• 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:
    Novel alpha -aryl- alpha -R1-1H-azole- ethanol compounds in which R1 is an halogenated cyclopropyl linked either directly or via an alkylene group to the alpha -carbon atom, are useful as plant fungicides and for treating fungus diseases in man and animals.
    公开号:SU1222193A3
    申请号:SU833657052
    申请日:1983-10-26
    公开日:1986-03-30
    发明作者:Шауб Фритц
    申请人:Сандос АГ (сн)；
    IPC主号:
    专利说明:

    . .one
    The invention relates to novel 1,2,4-triazole or imidazole derivatives having fungicidal activity and which can be used in agriculture,
    The purpose of the invention is to obtain new 1,2,4-triazoles or imidazolor with higher fungicidal activity. .
    The invention is illustrated by the following examples.
    Example 1. 2- (4-Chlorophenyl) -4- (2,2-dichlorocyclopropyl) -3,3-dimethyl- I- (1H-1,2,4-triazol-1-yl) butan-2-ol " . A. 5.1 g of Dodetsvdimethylsulfonyl methylsulfate is added to a solution of 1- (4-chlorophenyl) -3- (2,2-dichloro-cyclopropyl) -2,2-dimethylpropan-1-one in 30 ml of dry toluene at room temperature. temperature and the mixture is stirred for 15 minutes. 1.1 g of potassium hydroxide powder is added to the suspension, and the mixture is stirred for 2 hours at 35 G. After cooling, the reaction mixture is poured on ice and extracted with diethyl ether. The organic extracts of the successor are washed three times with water, then with a saturated aqueous solution of sodium chloride, then the resulting extracts are dried with magnesium sulfate and evaporated in vacuo. A colorless oil is obtained which consists in 50% of 2- (4-chlorofensh1) -2- (2-) 2,2-dichloro-cyclopropylC-, 1-dimethyl-ethyl) oxirane and 50% of. dodecylmethyl sulfide.
    B. The pure oxirane product, without separation, is added dropwise over 10 minutes to 1.0 g of 1,2,4-triaol preheated to 90 ° C, and the resulting mixture is stirred for 18 hours, maintaining the temperature. the reaction mixture. After cooling, the reaction mixture is poured onto ice and extracted with methylene chloride. The organic extracts are sequentially washed with water and a saturated solution of sodium chloride, dried over anhydrous magnesium sulphate and evaporated in aqum. The title compound is obtained after chromatography on silica gel, eluting first with hexane /: ethyl acetate (starting with a ratio of 9: 1, then 1: 1), and then with ethyl acetate, crystallized from diethyl ether / hexane to give colorless
    9JZ
    crystals so pl. 117-123 C (mixture of diastereoisomers).
    Example 2: By the method of Example 1, the following compounds of general formula (1a) are prepared:
    Y.
    -L 1 x
    UN-CH -C-IAVC X,
    6,
     V
    in the interaction of an azole with the corresponding axirane ... ,, (A) -C (CHP, X / X Cl / Cl, Y: N, Rf 0.24 (EАс);
    R24-C1, (A) -CH, i-, Br / Br, Y: N, Rf 0.30 (EAc);
    ,, Rs: H, (A), X., / X C1 / C1, Y: CH, m.p. G40-55 C;
    R.i 4-Cl, R32-Cl ,, (A) -CH (CH3) CH, 1-, X, / X C1 / C1, Y: N, Rf 0.28 () n | f 1,5598;
    Rj 4-Cl ,, ,,,. (A) n- -C (CH3) CH -, X / Xj Cl / Cl, Y: N, m.p. lOO-BO C;
     mixture of diastereoisomers, eac and acetate.

    mixture of isomers.


    Source compounds. EXAMPLE 3. 1- (4-Chlorophenyl) -3-, (2,2-dichlorocyclopropyl) -2,2-dimethylpropan-1-one.
    I. -.
    A. To a solution of 28 g of powdered potassium hydroxide in toluene, 45.6 g of 4-chlorophenylisopropyl ketone, then 8.1 g of tetrabutyl ammonium bromide are added at room temperature with stirring, and the temperature rises to. After stirring for 2 hours, 28.7 g of allyl chloride in 100 ml of toluene is added dropwise at room temperature, and the mixture is stirred at room temperature overnight. Then the mixture was poured into ice water, extracted with ether, the combined organic extracts were washed successively with water and a saturated solution of sodium chloride, dried with magnesium sulfate and evaporated. After fractional distillation of the residue from evaporation, I- (chlorophenl) 2,2-dimethylpent-4-en-1-one is obtained in the form of a colorless oil, b.p., 0.4 mm Hg.
    B. 500 g of a 501% caustic soda solution is slowly added to a solution of 64 g of 1- (4-chlorophenyl) -2,2-dimethyl-, pent-4-en-1-one in 500 ml of chloroform at 0 ° C, and 5 g of triethylbenzylammonium chloride (TEMA) are added to the mixture in portions over 15 minutes. After the addition is complete, the mixture is stirred for 8 hours at 0-5 ° C, and then after dilution with 500 ml of chloroform, another 18 hours at room temperature. The reaction mixture is extracted with ice and methylene chloride is extracted. The combined organic extracts are washed with water, dried with magnesium sulfate and evaporated in vacuo. The pure compound is obtained by chromatography on silica gel / hexane / diethyl ether (1-3%), 23 on sipicagel plates using hexane / diethyl ether 96: 4 as eluant.
    Note 4, According to the method of Example 3ft., The following compounds crawl (cf., Table 1):
    L.
    0 (L-C SCH5CHb - 3 L
    PRI me R 5, 4-Chlorophenyl-2 2-di chloro-1-scitterpropyl ketone,
    To a solution of 7.0 g of 1- (4-chlorofensh1) - 2-methylprop-2-en-1-one in 70 ml of chloropropyidyl) HJV / XajRt P
    4.14-C1 H C (CH) CHjBryBii HH H 0.34 nx / EA95: 5
    4.24-С1 Н СН (СНз) СН С1 / С1 НН Н 0.31 | x / ЕАс9: 1
    4.34-С1 Н С (СНз), 1 С1 / С1 НН Н .0,29 НХ / ЕАс9: 1
    HX / EAc hexane / ethyl acetate; A mixture of diastereoisomers.
    the form is slowly added at 0 ° C with an intestinal permixing of 16 g of a 50% aqueous solution of caustic soda, followed by the addition of 4.3 g of triethyl benzyl ammonium chloride. After the addition is complete, the cooling bath is removed until a strong exothermic reaction starts. Then the reaction mixture is cooled again so that the temperature is first maintained at 34-40 ° C and then slowly reduced to room temperature. After 5 hours, the reaction mixture was poured onto ice and then extracted with diethyl ether. The organic extracts are combined, washed with water, cjraraT magnesium sulfate and evaporated in vacuo. The residue is chromatographed on silica gel with hexane / diethyl ether (9: 1) to give the title compound of n 1.5689 and 24 (thin layer chromatography) using hexane / diethyl ether (9: 1) as eluant. ),
    PRI and MER 6, The antifungal activity of the compounds obtained by the proposed method is illustrated in the following table, where the concentrations are given, causing 90% death of fungi. As a comparison, propicone-aol having a high activity against powdered Meldi and rust (see tab. 2).
    Table 1
    Editor A.Dolinich
    Compiled by A. Orlov
    Tehred G.Gerber Proofreader V. Sinitska
    Order 1623/61 Circulation 379 Subscription VNIIPI USSR State Committee
    for inventions and discoveries 113035, Moscow, Zh-35, Raushsk nab., 4/5
    Branch ShSh Patent, Uzhgorod, 4 Project St.
    table 2
    权利要求:
    Claims (1)
    [1]
    METHOD FOR PRODUCING ASOLIC COMPOUNDS of general formula (I)
    R ^ RjjR ^ is hydrogen or methyl; Y is CH or N, characterized in that the azole of formula (II) where R 2 R 3 -
    N OH (A) l-81 halogenated cyclopropyl;
    0 or 1;
    CRt (R 5 or CRi, R s -CHR 6 , rfle CHR ^ is linked to R ^;
    hydrogen or halogen; halogen;
    where Y has the indicated meanings;
    M is hydrogen, an alkali metal or a trialkylsilyl group, is reacted with a compound of the general formula (III)
    Rt where A, p, R r , And g and R 3 have the indicated meanings, followed by isolation of the target product. , 1 .1222193
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    同族专利:
    公开号 | 公开日
    ZA838076B|1985-06-26|
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    NL8303651A|1984-05-16|
    BR8305935A|1984-06-05|
    KR840006479A|1984-11-30|
    IT8349185D0|1983-10-20|
    GB8328492D0|1983-11-23|
    PL244326A1|1984-09-24|
    FR2535321A1|1984-05-04|
    PT77558B|1986-04-16|
    ES526780A0|1985-05-01|
    FR2535321B1|1985-10-18|
    GR79636B|1984-10-31|
    GB2129000A|1984-05-10|
    IL70058D0|1984-01-31|
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    JPS5998061A|1984-06-06|
    AU2060283A|1984-05-03|
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    CS786283A2|1985-08-15|
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    GB2129000B|1986-03-19|
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    引用文献:
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    CH647513A5|1979-11-13|1985-01-31|Sandoz Ag|TRIAZOLE DERIVATIVES, THEIR PRODUCTION AND USE.|BG48681A3|1982-12-14|1991-04-15|Ciba Geigy Ag|Fungicide means|
    NL8402548A|1983-09-01|1985-04-01|Sandoz Ag|NEW AZOLE CONNECTIONS.|
    FR2606408B1|1983-09-01|1989-11-24|Sandoz Sa|NEW ETHANOL DERIVATIVE, ITS PREPARATION AND ITS USE AS A FUNGICIDE|
    GB8414519D0|1984-06-07|1984-07-11|Pfizer Ltd|Triazole antifungal agents|
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    EP0180850A3|1984-11-02|1987-05-27|Bayer Ag|Antimycotic azolyl-methyl-cyclopropyl-carbinol derivatives|
    GR852627B|1984-11-02|1986-03-03|Bayer Ag|
    DE3518916A1|1985-05-25|1986-11-27|Bayer Ag, 5090 Leverkusen|DICHLORCYCLOPROPYLALKYL-HYDROXYALKYL-AZOL DERIVATIVES|
    DE3530799A1|1985-08-29|1987-03-05|Hoechst Ag|AZOLYL-CYCLOPROPYL-ETHANOL DERIVATIVES, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE|
    GB8603951D0|1986-02-18|1986-03-26|Ici Plc|Heterocyclic compounds|
    DE3608792A1|1986-03-15|1987-09-24|Hoechst Ag|1,1-DISUBSTITUTED CYCLOPROPANE DERIVATIVES, METHOD FOR THEIR PRODUCTION AND THEIR USE|
    DE3644616A1|1986-12-29|1988-07-07|Lentia Gmbh|IMIDAZOLE DERIVATIVES, METHOD FOR THE PRODUCTION AND USE THEREOF|
    JPH0696530B2|1987-06-05|1994-11-30|呉羽化学工業株式会社|Azole antifungal agent|
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    DE3813874A1|1987-07-10|1989-01-19|Bayer Ag|HYDROXYALKYL-AZOLYL DERIVATIVES|
    DE3732385A1|1987-09-25|1989-04-06|Bayer Ag|HYDROXYALKYLCYCLOPROPYL1-1,2,4-TRIAZOLYL OR IMIDAZOLYL DERIVATIVES AND THEIR USE AS ANTIMYCOTIC AGENTS|
    US5770741A|1988-12-12|1998-06-23|Sandoz Ltd.|Process for cylopropane derivatives|
    DE3824435A1|1988-07-19|1990-01-25|Bayer Ag|SUBSTITUTED 2,2-DIHALOGENCYCLOPROPYL-HYDROXYETHYL-1,2,4-TRIAZOLES, METHODS AND 2,2-DIHALOGENCYCLOPROPYL-OXIRANES, CYCLOPROPYLKETONE AND HALOGENMETHYL-CYCLETELLUNGPRODUCTED OXYGENOZYLENOXIDE|
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    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    CH630082|1982-10-28|
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