene carbonate|
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    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    JP9434975A|JPS5910336B2|1975-08-01|1975-08-01|
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