前苏联专利SU1428189A3 Method of producing esters

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1. Claims for the Contracting States : BE CH DE FR GB IT LI LU NL SE In all the possible isomeric forms or in the form of mixtures, the compounds with the formula (I') see diagramm : EP0048186,P72,F1 in which the cyclopropane copula is of IR cis structure and the double bond is of Z geometry and in which A' represents either an alkyl radical containing from 1 to 18 carbon atoms or a benzyl radical possibly substituted by one or more radicals chosen from the group composed of the alkyl radicals containing from 1 to 4 carbon atoms, the alkenyl radicals containing from 2 to 6 carbon atoms, the alkenyloxy radicals containing from 2 to 6 carbon atoms, the alkadienyl radicals containing from 4 to 8 carbon atoms, the methylene dioxy radical and halogen atoms, or a group see diagramm : EP0048186,P72,F2 in which the substituent R1 represents a hydrogen atom or a methyl radical and the substituent R2 a monocyclic aryl radical or a group -CH2 -C -= CH or a group see diagramm : EP0048186,P72,F3 in which a represents a hydrogen atom or a methyl radical and R3 represents the radical -CH2 -CH=CH2 , -CH2 -CH=CH-CH3 , -CH2 -CH=CH-CH=CH2 , CH2 -CH=CH-CH2 -CH3 , or a group see diagramm : EP0048186,P72,F4 in which a represents a hydrogen atom or a methyl radical, R3 retains the same significance as previously, R'1 and R'2 , being identical or different, represent a hydrogen atom, a halogen atom, an alkyl radical containing from 1 to 6 carbon atoms, an aryl radical containing from 6 to 10 carbon atoms, an alkyloxy-carbonyl group including from 2 to 5 carbon atoms, or a cyano group, or a group see diagramm : EP0048186,P72,F5 in which B represents an oxygen or sulphur atom or a group see diagramm : EP0048186,P73,F1 or -CH2 - and R4 represents a hydrogen atom, a -C -= N radical, a methyl radical, a -CONH2 radical, a -CSNH2 radical or a -C -= CH radical, R5 represents a halogen atom or a methyl radical and n represents a number 0, 1 or 2, or a group see diagramm : EP0048186,P73,F2 or a group see diagramm : EP0048186,P73,F3 in which the substituents R6 , R7 , R8 , R9 represent a hydrogen atom, a chlorine atom, or a methyl radical and in which S/l symbolises an aromatic ring or a similar dihydro or tetrahydro ring, or a group see diagramm : EP0048186,P73,F4 or a group see diagramm : EP0048186,P73,F5 in which R10 represents a hydrogen atom or a radical CN, R12 represents a radical -CH2 - or an oxygen atom, R11 represents a thiazolyl or a thiadiazolyl radical, of which the bond with -CH-/R10 can be found at any one of the available positions R12 being attached to R11 by the carbon atom included between the sulphur atom and a nitrogen atom, or a group see diagramm : EP0048186,P73,F6 or a group see diagramm : EP0048186,P73,F7 in which R13 represents a hydrogen atom or a radical CN, or a group see diagramm : EP0048186,P74,F1 in which R13 is defined as above, and the benzoyl radical is in position 3 or 4, or a group see diagramm : EP0048186,P74,F2 in which R14 represents a hydrogen atom, a methyl, ethynyl or cyano radical and R15 and R16 , are different and represent a hydrogen, fluorine or bromine atom, or a group see diagramm : EP0048186,P74,F3 in which R14 is defined as above, each of the R17 's represents independently an alkyl group containing from 1 to 4 carbon atons, an alkoxy group containing from 1 to 4 carbon atoms, an alkylthio group containing from 1 to 4 carbon atoms, an alkylsulphonyl group containing from 1 to 4 carbon atoms, a trifluoromethyl, 3,4-methylenedioxy, chloro, fluoro or bromo group, p represents a numeral 0, 1 or 2, and B' represents an oxygen atom or a sulphur atom and R represents an alkyl radical containing from 1 to 18 carbon atoms, substituted by one or more identical or different groups chosen from the group constituted by the halogen atoms, the OH or SH groups, the OR' or SR' groups in which R' represents an alkyl radical containing from 1 to 8 carbon atoms, the groups NO2 or see diagramm : EP0048186,P74,F4 in which R" and R'", being identical or different, represent a hydrogen atom or an alkyl radical containing from 1 to 8 carbon atoms, the groups C -= N, SO3 H or PO4 H2 or the groups COalk1 , SO2 alk2 , or SO3 alk3 in which alk1 , alk2 and alk3 represent alkyl radicals containing from 1 to 18 carbon atoms or R represents an alkyl radical containing from 1 to 18 carbon atoms substituted by an aryl radical, itself possibly substituted by one or more OH, Oalk or alk groups containing from 1 to 18 carbon atoms, by one or more CF3 , OCF3 SCF3 , or by a group (G) : see diagramm : EP0048186,P74,F5 or R represents an alkyl radical containing from 1 to 18 carbon atoms, substituted on two adjacent carbons by a group (G1 ) see diagramm : EP0048186,P74,F6 or substituted by a group see diagramm : EP0048186,P75,F1 or R represents an aryl group containing from 6 to 14 carbon atoms, possibly substituted by one or more OH, Oalk or alk groups containing from 1 to 8 carbon atoms or by a CF3 , OCF3 or SCF3 group, or R represents a pyridinyl, furanyl, thiophenyl, oxazolyl or thiazolyl radical. 1. Claims for the Contracting State : AT Process for preparing in all the possible isomeric forms or in the form of mixtures, the compounds with the formula (I') see diagramm : EP0048186,P82,F3 in which the cyclopropane copula is of IR cis structure and the double bond of Z geometry and in which A' represents either an alkyl radical containing from 1 to 18 carbon atoms or a benzyl radical possibly substituted by one or more radicals chosen from the group constructed by the alkyl radicals containing from 1 to 4 carbon atoms, the alkenyl radicals containing from 2 to 6 carbon atoms, the alkenyloxy radicals containing from 2 to 6 carbon atoms, the alkadienyl radicals containing from 4 to 8 carbon atoms, the methylene dioxy radical and halogen atoms, or a group see diagramm : EP0048186,P82,F4 in which the substituent R1 represents a hydrogen atom or a methyl radical and the substituent R2 a monocyclic aryl or a -CH2 - C -= CH group, or a group see diagramm : EP0048186,P82,F5 in which a represents a hydrogen atom or a methyl radical and R3 represents the radical -CH2 -CH=CH2 , -CH2 -CH=CH-CH3 , -CH2 -CH=CH-CH=CH2 , CH2 -CH=CH-CH2 -CH3 , or a group see diagramm : EP0048186,P82,F6 in which a represents a hydrogen atom or a methyl radical, R3 retains the same significance as previously, R'1 and R'2 , being identical or different, represent a hydrogen atom, a halogen atom, an alkyl radical containing from 1 to 6 carbon atoms, an aryl radical containing from 6 to 10 carbon atoms, an alkyl-oxycarbonyl group containing from 2 to 5 carbon atoms, or a cyano group, or a group see diagramm : EP0048186,P83,F1 in which B represents an oxygen or sulphur atom or a group see diagramm : EP0048186,P83,F2 or -CH2 - and R4 represents a hydrogen atom, a -C -= N radical, a methyl radical, a -CONH2 radical, a -CSNH2 radical or a -C -= CH radical, R5 represents a halogen atom or a methyl radical and n represents a numeral 0, 1 or 2, or a group see diagramm : EP0048186,P83,F3 or a group see diagramm : EP0048186,P83,F4 in which the substituents R6 , R7 , R8 , R9 represent a hydrogen atom, a chlorine atom, or a methyl radical and in which S/l symbolises an aromatic ring or a similar dihydro or tetrahydro ring, or a group see diagramm : EP0048186,P83,F5 or a group see diagramm : EP0048186,P83,F6 in which R10 represents a hydrogen atom or a CN radical, R12 represents a -CH2 - radical or an oxygen atom, R11 represents a thiazolyl or a thiadiazolyl radical, of which the bond with -CH-/R10 can be found at any one of the available positions, R12 being attached to R11 by the carbon atom included between the sulphur atom and a nitrogen atom, or a group see diagramm : EP0048186,P84,F1 or a group see diagramm : EP0048186,P84,F2 in which R13 represents a hydrogen atom or a CN radical, or a group see diagramm : EP0048186,P84,F3 in which R13 is defined as above, and the benzoyl radical is in position 3 or 4, or a group see diagramm : EP0048186,P84,F4 in which R14 represents a hydrogen atom, a methyl, ethynyl or cyano radical and R15 and R16 , which are different, represent a hydrogen atom, a fluorine or a bromine atom, or a group see diagramm : EP0048186,P84,F5 in which R14 is defined as above, each of the R17 's represents independently an alkyl group containing from 1 to 4 carbon, an alkoxy group containing from 1 to 4 carbon atoms, an alkylthio group containing from 1 to 4 carbon atoms, an alkylsulphonyl group containing from 1 to 4 carbon atoms, a trifluoromethyl, 3,4-methylenedioxy, chloro, fluoro or bromo group, p represents a numeral 0, 1 or 2 and B' represents an oxygen atom or a sulphur atom and R represents an alkyl radical containing from 1 to 18 carbon atoms, substituted by one or more identical or different functional groups chosen from the group constituted by the halogen atoms, the OH or SH groups, the OR' or SR' groups in which R' represents an alkyl radical containing from 1 to 8 carbon atoms, the NO2 or see diagramm : EP0048186,P84,F6 groups in which R" and R'", which are identical or different, represent a hydrogen atom or an alkyl radical containing from 1 to 8 carbon atoms, the groups C -= N, SO3 H or PO4 H2 groups or the COalk1 , SO2 alk2 , or SO3 alk3 groups in which alk1 , alk2 and alk3 represent alkyl radicals containing from 1 to 18 carbon atoms, or R represents an alkyl radical containing from 1 to 18 carbon atoms substituted by an aryl radical, itself possibly substituted by one or more OH, Oalk or alk groups containing from 1 to 8 carbon atoms, by one or more CF3 , OCF3 SCF3 , or by a group (G) : see diagramm : EP0048186,P85,F1 or R represents an alkyl radical containing from 1 to 18 carbon atoms, substituted on two adjacent carbons by a group (G1 ) see diagramm : EP0048186,P85,F2 or su
公开号:SU1428189A3
申请号:SU813308436
申请日:1981-07-01
公开日:1988-09-30
发明作者:Мартель Жак；Тессье Жан；Теш Андре
申请人:Руссель Юклаф (Фирма)；
IPC主号:

专利说明:

cm
This invention relates to a process for the preparation of novel esters of cyclopropanecarboxylic acid derivatives of general formula
Р02С-СН СНсОаА
where the double bond has a Z or E geometry;
py:
A is the radical selected from the corpse of (IS) (.-Cyano-3-phenoxybenzyl; (IR) ck -methyl-3-phenoxybenzyl; (IR) -ethynyl-3-phenoxybenzyl; (IR) or (1KZ) -adiano- 6-phenoxy-2-pyr1-shchl-methyl; (IS) 2-methyl-4-oxo-3- (2-propinsh1) -2-cyclopenten-1-yl; c-cyano-3-phenoxybenzyl 1 R; (15) -2-methyl-4-oxo-3- (2-propynyl) -2 cyclopenten-1-yl; R is C-C alkyl, replaced by chlorine or fluorine.
The aim of the invention is to develop a process for the preparation of new compounds of general formula 1 having a higher insecticidal activity.
The method is illustrated by the following examples.
Example 1. (S) C-Cyano-3-phenoxybenzyl ester (1R, cis) 2, 2-dimethyl 3 (Z) -3- (2,2,2-trifluoroethoxy) 3-oxo-T-propynyl cyclopropane carboxylic acid
With stirring, mix 1.3 g of (1R, cis) 2,2-dimetsh1 3 (Z) -3-OKco 3- - (2,2., 2-trifluoroethoxy) -1-propini cyclopropane carboxylic acid,. Oj, 1 cm of pyridine and 15 cm of methylene chloride, and then 1.05 g of dicyclohexylcarbodiimide was added. Then 1.35 g of (S) oC-hydroxy, roxy 3-phenoxy-benzene-acetonitrile in solution in 5 cm of methylene are added. The mixture is stirred at room temperature for 5 hours, the insoluble BBiltecTBo is filtered off and rinsed with methylene chloride. A 2N hydrochloric acid solution is added to the filtrate. Decanted, washed with water, dried and brought to dryness. The resulting oil is chromatographed on silica (eluant: cyclohexane - ethyl).
ester of acetic acid 95-5). 1.33 g of the expected product are obtained. 42 ± 2 ° (, 7 benzene). NMR, CBC15, ppm; 1.26 and 1.28 (H met1shov 2); 1.97-2.11 (H carbon in 1 cyclopropane); 3.1 to 3.4 (H carbon in 3 cyclopropane); 6.5 to 6.9 (H of carbon in 1 radical is propynyl); 5.9 - 5.93 (H carbon in 2 radicals propynyl); 6.3 (H carbon carrying group CN); 4.3 to 4.7 (H radical, trifluoroethoxy).
Acid 1 used in example
get the following way.
Preparation of 1 (IR, cis) 2,2-dimethyl 3 (Z) 3- (2,2,2-trifluoroethoxy) 3-oxo-1-propynyl cyclopropane carbonic acid
Stage A.1,1-Dimethyl ethyl ether IR, cis (2,2-dimethyl-3-) 3-hydroxy-3-oxo 1-propynyl cyclopropane carboxylic ACID
Introduced 26 g of 1,1-dimethylstil
(IR, cis) 2,2-dimethyl-3-2,2-β-dibromovinyl cyclopropane carboxylic acid in 175 cm of anhydrous tetrahydrofuran. Then 60 cm of a 20% butyl solution is added at -65 ° C
0
five
0
five
0
five
lithium in cyclohexane Mix
1 hour at -60 ° C, and then a stream of carbon dioxide is passed through for 1.5 hours, the reaction mixture is poured into ice water, containing 1 caustic soda solution. Washed with ether. The alkaline water layer is acidified to
pH 4 and extracted with ether. The organic layers are dried and brought to dryness under reduced pressure. Get the product, which is recrystallized in petroleum ether (T. boil. 60-80 C). Then 8.3 g of the expected product are obtained, melting at 144 ° C.
NMR, CDCla, ppm:
1,22.and G, 37 (protons of methyls in
2 cyclopropane); 1.78 (proton p
1 and 3 cyclopropane); 1.47 (protons of tert-butyl) J8.25 (proton grouping
-SLEEP). 6
Stage B, 1,1-Dimethyl ethyl ester (IR, cis) 2,2-dimethyl-3h3-oxo-3- (2,2,2-trifluoroethoxy) -1-propynyl) cyclopropane carboxylic acid
4 g of the product obtained in stage A are introduced together with 3.5 dicyclohexylcarbodiimide into a solution containing 20 cm of methylene chloride and
1 cm of pyridine. The reaction mixture was incubated for 1 h with stirring. Then, 2.15 g of trifluoroethanol and 5 cm of methylene chloride are added. The mixture is kept under stirring for 20 hours. It is filtered and rinsed with methylene chloride. The filtrate is brought to dryness. Take sulfuric ether, washed with 1 n. hydrochloric acid and then with water and dried. 5 g of product are concentrated and concentrated, which is chromatographed on silica (eluant: benzene — ethyl acetate 95-5). 3.5 g of the expected product are obtained.
NMR CDCla, ppm: 1.2 and 1.37 (H methyles in 2); 1.77 (H carbon in 1 and 3 cyclopropane); 1.43 (H methyl radicals 1; 1-dimethylethyl); 4.3 to 4.7 (H trifluoroethoxy radical).
Stage B. (IR, cis) 2,2-Dimetsh1 3 3-oxo-3- (2,2,2-trifluoroethoxy) -1- -propinyl 3 cyclopropane carboxylic acid.
A mixture of 3.3 g is obtained under reflux. in the previous stage of the product.
ten
carbon in 1 cyclopropane); 3.07 to 3.38 (H carbon in 3 cyclopropane); 6.6 to 6.9 (H of carbon in 1 radical is propynyl); 5.9-6.0 (H carbon in 2 radicals propynyl); 4.3 to 4.7 (H radical of trifluoroethoxy).
Example 2 of (S) 2-Dimethyl-4-oxo-3- (2-propynyl) 2-cyclopentene-1-NLO ester (IR, cis) 2,2-dimethyl-3- (Z) -Z- oxo-3- (2,2,2-trifluoroztoxy) -1-propinyl cyclopropane carboxylic acid
1.9 g (IR, cis) 2.2-di g methyl 3 (ii) -3-6Kco-3- (2,2,2-trifluoroethoxy) -propynyl cyclopropane carboxylic acid, 12 cm of methylene chloride are mixed and 100 mg of dimethylaminopyridine. Then, 1., 4 g of dicyclohec2Q silcarbodiimide, then 1.1 g of (S) 3- - (2-propynyl) 1-hydroxy 2-methyl 1-4-oxo-cyclopent-2-ene and 5 cm of methylene chloride are introduced. The mixture is stirred at room temperature for
25 2 hours. Filter the insoluble material that has formed. The filtrate is washed with 0.5 but hydrochloric acid and then with water and brought to dryness. 3 g of product are obtained which are chromium35
30 cm of toluene and 100 mg of para-toluenesulfonic acid. The reflux is sustained and dosed on silicon dioxide (eluted from the gas evolution. It is cooled, washed with water and brought to dryness. 2.6 g of the expected product are obtained, which is used in this form in the next stage.
Step Go (IR, cis) 2,2-Dimethyl 3 (2) -3-oxo-3- (2,2,2-trifluoroethoxy) -1 -1-propinyl cyclopropane carboxylic acid.
500 mg of 10% palladium hydroxide on barium sulphate and 5 cm ethyl acetate are introduced into the flask connected to the hydrogenation unit. Add 2 g of 45
40
product obtained in the previous step, 45 cm ethyl acetate and 0.5 cm quinoline. Subjected to hydrogenation until the end of absorption. The resulting product is filtered. The filtrate is rinsed. hydrochloric acid and then water and bring to dryness. 2 g of product are obtained which is chromatographed on silica (eluant: cyclohexane - ethyl acetate acetic acid - acetic acid: 70-30-1). This gives 1.3 g of the desired product.
NMR spectrum, CBC1, ppm: 1.3 and 1.32 (H methyls in 2); 1.92-2.06 (H
50
55
ant: benzene - ethyl ester of acetic acid 95-5). The yield of the target product 2.2 g
ot-D + 38 ± 2.5 (to 0.5% benzene).
NMR spectrum, CDClI, Cho / million; 1.29 and 1.32 (H methyls in 2 cyclopropane); 1.97 - 2.11 (H in 1 cyclopropane); 3.05 to 3.37 (H in 3 cyclopropane); 6.7 to 7 (And carbon in 1 radical is propynyl); 5.9-6.1 (H carbon in 2 radicals propynyl); 4.3 to 4.75 (H trifluoroethoxy radical); 5.7 (H cyclopentene in s.COg); 2 (H methyl on cyclopentene); 4.8 to 5.25 (H in 3 propenyl on cyclopentene).
EXAMPLE 3 (IS) ((- Cyano-3-phenoxybenzyl; ether (IR, cis) 2,2-dimethyl-3 (Z) -Z-oxo-3 (phenylmethoxy) -1 -propinyl cyclopropane carboxylic acid
Cooking 1 „
Stage A. Chloride (IR, cis) 2,2-dimethyl 3- (Z; Z-oxo-3- (phenylmethoxy) -1-propynyl cyclopropane carboxylic acid.
A mixture of 1.6 g of (IR cis) 2,2-dimethyl 3- (Z) 3-oxo-3- (phenylmethoxy) -1-propynyl cyclopropane carbo is stirred in a stream of nitrogen for 5 hours.
ten
28189
carbon in 1 cyclopropane); 3.07 to 3.38 (H carbon in 3 cyclopropane); 6.6 to 6.9 (H of carbon in 1 radical is propynyl); 5.9-6.0 (H carbon in 2 radicals propynyl); 4.3 to 4.7 (H trifluoroethoxy radical).
Example 2 of (S) 2-Dimethyl-4-oxo-3- (2-propynyl) 2-cyclopentene-1-NLO ester (IR, cis) 2,2-dimethyl-3- (Z) -Z -oxo-3- (2,2,2-trifluoroztoxy) -1-propynyl cyclopropane carbonic acid
1.9 g (IR, cis) 2.2-di g methyl 3 (ii) -3-6Kco-3- (2,2,2-trifluoroethoxy) -propynyl cyclopropane carboxylic acid, 12 cm of methylene chloride are mixed and 100 mg of dimethylaminopyridine. Then, 1., 4 g of dicyclohek2Q silcarbodiimide, then 1.1 g of (S) 3- - (2-propynyl) 1-hydroxy 2-metsh1-4-oxo-cyclopent-2-ene and 5 cm of methylene chloride are added. Mixture stirred at room temperature for
25 2 hours. Filter the insoluble material that has formed. The filtrate is washed with 0.5 but hydrochloric acid and then with water and brought to dryness. Get 3 g of the product, which is chromium5
They are captured on silica (elu
five
0
0
five
ant: benzene - ethyl ester of acetic acid 95-5). The yield of the target product 2.2 g
ot-D + 38 ± 2.5 (to 0.5% benzene).
NMR spectrum, CDClI, Cho / million; 1.29 and 1.32 (H methyls in 2 cyclopropane); 1.97 - 2.11 (H in 1 cyclopropane); 3.05 to 3.37 (H in 3 cyclopropane); 6.7 to 7 (And carbon in 1 radical is propynyl); 5.9-6.1 (H carbon in 2 radicals propynyl); 4.3 to 4.75 (H trifluoroethoxy radical); 5.7 (H cyclopentene in s.COg); 2 (H methyl on cyclopentene); 4.8 to 5.25 (H in 3 propenyl on cyclopentene).
EXAMPLE 3 (IS) ((- Cyano-3-phenoxybenzyl; ether (IR, cis) 2,2-dimethyl-3 (Z) -Z-oxo-3 (phenylmethoxy) -1 -propinyl cyclopropane carboxylic acid
Cooking 1 „
Stage A. Chloride (IR, cis) 2,2-dimethyl 3- (Z; Z-oxo-3- (phenylmethoxy) -1-propynyl cyclopropane carboxylic acid.
A mixture of 1.6 g of (IR cis) 2,2-dimethyl 3- (Z) 3-oxo-3- (phenylmethoxy) -1-propynyl cyclopropane carbonic acid, 10 cm nopropene is stirred in a stream of nitrogen for 5 hours and 1 cm of embossed chloride, concentrated. 2 g of product are obtained, which is used in this form in the further stage.
Stage Bo SIS) - Cyano-3-phenoxy-base ester (IR, cis) 2,2-dimethyl-3- (Z) -3-oxy-3- (phenylmethoxy) -1 -1-propynylcyclopropane carboxylic acid.
1 g of the product obtained in stage A is introduced into a solution containing 700 m (S) with α-hydroxy 3-phenoxybenzene aceto-nitrile, 20 cm of benzene and 0.6 cm of pyridine. The reaction mixture is kept under stirring for 16 hours at room temperature, poured onto a mixture of ice water and 1 and hydrochloric acid. Mix the suspension and extract with benzene. The benzene extracts are washed with water, dried, filtered and brought to dryness. 1.5 g of product are obtained which is chromatographed on silica (eluant: cyclohexane — ethyl acetate 8-2).
861 mg of the expected product are obtained, melting at 83 C.
6, j, + 69 ± 5 ° (to 0.2%, benzene).
NMR spectrum, CDCla, h / mpn; 1.25 (H Methyl in 2 Cyclopropane); 6.33 (H carbon carrying group C N).
Preparation 2. (IR, cis) 2,2-Dimethyl-3- (Z) -3-okko-3- (phenylmethoxy) -1-propynyl cyclopropane carbonic acid.
Stage A, 1,1-Dimethyl ethyl ether (IR, cis) 2,2-dimethyl-3- (g) 2-carboxy ethenyl cyclopropane carboxylic acid
Subject to hydrogenation 2 g of 1,1-dimethyl ethyl ester (IR, cis) 2,2-dimethyl-3- (2-carboxyethyl) cyclopropane carboxylic acid in 40 cm of ethyl ester of acetic acid in the presence of 0.38 g of 10% hydroxide palladium on sulfuric acid and 0.4 cm quinoline. Filtered, washed the filtrate with 0.5 n. hydrochloric acid, and then with water until neutral, is concentrated to dryness under reduced pressure and 2 g of the expected product is obtained, melting at 94 ° C
Step B 1,1-Dimethyl ethyl ether (IR, cis) 2,2-dimesh-1- 3- (g) -3-oxo-3- (phenylmethoxy) -1-propynyl cyclopropane carboxylic acid.
2.4 g of the product obtained in stage A are introduced into 20 cm of ethyl acetate. Then 2.34 g, O-benzyl H, K-diisopropyl urea is added. The mixture is stirred for 16 hours at room temperature, filtered and the filtrate is concentrated under reduced pressure. 4.3 g of a yellow oil are obtained, which is chromatographed on silica (eluant: benzene cyclohexane: 7-3). 2 g of the expected product are obtained.
NMR spectrum, DCli, ppm: 1.22 and 1.28 (H methyls in 2 cyclopropane); 1.77-1.91 (H of carbon in 1 cyclopropane); 2.98 to 3.3 (carbon N carbon 3 cyclopropane); 6.5 to 6.8, (H carbon in 1 radical propynyl); 5.8 - 6 (H carbon in 2 radicals propynyl); 1.43 (H methyl radicals dimethylstil); 5.1 (H methoxy radical phenylmethoxy).
Step B (IR, cis) 2,2-dimethyl-3-t (Z) -3-oxo-3- (phenylmethoxy) -1-propynyl cyclopropane carboxylic acid.
A mixture containing 2 g of the product obtained in the preceding stage is heated to 90 ° C, 30 cm of toluene, and 100 mg of para-toluenesulfonic acid. Withstand with stirring for 2 hours. Dissolve to dryness and obtain 2 g of product which is chromatographed on silica (eluant: cyclohexane - ethyl acetate - acetic acid: 60-40-1).
Get 1,4. g target product
NMR spectrum, CDCl, ppm; 1.25 and 1.3 (H methyl in 2 cyclopropane); 1.84 - 1.98 (H carbon in 1 cyclopropane); 3.14 to 3.43 (H of carbon in 3 cyclopropane); 6.4 to 6.77 (H of carbon in 1 radical is propynyl); 5.98 (H carbon in 2 radicals propynyl).
EXAMPLE 4 "(15) -2-Methyl-4- -oxo-3 (2-propynyl) 2-cyclopentene-1-yl ester (IR, cis) 2,2-dimethyl-3 - (Z) -3-oxo-3- (phenylmethoxy) -1-propynylZcyclopropane carboxylic acid
1 g of chloride (IR, cis) 2,2-dimethyl-3- (g) 3-oxo-3- (fenylmethoxy). -1 -1 propynyl cyclopropane carboxylic acid is introduced into a mixture of 450 mg (S) 3 carboxylic acids can be obtained in the same way as ester (S), described below, by using the corresponding alcohol (RS).
PRI me R 8 "(S) d. -Cyano-3-phenoxybenzyl ester (IR, cis) 2,2-dimethyl-3 (X) -3-oxo-3-cyanomethoxy -1-propynyl cyclopropane carboxylic acid.
Stage A, (RS) cC -Cyano-3-phenoxy-benzyl ester (IR, cis) 2,2-dimethyl-3- (3-oxo-3-cyanomethoxy-1-propinyl) cyclopropane carboxylic acid.
Act as in example 7, but starting from 2 cm of chloroacetonitrile; after extraction with ether and elution with a mixture of cyclohexane-ethyl acetate (9: 1), 2.69 g of the desired product are obtained.
Stage B, (RS) e-Cyano-3-phenoxy-benzyl ether (IR, cis) 2,2-dimethyl-Z-C (g) - 3-oxo-3-cyanomethoxy--1-propinyl cyclopropane carbon acid.
Analogously to example 7, but starting from 2.69 g of the product obtained above, 2.02 g of the desired product is obtained after elution with a mixture: cyclohexane — ethyl acetate (9: 1)
Step In (S) dt -Cyano-3-phenoxy-benzyl ether (IR, cis) 2,2-dimethyl-3- (Z) -3-oxo-3-cyanomethoxy-1-propynyl cyclopropane carboxylic acid .
1.4 g of the product obtained in Step B are chromatographed on silica, eluting with methylene chloride, to give 0.41 g of the intended product.
el-j + 55 ± 1,5 ° (to 1% СНС1з).
PRI me R 9. (S) H.-Cyano-3-phenoxybenzyl ester (IR, cis) 2,2-dimethyl-3-G () - 3-oxo-3-ethoxyethoxy-1 - propynyl 5 cyclopropane carboxylic acid
Stage Av (S) with - Cyano-3-phenoxy-benzyl ester (IR, cis) 2,2-dime-TSH1-3-3-OXO-3-ETOXYETOXY-1-propinyl cyclopropane carboxylic acid
2 g (S) oL -Cyano-3-phenoxybenzyl ester (IR, cis) .2,2-dimesh1-3- (3-hydroxy-3-oxo-1-propynyl) cyclopropane carboxylic acid, 20 cm of chloride methylene and 0.7 cm of ethoxyethanol are cooled to O - (+5) C. 1.1 g of dicyclohexylcarboQ are added
five
0
five
0
-
Q

0
diimide, 5 cm of methylene chloride, and 15 mg of dimethylaminopyridine. Stir for 1 hour at room temperature for 2 hours. Filter, concentrate the filtrate to dryness and chromatograph the residue on silica, elute with a mixture of cyclohexane: ethyl acetate (75:25) and obtain 1.3 g of the intended product.
NMR, CDCls, Cho / million: 1.22-1.32 (protons of methyls to 2 cyclopropane); 1.93 (protons in 1 and 3 cyclopropane); 4.17 to 4.38 (protons in 1 COO-CH-SNGr-r); 3.55 to 3.73 (protons in 2 COO-CHi-CHg-O); 6.57 (proton on the same carbon as CN); 7 to 7.67 (protons of aromatic compounds; 1.08 - 1.2 - 1.3 and 1.52 (q protons of ethyl)
Stage B. (S. e. T. Cyano-3-phenoxy-benzyl ether (III, cis) 2,2-dimethyl-3- (Z) -3-oxo-3- (ethoxy ethoxy) -1-1 propinsh1 cyclopropane carboxylic acid.
Analogously to example 7 (stage B), but starting from 1.3 g of the product obtained above, 1.0 g of the desired product is obtained.
o () + 37.5 + 2.5 (, 5% CHCl j).
PRI me R 10. (S) -1-Cyano-3- -phenoxybenzyl ester (IR, cis) 2,2-dimethyl-3- (g) -3-oxo-3 (RS) (1-1- 1-trifluoromethyloxy) 1-propynyl cyclopropane carboxylic acid.
Similarly to Stage B of Example 7, consumed 2.6 g of (S) -cyano-3-phenoxybenzyl ester (IR, cis) 2,2-dimethyl-3H-oxo-3 (RS) 1,1,1-three fluoromethylethoxy) 1-propynyl cyclopropane carboxylic acid, after elution with a mixture of cyclohexane - ethyl acetate (9-1) receive 2.1 g of the target product.
0 (5. + 44 ± 2 (, 4% benzene).
Preparation of (S) rf.-Cyano-3-phenoxybenzyl ester (IR, cis) 2,2-dimel-3 3-oxo-3 (RS) 1,1,1-trifluoromethyl-ethoxy) propinyl cyclopropane carboxylic acid.
Act as in stage A of Example 9, consume 4.6 g of 1,1,1-trifluoromethylethanol and 3.8 g of (S) L-cyano-3-phenoxy-benzyl ester (IR, cis) 2.2 -dimethyl-3-3-oxo-3-hydroxypropyl cyclopropane carboxylic acid, obtained after elution with a mixture of cyclohexane-ethyl acetate acetic acid (8-2) 2.6 g of the target product.
Example 11 of (S) o.-Cyano-3-phenoxybenzyl ester (IR, cis) 2,2-dimethyl-3-L (Z) 3-oxo-3- (2,2-difluoro-ethoxy) -propinyl cyclopropane CARBONIC, ACID
Stage A. (iRp cis) 2,2-dimethyl 3- (3-oxo-3- (2 J, 2-difluoroethoxy) propynyl cyclopropane carboxylic acid tert-butyl ester.
. Act as in stage A of Example 9, but starting from 5 g of tert-butyl ether (IR, cis) 2,2-dimethyl-3- (3-hydroxy 3-oxy-1-propinyl) cyclopropane carboxylic acid, after elution with a mixture n-hexane-isopropyl ether (7-3) gives 5.25 g of the expected product. .
IR spectrum of CHCl j,: sop p Zhf 2232; ester 1725; asymmetric 1710; doubledimethyl
, M393
J380, t-butyl 1372.
Stage B. (IR, cis) 2,2-Dimethyl-3H-oxo-3 (2,2-difluoroethoxy) 1-propynyl cyclopropane carbon pva acid,
5.2 g of the product obtained above, 500 mg of para-, toluenesulfonic acid in 40 cm of toluene is heated with reflux for 25 minutes. After cooling, add 400 cm of ether, rinse with water, dry the organic layer and concentrate to dryness. Receive. - 4.1 g of the desired product.
Stage B. (S) o {.- Cyano-3-phenoxy-benzyl ether (IR, cis) 2,2-dime-3-oxo 3- (2,2-difluoroethoxy) - 1-propini.p: 3 cyclopropane carboxylic acid
Acting as in Stage A of Example 9, but starting from 4.1 g of the acid obtained above and 4.5 g of (S) cA-cyano-3-phenoxybenzyl alcohol, is obtained after elution with a mixture of petroleum ether (T. 40-70 ° C) -isopropyl ether (6-4) 4, 7 g of the expected product.
Y.K range SKS1z,. Cm: OH 3580;
s.par dm me and 392
(1380; conj. 2235; C O ester 1735; conj. S, huy., Ether 1725; aromatic compounds G 588 U488.
Stage G. (S) o (.- 1 Diano-3-phenoxy-benzyl ether (IR, cis) 2,2-dime (Z) 3-oxo-3 (2 5 2-difluoroethoxy) propinyl cyclopropane carboxylic acid.
4.7 of the product obtained above is subjected to hydrogenation in a manner similar to that of Step B of Example 7. After elution with an n-hexane-isopropyl ether mixture (7-3), 3.2 g of the expected product are obtained.
o T + 44 ± 2.5 (, 5% СНС1з).
Example 12. (S) ot-Cyano-3-phenoxybenzyl ester (IR, cis) 2, 2-dimethyl-3- (Z) -3- (2, .2-dichlorop: 5toxy) -1-propynyl cyclopropane carbonic acid.
Step A. Tert-butyl ether (IR, cis) 2,2-: dimethyl-3- (Z) -3- (2,2-dichloroethoxy) -1-propynyl cyclopropane carboxylic acid.
0 Act as in Example 9, Step A, starting from 4.8 g of tert-butyl ether (IR cis) 2,2-dimethyl-3 - (, 3-hydroxy-3-oxo-1-propynyl) cyclopropane carboxylic acid and 2 cm 2,2-dichloro5 ethanol. After elution with a mixture of cyclohexane and ethyl acetate (9-1), 5.6 g of the expected product are obtained.
Stage B, - (IR, cis) 2,2-Dimesh10 -3- (Z) -3- (2,2-Dicloroethoxy) -1-propynyl cyclopropanecarboxylic acid.
: Similar to Step B of Example 11, starting with 5.6 g of the product obtained above, 4.5 g of the expected product are obtained.
Step Bc (S) -Cyano-3-phenoxy-benzyl ester (IR, cis) 2,2-dimethyl-3- (Z) -3- (2,2-dichloroethoxy) -10-propinyl cyclopropane carboxylic acid. .
Similar to Step A of Example 9, starting from 3 g of the product obtained in Stage B and 2.25 g (S): -cyano-3-phenoxybenzyl alcohol, after elution with cyclohexane-ethyl acetate (8-3), and then (9-1) get g of the desired product,
+ 54 ± 2 ° (in benzene). (IR, cis) 2,2-dimethyl-3 (Z) -3- -oxo-3- (2 5 2 -difluoroethoxy) -1-propyl cyclopropane carboxylic acid and the corresponding alcohol. Similarly, stage A of example 9 receive
five
The following compounds:
a) (RS) d. -cyano-6-phenoxy-2-pyridylmethyl ether (IR, bottom) 2,2-dimethyl-3- (Z) -Z-oxo-3- (2,2-difluoro7. 1428189 -8 - ( 2-Propenyl) -1-hydroxy-2-methyl-4-lots are dissolved in 250 cm of tetrahydro-oxo-cyclopent-2-en-1-yl, 20 cm of benzene and 0.6 cm of pyridine. Stir for 16 hours and drink a mixture of ice water and 1N hydrochloric acid is extracted with benzene, the benzene layers are combined, washed with water and brought to dryness. 1.5 g of profurane is obtained. Then, 48 cm of 20% strength in butyl lithium in cyclohexane are introduced. The mixture is stirred for 1 hour at -65 ° C and 9.6 cm of fenh-ester, chlorogolic acid are introduced. The mixture was stirred at this temperature for 1 hour and, continuing to measure 8 -8 lots, dissolved in 250 cm of tetrahydrofuran. Then 48 cm of 20% butyllithium in cyclohexane were introduced in. The mixture was stirred for 1 hour at -65 ° C and introduced , 6 cm fenshivuyu ester, chloroic acid Then re-stirred at this temperature for 1 h and, continuing the mix
The product that was chromatographed was adjusted to room temperature by room-.
silicon dioxide (eluant: cyclohexane. Poured onto saturated water
the solution of primary sodium phosphate, extracted with ether, washed with water, dried and get 24.6 g of oil, which is cleaned by chromatography on a bio,
cyclopropane); 5.8 to 6.8 (H in 1 and 2 radicals propynyl); 5.2 (H methoxy radical, phenyl methoxy); 5.6 to 5.7 (H of cyclopentene WOSS); 2 (H methyl
f
San - ethyl acetate; 8-2).
The yield of the target product 500 mg
+ 37 + 2.5 (to 0.5% benzene). . Lremni acid kit (eluant: cyclohexane. NMR spectrum, CDClj, h „/ yn; 1.27 ethyl acetate: 9-1). and 1.31 (and methyl in 2 cyclopropane) .; 14, -4 g of the desired product 1.87–2 (H carbon in 1 cyclopro-H1-1R CDCls spectrum, ppm; 1.23 and pan) were isolated; 3.12 to 3.45 (H of carbon in 3 20 (H of methyl in 2 cyclopropane);
1.82 (H in 1 and 3 cycloprutane); 1.5 (H radical dimethylethyl); 7 to 7.6 (H aromatic compounds)
Stage B „1,1-Dimethyl Ethyl
cyclopentene); 4.8 to 5.2 (H pro 25 ether (IR, cis) 2,2-dimesh1-Zr1 (Z) 3-pytile on cyclopentene) -oxo-3-phenoxy-1-propynyl cyclopropyl and 5 „(S) c6-Cyano-3-fep carboxylic acid, noxybenzyl. ether (IR, cis) 2,2- In the presence of 800 mg of dimethyl hydroxide 3- (g) -3-oxo-3-phenoxy-1-palladium on sulfuric acid, propynyl cyclopropane carboxylic acid 0.8 cm quinol} and 20 cm ethyl lots. . Acetic ester is subjected to
Analogously to example 1, but starting from 1.5 g (IR, cis) 2. ,, 2-dimethyl-3 (X) - -3-oxo-3-phenoxy-1 g propinyl cyclopropane carboxylic acid and 1.45 g (S) 1 -hydroxy-3-phenoxybenzene of acetonitrile, 1.8 g of the expected product are obtained.
+ 54 ± 2.5 ° (to 0.5% in benzene).
NMR spectrum, CDClI, h / mpn; 1.25 (H in 2 cyclopropane); 1.97 - 2.12 (H in 1 cyclopropane); 3.25 to 3.6. (H in 3 cyclopropane); 6.6 to 7 (N in
1 radical propinyl); 6.1-6.3 (H in
2radical propynyl); 6.9 to 7.7 (H aromatic compounds of the radical 3-phenoxyphenyl) Preparation 3. (IR, cis) 2,2-dimethyl-3 (2) -3-oxo-3-phenoxy-1- -propynyl cyclopropane carboxylic acid
Stage A 1, 1-Dim-ethyl ethyl ester (IR, cis) 2,2-dimethyl-3- (3-oxo-3- -phenoxy-1-propynyl) cyclopropane carboxylic acid 55 la and 100 mg multi-hydrate paratoluene 25 g 1.1 - dimethyl ethyl ether. Sulfonic Acids Stop the reflux (IR, cis) 2,2-dimethyl-3- (2, 2 -di-) immediately after the end of the gas vybromvinil) cyclopropane carboxylic acid. Reduce to dry under diminish 40
hydrogenation 4 g of the product obtained in stage A in a solution in 60 cm-ethyl acetate, filtered and 200 cm 2n added. hydrochloric acid solution. Decanted, washed with water and dried. 4.1 g of an oil is obtained, which is purified on silica (eluant: cyclohexane - ethyl acetate: 95-5).
3.35 g of the expected product are obtained. NMR spectrum, CDCl1, ppm: 1.23 and 1.3 (H in 2 cyclopropane); 1.83-1.97 (H- in 1 cyclopropane); 3 to 3.33 (H in 3 cyclopropane); 1.44 (H radical of methylethyl); 6.7 to 7 (H in 1 radical propinyl); 7 to 7.5 (H aromatic compounds) „
Stage B (IR, cis) 2,2-Dimethyl-50-3- (Z) 3-oxo-3-phenoxy-1-propynyl} cyclopropane carboxylic acid. .
A mixture of 3.3 g of the product obtained in the previous step, 35 cm toluo, f is heated under reflux.
5 la and 100 mg para-toluene 0
hydrogenation 4 g of the product obtained in stage A in a solution in 60 cm-ethyl acetate, filtered and 200 cm 2n added. hydrochloric acid solution. Decanted, washed with water and dried. 4.1 g of an oil is obtained, which is purified on silica (eluant: cyclohexane - ethyl acetate: 95-5).
3.35 g of the expected product are obtained. NMR spectrum, CDCl1, ppm: 1.23 and 1.3 (H in 2 cyclopropane); 1.83-1.97 (H- in 1 cyclopropane); 3 to 3.33 (H in 3 cyclopropane); 1.44 (H radical of methylethyl); 6.7 to 7 (H in 1 radical propinyl); 7 to 7.5 (H aromatic compounds) „
Stage B (IR, cis) 2,2-Dimethyl-0 -3- (Z) 3-oxo-3-phenoxy-1-propynyl} cyclopropane carboxylic acid. .
A mixture of 3.3 g of the product obtained in the previous stage is heated under reflux with 35 cm of toluene pressure and 3.4 g of product is obtained which is chromatographed on silica (eluant: cyclohexane — ethyl acetate: acetic acid: 70-30-1). 2.4 g of the expected product are obtained, melting at
NMR spectrum, CDCl1, ppm: 1.25 to 1.33 (H methyls to 2 cyclopropane); 1.9 - 2.04 (H in 1 cyclopropane) 3.2 to 3.5 (H in 3 cyclopropane); 6.6 to 6j9 (H in 1 propynyl); 6.0 - 6.2 (H in 2 propynyl),
PRI me R 6o (IS) 2-Metsh1-4-ok- (2-propinyl) -2-piclopenten-1-methyl ester (IRj. Cis) 2,2-dimethyl- f (Z) -3 oxo - 3-phenoxy-1 propinyl cyclopropane carboxylic acid.
Analogously to example 2, but starting from 1.5 g (IR, cis) 2,2-dimethyl (Z) - 3 oxo-3-phenoxy-1-propinyl cyclopropane carboxylic acid and 1 g (S) - (2-propinyl) -1-hydroxy-2-methyl-4-oxo-cyclopent-2-ene-1-syl, 1.6 g of the expected product are obtained.
o (-D + 66 ± 2.5 (to 0.5% benzene).,.
NMR spectrum, C1) C1Z, Cho / million: 1.26 and 1.33 (H in 2 cyclopropane); 1.95-2.09 (H in 1 cyclopropane); 5.7 (H cycloprene c) | 4.8 to 5.2 (H in 3 propynyl on cyclopentene); 2 (H methyl on cyclopentene); 6.1 to 6.7 (N propynyl on cyclopropane) 7 to 7.7 (H aromatic compounds 1 o
PRI me R 7. (RS) -Ciano-3-phenoxybenzyl ester (IR, cis) 252-dimethyl-3-1 (2) -3-oxo-3-methoxy methoxy T-propinyl cyclopropane carboxylic acid "
Stud 11 -A. (RS) "t-Cyano-3-phenoxy-benzyl ether (IR, cis) 2,2-dimethyl-3- (3-oxo-3-methoxy methoxy-1-propynyl) cyclopropane carbon acid
Cool to + 10 ° C a solution of 3 g of (R) -cyano-3-phenoxybenzyl ester (IK, cis) 252-dimethyl-3- (3-G1-Shchroxy 3-oxo 1-propynyl) cyclopropane carboxylic acid in 30 cm without aqueous dimethylformamide, 300 mg of sodium hydride in oil are added in fractions, and then, within 15 minutes, 2.5 cm of a solution of chloromethylether, prepared as indicated in nyute. Mixed 24, poured into an aqueous solution of primary phosphate
five
0 5
0
with
0
sodium and extracted with ethyl acetate, washed with water and concentrated to dryness. The residue is chromatographed on silica (eluent: cyclohexane - ethyl acetate: 75-25) and collected
2g of the target product.
NMR, CDCli, ppm: 1.23 - 1.27 and 1.35 - 1.45 (protons of methyl to 2 cyclopropane); 1.95 (protons in 1 and
3cyclopropane); 5.28 (proton methylene methoxy methoxy); 3.5 (proton methyl methoxy methoxy); 6.42 and 6.47 (proton on the same carbon as CN); 6.92 to 7.58 (protons of aromatic compounds) „
To prepare a solution of chloromethyl ether, 4.5 cm methyl and 0.52 cm of methanol are mixed, and then 3.53 cm of acetyl chloride are slowly added. After stirring for 36 hours at room temperature, the desired solution is obtained.
Stage B. (RS) ° C - Cyano-3-phenoxy-benzyl ether (IR, cis) 2,2-dimethyl-3- (Z) -3-OKCo-3-MeTOKcn methoxy--1-propinyl cyclopropane carbon acids,
2.2 g of the product obtained as indicated above in 50 cm of ethyl acetate and in the presence of 450 mg of 10% palladium hydroxide on sulfuric acid barium in 30 cm of ethyl acetate and 0.5 cm of quinoline are hydrogeated, filtered, rinsed with 1N, hydrochloric acid, water and brought to dryness. The residue is chromatographed on silica, eluted with a mixture of cyclohexane-ethyl acetate (8-2) and 1.2 g of the expected product are collected.
+ 41 t 3 (to 0.3%, CHCl).
NMR spectrum, CDCl1, ppm: 1.27 - 1.28 and 1.33 - 1.35 (protons of methyl in 2 cyclopropane); 1.93 - 2.1 (proton in 1 cyclopropane); 3.17 to 3.5 (proton in 3 cyclopropane); 6.47 to 6.82 (proton ethylene in 1); 5.85 - 6.0 and 5.88 - 6.1 (ethylene proton in 2); 5.27 and 5.3 (proton CHg methoxy); 3.47 and 3.5 (protons of methyl methoxy); 6.4 (proton on the same carbon as CN); 6.92 to 7.67 (protons of aromatic compounds),
Used at the beginning of the example (RS) d. -cyano-3-phenoxybenzyl ether (IR, cis) 2,2-dimethyl-3- (3-hydroxy-3-oxo-1-propynyl) cyclopropane
ethoxy) -1-propynyl j cyclopropane carboxylic acid.
+ 50.5 ± 2 (, 8% CHCl j);
, b) (R) cL-cyano-3-phenoxybenzyl ester (1R, cis) 2,2-dimethyl-3- - and (2) -3-oxo-3- (2,2-cifluoroethoxy) -1 - - propikil cyclopropane carboxylic acid
+ 117.5 + 3 (, 6% CHClj);
c) 3-propargyl-2,5-dixoimidazolidinylmethyl ether (IR, cis) 2,2-dimethyl-3- (Z) -3-oxo-3-12,2-difluoroethoxy) -1-propynyl cyclopropane carboxylic acid,
oCi) + 18 ± 2 ° (SNS);
d) (R) cL-ethynyl-3-phenoxybenzyl ester (, 1R, cis) 2,2-dimethyl-3- -L (Z) -3-OKco-3- (2,2-difluoroethoxy) -1 -propinyl cyclopropane carboxylic acid.
cij) + 47 t 1.5 ° (CHCl3).
In the following examples, compounds are prepared analogously to stage A of example 9, starting from 1 (IR, cis) 2,2-dimethyl-3- (g) -3-oxo-3 (.2,2-difluoroethoxy) -1 -propinyl cyclopropane carboxylic acid and the corresponding alcohol ..;
EXAMPLE 13 (RS) with -Cyano-6-phenoxy-2-pyridyl methyl ether (IR, cis) 2,2-dimethyl-3-XE) -3-oxo-3 -. (2, 2-difluoroethoxy) -1-propynyl cyclopropane carboxylic acid.
Starting from 1 g of acid and 2 g of alcohol, 1.84 g of the desired product is obtained. Cc5 +50.5 i 2 Ck 0.8% CHCl j).
PRI me R 14. (R) s / - Cyano-3- -phenoxybenzyl ether (IR, cis) 2,2-dimesh-1-3- (g) -3-oxo-3- (2,2- - difluoroethoxy) -1-propinsh1 cyclopropane carboxylic acid.
Starting from 0.8 g of acid and 0.73 g of alcohol, 1.19 g of the expected product are obtained.
d. +117.5 + 3 ° (, 67a СНС1з).
Example 15. (3-propyl-2,5-dimetho-imidazolidinyl methyl ether) (IR, cis) 2,2-dimethyl-3- (g) -3-oxo-3- (2,2-difluoroethoxy) -1-propynyl cylopropane carboxylic acid.
Starting from 0.9 g of acid and 0.64 g of alcohol, 0.59 g of the expected product is obtained.
W (a 18 + 2 (CHClj)
Example 16. (R) (-ethynyl-3- -phenoxybenzyl ester (IR, cis) 2,2-dimethyl-3-t (Z) -3-oxo-3- (2.25
0
j
0
five
zo
dd
r
55
-difluoroethoxy) -1 -propinyl cyclopropane carboxylic acid.
Starting from 0.9 g of acid and 0.85 g of alcohol, 1.5 g of the expected product are obtained.
сА- + 47 + 1,5 ° (CHCls).
(IR, cis) 2,2-dimethyl-3- (Z) -3- -oxo-3- (2,2-difluoroethoxy) -1-propynyl; cyclopropane carboxylic acid was obtained in the same manner as the acid described in preparation 6, starting from 2,2-difluoroethanol 2 ° (IR, cis) 2,2-dimethyl-3- (Z) -3- -oxo-3- (2-fluoroethoxy) -1-propinyl cyclopropane carbon acid and the corresponding alcohol.
PRI me R 17. 3-Propargyl-2,5-β-dioxoimidazolidinyl methyl ether (IR, cis) 2,2-dimethyl-3- (Z) -3-OKco-3- (2-fluoroethoxy) -1 -propinyl cyclopropane carboxylic acid
Starting from 1 g of acid and 0.73 g of alcohol, 0.79 g of the expected product is obtained.
o (.j 18 ± 2 ° (SNS).
Example IS.fRS) with Cyano (6-phenoxy-2-pyridyl) methyl ester (IR, cis) 2,2-dimethyl-3- (Z) -3-oxo-3- (2-fluoroethoxy) - 1-propinyl cyclopropane carboxylic acid
Starting from 0.9 g of acid and 1 g of alcohol, 1.63 g of desired product is obtained.
SU + 49.5 + 2.5 (, 5% CHClj)
Example 19. (R) dL -Methyl-3-β-fgnoxybenzyl ether (IR, cis) 2,2-dimetsI-3- (Z) -3-oxo-3- (2-fluoroethoxy) -1-propynyl cyclopropane carboxylic acid
Starting with 1 g of acid and 0.93 g of alcohol, 1.5 g of the expected product are obtained.
+ 123 ± 1.5 ° (CHClj).
Example 20. Ethynyl-3-phenoxy-sibenzyl ester (IR, cis) 2,2-dimethyl-3- {(Z) -3-oxo-3- (2-fluoroethoxy) -1- propynyl cyclopropane carboxylic acid .
Starting from 1 g of acid and 0.975 g of alcohol, 1.58 g of desired product is obtained.
(L; and + 47 ± 1.5 (СНС1з).
(IR, cis) 2,2-dimethyl-3- (g; -3-oxo-3- (2-fluoroethoxy) -1-propynyl cyclopropane carboxylic acid was obtained in the same manner as the acid described in the preparation method 6, starting from 2-fluoroethanol.
3 (IR, cis). 2,2-dimethyl-3- (g) -3- -oxo-3- {2- (1,1,1,3,3,3-hexafluoro) propoxy) -1-propynyl cyclopropane carboxylic acid (preparation 6) and the corresponding alcohol.
EXAMPLE 21 (R) CK - Ethiyl-3-phenoxybenzyl ester (IR, cis 2,2-dimethyl-3- (Z) -3-oxo-3- (2- (1.1 , 1,353,3-hexafluoro) propoxy) -1 propi-HmiJ cyclopropane carboxylic acid
Starting from 2 g of acid and 1.39 g of alcohol, O 82 g of the expected product is obtained.
, + 31.5 + 1.5 (k-1% СНС1з).
Example 22. (R) s / C-Methyl-3-β-phenoxybenzyl ester (IR-Cis) 2,2-dimethyl-3-i (Z).-3-oKco-3- (2- (1.1, 153, 3,3-hexafluoro) propoxy) -1-propinyl cyclopropane carboxylic acid
Starting from 1.5 g of acid and 1.01 g of alcohol, 0.56 g of the desired product is obtained.
oSV + 97 ± 2 ° (СНС1з).
Example 23. (S) o (-Cyano-3-α-phenoxybenzyl ester (IR, cis) 2,2-dimethyl-3-C (g) -3-oxo-3- (2- (1,1, 1, 3,3,3-Hexacoptop) of the band) t-1-propane-J-cyclopropane carboxylic acid
Starting from 4 g of acid and 2.7 g of alcohol, 4.8 g of the target product „
oCD + 23.5 + 2 ° (, 5% benzene).
EXAMPLE 24 3,4,5,6-Tetrahydrophthalimido methyl ester (IR, cis) 2,2-dimethyl-3- (Z) -3-OKCo 3- (2 (1.1 , 1,3,3,3-hexafluoro) propoxy) -1-propynyl cyclopropane carboxylic acid.
Starting with 3 g of acid and 1.65 alcohol, 1.755 g of targeted product is obtained. .
сСв -30 ± (СНС1з).
EXAMPLE 25, (RS) -Ciano-6-phenoxy-2-pyridine methyl ester (IR, cis) 2, 2-dimethyl-3- (Z) -3-oxo-3- (2 - - (1J1,1,3ЗЗ, 3-hexafluoro) propoxy) -1- -propynnnl cyclopropane carboxylic
ACID
Outcome From 3.1 g of acid and 2.1 g of alcohol, 0.981 g of desired product is obtained.
oCj: + 33-, 5 ± 2.5 (, 2% СНС) ,. ; (3; R, cis) 2, 2-dimethyl-3- (Z) -3-oxo-3- (2,2-J 2-trifluoroethoxy) -1-pro; 1 Shnol cyclopropane carboxylic acid (preparation 1) and the corresponding alcohol.
EXAMPLE 26. 3-Propargyl-2,5-β-dioxoimide: (IR, cis) -2,2-dimethyl-3- (Z) -3-oxo-3 (2.2, 2-trifluoroethoxy) -1-propynyl cyclopropane carboxylic acid
Starting from 1.5 g of acid and 0.95 alcohol, 1.04 g of the expected product is obtained. .
o (.j, 1 ° (benzene).
Example 27. (R) cA-Methyl-3- -phenoxybenzyl ester (IR, cis) 2,2-dimethyl-3- (Z) -3-oxo-3- (2,2,2-trifluoroethoxy) -1 -propinyl cyclopropane carboxylic acid.
Starting from 1.5 g of acid and 1.2 g of alcohol, 2.13 g of the expected product are obtained.
cX.j .t08,5 ± 2 ° (CHClj).
Example 2B 3,4,5,6-Tetrahydrophthalimidomethyl ether (IR, cis) 2,2-dimethyl-3- (Z) -3-oxo-3- (2,2,2-trifluoroethoxy) -1-propynyl cyclopropane carboxylic acid.
Starting from 1.5 g of acid and 1.02 g of alcohol, 2 g of the desired product are obtained.
) + 2.5 + 2 (, 5% CHC1e).
Pr and m-e-p 29o (R) s.-3-3-phenoxybenzyl ester (IR, cis) 2,2-dimethyl-3-L (Z) -3-oftco-3- ( 2,2,2-tri-tetraethoxy) -1-propynyl cyclopropane carboxylic acid.
Starting from 1 g of acid and 0.9 g of alcohol, 1.5 of the desired product are obtained.
). + 42 ± 1.5 ° (СНС1з) о
Example 30. (RS) H.-Cyan-6-β-phenoxy-2-pyridyl methyl ester (IR, cis} 2,2-dimethyl-3-G (Z) -3-occo-3- (2.2 , 2-trifluoroethoxy) -1-propynyl cyclopropane carboxylic acid.
Starting from 2.8 g of acid and 2.4 g of alcohol, 3.9 g of the expected product are obtained.
) + 46.5 + 2 (, 7% CHCl3). 5 (S) with -Cnano-3-phenoxybenzyl ester (IR, cis) 2,2-dimethyl-3- (Z) 3-hydroxy-3-oxo-1-propynyl cyclopropane carboxylic acid (preparation 7) and the corresponding alcohol.
The values of the radicals R and L of the target product, the general formula T, obtained according to the examples described above, are listed in the table.
sixteen
(IR) c -Etinyl-3-phenoxybenzyl
(IR) cA-Methyl-3-phenoxybenzyl
CIS) Cyano-3-phenoxybenzyl
3,3,5,6-Tetrahydrophthalimidomethyl
(IRS) ck-11iano-6-phenoxy-2-pyridylmethyl
3-11 pararyl-2,4-dioxoimidazolidinylmethyl
(IR) oC-Methyl-3-phenoxybenzyl
3,4,5,6-Tetrahydrophthalimidomethyl
(IR) oC -Ensh1-3-phenoxybenzyl
(IR) oL -Ciaio-b-phenoxy-2-pyridylmethyl
(1,1,1,3,3,3-Hexafluoro) -propyl
(1,1,1,3,3,3-Hexafluoro) -propyl
(1,1,1,3,3,3 Hexafluoro) propyl
(1,1,1,3,3,3-Hexafluoro) -propyl
(1,1,1,3,3,3-Hexafluoro) -propyl
Trifluoroethyl
Trifluoroethyl Trifluoroethyl
Trifluoroethyl Trifluoroethyl
Example31. Investigation of the lethal effect on domestic flies Insects under investigation are
home flies females 4/5 days old your environment and control mortality
after 24, 48 hrs 3 and 5 days.
The result, expressed as
in lethal concentration50 (CLso).
They act by topically applying 1 µm acetone solution to the insects ’spinal thorax using an Arnold micromanipulator. 50 individuals are used per dose and per treatment. Mortality control was performed 24 hours after treatment.
The result, expressed in DLso or dose (ng nanograms), is necessary to kill 50% of the insects.
I
ten
15
Example Compound
one
3
CLso, mg / m
0.216 1.273 0.151 0.100 0.259 0.060 0.055 0.034 0.216
Connection of example 1 2 9 and 13 15 16 17 18 20 24 25
DLso ng / ns. 1.11 9.56 11.31 5.11 10.05 9.64 2.26 10.97 0.96 0.735 0.82 1.05
In the proposed method, the lethal doses of products in the majority of cases are less than in the known method for which the value of DLso varies (in the same test conditions) from 11.4 to 25.7 ng / ns
Example 32. Investigation of the activity of spinal contact on Prussian cockroaches (compound of example 1).
The insects under study are Prussian cockroaches (Blatella gaxmanias). There is a pouring on the bottom of a Petri dish with a diameter of 20 cm acetone solution of a certain concentration
After the cake, 20 male cockroaches are injected for 1 hour at one concentration, and then the insects are moved to a healthy environment and mortality is controlled.
Example Compound
one
3
eleven
sixteen
17
18
20
24
25
CLso, mg / m
0.216 1.273 0.151 0.100 0.259 0.060 0.055 0.034 0.216
The lethal concentration of the compounds in this method is significantly less than in the known method (1.95 - 3.1 mg / m).
Thus, the compounds of general formula I have a greater insecticidal activity.

权利要求:
Claims (1)
[1]
Invention Formula
"
The method of producing esters - derivatives of cyclopropanecarboxylic acid of the general formula
B02S-CH SN -SOGL
where the double bond has a geometry L or E;
And - hydrocarbon radical selected from the group:
(IS) oL - “cyano-3-phenoxybenzyl; (k-cyano-3-phenoxybenz1 1 R; (1R) (k-methyl-3-phenoxybenzyl; (IS) 2-methyl-4-oxo-3- (2-propynyl) -2-cyclopentene-1- silt;
23U2818924
{1K) L. ethylene-3-phenoxybenzyl; where R has the specified value, (1R) or (15K) -cyano-6-phenoxy-2-or a functional derivative of this α-pyridylmethyl, the acid is reacted
R is alkyl substituted by fluoro. with an alcohol of general formula, rum or chlorine; and with the fact that the acid is totalA HE,
Formulas where A has the indicated meanings
in an organic solvent at com. 0 at natural temperature in the presence of
As a base of pyridine or divooC-CH CH- - -COjH yetilaminopyridine and, if necessary, dicyclohexylcarbodiimide.

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同族专利:

公开号 | 公开日

PT73300B|1983-06-15|

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JPH01156943A|1989-06-20|

AU544753B2|1985-06-13|

JPS5745140A|1982-03-13|

KR850000512B1|1985-04-12|

ZA814304B|1982-07-28|

DD204027A5|1983-11-16|

EG15179A|1989-06-30|

JPS6023342A|1985-02-05|

CA1242644A|1988-10-04|

FR2539956B2|1985-05-03|

EP0048186B1|1985-05-02|

DK306290A|1990-12-27|

IE51451B1|1986-12-24|

ES8301198A1|1982-11-16|

FI812074L|1982-01-03|

AU7246581A|1982-01-07|

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DE3170263D1|1985-06-05|

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CA1237134A|1988-05-24|

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JPH0417941B2|1992-03-26|

IE811479L|1982-01-02|

ES8305301A1|1983-04-01|

AT13054T|1985-05-15|

MA19192A1|1981-12-31|

KR830006165A|1983-09-17|

FR2486073B1|1983-08-19|

ZW15081A1|1981-12-09|

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JPH04234830A|1992-08-24|

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PT73300A|1981-08-01|

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DK163875B|1992-04-13|

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AU558842B2|1987-02-12|

DD202284A5|1983-09-07|

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引用文献:

公开号 | 申请日 | 公开日 | 申请人 | 专利标题

BE660565A|1963-03-18|

JPS5220473B1|1970-06-29|1977-06-03|

JPS515450B1|1971-06-29|1976-02-20|

DE2326077C2|1972-05-25|1985-12-12|National Research Development Corp., London|Unsaturated cyclopropanecarboxylic acids and their derivatives, their preparation and insecticides containing them|

HU176939B|1978-02-23|1981-06-28|Chinoin Gyogyszer Es Vegyeszet|Process for pproducing derivatives of esters of chrisanthemic acid|

FR2455025B1|1979-04-26|1981-12-24|Roussel Uclaf|

FR2486073B1|1980-07-02|1983-08-19|Roussel Uclaf|AU580770B2|1980-04-16|1989-02-02|Roussel-Uclaf|Derivatives of cyclopropane carboxylic acid, their preparation, and use|

FR2486073B1|1980-07-02|1983-08-19|Roussel Uclaf|

FR2514760B1|1981-10-16|1984-01-13|Roussel Uclaf|

FR2533416B1|1982-09-29|1988-09-02|Roussel Uclaf|NOVEL PESTICIDE COMPOSITIONS CONTAINING A PHOTOSTABILIZER|

FR2536392B2|1982-11-22|1985-04-12|Roussel Uclaf|

FR2536748B1|1982-11-25|1985-04-12|Roussel Uclaf|

US4584304A|1984-06-08|1986-04-22|Shell Oil Company|2-pyridinylmethyl oxyiminocyclopropanecarboxylates as pesticides|

FR2610624B1|1987-02-06|1989-06-09|Roussel Uclaf|NOVEL ESTERS OF PYRETHRIC ACID-LIKE CYCLOPROPANECARBOXYLIC ACIDS, THEIR PREPARATION PROCESS AND THEIR APPLICATION TO PEST CONTROL|

JP3694915B2|1994-06-17|2005-09-14|住友化学株式会社|Ester compounds and pest control agents containing the same as active ingredients|

US5852048A|1995-03-01|1998-12-22|Sumitomo Chemical Company, Limited|Ester compound and a pesticidal agent containing the same as an active ingredient|

DE102004001271A1|2004-01-08|2005-08-04|Bayer Cropscience Ag|Drug combinations with insecticidal properties|

DE102007045953B4|2007-09-26|2018-07-05|Bayer Intellectual Property Gmbh|Drug combinations with insecticidal and acaricidal properties|

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DE102009028001A1|2009-07-24|2011-01-27|Bayer Cropscience Ag|Use of an active agent combination dec-3-en-2-one compound, and an agent e.g. alanycarb, aldicarb, acephate, camphechlor or chlordane) for combating animal pests e.g. insects, acarids and helminths|

EP2382865A1|2010-04-28|2011-11-02|Bayer CropScience AG|Synergistic active agent compounds|

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法律状态:

优先权:

申请号 | 申请日 | 专利标题

FR8014722A|FR2486073B1|1980-07-02|1980-07-02|MD94-0271A| MD221C2|1980-07-02|1994-09-08|Method of ester obtaining - derivatives of the cyclopropan-carbonic acid|

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