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    • 专利摘要:
    L'invention concerne les composés: où A est un oxygène, un méthylène ou un carbonyle, R est un alcoyle (1 à 8 carbones) linéaire, ramifié ou cyclique, saturé ou insaturé, et la double liaison est Z, sous toutes leurs formes stéréoisomères possibles ou sous forme de mélanges de stéréoisomères. L'invention concerne également la préparation des composés 1, leur application à la lutte contre les parasites des végétaux, les parasites domestiques et les parasites des animaux à sang chaud, les compositions les renfermant, des associations les renfermant et nouveaux intermédiaires obtenus.
    公开号:SU1210661A3
    申请号:SU813270851
    申请日:1981-04-13
    公开日:1986-02-07
    发明作者:Мартель Жак；Тессье Жан；Теш Андре
    申请人:Руссель-Юклаф (Фирма)；
    IPC主号:
    专利说明:

    i
    This invention relates to an "
    chemistry and concerns, in particular, the synthesis of new derivatives of cyclopropanecarboxylic acid of the general formula
    CN-CH O
    O / O-s-nk-nc / VV2
    X, 1H
    -Chn CHj
    where R is saturated or unsaturated, straight-chained or branched C, -C5 alkyl or C -C-cycloalkyl, the double bond has a geometry j
    CO-.R
    (j.)
    in the form of stereoisomers or their mixtures which have acaridic, insecticidal and nematocidal properties.
    The aim of the invention is a method for the preparation of new compounds having acricidal, insecticidal and nematocidal properties.
    Example 1. (5) (-Cyano-3-phenoxybenzyl (1K cis) 2,2-dimethyl 3 (2) 2- (methoxycarbonyl) -ethenyl} cyclopropanecarboxylate.
    7 g (1K, cis) 2,2-dimethyl- (2) 3 (2-methoxycarbonyl) -ethenyl) J - cyclopropanecarboxylic acid, 7.3 g of dicyclohexylcarbodiimide and 3 cm of pyridine in 50 cm-methylene chloride are added. Then 8 g of (5) oi cyano-3-phenoxybenzyl alcohol is added. The reaction mixture is stirred at room temperature for 1b, filtered, the filtrate is brought to dryness under reduced pressure, and 20 g of product are obtained, which is recrystallized in isopropyl ether. Obtain 10.5 g of the desired product with so pl. 98 C.
    Spectrum of PNR, CDCE ,, ppm: 1.23 and 1.26 protons of methyls in the 2-position; 1.93-2.07 proton carbon in 1-position; 3.2-3.34-3.37-3.50 proton carbon in the 3-position 6.35 proton carbon, carrying the CAC group; 5.8-6.05 proton of ethyl carbon bearing the group, 6.35-6.51 and 6.55-6.72 proton of ethylene carbon in position on cyclopropane 3.72 protons of methoxycarbonyl group; 6,9-7,6 protons of aromatic compounds.
    Example 2. (R) ot-Cyano-3- phenrxybenzyl- (1R numbers) 2,2-dimethyl210661
    3- (2) 2 (methoxycarbonyl) -stenyl cyclopropanecarboxylate.
    As in Example 1, starting from 1.5 g (1R, i5ac) 2,2-dimethyl 3 (Z) 2 (marks5 sicarbonyl) ethenyl-cyclopropanecarboxylic acid and 1.9 g (P) l-cyano-3-phenoxybenzene alcohol, 4.3 g of crude desired product are obtained, which is chromatographed on silica using silica (solvent: cyclohexane-ethyl acetate 9-1). 2.5 g of the expected product are obtained. G: +23.51 2.5 °. (, 5% benzene).
    PMR spectrum, CDC6j, ppm: 1.32 proton tones of methyls in the 2-position 1.92–2.06 proton carbon in the 1-position 3.17–3.45 proton carbon in 3-position; 6.3 proton carbon carrying group C N; 5.8-5.98 proton
    20 ethylene carbon, Hecyiuero
    group 6.3-6.7 proton of ethylene carbon in the position of cyclopropane 3.7 protons of the methoxycarbonyl group, 6.9-7.6 protons
    25 aromatic compounds.
     Example 3. (IR.UWC) 2,2-Dimethyl-3- (2) 2- (methoxycarbonyl) ethenyl cyclopropanecarboxylic acid.
    30 Stage A.
     tert-Butyl (1H, t; ii (C) 2,2-dimethyl-3-2 (methoxycarbonyl) -penyl cyclopropanecarboxylate.
    55 g of tert-butyl (1K, c1 / s) of 5 2,2-dimethyl-3- (2,2-dibromovinyl) -cyclopropanecarboxylate in 550 cm of tetrahydrofuran are introduced. Cool to -.70 ° C, add over 40 minutes. 132 cm of a solution of butyl lithium in cyclohexane (at 20%) and stirred for 30 min at -65 s, then 12.5 cm of methyl chloroform is added. After 2 h of reaction, the temperature is again set to -20 ° C, the resulting mixture is poured into an aqueous solution of sodium hydrogen phosphate and extracted with ether. The mixture is washed and brought to dryness under reduced pressure. 38.3 g of product are obtained which is chromatographed on silica with the solvent: cyclohexane-ethyl acetate (8-2). 17.2 g of the expected product are obtained.
    Stage V.,
    45
    55
    tert-Butyl (1D, (, ac) 2,2-dimethyl- 3- (Z) 2- (methoxycarbonyl) ethenyl cyclopropanecarboxylate.
    12 g of the product obtained in stage A are hydrogenated in 240 cm of ethyl acetate in the presence of 2.4 g of palladium hydroxide (10%) on barium sulfate and 2.4 cm of quinoline. Filtered and dried. 11 g of the desired product is obtained in this way.
    Stage C.
    (IRtjuc) 2,2-dimethyl-3-G (2) 2- (methoxycarbonyl) ethenylcyclopropane carboxylic acid.
    The solution containing 13.5 g of the product obtained in stage B, 100 cm of toluene and 400 g of para-toluenesulfonic acid hydrated is heated under reflux for 3 hours. Dry under reduced pressure to obtain 11.2 g of product which is chromatographed on silica with a solvent: cyclohexane-ethyl acetate-acetic. to the acid (60-39-1). It is brought to dryness under reduced pressure and 9.6 are obtained. g the desired product with so pl,
    ., 5 i 2 ° (ence,).
    Spectrum Ш4Р, CDCBj, ppm: 1,3 protons of methyls in position 2 of cyclopropane; 1.86-2 proton at position 1 of cyclopropane 3; 1-3.28-3.43; proton at position 3 of vanclopropane; 5.8-5.99 proton ethylene carbon in s. -the position of the group, 6.42-6.58 and 6.61-6.77 proton of ethylene carbon in the position of the group COjCH ,, 8.63 proton of the group COgH.
    Example 4. (5) o1-Cyano 3-phenoxybenzyl- (1 R tjac) 2,2-dimetip 3 ;; (2) 2 (ethoxycarbonyl) -enesh1 cyc lopropanecarboxylate.
    As in Example 1, starting with 1.25 g of (1R,) 2,2-dimethyl 3 (Z) 2- (ethoxycarbonyl) -ethenylcyclopropanecarboxylic acid and 1.45 g (5) of cyano-3-phenoxybenzyl alcohol, 4.1 g of the crude product in crude form which is subjected to silica chromatography (solvent cyclohexane-ethyl acetate 9-1). 1.95 g of the expected product are obtained. Wj): -f57.51 s (, 3%, in benzene).
    PMR spectrum, CDCEjM.A .: 1.25-1.27 proton methyl in position 2 of cyclopropane 1.92-2.06 proton carbon in position 1 of cyclopropane; 3.2 - 3.36 and 3.8-3.52 proton carbon in position 3 of cyclopropane; 5.83-6.03
    1210661
    the proton of ethylene carbon bearing the ethoxycarbonyl group, 6.38-6.73 proton of ethylene carbon in pf. -position of cyclopropane J 6.35 5 carbon proton, bearing the CM group; 1.18-1.3-1.41 protons of ethylmethyl; 4.01–4.13–4.25–4.36 protons of ethylmethylene.
    Example 5. (1K, cis) 2,2-di10 methyl (7) 3-ethoxycarbonyl) ethenyl cyclopropanecarboxylic acid. Stage A.
    treg-Butyl (1R, Cys) 2,2-dimethyl 3 carboxyethinyl cyclopropanecarbok15 silate.
    26 g of tert-butyl (1R, tiUc) 2,2-dimethyl-3- (2,2-dibromovinyl) -cyclopropanecarboxylate are introduced in 175 cm of anhydrous tetrahydrofuran. Then
    20 was added at -65 ° C with 60 cm of a 20% butyl lithium solution in cyclohexane. Stirred for 1 h at. then carbon dioxide is bubbled through for 1 h 30 min, drinking the reaction mixture into ice water, combined with normal sodium. Washed with ether. The alkaline aqueous phase is acidified to pH 4 and extracted with ether. Dried
    30 the organic phases are brought to dryness under reduced pressure. A product is obtained which is recrystallized in petroleum ether (mp 60-80 ° C). 8.3 g of the desired product are obtained with a mp. 144 ° C.
    Spectrum, CDC6, Suym.d.: 1.22 and 1.37 protons of methyls in position 2 of cyclopropane; 1.78 protons at position 1 and 3 of cyclopropane; 1.47 protons of terbutyl 8.25 protons of the COOH group.
    Stage B.
    Treg-Butyl (1R, t4uc) 2,2-dimethyl-, 3- (ethoxycarboxyethyl) cyclopropanecarboxylate.
    40
    45
    4 g of the product obtained in step A, 3.4 g of dicyclohexyl-carbodiimide and 6 mg of 4-dimethylaminopyridine in 30 cm of methyl chloride are introduced. 1.5 cm of ethanol are then added and the mixture is left stirred for 16 hours at 20 ° C. The filtrate is filtered and the filtrate is concentrated under reduced pressure. 5.5 g of product are obtained, which is purified by chromatography on silica with a solvent: cyclohexane-ethyl acetate (9-1). 4.25 g of the expected product are obtained.
    -RayP spectrum: CDce,,, ppm: 1.18-1.21 and 1.36-1.47 protons in position 2 of cyclopropane 1.73 and 1.82. Protons in position 1 and 3 of cyclopropane; 1.47 protons of t-butyl; 1,27- 1,38-1,5 and 4,0-4,13-3,25-4,36 ethyl protons. Stage C.
    tert-Vutyl- (1K, mis) 2,2-dimethyl- 3 - () - 2- (ethoxycarbonyl) -ethenyl 3. cyclopropane.
    Hydrogenation of 4.3 g of the product obtained in the previous stage is carried out in 100 cm of ethyl acetate in the presence of 800 mg of Pd (OH) 2Ba504 catalyst and 0.8 cm of quinoline. Filter, adjust the filtrate to pH below 7 with 2 n. hydrochloric acid and washed with water. Dry dry under reduced pressure. 4.6 g of product are obtained which is chromatographed on silica with the solvent: cyclohexane-ethyl acetate (95-5). 2.5 g of the desired product are obtained.
    PMR spectrum, CDCtj, ppm: 1.25 and 1.28 protons of methyls in position 2 of cyclopropane; 1.78-1.93 proton in position 1 of cyclopropane; 2.98-3.1-3.2 proton in position 3 of cyclopropane; 6.4-6.6-6.8 proton of ethylene carbon in position about cyclopropane; 5.7-5.9 proton ethylene carbon bearing ethoxycarbonyl group; 4.0-4.13-4.25-4.36 proton ethoxymethylene.
    ; Stage D.
    (1Rf4Uc) 2,2-Dimesh1-3 (g) 2 (ztoxycarbonyl) -ethenyl cyclopropanecarboxylic acid.
    2.3 g of the product obtained in stage C and 20 mg of hydrated p-toluenesulfonic acid in 20 cm of toluene are introduced. The mixture is heated under reflux for 40 minutes, brought to dryness under reduced pressure and prepared. 2.1 g of the residue which is chromatagrafted onto silica with the solvent: cyclohexane-ethyl acetate-acetic acid (60-39-1) 1.5 g of product are recovered, which is recrystallized in cyclohexane. Obtain 1.5 g of the desired product with so pl. 96 C.
    PMR spectrum,,, ppm: 1.3 and 1.32 protons of methyls in position
    five
    Q 5
    Q
    five
    0
    five
    2 cyclopropane J 1.86-2.02 proton carbon in position 1 cyclopropane, 3.15-3.28-3.3-3.45 proton carbon-. genus at position 3 of cyclopropane 6.38-6.53 and 6.55-6.73 proton of ethylene carbon branched to cyclopropane; 5.78-5.96 proton of ethylene carbon bearing the ethoxycarbonyl group; 1.18-1.3-1.41 protons of methyl of the ethoxycarbonyl group; 4, -0-4,13 and 4.25-4.36 protons of methylene of the ethoxycarbonyl group.
    Ex. 6. (5) l-Cyano-3-phenoxybenzyl- (1R cos) -2,2-dimethyl 3 (g) 2- (propoxycarbonyl) -ethenyl cyclopropanecarboxylate.
    As in Example 1, starting from 1.5 g (1D, shch / s) 2,2-dimethyl-3- (Z) 2- (n-propoxycarbonyl) -ethenyl-cyclopropanecarboxylic acid and 1.7 g ( 5) s. -cyano-3-phenoxybenzyl alcohol, 4.1 g of product are obtained which is chromatographed on silica (eluent: n-hexane-isopropyl ether 7-3). 2.2 g of the expected product are obtained. Wj,: + 52 ± 2.5 ° (, 5% benzene).
    Spectrum Ø 1P, CDCEj, ppm: 1.25-1.28 protons of methyls in position 2 of cyclopropane; 1,94-2,03 pro-, tone of carbon in the discharge of 1 cyclopropane; 3.29-3.39-3.49 proton carbon in position 3 of cyclopropane; 6.33 carbon proton carrying the C5N group, 5.89-6.01 proton of ethylene carbon, bearing the propoxycarbonyl group of 6.41-6.52 and 6.53-6.64 proton of ethylene carbon combined with cyclopropane; 4.02-4.09-4.15 proton of methylene of the 1 propoxycarbonyl group; 0.88-0.96-1.04 proton of the methyl propoxycarbonyl group.
    Example 7. (1, K tit / c) 2,2-Dimethyl 3 (7) 2- (n-propoxycarbonyl) ethenyl cyclopropanecarboxylic acid.
    Stage A.
    tert-Butyl- (1R, cx) 2,2-dimethyl opoxycarbonylethenyl-cyclopropanecarboxylate.
    Introduced 22.8 g of tert-butyl (IH tsos) 2,2-dimethyl-3- (2,2-dibromovinyl) -. cyclopropanecarboxylate, 250 tetrahydrofuran, then at, 55 cm of a 20% solution of butyl lithium in cyclohexane, is maintained at
    -65 ° C for 1 h and introduced at -65 C for 15 min 8 cm (t-propyl chloroformate. Maintain agitation for 1 h at -65 C again raise the temperature to a room for 1 h and stir again for 1 h at poured into a saturated aqueous solution of sodium hydrogen phosphate, stirred, extracted with ether and washed with water. Dried and brought to
    I. - dry under reduced pressure. In this way, 19.5 g of a liquid oil is obtained, which is purified by chromatography on silica with the solvent cyclohexane-ethyl acetate (9-1). 11.5 g of the expected product are obtained.
    Nuclear Magnetic Resonance Spectrum, СОсе ,,, ppm: 1.17 and 1.37 protons of methyls in position 2 of cyclopropane 1.72 proton 6, positions 1 and 3 of cyclopropane; 1.44 proton tert-butyl 4,0-4,12-2,23 methylene proton in position 1 propoxycarbonyl; 0.83-0.95-1.06 protons of methyl propoxycarbonyl.
    Stage V. treg-Butyl (1B cis) 2,2-dimethyl 3- () 2 (n-propoxycarbonyl) -eneth1 cyclopropanecarboxylate.
    7 g of tert-butyl () 2,2-dimethyl-3- (n-propoxycarbonyl-ethenyl) -cyclopropanecarboxylate are hydrated in 140 cm of ethyl acetate in the presence of 1.4 g of 10% palladium hydroxide on barium sulfate and 1.4 cm quinoline Wash the filtrate with a solution of 2 n. hydrochloric acid is then washed with water, dried and brought to dryness under reduced pressure. 7.2 g of product are obtained which is chromatographed on silica with the solvent cyclohexane-ethyl acetate (95-5). 6.1 g of the expected product are obtained.
    NMR spectrum, CDCgj, ppm: 1.25 and 1.29 protons of methyls in position 2 of cyclopropane} 1.5-2.03 proton carbon in position 1 of cyclopropane 3.03-3.35 proton carbon in position 3 of cyclopropane 6.5-6.66 and 6.69-6.85 proton of ethylene carbon combined with cyclopropane; 5.82-6.0 proton ethylene carbon bearing a propoxycarbonyl group; 4.02-4.12-4.23 proton of methylene in position 1 of the propoxycarbonyl group of 0.86-0.98-1.1 proton of the methyl of propoxycarbonyl group.
    106618
    Stage C.
    (1R, cis) 2,2-dimethyl-3 (2) 2 (n-propoxycarbonyl) ethenyl-cyclopropancarboxylic acid. 5 Heat a mixture of 5.8 products obtained in Stage B, 200 mg of hydrated P-toluene sulphonic acid and 60 cm of toluene under reflux for 1 h. The solution is brought to dryness under reduced pressure and 5 g of product are obtained which are chromatographed on silica with a solvent: cyclohexane-ethyl acetate-acetic acid (705 29-1). 4.2 g of sought product is obtained.
    Spectrum of the NDP, SOC,, ppm: 1.27 and 1.29 N methyls in position 2 cyclopropane, 1.86-2 N in position 1
    0 cyclopropane; 3.13-3.45 N in position 3 of cyclopropane; 5,8-Ь Н ethylene carbon bearing group
     COgCHj CH —CHjV 6.4-6.56-6.59 N ethylene carbon combined with
    5icyclopropane 3.98-4.08-4.18 N methylene in position 1 of the propoxycarbonyl group; 0.83-0.95-1.06 N of the methyl propoxycarbonyl group. Example 8. (S) oi-Cyano-3d phenoxybenzyl (1R, c "c) 2,2-dimethyl- 3-C (2) 2- (isopropyloxycarbonyl) -ethenylJ-cyclopropancaproboxlate. As in Example 1, starting from 900 mg of (1Rti, c) 2,2-dimethyl 3- (Z) 2- (isopropyloxyarb onyl) -e lopropancarboxylic acid and 900 mg (S) (L) -cyano-3- phenoxybenzyl alcohol, 1.8 g of the expected product are obtained in crude form, which is chromatographed on silica (solvent: cyclohexane-ethyl acetate 9-1). 1.2 g of the expected product are obtained. : + 34 ± 2 (, 4% in benzene).
     . PMR spectrum, CDCgj, ppm 1,25 and 1,27 protons of methyls in position 2. cyclopropane; 1.92-2.05 proton carbon in position 1 of cyclopropane; 3.25-3., 39 and 3.42-3.56 proton carbon in position 3 of cyclopropane; 6.3 carbon proton carrying a CsN group; 5,8-6 proton of ethylene carbon bearing isopropyloxy group; 6.35-6.51 and 6.55-6.71 proton eton.le5 new carbon, connected to cyclopropane, 5.08 proton isopropyl; - 1.23-1.34 proton methyls and isopropyl.
    five
    0
    Example 9. (1R (aus)) 2,2-. Dimethyl-3 (2) 2 (isogropyloxycaronon) -ethenyl cyclopropanecarboxylic acid.
    Stage A. tert-Butyl (iRtjuc) 2,2-dimethyl 3- (X) 2-carboxyethenyl cyclopropanecarboxylate.
    2 g of tert-butyl (1Kc “e) 2,2-dimethyl-C 2-carboxyethynyl diclopropanecarboxylate in 40 cm of ethyl acetate are hydrogenated in the presence of 0.38 g of 10% palladium hydroxide on barium sulfate and 0.4 see quinoline. Filter, wash the filtrate with 0.5 and. hydrochloric acid, then with water until neutral, dried, concentrated to dryness under reduced pressure, and 2 g of the desired product is obtained with mp. 94 C.
    Stage B. gret-Butyl () 2,2-dimethyl-3-G () 2- (isopropyloxycarbonyl) -ethenyl-cyclo-p-carboxylcarboxylate.
    2.7 g of treg-butyl (1Kc1 (c) 2,2-dimethyl 3- (Z) 2-carboxy) ethylene 1 cyclopropanecarboxylate in 10 cm of ethyl acetate are mixed, then 2 g of O-isopropyl K, N-diisopropyl urea and stirred for 1 h at room temperature. The mixture is maintained under reflux for 1 hour and 30 minutes, allowed to reach 20 ° C, the insoluble part is filtered and the filtrate is brought to dryness under reduced pressure. 3.5 g of oil are obtained, which are chromatographed “on silica with a solvent: benzene-cyclohexane (7-3). Obtain 1 g of the desired product, which is used in the same form in the next stage.
    Stage C.
    (1R cis) 2,2-Dimesh1-3- (g) 2- (isopropyloxycarbonyl) -ethenyl-cyclopropanecarboxylate.
    Mix the mixture containing 1.4 g tert-butyl () 2,2-dimethyl-3- (7) 2 (isopropyloxycarbonyl) etenyl1cyclopropanecarboxylate, 100 mg (and toluene sulphonic acid and 14 cm of toluene. Brought to dryness under reduced pressure. A residue is obtained which is recrystallized from isopropyl ether. Cool, remove moisture, dry and obtain 900 mg of the desired product with mp 98 ° C .
    1066110
    Example 10. (S) ot-cyano-3-phenoxybenzyl (1H, cis) 2,2-dimethyl-Z-t (Z) 2- (n-utoxycarbonl) ethenyl cyclopropanecarboxylate. 5 Stir in an inert atmosphere 2 g (11R C14c) 2, .2-dimethyl-3- (g) 2- (I-butoxycarbonsh1) ethenyl
    cyclopropanecarboxylic acid, 20 cm of methylene chloride and.
    10 1.1 cm of pyridine, then 1.7 g of dicyclohexylcarbodiimide is added and stirred for an additional 30 minutes, 3 cm of methylene chloride containing are added. 2 g (5) l-cyano-3-phenoxy) benzyl alcohol, and stirred for 16 hours at room temperature. Filter the formed dicyclohexyl moistened wine, concentrate the filtrate to dryness, chromatograph
    20 residue on silica, with a solvent: a mixture of H-hexane - isopropyl ether (8-2). 3.1 g of the desired product are obtained, about -4-51 + 2 ° (, 4% in benzene 25).
    PMR spectrum, CDCEj, ppm: 1,25-1,27 protons of methyls in position 2. Cyclopropane; 1.92-2.07 proton in position 1 of cyclopropane} 3.2230 3.37-3.53 proton in position 3 of cyclopropane; 6.5 (t,) proton in position 1 of the allyl chain, - 5.8-5.85 proton in position 2 of the allyl chain - 6.35 proton, which carries the same TOT
    j carbon as C.
    Example 11. 2,2-Dimethyl-3- (Z) 2- (n-butoxycarbonyl) -ethenyl cyclopropanecarboxylic acid.
    Stage A. 40
    tert-butyl (15) 2,2-; cimethyl- 3- (n-butoxycarbonylethynyl) cyclopropanecarboxylate.
    4 g tert-butyl are mixed (1R
    45 Ciuc) 2,2-dimesh-1- 3- (2-carboxyethylenyl) cyclopropanecarboxylate, 40 cm of methylene chloride and 6 mg of 4-dimethylaminopyridine, then 3.4 g of dicyclohexylcarbodiimide is added.
    50 After 30 minutes of stirring under an inert atmosphere, 4 cm of a mixture of (1-1) -B-tanol and methylene chloride are added over 5 minutes and stirred for an additional 3 hours at room temperature. The formed dicyclohexyl urea is filtered, the filtrate is concentrated to dryness under reduced pressure and the residue is left
    chromatography on silica by elution with a mixture of cyclohexane-ethyl acetate (9-1,). 4.7 g of the expected product are obtained.
    Spectrum PMR, SBSVZ, ppm: 1.22 and 1.4 protons of methyls in position 2 of cyclopropane; 1.75 protons at position 1 and 3 of cyclopropane; 4.15 proton at position 1 of butoxyl; 1.48 protons, treg-butyl.
    Stage B.
    tert-butyl (1R) i-2,2-dimethyl-3- (7) 2- (m-butoxycarbons1) ethenyl cyclopropanecarboxylate.
    800 mg of palladium hydroxide on sulfate, barium in 20 cm of ethyl acetate are stirred in a hydrogen atmosphere for 15 minutes, then 4.7 g of the product obtained in the previous stage are added in 50 cm of ethyl acetate, 0.8 cm of quinoline and left hydrogen atmosphere for 30 min. The catalyst was removed by filtering with lium, the filtrate was washed with normal hydrochloric acid, then with water, dried, and concentrated to dryness. under reduced pressure, the residue is chromatographed on silica by elution with a mixture of cyclohexane-ethyl acetate (95-5). 3.4 g of the expected product are obtained.
    PMR spectrum, CDCE,, ppm: 1.25 and 1.28 protons of methyls in the position of cyclopropane, 1.76 and 1.90 proton in position 1 of cyclopropane and 2.96-3.3 protons c. position 3 of cyclopropane, 6.45-6.6 and 6.6 to 6.8 proton at position 1 of allyl chain} 5.75 and 5.95 proton at position 2 of allyl chain; 4.12 (t.) Proton in position 1 tert butyl; 1,45 protons tert-butyl.
    Stage C.
    (1RUOc) 2,2-Dimetsh1-3- (g) 2- (n-butoxycarbonyl) etnyl-cyclopropanecarboxylic acid.
    3.3 g of the product obtained in the previous step are mixed with 350 mg of para-toluenesulfonic acid in 40 cm of toluene. The mixture is refluxed until cessation of the release of isobutylene gas for approximately 40 minutes. The mixture is concentrated to dryness under reduced pressure, chromatographed on silica with the residue by elution with a mixture of cyclohexane-ethyl acetate-acetic acid.
    21066112
    acid (75-25-1). 2 g of the expected product are obtained.
    PMR spectrum, CDCE, ppm: 1.26 and 1.3 methyl protons in position 2 5 cyclopropane, 1.85-1.99 proton, in position 1 cyclopropane; 3.13-3.47 proton at position 3 of cyclopropane; 6.4-6.57 and 6j59-6.75 proton in position 1 of the allyl chain 5.8-5.99
    10 proton at position 2 of allyl chain.
    Example 12. (S) l -Cyano-3-phenoxybenzyl (1R, ccc) 2,2-dimethyl-3-pZ) 2- (pentyloxycarbonyl) -THeIlCl cyclopropanecarboxylate.
    t5 As in Example 10, 3.05 g of (1R) 2,2-dimethyl 3- (7) -2- (pentyloxycarbonyl) ethenyl cyclopropanecarboxylic acid, 1.5 cm pyridine, 2.4 g dicyclohexylcarboxylate diimide and 2.7 g (5) of α-cyano-3-phenoxybenzyl alcohol in 20 cm of methylene chloride. Chromatograph a second time on silica by elution with a mixture of
    25 hexane-simple ethyl ether
    (9-1) and get 3.5 g of the target product.
    PMR spectrum, CDCBj, ppm: 1,25-1,27 protons of methyls in position 2
    30 cyclopropane 1.92-2.07 proton in position 1 of cyclopropane; 3.37 (t.) Proton in position 3 of cyclopropane. 6.3-6.5 and 6.53-6.7 proton in position 1 of the allyl chain; 5.8-6 proton
    , - in position 2 of the allyl chain; 6.3, a proton that carries the same carbon as the SI; 6.9-7.6 protons of the aromatic compound.
    The starting acid is prepared as follows.
    Stage A.
    tert-Butyl (1R, cx) 2,2-dimethyl-3-pentyloxycarbonylethenyl cyclopropanecarboxylate.
    45 As in stage A of Example 10, 3-g tert-butyl (1R, (is) 2,2-dimesh1 1 3- (2-carboxyethynyl) - cyclopropanecarboxylate and 2 cm H-amyl alcohol) are used.
    50 After chromatography of the residue on silica by elution with a hexane-isopropyl ether mixture (8-2), 2.7 g of the expected product are obtained.
    55 Stage B.
    (1R tjuc) 2,2-Dimethyl-3- (pentoxycarbonylethynyl) -cyclopropanecarboxylic acid.
    13
    5.24 g of the product obtained in the previous stage, 50 cm of toluene and 250 mg of toluenesulfonic acid are mixed. Support with reflux until gas evolution ceases, then is concentrated to dryness under reduced pressure. 4.8 g of crude product are obtained, used in the same form.
    to continue the synthesis. I -
    Stage C.
    (1R cis) 2,2-Dimethyl-3 - () 2- (tyloxycarbonyl pen) ethenyl cyclopropanecarboxylic acid.
    4.8 g of the product obtained in the preceding stage are hydrogenated in 50 cm of ethyl acetate and 1 cm of quinrlin in the presence of 1 g of barium sulfate, containing 10% palladium hydroxide in suspension in 50 cm of ethyl acetate. The catalyst is removed, the filtrate is washed with normal hydrochloric acid, then with water, it is concentrated, concentrated to dryness under reduced pressure, and the residue is subjected to chromatography on silica by elution with a mixture of cyclohexane-ethyl acetate / acetic acid (70-30-1). 3 g of the expected product are obtained.
    PMR spectrum, CDCEj, ppm: 1.3 and 1.32 protons of methyls in position 2 of cyclopropane; 1.85-1.99 proton at position 1 of cyclopropane} 3.15-3.45 proton at position 3 of cyclopropane; 6.4-6.75 proton in position 1 of the allyl chain; 5.78-5.96 proton in position 2 of the allyl chain.
    P. p and mep 13. (5) o4-Cyano-3-phenoxy & Ensyl- (1R, dis) 2,2-dimethyl- 3- (2) 2- (R5) 1-metshprosh1oxycarbonyl) ethenyl cyclopropanecarboxylate.
    As in Example 10, 1.83 g of (IR DSP) 2,2-dimethyl-3- (Z) 2- (RS) 1-methylpropyloxycarbonyl) ethenyl cyclopropanecarboxylic acid are derived. 2.6 g of the expected product are obtained. , + 480 ± 2.5 ° (.%, Benzene).
    PMR spectrum, CDC6,, MD: 1.22-1.33 protons of methyls in position 2 of cyclopropane; 1.88-2.02 proton in position 1. cyclopropane, 3.21-3.5 proton in position 3 of cyclopropane, 6.35-6.68 proton in position .1 of the allyl chain; 5.8-6 proton in position 2 of the allyl chain; 4.92 (m); proton in position 1 of the cut; 6.35 proton.
    210661
    which carries the same carbon as CN.
    The original acid can be obtained in the following way. 5 Stage A,
    Tert-Butyl (1B, ijuc) 2,2-dimethyl- 3- (R6) - 1-methylpropyloxycarbonyl) -ethenyl3 cyclopropanecarboxyl.
    As in Step A of Example 12, 10, 2 cm of 1-meter-propanol alcohol is used. The residue is chromatographed on silica by elution with a mixture of n-hexane-isopropyl ether (8-2) and J5 3.5 g of the expected product is obtained.
    The spectrum of the NDP, CDCE,, ppm: 1,2-1,4 protons of methyls in position 2 of cyclopropane, 1.73 protons in position 1 and 3 of cyclopropaneJ 4.92 pro 2Q tone in position 1 of propyl. Stage B.
    tert-Butyl (1R cis) 2,2-dimethyl-3- (Z) 2- (R5) -1-methylpropyloxycarbonyl) -entenyl cyclopropanecarbok-25 silate.
    3 g of the product obtained in Step B of Example 7 is hydrogenated. The residue is chromatographed on silica by elution with a mixture of n-, d hexane-isopropyl ether (9-1) and 2.5 g of the expected product are obtained.
    Stage C.
    (1R t / iuc) 2,2-dimethyl-3- (7) 2- (RS) 1-methylpropyloxycarbonyl) ethenyl cyclopropanecarboxylic acid ..
    As in Step C of Example 12, 3 g of the product obtained is obtained. in the previous step B. - The residue is chromatographed on silica by elution with a mixture of cyclohexane-ethyl acetate-acetic acid (70-30-1) and 1.85 g of the expected product is obtained.
    IR spectrum (СНСе,),. OH: acid 35lOj acid 1.735 and ester 1710 - 1700 {assoc. 1637; Double Me 1381.
    Example 14. (5) ct -Cyano-3-phenoxybenz1- (1E, Ufc) 2,2-dimethyl-3 () 2- (cyclohexyloxycarbonyl) ethenyl cyclopropanecarboxyl.
    As in Example 10, the outcome is
    from 2.5 g (1R tiuc) 2,2-dimethyl-Z- (Z) 2- (1 × tclohexyloxycarbonyl) ethene of cyclopropanecarboxylic acid and 2.2 g of about-cyano-3-phenoxy 15
    benzyl alcohol. The mixture was eluted with hexane-ethyl ether (9-1). 1.883 g of the expected product are obtained. +41 12.6 (, 5%, CHCBj).
    The spectrum of the NDP, CDCe ,, ppm: 1.26 protons of types in position 2 of cyclopropane 1.92-2.05 protons in position 1 of cyclopropane; 3.23-3.55 proton at position 3 of cyclopropane; 6.3–6.6 proton in position 1 of the Alpyl chain j5.8–5.99 proton in position 2 of Alpil, 3 proton, which carries the same carbon as the CN f 4.8 proton in position 1 of cyclohexyl.
    . The original acid is also obtained as follows.
    Stage A.
    ; tert-Butyl (1R cis) 2,2-dimethyl 3- (cyclohexyloxycarbonylethynyl) cyclopropanecarboxylate. As in Example 12, it is derived from 2 cm of cyclohexanol. 3.67 g of the expected product are obtained.
    IR spectrum (SNCE,), mat. 2225 {ester + sopr 1729 - 1700, double di2 1392 - 1380 tert-butyl 1370.
    Stage B.
    tert-Butyl (1H c11c) -2,2-dimethyl 3- (Z) 2- (cyclohexyloxycarbonyl) -ethenyl cyclopropanecarboxylate.
    As in Example 12, 3.67 g of the product obtained in Stage A are produced, and 3.4 g of the crude product used in the same form for the next step is obtained.
    IR (CHCKj), cm: C 0: 715 C: 1634.
    Stage C.
    (1R DSP) 2,2-Limethyl-3- (g) 2- (cyclohexyloxycarbonyl) -ethenyl cyclopropanecarboxylic acid.
    As in Example 12, starting from 3.404 g of the product obtained in Step B, the cyclohexane-ethyl acetate-acetic acid system (70-30-1) is used for chromatography. 2.5 g of the expected product are obtained.
    IR spectrum (CHCBj), cm: OH acid 3S10} acid 1735 and ester 1707 doubled with di Me 1380J 1638.
    Example 15. (5) "-Piano-3-phenoxybenzyl- (11," tic) -2,2-dime210661I
    Tyl-3- (2) 2- (cyclobutyloxycarbenyl) ethenyl cyclopropanecarboxylate.
    As in the next step, it proceeds from 1.8 g (15, cis) 2,2-dimethyl 5 3- (Z) 2- (cyclobutyloxycarbonyl) ethenyl cyclopropanecarboxylic acid and 2 g (S) oc-Cyano-3- phenoxybenzyl alcohol. Two consecutive chromatography were performed on
    10 silica by elution with a mixture of cyclohexane-ethyl acetate (9-1), then a second mixture and -hexane-isopropyl ether (8-2). 3 g of the desired product are obtained.
    15 + 45.5 ± 2 ° (, 6%, CHCe,).
    Spectrum PMR, SLSe ,, ppm: 1.25-1.26 protons of methyls in position 2 of cyclopropane; 3.4 proton at position 3 of cyclopropane; 6.5-6.7 proton
    20 in position 1 of the alpyl chain; 5,8-6,0 proton in position 2 of the allyl chain; 5.1 proton in position .1 of cyclobutyl 6.4 proton, which carries the same carbon as C N.
    The original acid is obtained as follows.
    Stage A.
    tert-Butyl (1R or) 2,2-dimethyl 3- (Z) 2- (cyclobutyloxycarbonyl) ethenyl cyclopropanecarboxylate.
    4 g tert-butyl (IF tiuc) 2,2-dimethyl-3- (2) 2-carboxy-ethenylP-cyclopropanecarboxylate are dissolved in
    35 to 20 cm of methylene chloride, then 1.7 cm of cyclobutanol is added. The temperature is set at 0-5 ° C, 3.45 g of dicyclohexylcarbodiimide and 28 mg of dimethylaminopyridide per 20 cm of methylene chloride are added. Stir for 2 hours at 5 ° C and 2 hours at room temperature. The formed dicyclohexyl urea is removed, the filtrate is concentrated to dryness
    5 and chromatographed on silica by elution with an n-hex mixture; San isoprotein ether (9-1). 2.3 g of the expected product are obtained.
    50 PMR spectrum, CDCP,, ppm: 1,23-1,26 protons of methyls in position 2 of cyclopropane 1.77-1.9 protons in position 1 of cyclopropane; 2.95-3.28 proton in position 3 of cyclopropane,
    55 6.4-6.8 proton in position 1 of the allyl chain; 5.6-5.9 proton in position 2 of the allyl chain; 5 proton in position 1 of cyclobutyl.
    17
    Stalin V.
    (1 Hz ((c) 2,2-Dnmetip-3- (2) 2- (cyclobutyloxycarbonyl) ethenyl cyclopropanecarboxylic acid.
    Heated under reflux for 15.min 2.3 g of the product obtained at the previous stage, 25 cm of toluene and 250 mg of h-toluene-sulfonic acid, cooled and stirred for 2 hours at 0-5 ° C. Filter out the insoluble material and concentrate the dry land filtrate to obtain 1.8 g of the intended product.
    IR spectrum, cm: HE: acid 3500; Acid 1733 + ester .Cool.1702, doubled. di Me 1390 and 1380.
    Example 16 (b) ot-Cyano-3-phenoxybenzyl- (1B, Cys) -2,2-dimethyl- 3- (Z) 2- (propargyloxycarbonyl) ethenylJ cyclopropanecarboxylate.
    As in Example 15, out of 1.59 g of the product obtained in the previous step and 1.8 g of (5) o6-cyano 3-phenoxybenzyl slip. After .2 hours of reaction, the filtrate is concentrated to dryness under reduced pressure, and the residue is chromatographed on silica by elution with a mixture of cyclohexaneethyl acetate (9-1). 2.36 g of the expected product are obtained. +44 ± 1, 50
    (, system,).
    Spectrum GO-IP, CDCSj, ppm : 1.23-1.27 protons of methyls in position 2 of cyclopropane; 1.93-2.07 proton at position 1 of cyclopropane; 3.18-3.5 in position 3 of cyclopropane; 6.46-6.65 and 6.62-6.82 proton in position 1 of the allyl chain 5.87-6.05 proton in position 2 of the allyl chain 4.72-4.73 protons in position 1 about pargil; 2.47 (t.) Proton in position 3 of propargyl; 6.3 proton, which carries the same carbon as CN, 6.92-7.6 protons of the aromatic compound.
    The original acid is obtained as follows.
    Stage L.
    tert-Butyl (1R cis) 2,2-dimethyl 3- | (Z) 2- (propargyloxycarbonyl) ethenyl cyclopropanecarboxylate.
    As in Example 15, 3.6 g -gret-butyl (1R, 1, ug) 2,2-dimethyl-3- (,) 2-carboxyethenyl cyclopropylcarboxylate and 1 cm
    10661IP
    propargyl alcohol. Stir for 16 hours at. The insoluble part is filtered, the filtrate is diluted with methylene chloride, washed with 0.1N hydrochloric acid, then neutralized with water, dried and concentrated to dryness under reduced pressure. The residue is absorbed with a mixture of cyclohexane-ethyl acetate (9-1) 10 and stirred for 1 hour 30 minutes at 20 ° C. The insoluble part is removed, the filtrate is concentrated to dryness and the residue is chromatographed on silica by elution with 15 mixture of cyclohexane-ethyl acetate (9-1) . 2.1 g of the expected product are obtained.
    IR spectrum (SNSC), cm-3300 and 2225; ester and adj. 1712; resist 1629.
    thirty
    20
    I
    Stage V ..
    (1R t (Uc) 2,2-Dimethyl 3- (Z) -2-propargyloxycarbonyl) ethenyl Cyclo-propanecarboxylic acid.
     Within 10 minutes, heated with reflux 2, O g of the product obtained at the preceding stage in a solution of 20 cm of anhydrous toluene with 0.2 g of h-toluene sulfonic acid, cooled and stirred for 30 minutes at O C. The insoluble part is filtered and the filtrate concentrated to dryness to obtain 1.59 g of the expected product used in the same
    35 form for the next stage.
    Example 17. The study of the lethal effect of the compounds of examples 1,4 and 8 on domestic flies.
    The experimental insects are
    40 domestic flies, females aged
    4 days They work using topical medication (1 liter of acetone solution), depositing it on the dorsal side of insects with the help of Arnold cro-ampulla tor. 50 individuals are used for one treatment. Mortality is monitored 24 hours after treatment.
    50 The result obtained, expressed in the lethal dose required for the death of 50% of insects (LD, ng / individual) is as follows:
    Example Compound
    one
    four
    eight
    Lp dng / individual
    7,128 3,494 2,781
    nineteen
    PRI me R 18. Investigation of the lethal effect on larvae of Sopodtera littoralis.
    The experiments were carried out with the use of topical medication (acetone solution), deposited with the help of an Arnold manipulator onto the dorsal side of the larvae. 10-15 larvae are used for one dose of the test substance. Larvae of the fourth larval stage are used, i.e. Approximately 10 days of dilution at 65% relative humidity. After processing, the individuals are placed in an artificial nutrient.
    Wednesday (Wednesday Poitou). I
    Mortality control is carried out 48 hours after treatment.
    The following result was obtained:


    Example Compound
    LD, - ng / individual
    L. 3.602
    43,260
    8-7,920
    Example 19. The study of the activity of substances of examples 1.4 and 8 on the larvae of Epilachna Vasivestris.
    The experiments were cured by using a topical medication using a method similar to that used for Spodoptera larvae. Use the larvae before the last larval stage. After processing, the larvae feed on the beans. Mortality control is carried out after 7. h after treatment.
    Get the following result:
    Example Compound
    Bbs-ng / individual
     50

    7,128 31,786
    20
    1 4 8
    8,290 8,850 - 3,705
    Example 20. The study of shock activity on the housefly.
    The experimental insects are domestic flies, females at the age of 4 days. Work by direct spraying in a Kearns and March chamber, using a mixture of acetone (5%) and Isopar (petroleum solvent) as solvent (the amount of solvent used is 2 ml / s). 50 insects are used in one treatment. The control is carried out every minute up to 10 minutes, then up to 15 minutes and the CT is determined by conventional methods.
    Get the following result:
    Example Compound
    one
    4 8
    CT "(min
    50
    With 0.25 g / l)
    1.226 3.340 4.390
    Table 1 shows the data on the biological tests of compounds of formula 1 with respect to Musca Domestica, Blatella Germanica, Spodoptera Littoralis, Tetranychus Urtikal in comparison with (K, 3) -o1-cyano-3-phenoxybenzyl n ( 4-chlorophenyl) -3-methylbutyrate (fenovalerate) - product S.
    Compounds of general formula T have an increased acaricidal, insecticidal, and nematogic activity as compared to (R, S) -C 3-phenoxybenzene R, (4-chlorophenyl) -3-methyl butyrate.

    3.602 23.055
    4791,199 5000
    21











    3
    4,459
    1,788 31,802
    17,786
    1,382 31,726
    22,956
    1.78.4 31,778
    17,762
    1,136 31,680
    27; 887
    1,644 31,693
    19,277
    1,722 31,791
    4,962
    0,190 1,301
    6,847
    0,250 1,295
    5.180
    0,150 1,327
    8,846
    0,938 1,334
    1,422
    0.735 1.303
    1,772
    1,694 1,310
    1210661
    22 Continuation of table 1






    1,04358
    2.920 700 5000
    1.711
    5000 5000
    1640,500 5000
    3.04785
    2268,800 5000
    2.28
    5000. 5000
    844,440 5000
    Relative strength of action
    Product of Example 14
    Product S
    Relative strength of action
    Product of Example 15
    Product 5
    Relative strength of action
    Product of Example 16
    Product S
    Relative strength of action



    Editor N.Egorova
    Compiled by A. Alexandrov
    Tehred A. Babinets Corrector L. Patay
    Order 541/61 Circulation 379. Subscription
    VNIIPI USSR State Committee
    for inventions and discoveries 113035, Moscow, Zh-35, Raushsk nab., 4/5
    Branch PPP Patent, Uzhgorod, st. Project, 4

    0.320
    100 23,094
    5.921
    5000 5000
    0.827930 0.230


    6,015 23,103
    3,840
    7,778 23,013
    2,918
    825,240 5000
    6,058
    5000 5000
    权利要求:
    Claims (1)
    [1]
    A method of obtaining derivatives of cyclopropanecarboxylic acid of the General formula CM ^ CH about
    Ph0- / O / X 0- C-CH-CH co, R
    4 'where And is a saturated or unsaturated, straight or branched C, -C 6 alkyl or C 4 -C 6 cycloalkyl;
    double bond has geometry Z; in the form of stereoisomers or mixtures thereof, characterized in that the acid of the General formula
    HO-C-CH-CH / C0 2 R
    II η C / ' υ χ 11 Η
    CH 3 CH 3 where the double bond has the configuration ζ,
    R has the indicated meanings, is reacted with an alcohol of the formula in methylene chloride medium in the presence of dicyclohexylcarbodiimide and an organic base such as pyridine or dimethylaminoniridine.
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    EP2067794A1|2007-12-06|2009-06-10|Borealis Technology OY|Use of a Ziegler-Natta procatalyst containing a trans-esterification product of a lower alcohol and a phthalic ester for the production of reactor grade thermoplastic polyolefins with improved paintability|
    WO2021022059A1|2019-07-30|2021-02-04|University Of Florida Research Foundation, Incorporated|Synergistic mixtures for arthropod toxicity and repellency|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    FR8008491A|FR2480748B1|1980-04-16|1980-04-16|
    FR8020478A|FR2490635B2|1980-04-16|1980-09-24|
    FR8217056A|FR2534250B2|1980-04-16|1982-10-12|NOVEL DERIVATIVES OF CYCLOPROPANE CARBOXYLIC ACID, PROCESS FOR THEIR PREPARATION AND THEIR APPLICATION TO THE CONTROL OF PESTS|
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