Method of producing derivatives of cyclopropancarboxylic acid as racemates or optically active antip

专利摘要:
1. Claims (for the contracting States : BE, CH, DE, FR, GB, IT, LI, LU, NL, SE) In all the possible isomer forms, the compounds with the formula (I') : see diagramm : EP0041021,P51,F1 in which the double bond has Z geometry, the cyclopropane copula is of 1R cis structure and A' represents : either an alkyl radical containing 1-18 carbon atoms, or a benzyl radical possibly substituted by one or more radicals chosen from the group constituted by alkyl radicals containing 1-4 carbon atoms, alkenyl radicals containing 2-6 carbon atoms, alkenyloxy radicals containing 2-6 carbon atoms, alkadienyl radicals containing 4-8 carbon atoms, the methylenedioxy residue, and the halogen atoms, or a see diagramm : EP0041021,P51,F2 group, in which the substituent R1 represents a hydrogen atom or a methyl radical and the substituent R2 represents a monocyclic aryl or a -CH2 -C -= CH group and notably a 5-benzyl-3-furylmethyl group, or a see diagramm : EP0041021,P51,F3 group in which R3 represents an aliphatic organic radical containing 2-6 carbon atoms and one or more carbon-carbon unsaturations and notably the radicals -CH2 -CH=CH2 , -CH2 -CH=CH-CH3 , -CH2 -CH=CH-C2 H5 , -CH2 -CH=CH-CH=CH2 , or a see diagramm : EP0041021,P51,F4 group, in which R3 retains the same significance as previously, each of R'1 and R'2 , identical or different, represents a hydrogen atom, a halogen atom, an alkyl radical containing 1-6 carbon atoms, an aryl radical containing 6-10 carbon atoms, an alkyloxycarbonyl group containing 2-5 carbon atoms, or a cyano group, or a see diagramm : EP0041021,P51,F5 group, in which B represents a CH2 group, or a C=O group, or a hetero element chosen from oxygen and sulphur, R4 represents a hydrogen atom, 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, and notably the 3-phenoxybenzyl, alpha-ethynyl-3-phenoxybenzyl, 3-benzoylbenzyl, 1-(3-phenoxyphenyl) ethyl or alpha-thioamido-3-phenoxybenzyl groups, or a see diagramm : EP0041021,P52,F1 group, or a see diagramm : EP0041021,P52,F2 group, in which each of the substituents R6 , R7 , R8 , R9 represents a hydrogen atom, a chlorine atom, or a methyl radical and in which S/I signifies an aromatic ring or a similar dihydro or tetrahydro ring, or a see diagramm : EP0041021,P52,F3 group, or a see diagramm : EP0041021,P52,F4 group, 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 thiadiazolyl radical of which the bond with see diagramm : EP0041021,P52,F5 may be found at any one of the available positions, R12 being linked to R11 by the carbon atom situated between the sulphur atom and a nitrogen atom, or a see diagramm : EP0041021,P52,F6 group, or a see diagramm : EP0041021,P53,F1 group in which R13 represents a hydrogen atom or a CN radical, or a see diagramm : EP0041021,P53,F2 group, in which R13 is defined as above and the benzoyl radical is in position 3 or 4, or a see diagramm : EP0041021,P53,F3 group, in which R14 represents a hydrogen atom, a methyl, ethynyl or cyano radical and R15 and R16 , which are different from one another, represents a hydrogen, fluorine or bromine atom, or a see diagramm : EP0041021,P53,F4 group in which R14 is defined as above, each of the R17 's represents, independently, an alkyl group containing 1-4 carbon atoms, an alkoxy group containing 1-4 carbon atoms, an alkylthio group containing 1-4 carbon atoms, an alkylsulphonyl group containing 1-4 carbon atoms, or 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, linear, branched or cyclic, saturated or unsaturated, containing 1-18 carbon atoms, as well as the mixtures of these isomers. 1. Claims (for the contracting State AT) Preparation process for all the possible isomer forms, of compounds with the formula (I') : see diagramm : EP0041021,P57,F2 in which the double bond has Z geometry, A' represents : either an alkyl radical containing 1-18 carbon atoms, or a benzyl radical possibly substituted by one or more radicals chosen from the group constituted by the alkyl radicals containing 1-4 carbon atoms, the alkenyl radicals containing 2-6 carbon atoms, the alkenyloxy radicals containing 2-6 carbon atoms, the alkadienyl radicals containing 4-8 carbon atoms, the methylene dioxy residue, and the halogen atoms, or a see diagramm : EP0041021,P58,F1 group, in which the substituent R1 represents a hydrogen atom or a methyl radical and the substituent R2 represents a monocyclic aryl or a -CH2 -C -= CH group and notably a 5-benzyl-3-furylmethyl group, or a see diagramm : EP0041021,P58,F2 group, in which R3 represents an aliphatic organic radical containing 2-6 carbon atoms and or more carbon-carbon unsaturations and notably the -CH2 -CH=CH2 , -CH2 CH=CH-CH3 , -CH2 CH=CH-C2 H5 , -CH2 -CH=CH-CH=CH2 radicals, or a see diagramm : EP0041021,P58,F3 group, in which R3 retains the same significance as previously, R'1 and R'2 identical or different, each represent a hydrogen atom, a halogen atom, an alkyl radical containing 1-6 carbons atoms, an aryl radical containing 6-10 carbon atoms, an alkyloxycarbonyl group containing 2-5 carbon atoms, or a cyano group, or a see diagramm : EP0041021,P58,F4 group, in which B represents a CH2 or C=O group, or a hetero element chosen from oxygen and sulphur, R4 represents a hydrogen atom, 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 numerical 0, 1 or 2, and notably the 3-phenoxybenzyl, alpha-ethynyl-3-phenoxybenzyl, 3-benzoylbenzyl, 1-(3-phenoxyphenyl)ethyl or alpha-thiomado-3-phenoxybenzyl group, or a see diagramm : EP0041021,P58,F5 group or a see diagramm : EP0041021,P59,F1 group, in which each of the substituents R6 , R7 , R8 , R9 , represents a hydrogen atom, a chlorine atom or a methyl radical and in which S/I signifies an aromatic ring or a similar dihydro or tetrahydro ring, or a see diagramm : EP0041021,P59,F2 group, or a see diagramm : EP0041021,P59,F3 group 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 thiadiazolyl radical of which the bond with see diagramm : EP0041021,P59,F4 may be found in any of the available positions, R12 being linked to R11 by the carbon atom situated between the sulphur atom and a nitrogen atom, or a see diagramm : EP0041021,P59,F5 group, or a see diagramm : EP0041021,P59,F6 group, in which R13 represents a hydrogen atom or a CN radical, or a see diagramm : EP0041021,P60,F1 group, in which R13 is defined as above and the benzoyl radical is in position 3 or 4, or a see diagramm : EP0041021,P60,F2 group, in which R14 represents a hydrogen atom, a methyl, ethynyl or cyano radical, and each of R15 and R16 , which are different, represents a hydrogen, fluorine or bromine atom, or a see diagramm : EP0041021,P60,F3 group, in which R14 is defined as above, each of the R17 's represents, independently, an alkyl group containing 1-4 carbon atoms, an alkoxy group containing 1-4 carbon atoms, an alkylthio group containing 1-4 carbon atoms, an alkylsulphonyl group containing 1-4 carbon atoms, or 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, linear branched or cyclic, saturated or unsaturated, containing 1-18 carbon atoms, as well as the mixtures of these isomers, characterized in that an acid with the formula (II) : see diagramm : EP0041021,P60,F4 in which the double bond has Z geometry, R being defined as previously, or a functional derivative of this acid, is submitted to the action of an alcohol with the formula (III) : A'OH in which A' retains the same significance as previously, and in this way the corresponding compound with the formula (I') is obtained.
公开号:SU1342408A3
申请号:SU813284396
申请日:1981-05-15
公开日:1987-09-30
发明作者:Мартель Жак；Тессье Жак；Теш Андре
申请人:Руссель-Юклаф (Фирма)；
IPC主号:

专利说明:

This invention relates to a process for the preparation of new derivatives of cyclopropane carboxylic acid of the general formula

C02A
(I)
where the double bond has a geometry Z; And 3-phenoxybenzyl, 3-benzyl-3-furylmethyl, 3-phenylmethyl-3-furanylmethyl, oi-thioamido-3-phenoxybenzyl, 3-phenoxyphenyl ethyl (2-phenoxy-3-thiazo-1) 1-methyl 3-benzoylbenzyl 3-phenoxy-3 -bromophenoxybenzyl, 4-oxo-4 (n) -pyransch1, 2 propynyl-2,4-dioxoimidazolidinylmethyl, hexahydro-1,3-dioxo 2n - iso-. indolylmethyl, 2-methyl-4-oxopropenylcyclopenyl, cyano-phenoxypyridylmethyl, phenoxypyridylmethyl, phenoxypyridyl-et-yl, phenoxypyridyl-propinyl, cyanophenoxy-5-thiazolylmethyl; R is a linear or branched C., Su-alkyl, or C4-C5 is cycloalkyl, or C4-C5-alklIcyclic alkyls that possess an insecticidal active.
The purpose of the invention is a method of obtaining ™, PG1 compounds with a more insecticidal activity.
The invention is illustrated by the following examples.
Example 1. DS 2-Methyl-4-ox-co-3- (2-propenyl) -2-cyclopenten-1-: | -yl ester 1 R cis, lg12,2-dimethyl-3 - (3-methoxy -Z-oxo-1-propenyl; CEC. P6 proPa-N-carboxylic acid;
- Stage A. Chloride 1 R cis, Z; 2,2-dimethyl 3- (3-methoxy-3-oxo-1-propene) cyclopropanecarboxylic acid.
At 0 ° C, 1 cm of tistil chloride is injected into mixtures containing 1.8 g of 1 R cis, L Z 2,2-dimethyl-3- {2-mb-, xyxi-3-oxo 1-propenyl) cshslopropanecarboic acid and 10 cm isoprene
0
5 5 o Q
with
Q
five
The mixture is kept under stirring for 30 minutes at 0 ° C and then for 4 hours at 20 ° C. It is concentrated to dryness under reduced pressure at 30 ° C. A product is obtained, which is used in the next stage.
Stage B. l 5 2-Metsh1-4-oxo-3- - (2-propenyl) -2-cyclopenten-1-yl ester 1H cis, Z 2,2-dimethyl-3- - (3-methoxy-3 -oxo- -propenyl) cyclopropanecarboxylic acid.
761 mg of 4 V -hydroxy-3-methyl-2- (2-propenyl) -2-cyclopen-ten-1-one, 3 cm of benzene, 0.4 cm of pyridine are mixed. The solution is cooled to 10 ° C and 888 mg of 1 R cis, uZ 2, .2-dimethyl-3-) 3-methoxy-3-oxo--1-propenyl cyclopropanecarboxylic acid chloride in 9 cm of benzene is added. The reaction mixture is kept under stirring for 16 hours. “Pour into water, remove organic layer and wash it with water. Dry, filter and bring to dryness. 1.9 g of product is obtained which is chromatographed on silica, eluted with a mixture of benzene and ethyl acetate (93: 5). Get it. 1.06 g of the desired product.
   + 71.3 + 2.3 ° (to 0.3%, СНС1з). .
NMR (CDCl1). Ppm: 1.3 and 1.32 hydrogen methyl in position 2; 1.9-
2.03H at position 1 of cyclopropane; 3.1 - 3.3 - 3.4 N in the 3 position of cyclopropane, 6.3 to 6.8 carbon in the 1 position of the ethenyl radical; 3.8 -
6.04H carbon in position 2 of the radical ethenyl; 3.7 N groupings of methoxy; 3.6 to 3.8 N of carbon in position 4 of the 4 S 3-metsh1-1-oxo-cyclo-pent-2-en-4-yl radical; 2.93 - 3 N carbon in position 1 of the propenyl radical; 5.3 - 6.2 N carbon in position 2 of the radical propenyl, 4.8 - 3.2 And carbon in position 3 of the radical prspen.
Example 2.l-s 2-Methyl-4-ox- (2-propensh1) -2-cyclopenten-1-h-nsyl ester IR cis, 2-dimethyl- -3- (3-etxi-3-oxo- 1-propenyl) cyclic-pspancarboxylic acid,
1 g of dicyclohexylcarbodiimide, 6 mg of 4-dimethylaminopyridine and 12 cm of methylene chloride are introduced into a flask containing 1.1 g of iR cis, iZ 2,2-dimethyl-3- (3-ethoxy-3 ox-1gproproyl) cyclopropanecarboxylic acid . Then ppibavl pcs 900 mg 4 s14-hydroxy-3-methyl-2 (2-propenyl) -2-cyclopentene-l-OHa, dissolved in 1 cm of methylene chloride. The reaction mixture is kept under stirring for 16 hours. It is filtered and concentrated to dryness under reduced pressure. 2.4 g of product are obtained, which is purified by chromatography on silica, eluting with n-hexane-isopropyl ether (6: 4). Get
1.3 g of the target product.
oi + 34 jf 2 ° (to 0.6% in benzene).
NMR (CDC1,), ppm: 1.27 N methyls in position 2; 3.1 - 3.4 N of carbon in position 3 of cialopropane;
6.4- 6.8 N carbon in position 1 of the radical ethenyl; 5.8 - 6 .N carbon
in position 2 of the radical, ethenyl; 1.17, 1.28, 1.4, and 4 to 4.4 N of the ethoxy group; 4.7-- 5.2 N carbon in the position of the radical propenyl.
Example 3. Rh3-Methyl-4-oxo-3- (2-propenyl) -2-cyclopenten-1- -yl cis, 2-dimethyl-3- (3-oxo-3-propoxy-1- propenyl) cyclopropanecarboxylic acid.
Analogously to example 2, but starting from 1.5 g of cis, U, 2-dimetsI-3- (3-oxo-3-propoxy-1-propenyl) cyclopropycarboxylic acid and 1j1 g 4sJ 4-hydroxy-3-methyl-2 - (2-propenyl -2-cyclopenten-1-one, 3.1 g of the expected product are obtained, which is purified by chromatography on silica; eluting with hexane-isopropyl ether (7: 3). Dissolve to dryness and obtain g of the desired product.
oil- + 39.5 + 2.5 ° (to 0.5% in
ten
15
20
benzene).
NMR (HC1,) ppm: 1.3 and 1.31 N methyl; in position 2 cyclopropane; 3.1 - 3.42 N on carbon in position 3 of cyclopropane; 6.4 - 6.8 N carbon in position 1 of the radical ethenyl; 5.8 - 6 N carbon in position 2 radical ethenyl; 4 - 4.08 - 4.2 N of the propoxy radical in oiCO, j ,; 0.83 - 0.95 - 1.06 N of the propoxy radical in 5.6 - 5.7 N of carbon in position 4 of the radical 4S 3-methyl-2- (2-propens1) -1-oxo-cyclopent-2-ene -4-yl; 2 N of methyl in position 3 of radical 4z 3-methyl-2 - (2-propenyl) -2-oxo-cyclopent-2-ene- 4.7-5.2 N of carbon in position 3 of propenyl radical.
1R cis yl ester, Zl2,2-dimethyl-3-C3 - (1-methyl ethoxy) -3-oxo-1-propenyl cyclopropanecarboxylic acid.
Stage A. Chloride iR cis, 2- dimethyl-3-L3- (1-methylethoxy) -3-oxo--1-propenyl cyclopropanecarboxylic acid.
A mixture of 900 mg of IR cis, U, 2-dimethyl-3- 3- (1-methyl ethoxy) -2-oxo-1-propenyl cyclopropanecarboxylic acid, 9 cm of isoprene and 1 cm of mixture is stirred for 4 hours at room temperature. thionyl. Adjust to dryness and obtain 1.4 g of product, which is consumed in this form in the next step.
Stage B. is 2-Methyl-4-oxo-3- - (2-propenyl) cyclopenten-1-yl ester IR cis U, 2-dimethyl-3-3- - (1-methylethoxy) -3-oxo-1 -propenyl cyclopropanecarboxylic acid.
To a mixture containing 1.4 g of the product obtained in stage A, 10 cm of benzene and 750 mg of 4sJ 4-hydroxy-3-methyl-2- (2-propenyl) -cyclopent-2-en-1-one, added 1.5 cm pyridine. The reaction mixture was stirred under stirring for 3 hours and then poured into a mixture of ice water and 2N. hydrochloric acid (CW cm and 20 cm). The aqueous suspension is extracted with ethyl acetate. The organic layers are washed with water until neutral, dried, filtered and the filtrate is concentrated to dryness under reduced pressure. 2.3 g of product are obtained, which are chromatographed on silica, eluting with a mixture of cyclohexane and ethyl acetate (8: 2). 386 mg of the expected product are obtained.
25
thirty
35
40
45
50
55
MO + 26 jf 2 ° (to 0.5% in benzene).
NMR (CDCl 3) ppm: 1.28 and 1.32 N methyls in position 2 of cyclopropane; 1.88 - 2 N carbon in position 1 of cyclopropane; 3.11 - 3.4 N of carbon in position 3 of cyclopropane; 6.4 - 6.8 N carbon in position 1 of the radical ethenyl; 5.8 6 N carbon in position 2 radical ethenyl; 5 N carbon isopropyl 1.3 N carbon isopropyl 4.8 to 5.2 N carbon in position 3 of the propenyl radical; 5.7 N of carbon in position 4 of pa; Example 4. 1з32-Methyl-4-okidka 4s33-methyl-2- (2-propenyl) -1-co-3- (2-propenyl) -2-cyclopenten-1- -oxo-cyclopent-2-en-4-yl; 2 N coal
ten
15
20
42408
1R cis yl ester, Zl2,2-dimethyl-3-C3 - (1-methyl ethoxy) -3-oxo-1-propenyl cyclopropanecarboxylic acid.
Stage A. Chloride iR cis, 2-, -dimethyl-3-L3- (1-methylethoxy) -3-oxo--1-propenyl cyclopropanecarboxylic acid.
A mixture of 900 mg of IR cis, U, 2-dimethyl-3- 3- (1-methyl ethoxy) -2-oxo-1-propenyl cyclopropanecarboxylic acid, 9 cm of isoprene and 1 cm of mixture is stirred for 4 hours at room temperature. thionyl. Adjust to dryness and obtain 1.4 g of product, which is consumed in this form in the next step.
Stage B. is 2-Methyl-4-oxo-3- - (2-propenyl) cyclopenten-1-yl ester IR cis U, 2-dimethyl-3-3- - (1-methylethoxy) -3-oxo-1 -propenyl cyclopropanecarboxylic acid.
To a mixture containing 1.4 g of the product obtained in stage A, 10 cm of benzene and 750 mg of 4sJ 4-hydroxy-3-methyl-2- (2-propenyl) -cyclopent-2-en-1-one, added 1.5 cm pyridine. The reaction mixture was stirred for 3 hours and then poured into a mixture of ice water and 2N. hydrochloric acid (CW cm and 20 cm). The aqueous suspension is extracted with ethyl acetate. The organic layers are washed with water until neutral, dried, filtered and the filtrate is concentrated to dryness under reduced pressure. 2.3 g of product are obtained, which are chromatographed on silica, eluting with a mixture of cyclohexane and ethyl acetate (8: 2). 386 mg of the expected product are obtained.
25
thirty
35
40
45
50
55
MO + 26 jf 2 ° (to 0.5% in benzene).
NMR (CDCl 3) ppm: 1.28 and 1.32 N methyls in position 2 of cyclopropane; 1.88 - 2 N carbon in position 1 of cyclopropane; 3.11 - 3.4 N of carbon in position 3 of cyclopropane; 6.4 - 6.8 N carbon in position 1 of the radical ethenyl; 5.8 6 N carbon in position 2 radical ethenyl; 5 N carbon isopropyl 1.3 N carbon isopropyl 4.8 to 5.2 N carbon in position 3 of the propenyl radical; 5.7 N carbon in position 4 of the radical 4s33-methyl-2- (2-propenyl) -1-oxo-cyclopent-2-en-4-yl; 2 N carbon in position 3 of the radical thyl-2- (2-propenyl) -1 -oxo-cyclopent--2-en 4 yl,
Example 5. K8 Cyano- (noxy-2-pyridine) IR cis methyl ester, 2-dimethyl-3- (3-methoxy-3-oxo-I-propylene) cyclopropanocarboxylic acid.
4.96 g of IR cis, U, 2-dimethyl-3- (3-methoxy-3-oxo-1-propenyl) cyclo propancarboxylic acid is introduced into 75 cm of methylene chloride. Then add 2 cm of pyridine, then 5.2 g of dicyclohexylcarbodiimide. The mixture is stirred for several minutes and 5.9 g of H, 8-3 (x:, - hydroxy-6-fvnoxy-2-α-pyridine acetonitrile and then 0.1 g of 4-dimethylamino pyridine are introduced. The reaction mixture is held for 1 h. The filtrate is concentrated under reduced pressure. The residue is chromatographed on a column and the mixture is cycled with a mixture of cyclohexane and ethyl acetate (85:15), 7.7 g of the expected product are obtained.
Ir + 59 4- 2.5 (to 0.5% СНС1,).
NMR (CDC1,), ppm: 6.3 N on carbon bearing the SI group; , 22 - 1.27 and 1.3 N methyls in position 2 of cyclopropane 3.17 - 3.5 N carbon in position 3 of cyclopropane; 3.7 N group methoxy; 5.8 6.0 N ethylene to carboxyl; 6.3 - 6.6 N ethylene per B carboxyl; 6.9 - 7 N on carbons at positions 3 and 5 of pyridine; 7.7 - 7.8 - 7.9 N on carbon in position 4 of pyridine.
Example 6. (1,3,4,5,6,7-Hex sagidro-1 3-dioxo-2H-isoindol-2-yl) methyl ester iR cis, AzJ-2,2-dimethyl-3- ( 2-methoxy-3-oxo-1-propenyl) cyclopropanecarboxylic acid.
Analogously to example 1, (stage B) but starting from 1.5 g of chloride iR cis, uZ3-2,2-dimethyl 3- (3-methoxycarbonyl ethenyl) cylopropanecarboxylic acid
and Is4 g 1,3,4,5,6,7-hexagipro-2-hydroxymethyl 1H-from onndol-1,3- (2H) -dione, 3 g of product are obtained, which is chromatographed on silica, eluting a mixture of cyclohexane-ethyl acetate (8: 2), is brought to dryness and 1.86 g of the expected product is obtained.
NMR (CDC1,), h. / L: 1.27 and 1.3 N methyls in position 2 of cyclopropane;
-


-

ten
-, th
342408 6
 - 1.93 N on carbon in position 1 of cyclopropane; 3.06 - 3.53 N on carbon in position 3 of cyclopropane; 5, and 6.4-6.8 N of carbon in position 2 of the ethyl radical; 3.7 N of methyl; methoxy; 1.6 to 2 N carbons in positions 3, 4, 5, 6, and 7 of the indole; 5.5 N methylene in oi
COj combined with carbon in 1 cyclopropane.
Example 7. 5- (Phenylmethyl) -3-furansh methyl cis, 2-dimethyl-3- (3-methoxy-3-oxo15 1-propenyl) cyclopropanecarboxylic acid.
Analogously to Example 1, but starting from 3.22 g of iR cis chloride, 2- dimethyl-3- (3-methoxy-3-oxo-1-pro20-penyl) cyclopropanecarboxylic acid and 2.8 g of 5- L-3-fluorynyl-methanol) gives 6.3 g of product, which is chromatographed on silica, eluting with a mixture of cyclohexane-ethyl acetate (8: 2). 2.33 g of the expected product are obtained.
oi, +48 + 1.5 ° (to 0.7% GHC1,), NMR (CDClj), ppm: 1.26 -1.28N methyls in position 2 of cyclopropane; 1.86 - 2.02 N carbon in position I of cyclopropane; 3.0 to 3.3 N carbon in position 3 of cyclopropane; 6.4 - 6.8 N carbon- in position 1 of the ethenyl radical; 5.8 - 5.9 N of carbon in position 2 of the ethenyl radical; 3,7H methoxy group; 4.9 N groups of CH in uiCO, combined with carbon in position 1 of the group of cyclopropane; 7.3 N carbon in position 2 of the furanyl radical; 6 H carbon in position 4 of the furanyl radical; 7.2 N in the aromatic der.
Example 8. 1- (2-Propenyl) ds -2,4-dioxoimidazolidin-3-yl methyl ether QR, cis, U, 2-dimethyl-3- (3-propoxy-3-oxo-1-propenyl) cyclopropanecarboxylic acid.
1.2 g of iR, cis, 2 dimesh-1-3- (3-propoxy-3-oxo-1-pro
25
thirty
35
40
50
penyl) cyclopropanecarboxylic acid,
3 , t 3
cm
20 cm of methylene chloride, 100 4-dimethylaminopyridine. Then, 1 g of dicycloheg gg of silcarbodiimide is introduced into the resulting solution. With stirring, 900 mg of 3-hydroxymethyl-1- (2-straight opinyl) -2,4-imide az olyldione,
Stir for 16 hours at 20 ° C. and filter. The filtrate is washed
1N hydrochloric acid, and dusted with water until neutral, dried and brought to dryness under reduced pressure. An oil is obtained which is chromatographed on silica and eluted with a mixture of benzene and ethyl acetate (8: 2). 1.2 g of the expected product are obtained.
MD 2 j 1 ° (to 0.5% in benzene).
NMR (CDC1}) ppm: 1.25 and 1.28 N methyls in position 2; 1.84-1.97 N of carbon in position 1 of cycling acids and alcohols, the following compounds were obtained.
Example 10. oi. CZ Cyano 3- - (4-bromophenoxy) fensh 1 methyl ester of PR cis, 2-dimethyl-3- (3-methoxy-3-oxy-1-propylene) -cyclopropane-1-carboxylic acid. Yield 10%.
Analysis 0 (484,342)
Calculated,%: C 59.51; H 4.58; Br 16.50; N 2.89.
Found,%: C 59.7; H 4.6; Br 16.2; N 2.8.
NMR spectrum (CDCl,); peaks from 1.26
ten
propane; 3.0 to 3.4 N of carbon in the range of up to 1.34 h / mpn. appropriate water
3 cyclopropane; 6.4 to 6.7 N carbon in position 1 of the ethenyl radical; 5.6–5.8 N of carbon in position 2 of the ethenyl radical, 4–4.1–4.2 N of propoxy in position o, 0.83– 0.95– 1.07 N of propoxy in position 2.33. 2.37 - 2.41 N of carbon in position 3 of the propynyl radical; 4 H - carbon in position 3 of the radical 2,5-dioxyimidazole idinyl; 4.2 - 4.3 N methylene in triple bond.
Example 9. Metaphenoxy-benzyl ester IE cis, 2-dimethyl-3- (3-oxo-3-methoxy-1-propenyl) cyclopropane-1-carboxylic acid.
2 g of IR cis, and 2-dimethyl-3- - (3-oxo-3-methoxy-1-propenyl) cyclo- are introduced into 20 cm of methylene chloride. propane-1-carboxylic acid, 0.9 cm of pyridine, 2.5 g of dicyclohexylcarbodimimide, stirred for 10 minutes, 2.4 g of metaphenoxybenzyl alcohol added, moved over
20
maternity paired methyl; peaks from 1.97 to 2.06 and from 3.22 to 3.48 ppm, corresponding to the hydrogens in position 1 and 3 of cyclopropyl; peaks at 3.7 to 3.73 ppm, corresponding to hydrogens,; peaks at 5.85 - 5.98 and 5.9 - 6.03 ppm, corresponding to ethylene hydrogens (from the ester side); peak at
25 6.33 ppm, corresponding to —CH — CN hydrogen; peaks from 6.43 to 6.67 ppm, corresponding to new hydrogens (from the side of cyclopropyl); peaks from 6.85 to 7., .52 ppm, corresponding to bromophenyl hydrogen; peaks from 6.94 to 7.55 ppm, corresponding to the hydrogens of another aroma.
Example 11. 4-Oxo-4H-25-25-ran-3-yl ester of iR cis, 2- dimethyl-2- (3-methoxy-3-oxo-1-propyl) cyclopropane-1-carboxylic acid. M.p. 106 ° C. Yield 48.6%.
MD: + 153 jb 2.5 ° (to 0.8%,
40 mg of dimethylamino-40 benzene was added.
Md:
With phenyl) these -2,2-dime -1 t-pr open 45 acids.
pyridine, stirred for 2.5 hours, the formed insoluble material is removed by filtration, the filtrate is concentrated to dryness under reduced pressure, the residue is chromatographed on silica, eluting with a mixture of cyclohexane and ethyl acetate (9: 1), and 3 g of metaphenoxybenzyl ether are obtained IR cis, cs-2,2-dimethyl-3- (3-hydroxy-3-methoxy-1-propenyl) cycloprotic 1-carboxylic acid.
totlj,: +. + 1.2 (to 1%, chloroform).
Analysis (380, 444)
Calculated,%: C, 72.61; H 6.36.
Found,:; C, 72.7; H 6.4.
Similar to the method described in example 9, but based on the corresponding
acids and alcohols, the following compounds were obtained.
Example 10. oi. CZ Cyano 3- - (4-bromophenoxy) fensh 1 methyl ester of PR cis, 2-dimethyl-3- (3-methoxy-3-oxy-1-propylene) -cyclopropane-1-carboxylic acid. Yield 10%.
Analysis 0 (484,342)
Calculated,%: C 59.51; H 4.58; Br 16.50; N 2.89.
Found,%: C 59.7; H 4.6; Br 16.2; N 2.8.
NMR spectrum (CDCl,); peaks from 1.26
0
§ up to 1.34 h / mpn appropriate water
up to 1.34 h / mpn. appropriate water
benzene).
maternity paired methyl; peaks from 1.97 to 2.06 and from 3.22 to 3.48 ppm, corresponding to the hydrogens in position 1 and 3 of cyclopropyl; peaks at 3.7 to 3.73 ppm, corresponding to hydrogens,; peaks at 5.85 - 5.98 and 5.9 - 6.03 ppm, corresponding to ethylene hydrogens (from the ester side); peak at
6.33 ppm corresponding to —CH — CN hydrogen; peaks from 6.43 to 6.67 ppm, corresponding to new hydrogens (from the side of cyclopropyl); peaks from 6.85 to 7., .52 ppm, corresponding to bromophenyl hydrogens; peaks from 6.94 to 7.55 ppm, corresponding to the hydrogens of another aroma.
Example 11. 4-Oxo-4H -lpran-3-yl ester of iR cis, 2- dimethyl-2- (3-methoxy-3-oxo-1-prop; NIL) cyclopropane-1-carboxylic acid . M.p. 106 ° C. Yield 48.6%.
MD: + 153 jb 2.5 ° (to 0.8%,
benzene).
Example 12. IR (3-phenoxyphenyl) ethyl 1R cis, -2,2-dimethyl-3- (3-from ODA-opoxy-3-oxo--1 t-pripenyl) cyclopropan-1 -carbonic acid .
AND,
+ 140. + 2.5 (to 1%, benzene). Yield 64%.
Example 13. IR (3-phenoxyphenyl) ethyl ester 0 CIS, -2,2-dimethyl-3- (3-ethoxy-3-OKCO-1-j-propenyl) cyclopropane-1-carboxylic acid.
MD: + 145 nh 2.5 (to 1%, benzo & 31% 43%.
Example 14. 1 fR (3-Phenoxol-phenyl) ethyl ester IR cis, -2,2-dimethyl-3- (3-methoxy-3-oxo-1-propenyl) cyclopropane-1-carboxylic acid.
and: + 130.5 + 2.5 reforms Выход Yield 67%,
Example 15. RS oi-UHaHo (3- -benzoylphenyl) methyl ester iR cis, 4Zl-2,2 dimethyl-3- (3 methoxy-3-oxo -1-pripenyl) cyclopropane-1-carboxylic acid.
MI: + 43 jb 1 ° (to 1%, toluene). Yield 80%.
Example 16. (3-Benzoylphenyl) 1R cis methyl ester, 2- dime. (3 methoxy-3-bx-1-propanoyl) cyclopropane-1-carboxylic acid.
 + 52 JH 1.5 ° (to 1%, chloroform). Yield 79%.
Example 17. (2,3,4,5,6-Pentafluorophenyl) methyl 1R cis.
P42408 O
(to 1%, chloxy-3-oxo-1-propenyl) cyclopropane-1-carboxylic acid. M.p. 66 C.
MD + 7 jf 1 ° (to 1.2%, chloroform). Exit 87, 4%.
Example 23. 1R 3-Phenoxy-phenyl -2-propiv-1-yl ester of IR cis, 2-dimethyl-3- (3-n-propoxy-3-OK co 1-pro penyl) cyclopropan-1 - -carboxylic acid.
Mjj + 48 + 2 ° (to 1%, chloroform).
Example 24. (4-Benzor sphe-nsh1) iR cis methyl ester, {Zj-2,2-dimethyl-3- (3-methoxy-3-oxo-1-pro 15 penyl) cyclopropane-1-carboxylic acid.
ten
W,
+ 46 + 2 (, chloroform). Yield 81%.
Example 25. RS Cyano-2- (, 2-dimetsI-3- (3-methoxy-3-oco, 20 enoxypyridyl) methyl ester iR
-1-propenyl) cyclopropan-1-carboxylic
acids,
oilj,: + 29.5 1 2 ° (to 0.8%, chloroform). Bykhop 76,
Example 18. RS Cyano (2,3,4, 25 forms). Yield 74%
cis, i, 2-dimethyl-3- (3-oco-3-tert-butoxy-1-propenyl) cyclopropane-β-carboxylic acid,
And: + 68 + 1.5 ° (to 1%, chloro5, 6-pentafluorophenyl) methyl ester E cis, D z3-2,2-dimethyl-3-3 (3-methoxy-3-oxo-1-propenyl ) cyclopropane-l-carboxylic acid. The output of 79.8%,
Analysis: C, 8H, 4-F5NO (403.31).
Calculated,%: C 53.61; H 3.50; .I 3,47; F 23.55.
Found,%: C 53.9; H 3.5; N 3,4 | F -23,7,
Example 19. Ez Cyano-2- (6- -phenoxypyridyl) methyl ester lE grs, L Zj-2, 2-dimetsI-3 (3 o-co-3 n-proproxy-1-propenyl) cyclopropane-1-carboxylic acid.
 (417.466), EXAMPLE 26, RS l; HaHo (4-6eH-zoylphenyl) methyl iR cis, 2-dimethyl-3 (3-methoxy-3-oxo--1-propenyl) cyclopropane-1-carboxylic acid 30 .
Analysis: With a stroke of 37%,
Calculated,%: C 71.93; H 5.85; N 3.35,.
Found,%: C 71.9; H 5.8; N 3.2
Example 27, (3-Protin-2-yl--2,3-dioxoimidazolidinyl) methyl 1R cis, yZZ-2,2-dimethyl-3- (3-OXO-3-tertbutoxy-propenyl) -cyclopropane ™ -carboxylic acid,
35
MP - +55 + 2.5 ° roform), Yield 91%,
Example 20, NIL) this. Lis ester of E cis, 2 (to 0.5%, chlo-R (3-phenoxyphe Example 27, (3-Propyn-2-yl--2,3-dioxoimidazolidine) methyl ester 1R cis yZZ-2,2-dimethyl-3- (3-OXO-3-tert-butoxy- -propenyl) -cyclopropane ™ -carboxylic acid,
Wo: + 31 + .2 ° (to 0.5%, chloroform). Yield 40%
Example 28, (3-Propin-2-yl40
-dimethyl-3- (3-propoxy-3-oxo-1-pro 45 2,5-dioxoimidazolidinyl) methyl
1R cis, DZl-2,2-dimethyl-3- (3- - from opropoxy-3 oxo-1-propenyl) -cyclopropan-1-cyrboxylic acid ester, T, mp, 78 C, Yield 65.5%,
MD: + 15.5 + 1 ° (to 1%, chloroform),
Example 29, (3-Propin-2-Sh1--2,5-dioxoimidazolidinyl) methyl ester IR cis, 2-dimethyl-3- (3 penyl) cyclopropane-1-carboxylic acid,
ci: + 123 + 2 (to 0.9%, chloroform). Yield 68%.
Example 21, 1 R (3-phenoxyphenyl) 2-Pronin-1-yl ester iR cis, B Zj-2,2-dimethyl-3- (3-methoxy-3-oxo-1-propenyl-cyclopropane 1-carboxylic acid.
50
 : + 55.5 + 1.3 (to 1%, chloro-gg-cyclobutoxy-3-oxo-1-propenyl) -cycroform), 55%,
Example 22, (3-Phenoxyphenyl) -2-propyn-1-yl ester 1R cis, yZZ-2,2-dimethyl-3- (3-isoproplopropane-1-carboxylic acid,
3
1.53 g (IR cis, U Z), 2-dimethyl-3- (2-cyclobutoxycarbonylethynyl) cyclopropanecarl are introduced into 20 cm of acetone.
W,
+ 46 + 2 (, chloroform). Yield 81%.
Example 25. RS Cyano-2- (6 enoxopyridyl) methyl ester iR
Enoxipyridyl) methyl iR
cis, i, 2-dimethyl-3- (3-oco-3-tert-butoxy-1-propenyl) cyclopropane-β-carboxylic acid,
And: + 68 + 1.5 ° (to 1%, chloroform). Yield 74%
 (417.466), EXAMPLE 26, RS l; HaHo (4-6eH-zoylphenyl) methyl iR cis, 2-dimethyl-3 (3-methoxy-3-oxo--1-propenyl) cyclopropane-1-carboxylic acid.
Analysis: With a stroke of 37%,
Calculated,%: C 71.93; H 5.85; N 3.35,.
Found,%: C 71.9; H 5.8; N 3.2
Example 27, (3-Protin-2-yl--2,3-dioxoimidazolidinyl) methyl 1R cis, yZZ-2,2-dimethyl-3- (3-OXO-3-tertbutoxy-propenyl) -cyclopropane ™ -carboxylic acid,
Wo: + 31 + .2 ° (to 0.5%, chloroform). Yield 40%
Example 28, (3-Propin-2-yl
50
-cyclobutoxy-3-oxo-1-propenyl) -cyclopropane-1-carboxylic acid,
3
1.53 g (IR cis, UZ), 2-dimethyl-3- (2-cyclo-butoxycarbonylethynyl) cyclopropanecarboxylic acid, 1.08 g (3 propargyl -2,5-dioxoimide az olidine- 1-Sh1) methane (added dropwise at 0 C) and 0.015 g of dimethylaminopyridine in 1 O cm acetone, stirred for 16 hours at 20 ° C, filtered, concentrated to dryness by distillation under reduced pressure, the residue was chromatographed
penyl) cyclopropane-1-carboxylic acid.
WB: + 41 + 2 ° (to 0.5%, chloroform). Yield 95%.
Example 37. (1,3,4,5,6,7-β-Hexahydro-1,3-dioxo-2H-isoindole--2-yl) iR methyl ester, cis -2,2-dimethyl-3- (3 -oxo-3-isopropoxy
silicon dioxide, eluting with a mixture of cyc-IQ hypropenyl) cyclopropane-1-carboxylic
lehexane and ethyl acetate (6: 4), and 0.850 g of substance is obtained.
Wj: + 18 H1 1 ° (to 1.2%, chloroform). Yield 34%.
Example 30. Analogously to example 29, (3-propyn-2, yl-2,5-β-dioxoimidazolidinyl) methyl ester tlR cis, is obtained. U, 2-dimethyl-3- (3-isobutoxy-3-oxo-1-propenyl) cyclopropane-1-carboxylic acid.
M: + 20.5 + 1.5 ° (to 1%, chloroform). The output of 30.5%.
Example 31 (3-Propine-2-yl--2.5 dioxoimidazolidinyl) methyl ester IR cis, DZ) -2,2-dimets-3- (3-oxo-3-ethoxy-1 propenyl) cyclopropane 1- carboxylic acid. Yield 19%.
MD: + 10 jb 4 ° (to 0.2%, chloroform).
Example 32. 1 n (3-Phenoxy-. Phenyl) -2-propyn-1-yl ester iR cis, b, 2-dimethyl-3- (3-ethoxy-3-oxo-1-propenyl) cyclopropan-1 -carboxylic acid. Yield 76.7%.
MD: + 48.5 + 2 ° (chloroform).
Example 33. (5-Benzyl-3-fumethyl ester of 1R cis, and -2,2-dimethyl-3- (3-ox9-3-isopropoxy-1-propenyl) cyclopropane-1-carboxylic acid.
ood: + 44 j 2 ° (to 0.4%, chloroform).
Example 34. IR cis metaphenoxy benzyl ester, U, 2-dimethyl-3- (3-oxo-3-isopropoxypropenyl cyclopropane-1-carboxylic acid.
 : + 42 jf 2 ° (to 0.5%, chloroform). Yield 91%.
Example 35. RS UHaHO-2- (6-phenoxy-pyridyl) iR cis methyl ester, U, 2-dimethyl-3-Z-oxo-3- (cyclopropylmethoxy) propenyl 1-cyclopropane-1-carboxylic acid. Yield 80%.
{.one. : +53 1 2 ° (to 0.5%, chloroform).
Example 36. (5-Benzyl-3-furyl) 1H cis methyl ester, 2-dimethyl-3- (3-oxo-3-n-propoxy-seo 15
20
50
55
(to 0.5% chloro
acid. M.p. 94 ° C.
 W: -22.5 + 2 forms). Yield 71%.
Example 38 (1,3,4,5,6,7-β-Hexahydro-1,3-dioxo-2H-isoindol--2-yl) 1R methyl ester, cis iZ -2,2-dimethyl-3- ( 3-oxo-3-n-propoxy--1-propenyl) cyclopropane-1-carboxylic acid.
Id: -15 ° (to 0.15%, carbon tetrachloride). Yield 94%.
Example 39. IR cis, 2-dimethyl-3- (3-oxo-3-n-propoxy-pro-25 NIL) cyclopropane-1-carboxylic acid metaphenoxy benzyl ester IR
Id: + 40 jb 2 (to 0.5%, chloroform). Yield 96%.
Example 40. IR cis metaphenoxyben zyl ester, (3-OKc 30 -3-cyclopropylmethoxy-1-propenyl) cyclopropane-1-carboxylic acid.
Eve: + 46.5 1 2 ° (to 0.6%, chloroform). Yield 90%.
Example 41. (3-Phenoxy phenyl) 1R cis ethyl ester, -2,2-dimethyl-3- (3-cyclobutoxy-3-ca co-1-propenyl) cyclopropane-1-carbonic acid.
FP: + 125.5 +; 2 ° (to 1%, 40 reforms).
Example 42 (1,3,4,5,6,7-β-Hexahydro-1,3-dioxo-2H-isoindol--2-yl) IR cis methyl ester, -2,2-dimethyl-3- (3 -oxo-3-cyclopropyl methoxy-1-propenyl) cyclopropane-1-ka carboxylic acid. M.p. 102 ° C.
1 „: - 6.5 + 2 ° forms), Output 8 3%.
Example 43, (5-Benzyl-3 tfuyl) methyl E cis ester, & Z - -2,2-dimethyl-3- (3-oxo-3-cyclopropyl methoxy-1-propenyl) cyclocropane-1-ka carboxylic acid.
Mp: + 42 jf 2 ° (to 0.7%, chloroform). Yield 83%.
Example 44, in 2-Methyl-4-oxo-3- (2-propylene) 2-IJl; cyclopentenyl ester IR cis, th., 2-dimethyl -2-C-oxo-3 (cyclochloxy-methoxy) -one
35
45
(to 0.3% chlorine
penyl) cyclopropane-1-carboxylic acid.
WB: + 41 + 2 ° (to 0.5%, chloroform). Yield 95%.
Example 37. (1,3,4,5,6,7-β-Hexahydro-1,3-dioxo-2H-isoindole--2-yl) iR methyl ester, cis -2,2-dimethyl-3- (3 -oxo-3-isopropoxy
sypropenyl) cyclopropan-1-carboxylic
(to 0.5% chloro-
acid. M.p. 94 ° C.
 W: -22.5 + 2 forms). Yield 71%.
Example 38 (1,3,4,5,6,7-β-Hexahydro-1,3-dioxo-2H-isoindol--2-yl) 1R methyl ester, cis iZ - -2,2-dimethyl-3- (3-oxo-3n-propoxy-1-propenyl) cyclopropane-1-carboxylic acid.
Id: -15 ° (to 0.15%, carbon tetrachloride). Yield 94%.
Example 39. Metaphenoxybenzyl ester IR cis, 2-dimethyl-3- (3-oxo-3-n-propoxy-pro-NILE) cyclopropane-1-carboxylic acid,
Id: + 40 jb 2 (to 0.5%, chloroform). Yield 96%.
Example 40. IR cis metaphenoxy benzyl ester, (3-OKco-3-cyclopropylmethoxy-1-propenyl) cyclopropane-1-carboxylic acid.
Eve: + 46.5 1 2 ° (to 0.6%, chloroform). Yield 90%.
Example 41. (3-Phenoxyphenyl) ethyl 1R cis, -2,2-dimethyl-3- (3-cyclobutoxy-3-ox-1-propenyl) cyclopropane-1-carboxylic acid.
FP: + 125.5 +; 2 ° (to 1%, chlo-reform).
Example 42 (1,3,4,5,6,7-β-Hexahydro-1,3-dioxo-2H-isoindol--2-yl) IR cis methyl ester, -2,2-dimethyl-3- (3 -oxo-3-cyclopropyl-methoxy-1-propenyl) cyclopropane-1-carboxylic acid. M.p. 102 ° C.
1 „: - 6.5 + 2 ° forms), Output 8 3%.
Example 43, (5-Benzyl-3 tfuryl) E cis methyl ester, & Z is -2,2-dimethyl-3- (3-oxo-3-cyclopropylmethoxy-1-propenyl) cyclocropane-1-carboxylic acid.
Mp: + 42 jf 2 ° (to 0.7%, chloroform). Yield 83%.
Example 44, in 2-Methyl-4-oxo-3- (2-propylene) 2-IJl; iclopentenyl ester IR cis, th., 2-dimethyJH-2-3-oxo-3 (cycloproxy-methoxy )-one
(to 0.3%, chloropropenyl-cyclopropane-1-carboxylic acid.
 : + 64.5 + 2.5 (to 1%, reform) ,,
Example 45. Analogously to Example 29, an IR cis (3-propyn-2-yl-2.5-β-dioxoimidazolidinyl) methylester ester, l, 2-dimethyl-3- (3-cyclo6i83 ppm, corresponding to ethylene hydrogen ( side of cyclopropyl) and hydrogen CO2-CH2; - peaks at 6.9- from 7.55 h / million, corresponding to the hydrogen of the aromatic villages.
Example 51. RS l- (4-Ftop-3-phenoxyphenyl) -2-propyne-1-yl ester IR cis & , 2-dimethyl-3- 3- (1, 1-pentyl-hydroxy-3-oxo-1-propenyl) cyclo-y-dimethyl-ethoxy) -3-oxo-1-propenyl
propane-1-carboxylic acid.
 + 15.5 + 1.5 ° (to 1%, chloroform). Yield 34.5%.
Approximately 46. K8 Cyano-2- (b- -phenoxy-6-pyridinyl) methyl ester IR cis, 2-dimethyl-3- (3-oxo-3 -diclopentyloxy-1-propenyl) -cyclopropane 1-carboxylic acid.
Мз: + 1 ° (to 0.9%, benzene) .. Yield 66%.
cyclopropane-1-carboxylic acid. The yield is 86.3%.
NMR spectrum (CDCl1): peaks at 1.22 - 1.31 ppm, corresponding to
15 hydrogens paired methyl; peaks at 1.47 - 1.5 ppm, corresponding to tert-butyl hydrogens; peaks at 1.87 to 2.01 and 3.12 to 3.43 ppm, corresponding to the hydrogens in
20 1 and 3 cyclopropyl; peaks at 2.6 - 2.65 ppm, corresponding to hydrogen. CH; peaks at 5.7 to 5.9 h, ppm, corresponding to ethylene hydrogen (ester side); peaks at
Example 47. (3-Proshga-2-yl--2,5-dioxoimidazolidinyl) methyl ester E cis, 2-dimethyl-3- (3-methoxy-3-oxo-1-propylene) cyclopropan-1 -carboxylic acid.
 : + 1 (to 0.5%, benzene). Yield 56%.
Example 48. Analogously to example 29, (3-propyn-2-yl-2,5-dioxoimidazolidinyl) methyl ester of an IR of cis, U, 2-dimethyl-2 (3-in-β-butoxy-3-oxo-1- propenyl) -cyclopropan-1-carboxylic acid.
20 1 and 3 cyclopropyl; peaks at 2.6 - 2.65 ppm, corresponding to hydrogen. CH; peaks at 5.7 to 5.9 h, ppm, corresponding to ethylene hydrogen (ester side); peaks at
25 6.28 - 6.72 ppm corresponding to ethylene hydrogen (cyclo side
propyl) and hydrogen CO, -CH; peaks
Mj,: + .16,5 + I (to 0.8%, chloroform). Yield 34%.
Example 49. fs Cyano-3-phenoxy-4-fluorophenyl methyl iR cis, Uz3-2,2-dimethyl-3- (3-methoxy-3-oxo-1-propenyl) cyclopropan-1-car - bonoic acid.
Ip: + 56.5 + 2.5 ° (to 0.5%, benzene). Yield 62%.
Example 50. RS l- (4-Ftop-3-phenoxyphenyl) -2-propin-l-yl ester
35
at 6.91 - 7.55 ppm, the corresponding hydrogen in the aromatic nuclei.
Example 52. (6-Phenox-2-pyrndinyl) 2-propyn-1-yl J ester IR cis, U, 2-dimethyl-3T (3-metoxy-3-oco-1-propenyl) -cyclo- propane-1-carboxylic acid. Output 90%.
NMR spectrum (CDCl1): peaks at 1.23 - 1.31 ppm, corresponding to hydrogens of paired methyl; peaks at 1.96 - 2.1 and 3.13 - 3.47 ppm, corresponding to the hydrogens in position 1 and 3 of cyclopropyl; ; peaks at 2.59 to 2.63 ppm, corresponding to hydrogen ggSN; peak at 3.73 ppm, hydrogen-corresponding peak
ethylene hydrogen (side
 isc 1 1 mzul; w 11, iihch-i
I.1R cis, dZJ-2,2-dimethyl-2- (3-methoxy, 91– 7.55 ppm, corresponding to 3 oxo-propylene.) - cyclopropane-1-carcass hydrogens of aromatic dermatics, boic acid. Vcode 75.4%. At 5.67 - 6.02 h / mp, corresponding to the NMR spectrum (SBS1e): peaks at 1.22 - 1532 ppm, corresponding to the hydrogen of paired methyl; peaks at 1.09 - 2.05 and 3.1 - 3.43 h, ppm, corresponding to the hydrogens in position 1 and 3 of cyclopropyl; - peaks at 2.62 - 2.66 ppm corresponding to hydrogen
ester); - peaks at 6.3 - 6.34 ppm, corresponding to hydrogen CO2-CH; peaks at 6.43 - - 6.88 ppm, corresponding to ethyl hydrogen (cyclopropyl side); peaks at 6.75 - 7.9 ppm, hydrogen - peaks at 3.72 - 3.73 ppm gg house of aromatic nuclei, corresponding to hydrogens,; Example 53. 1- (6-phenoxy-peaks at 5.8 - 6 hours / mpn, corresponding to - 2-gshridinyl) 2-propyn-1-ylbm ether
ethylene hydrogen (iR cis side, d, 2-dimethyl-3 3- (1, 1 ester); - peaks at 6.38 - dimethylethoxy) -3-oxo-1-propenyl-6i83 ppm, corresponding ethylene hydrogen (cyclopropyl side) and hydrogen CO2-CH2; - peaks at 6.9- 7.55 h, ppm, corresponding to hydrogen ions of the aromatic villages.
Example 51. RS l- (4-Ftop-3-phenoxyphenyl) -2-propyne-1-yl IR cis ester, & , 2-dimethyl-3- 3- (1, 1-dimethyl-ethoxy) -3-oxo-1-propenyl
cyclopropane-1-carboxylic acid. The yield is 86.3%.
NMR spectrum (CDCl1): peaks at 1.22 - 1.31 ppm, corresponding to
paired methyl; peaks at 1.47 - 1.5 ppm, corresponding to tert-butyl hydrogens; peaks at 1.87 - 2.01 and 3.12 - 3.43 ppm, corresponding to the hydrogen in position
1 and 3 cyclopropyl; peaks at 2.6 - 2.65 ppm, corresponding to hydrogen. CH; peaks at 5.7 to 5.9 h, ppm, corresponding to ethylene hydrogen (ester side); peaks at
6.28 - 6.72 ppm corresponding to ethylene hydrogen (cyclo side
propyl) and hydrogen CO, -CH; peaks
ZO
35
at 6.91 - 7.55 ppm, the corresponding hydrogen in the aromatic nuclei.
Example 52. (6-Phenox-2-pyrndinyl) 2-propyn-1-yl J ester IR cis, U, 2-dimethyl-3T (3-metoxy-3-oco-1-propenyl) -cyclo- propane-1-carboxylic acid. Output 90%.
NMR spectrum (CDCl1): peaks at 1.23 - 1.31 ppm, corresponding to hydrogens of paired methyl; peaks at 1.96 - 2.1 and 3.13 - 3.47 ppm, corresponding to the hydrogens in position 1 and 3 of cyclopropyl; ; peaks at 2.59 to 2.63 ppm, corresponding to hydrogen ggSN; peak at 3.73 ppm, hydrogen-corresponding peak
 isc 1 1 mzul; w 11, iihch-i
 p, 91– 7.55 ppm, corresponding to the aromatic nucleus hydrogen, with 5.67–6.02 ppm; corresponding to ethylene hydrogen (side
15
cyclopropane-1 carboxylic acid. Yield 95%.
NMR spectrum (CDCI ,,): peaks at 1.24 - 1.32 ppm, corresponding to hydrogens of paired methyl; peak at 1.5 ppm, corresponding to tert-butyl hydrogens; peaks at 1.93 - 2.07 and 3.13 - 3.46 ppm, corresponding to the hydrogens in position 1 and 3 of cyclopropyl; peaks at 2.59 - 2.63 ppm, corresponding to hydrogen ggSN; peaks at 5.68 to 5.90 ppm correspond to ethylene hydrogen (ester side); peaks at 6.3–6.34 ppm, corresponding to hydrogen COj, peaks at 6.47– 6.86 ppm, corresponding to ethylene hydrogen (diclopropyl side); peaks at 6.75 - 7.9 h / mp, corresponding to the hydrogens of the aromatic region.
Example 54. Phenylmethyl ester 1R 1CHS, 2-dimethyl-3- 3- (1,1-dimethylethoxy) 3-oxo-1-propenyl cyclopropane-1-carboxylic acid.
1.7 g of (1Ecis, l of g) -2,2-dimethyl-3- 3- (1, 1-dimethylethoxy) -3-oxo-propynyl are introduced into 20 cm of n-pentane.
cyclopropanecarboxylic acid heating with ethylene hydrogen
(side of the ester); peaks 6.37–6.73 ppm, corresponding to ethylene hydrogen (cyclopropyl side); the peaks at 7.58–7.7 ppm, corresponding to the waters of the pyridyl core.
The reaction mixture is heated under reflux, 1. 1 ml of thionium chloride solution in 5 cm of n-pentane is slowly introduced, heated under reflux for 4 hours, cooled and concentrated to dryness by distillation under reduced pressure. The dry extract is acid chloride.
Esterification.
The previously obtained acid chloride is dissolved in 20 cm of benzene, cooled under OC, 1.4 g of pyridine is added, stirred for 10 minutes at 0 ° C, and a solution of 1.1 g of benzyl alcohol c is gradually introduced. 10 cm of benzene, stirred for 18 hours at 20 ° C, inject the reaction mixture into an aqueous solution of hydrochloric acid and ice, extract with benzene, filter, concentrate to dryness under reduced pressure, chromatograph the precipitate on silica, and elute with a mixture of hexane and simple isopropyl ether (8: 2), and receive 1.31 g of the target product.
NMR spectrum: - peaks at 1.28 - 1.32 ppm, corresponding to paired methyl hydrogen; peak at
4240816
1.5 ppm corresponding to t-butyl; peaks at 1.9 - 2.04 and 3.08 - 3.42 ppm, corresponding to the hydrogens in position 1 and 3 of cyclopropyl; peak at .5.15 ppm, corresponding to hydrogens, -; - peaks at 5.72–5.92 ppm, corresponding to ethylene hydrogens (side of the 1Q th ether); peaks at 6.38-6.75 ppm, corresponding to ethylene hydrogens (cyclopropyl side); peak at 7.4 ppm, corresponding to aromatic hydrogen hydrogens.
Example 55. (6-Phenoxy-2-pyridinyl) methyl 1R cis ester, -2,2-dimethyl-3-3- (1,1-dimethylethoxy) 3-oxo-1-propenyl cyclopropane-1-carboxyl ester bonic acid. Yield 66%.
NMR spectrum (CDCl1): peaks at 1.3-1.32 ppm, corresponding to hydrogen paired methyls; a peak at 1.51 ppm corresponding to tert-butyl hydrogen; peaks at 1.96 - 2.11 and 3.13-3.47 ppm, corresponding to the hydrogens in position 1 and 3 of cyclopropyl; peak at 5, 13 ppm, corresponding to hydrogens, -; peaks at 5.73-5.92 ppm, respectively 15
20
25
0 Vetant ethylene hydrogen
five
0
five
0
five
(side of the ester); peaks at 6.37–6.73 ppm, corresponding to ethylene hydrogen (cyclopropyl side); peaks at 7.58 - 7.72 - - 7.85 ppm, corresponding to pyridyl hydrogen.
Example 56. (6-Phenoxy-2- -pyrphenyl) methyl ester iR cis, i Z -2,2-dimethyl-3- (3-methoxy-3-oxo -1-propenyl) cyclopropane-1-carboxylic acid. Yield 56%.
NMR spectrum (CDCl1): peak at 1.3 ppm, corresponding to paired methyl; peaks at 1.98-2.13 and 3.13-3.45 ppm, corresponding to the hydrogens in position 1 and 3 of cyclopropyl; peak at 3.74 ppm, corresponding to hydrogens,; a peak at 5.12 ppm, a hydrogen-corresponding peak at 5.82–6.02 and 6.5–6.87 ppm, corresponding to ethylene hydrogen; peaks at 7-7.85 ppm, corresponding to the aromatic hydrogens.
Example 57. (6-Phenox-2-pyridinyl) ethyl 1R cis, UZ -2,2-dimethyl-3-3- (1,1-dimethyl-ethoxy) -3-oxo-1-propenyl cyclopropane-1 -carboxylic acid. Yield 85%
17
NMR spectrum (CDCl,): peaks at 1.25-1.32 ppm, corresponding to hydrogens of paired methyl; peaks at 1.47-1.57 ppm, corresponding to
prenatal CDj-CH-; CH.
peak at 1.5 h, ppm
hydrogen-corresponding tert-butyl; peaks at 1.95-2.09 and 3.12 - 3.43 h, ppm, corresponding to the hydrogen in position 1 and 3 of cyclopropyl; peaks at 5.63-5.97 ppm / ml corresponding to hydrogen COj-CH; - peaks at 5.67-5.92 and 6.32-6.75 ppm, corresponding to ethylene hydrogen; peaks at 6.67-7.5 ppm, corresponding to aromatic hydrogens; peaks at 7.55–6.83 ppm, corresponding to pyridyl hydrogens.
Example 58. RS 1- (6-Phenoxy-2-pyridinyl) ethyl ester 1Ecis, 2-dimethyl-3- (3-methoxy-3-oxo10
15
20
Example 62. (3-Propin-2-yl--2,5-dioxoimidazolidinyl) methyl methyl ester IR cis, 2-dimethyl-3- (3-cyclopropylmethoxy-3-oxo-1-propenyl) cyclopropanecarboxylic acid. d) 1 coming 47.2%.
H5: 14 + 2 ° (to 0.5%, chloroform).
Example 63. l K1 (3-phenoxyphenyl) -2-propyne-1-yl ester IR cis & Z -2,2-dimethyl-3- (3-cyclopropyl-methoxy-3-oxo-1-propenyl) cyclopropanecarboxylic acid. Yield 81.8%.
Of: + 46 +; 2 ° (to 0.5%, chloroform).
Example 64 Analogously to Example 29, (3-propyn-2-yl-2,5-β-dioxoimidaz olidinyl) methyl ester is obtained
-1-Propenyl) cyclopropan-1-carboxylic 25 C CIS, Lz3-2,2-dimethyl-3 (3-H-by-acids. Yield 81.3%.
NMR spectrum (CDCl1): peaks at 1.25-1.3 ppm, corresponding to hydrogen paired methyl; peaks at
toxy-3-oxo-I-propenyl) -cyclopropane-carboxylic acid. Yield 34.5%.
And „: + 17 + 1Mk 1%, chloro1, 43-1.57 h, ppm, corresponding to water-JQ forms).
And „: + 17 + 1Mk 1%, chloropics at 1.97 2, 1 1
Example 65. C Cyano- (3-phenoxy-4-fluorophenyl) methane ester iR cis, uZ -2, 2-dimethyl-3- (3-ethoxy-3-oxo-1-propylene) cyclopropancarbone-
to CO-CH-;
CH,
and 3.1-3.42 ppm, corresponding to the hydrogens in position 1 and 3 cyclic flash; peaks at 5.63 - 6.08 h, ppm, corresponding to hydrogen CO2-CH; peaks at 6.67–6.8 and 7–7.67 ppm, corresponding to the hydrogen of aromatic nuclei; peaks at 7.55-7.83 ppm, corresponding to pyridyl hydrogens.
Example 59 about 3- (Phenylcarbonyl) phenyl methyl ester IE cis, uZ -2,2-dimethyl-3H- (1,1-dimethylethoxy) -3-oxo- -propenyl cyclopropane- - 45 D ° P 0.2 water solution of 2 n. Chloe.
about, IIIV 3 cm of dichloroethane, 1.5 g of bg-cyano-3-phenoxy-4-fluorobenzyl alcohol are introduced, 0.8 cm of pyridine is added at + 5 ° C, 40 solution of 1.55 is introduced over 10 min g of chloride (1R cis, uZ - -2,2-dimethyl-3- (3-oxo-3-ethoxypro-pargyl) cyclopropanecarboxylic acid in 3 cm of dichloroethane, stirred for 18 hours at 20 ° C, acidified
-carboxylic acid. The yield is 78%. Analysis: (434.537) Calculated,%: C 74.63; H 6.96. Found,%: C 74.60; And 7.00 "
Example 60. R (3-Phenoxy-phenyl) 2-propyne-1-sh10vm ether Cis, U z3-2,2-dimethyl-3- (3-tert-butoxy-3-oxo-1-propeyl) cyclopropane -1-carboxylic acid. The output of 80.8%.
 + 58 + 1.5 ° (to 1.2%, chloroform).
Example 61. IR (3-phenoxyphenyl) ethyl ester 1R cis, u., 2
hydrofluoric acid, extracted with dichloroethane, washed with water, the organic phases are concentrated by dryness by distillation under reduced pressure, and chromatographed. precipitate on silica, eluting with a mixture of i-hexane and ethyl ether (8: 2), and obtain 2.0 g of product. & 1% 74%.
55 WB: +, 5 + 2 ° (to 0.5%, chloroform),
Example 66. CiNo (3-phenoc si-4-fluorophenyl) cis methyl ester, U, 2-dimethyl-3- (3-iso proposes
34240818.
-dimethyl-3- (3-cyclopropylmethoxy-3-oxo-1-propenyl) cyclopropanecarboxylic acid. The yield is 76.5%.
MP + 121 + 3 (to 0.6%, chloroform).
Example 62. (3-Propin-2-yl--2,5-dioxoimidazolidinyl) methyl methyl ester IR cis, 2-dimethyl-3- (3-cyclopropylmethoxy-3-oxo-1-propenyl) cyclopropanecarboxylic acid. d) 1 coming 47.2%.
H5: 14 + 2 ° (to 0.5%, chloroform).
Example 63. l K1 (3-phenoxyphenyl) -2-propyne-1-yl ester IR cis & Z -2,2-dimethyl-3- (3-cyclopropyl-methoxy-3-oxo-1-propenyl) cyclopropanecarboxylic acid. Yield 81.8%.
Of: + 46 +; 2 ° (to 0.5%, chloroform).
Example 64 Analogously to Example 29, (3-propyn-2-yl-2,5-β-dioxoimidaz olidinyl) methyl ester is obtained
 With CIS, LZ3-2,2-dimethyl-3 (3-H-byform).
toxy-3-oxo-I-propenyl) -cyclopropane-carboxylic acid. Yield 34.5%.
And „: + 17 + 1Mk 1%, chloroform).
Example 65. From the cyano- (3-phenoxy-4-fluorophenyl) methane ester iR cis, uZ -2, 2-dimethyl-3- (3-ethoxy-3-oxo-1-propylene) cyclopropanocarboxy-
45 D ° P 0.2 water solution of 2 n. Chloe., - acid.
about, IIIV 3 cm of dichloroethane, 1.5 g of bg-cyano-3-phenoxy-4-fluorobenzyl alcohol are introduced, 0.8 cm of pyridine is added at + 5 ° C, 40 solution of 1.55 is introduced over 10 min g of chloride (1R cis, uZ - -2,2-dimethyl-3- (3-oxo-3-ethoxypro-pargyl) cyclopropanecarboxylic acid in 3 cm of dichloroethane, stirred for 18 hours at 20 ° C, acidified
D ° P 0.2 with an aqueous solution of 2N hydrochloric acid, extracted with dichloroethane, washed with water, the organic phases are concentrated by dryness by distillation under reduced pressure, the residue is chromatographed on silica, eluted with a mixture of i-hexane and ethyl ether (8: 2), and obtain 2.0 g of product. & 1% 74%.
WB: +, 5 + 2 ° (to 0.5%, chloroform),
Example 66. CiOH (3-phenoxy-4-fluorophenyl) methyl ester cis, U, 2-dimethyl-3- (3-isopropoxy 1913
si-3-oxo-1-propenyl) cyclopropanecarboxylic acid. Yield 49%. °
Id: + 50 + 2 ° (to 0.3%, chloroform).
Example 67. S Cyano (3-phenoxy-4-fluorophenyl) methyl ester of IK cis, L, 2-dimethyl-3- (3-cyclopr-propylmethoxy-3-oxo-1-propenyl) -cyclopropanecarboxylic acid. Yield 67%.
Wi5: + 53 ° (to 0.25%, chloroform.
Example 68 (2,3,4,5,6-pentafluorophenyl) methyl 1R cis, 2-dimethyl-3- (3-tert-butoxy-3-oxo-1-propenyl) cyclopropanecarboxylic acid . Yield 93%,
Er: +37.5 4-1.5 ° (to 1%, chloroform).
Example 69. (3-Phenoxy-4-β-fluorophenyl) methyl ester iP, cis, UZ -2,2-dimethyl- (3-tert-butoxy-3-oxo-1-propenyl) cyclopropanecarboxylic acid. Yield 92%,
Ip: + 55.5 + 2.5 (to 0.5%, chloroform).
Example 70. (3-Phenoxy-4-α-fluorophenyl) iR cis methyl ester, UZ -2,2-dimethyl-3- (3-methoxy-2-oxo--1-propenyl) cyclopropanecarboxylic acid. Yield 86%.
Er: + 50.5 + 2.5 ° (to 0.75%, chloroform).
Example 71. 1E81 (3-Phenoxy-4-fluorophenyl) 1R cis ethyl ester, Uzi-2,2-dimethyl-3- (3-tret-by-to-3-o-1-propenyl) cyclopropane-carboxylic acid. Yield 89%.
NMR spectrum (CDC1,): - peaks at 1.19-1.28 ppm, corresponding to paired methyl; peaks at 1.48-1.5 ppm, corresponding to tert-butyl hydrogen; peaks at 1.41- 1.53 ppm, corresponding to hydrogen. I will give SO.-CH; peaks at 1.85-1.99 and
CH,
3.07-3.38 ppm, corresponding to hydrogens at position 1 and 3 cyclopropyl, peaks at 5.58-6 and 6.27 - 6.7 h, ppm, corresponding to ethylene hydrogens; - peaks at 6.27 - 6.7 ppm, corresponding to hydrogen COj-CH; - peaks at 6.92-7.53 ppm, corresponding to the aromatic hydrogens.
Example 72. jjRsJ (3-phenoxy-4-fluorophenyl) ethyl iR cis, U, 2-dimethyl-3- (3-methoxy-3-ox-1-propenyl) cyclopropanecarboxylic acid.
2408
20
NMR spectrum (CDCl,): peaks at 1.19-1.29.4 ppm, corresponding to hydrogens of paired methyl; peaks at 1.41-1.54 ppm, corresponding to CO-CH- hydrogens; - peaks at 1.87 CH,
2.02 and 3.07-3.22 ppm, corresponding to the hydrogens in position 1 and 3 cyclopropyl; peaks at 5.82 6, -17 h / mp, corresponding to hydrogen COj-CH; at 5.93 to 6.2 and 6.58 - 7 ppm, corresponding to ethylenic hydrogen bees; peaks at 7.03-7.72 ppm, corresponding to the aromatic hydrogens.
Example 73. 5-Benzyl-3-fluorylmethyl ester iR cis, t ,, 2- dimethyl-3- (3-tert-butoxy-3-oxo-1-propenyl) cyclopropanecarboxylic acid. lots. Yield 86%.
Id +54,5 4 1,5 (to 1%, chloroform).
Example 74. ls 2-MeTiui-4-OK-co-3- (2-propenyl) cyclopenten-1-yl ester IR cis, 2-dimethyl-3- (3-tert-butoxy-3-oxo-1 -propenyl) cyclopropanecarboxylic acid. Exit 98%.
1 Yves: + 73 ° (to 0.25%, chloroform).
Example 75. (2-Phenoxy-5-β-thiazolyl) methyl iR cis ester, iiZ -2,2-dimethyl-3- (3-methoxy-3-ox6 -1 -1 propenyl) cyclopropanecarboxylic acid. T.PL.- 62 C.
Id: +60.5 + 1.5 ° (to 1.5%, benzene).
Example 76. RS Tiamido- (i) i-e-Noxiphenylmethyl ester iR cis, 2-dimethyl-3- (3-methoxy-3-oxo--1-propenyl) cyclopropanecarboxylic acid. 75% yield.
IR spectrum, cm: 1632 (C C); 3475 - 3365 (С S); 1713 - 1736
t with o)
NMR spectrum, (CDC1,): - peaks at 1.25-1.27-1.30 ppm, corresponding to paired methyl; - peaks at 1.97-2.11 ppm, corresponding to the hydrogen in position 1 of cyclopropyl; peaks at 3.08-3.43 ppm, corresponding to hydrogen in position 3 of cyclopropnl; peaks at 3.69-3.72 ppm hydromethyl-corresponding methyl; peaks at 5.73–5.92 and 5.8–5.99 ppm, corresponding to e Lshenovom hydrogen in oi-CO -CHjV
21
peaks at 6.32–6.66 ppm corresponding to ethylene hydrogen in position 1 .; peak at 6.42 h / min, corresponding to hydrogen combined with carbon, bearing the group-C-CN.
ten
15
20
25
S
Example 77. (2-Phenoxy-5-β-thiazolyl) iR cis methyl ester, 2-dimethyl-3 (3-tert-butoxy-3-- oxo-1-propenyl) cycloprphencarboxylic acid,
And,: + 68 + 1.5 ° (to 1% -, chloroform).
Example 78. Cyano (2-phenoxy-5-tyazolyl) IR cis, U, 2-dimethyl-3- (3-methoxy-3-OXO -1-propenyl) cyclopropanecarboxylic acid methyl ester. Yield 54.3%.
d: + 60 + 2 ° (to 1%, chloroform) ..
Example 79. CZ Cyano (2-phenoxy-5-thiazolyl) methyl 1R cis, d z3-2,2-dimethyl-3- (3-tert-butoxy-3-oxo-1-propenyl) cyclopropane - carboxylic acid. The yield is 66.5%.
And,: + 65 + 2 ° (to 0.5%, chloroform).
Example 80. X K 3-Phenoxy-phenylethyl ester iH trans, -2,2-dimethyl-3- (3-isopropoxy-3-oxo--1-propenyl) cyclopropanecarboxylic acid.
 + 59 4; 1.5 ° (to 1%, chlorine-35 ores).
Below are examples of the preparation of intermediates, which are also new compounds.
Example 81. iR cis, D Z - 2 5 2-Dimethyl-3- (3-methoxy-3-ca co-1 -propenyl) -cyclopropanecarboxylic acid, ota.
Stage A. tlR cisZ-2,2-dimethyl-3- (3-methoxy-3- -OKCO-l-propenyl) cyclopropanecarboxylic acid tlR ester.
55 g of iR tert-butyl ester, 2-dimethyl-3- (2,2-dibromvinsh1) cyclopropanecarboxylic acid are introduced
thirty
40
45
50
in 550
cm
about
tetrahydrofuran. Cool
to -70 ° C for 132 minutes, add 132 cm of a 20% butyl lithium solution in cyclohexane and mix for 30 minutes at -65 ° C. Then 12.5 cm of chloroholic acid methyl ester is added. After 2 hours of reaction at -70 ° C, the temperature is allowed to rise to -20 ° C, the resulting
ten
15
20
25

-
35
-,

34240822,
the mixture into an aqueous solution of primary sodium phosphate and extracted with ether. Wash, dry and bring to dryness under reduced pressure. 38.3 g of product are obtained, which are chromatographed on silica, eluting with a mixture of cyclohexane and ethyl acetate (8: 2). 17.2 g of the expected product are obtained.
Stage B. IR cis t-butyl ester, 2-dimethyl-3- (3-methoxy-ci-3-oxo-propenyl) cyclopropanecarboxylic acid.
Produces hydrogenation of 12 g A of product in
g of the target product, CIS, 2-Dime30
40
45
50
t
- 55
obtained in stage 240 cm of ethyl acetate, in the presence of 2.4 g of 10% palladium hydroxide on barium sulfate and 2.4 cm of quinoline. Filtered and dried. Get 11
Stage B, 1R
Tyl-3- (3-methoxy-3-oxo-1-propenyl) cyclopropanecarboxylic acid.
The solution containing 13.5 g of the product obtained in stage B, 100 cm of toluene and 400 g of hydrated p-toluenesulfonic acid is heated under reflux for 3 hours. Adjust to dryness under reduced pressure to obtain 11.2 g of product, which is chromatographed on silica, eluting with a mixture of cyclohexane - ethyl, acetic acid ester - acetic acid (60: 39; 1). Reduce to dry under reduced pressure and obtain 9.6 g of the expected product, T.Sh1. Software C.
WD ° + 75,5 4 2 (to 1%, CHClj).
NMR (CDCl,), ppm: 1.3 (protons of the methyls in position 2 of cyclopropane); 1.86-2 (protons in position 1 of cyclopropane); 3.1 - 3.28 - 3.43 (proton in position 3 of cyclopropane); 5.8 - 5.99 (ethylene proton in the ot grouping position); 6.42 - 6.57 (ethylene proton in the position of the ft grouping,); 6.61 - 6.77 (proton grouping); 8, bz - 3.71 (protons methoxy).
 Example 82. IR cis, -252-Dimethyl-3- (3-ethoxy-3-oxo-. -1-propenyl) -cyclopropanecarboxylic acid.
Stage A. iR cis, L., 2-dimethyl-3- (3-hydroxy-3-oxo-1-propynyl) cyclopropanecarboxylic acid tert-butyl ester.
23
26 g of 1R cis 2., 2-dimethyl-3- (2,2-dibr & mvinyl) cyclopropanecarboxylic acid tert-butyl ester are introduced into 175 cm of anhydrous tetrahydrofuran. Then at -65 ° C, 60 cm of a 20% butyllithium solution in cyclohexane is added. The mixture is stirred at -60 ° C for 1 hour, and then carbon dioxide is passed in for 1.5 hours, the reaction mixture is poured into ice-cold water containing an L 1 HI sodium hydroxide solution. Washed with ether. The alkaline aqueous layer is acidified to pH 4 and extracted with ether. The organic layers are dried, brought to dryness under reduced pressure. A product is obtained which is recrystallized in lithrolene ether (mp. 60-80 s). After recrystallization, 8.3 g of the expected product are obtained, melting at 144 ° C.
NMR (CDCl 3) ppm: 1.22 and 1.37 (protons of the methyls in position 2 of cyclopropane); 1.78 (proton in position 1 and 3 cyclopropane); 1.47 (protons of t-butyl); 8.25 (proton grouping
-SLEEP.). II
Stage B. IR cis 2,2-dimethyl-3- (3-ethoxy-3-oxo-1-propynyl) cyclopropanecarboxylic acid t-butyl ester.
4 g of the product obtained in stage A, 3.4 g of dicyclohexylcarbodiimide and 6 mg of 4-dimethylaminopyridine are introduced into 30 cm of methylene chloride. Then add 1.5 cm of ethanol and
stir for 16 hours at 20 ° C. Filtrate and concentrate the filtrate under reduced pressure. 5.5 g of product are obtained, which is purified by chromatography on silica, eluting with a mixture of cyclohexane and ethyl acetate (9: 1). 4.25 g of the expected product are obtained.
NMR (CBC1), ppm: 1.18 - 1., 21 and 1.36 - (protons in position 2 of cyclopropane); 1.73 and 1.82 (protons in position 1 and 3 of cyclopropane); 1.47 (protons of tert-butyl); 1.27 - 1.38 - 1.5 and 4.0 - 4.13 - 4.25 - 4.36 (ethyl protons) o
Stage B. iR cis, L, 2-dimethyl-3- (3-ethoxy-3-oxo-1-propenyl) cyclopropanecarboxylic acid tert-butyl ester.
4.3 g of the product obtained in the previous stage are hydrogenated in 100 cm of ethyl acetate
4240824
the presence of 800 mg of palladium hydroxide and 0.8 cm quinoline. Filter, adjust the filtrate to pH below 7 with 2N hydrochloric acid and wash with water. Dry and bring to dryness under reduced pressure. 4.6 g of product are obtained, which are chromatographed on silica, eluirs with a mixture of cyclo-1Q hexane-ethyl acetate (95: 5). 2.5 g of the expected product are obtained.
0
NMR (CDCl1), ppm: 1.25 and 1.28 (protons of methyls in position 2 of cycl-5 propane); 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 with cyc-Q of lopropane); 5.7 - 5.9 (of ethylene carbon, carrying an ethoxy carbonyl moiety); 4.0 - 4.13 - 4.25 - 4.36 (methylene ethoxy proton). Step G. 1R cis, and, 2-Dime-5 Tyl-3- (3-Ethoxy-3-oxo-1-propenyl) cyclopropanecarboxylic acid.
2.3 g of the product prepared in stage B and 20 mg of hydrated para-toluenesulfonic acid are introduced into 20 cm of toluene. The mixture is heated under reflux for 40 minutes, brought to dryness under reduced pressure, and 2.1 g of residue is obtained which is chromatographed on silica, eluting with a mixture of cyclohexane-ethyl acetate and acetic acid (60: 39: 1). 1.7 g of product is recovered which is recrystallized in cyclohexane. Obtain 1.5 g of the target. product melted at 96 ° C.
NMR (CDCl1), h / min: 1.3 and 1.32 (protons of methyls in position 2 of cyclopropane); 1.86 - 2.02 (proton carbon in position 1 of cyclopropane); 3.15–3.28 and 3.3–3.45 (proton carbon in position 2 of cyclopropane); 6.38 p 6.534 and 6.55 - 6.75 (proton of ethylene carbon on cyclopropane); 5.78-5.96 (an ethylene carbon proton carrying an ethoxycarbon group); 1.18 - 1.3 - 1.41 (protons of the methyl group of ethoxycarbonyl); 4,0 - 4,13 and 4,25 - 4,36 (protons of methylene of the ethoxycarbonyl group).
Example 83. 1R cis, -2,2-dimethyl-3- (3-propoxy-3-oxo-1-propenyl) cyclopropanecarboxylic acid. .
five
0
five
0
five
25
Stage A. 1R, 2-dimethyl-3-propoxy-3-oxo-1-propinyl) cyclopropanecarboxylic acid tert-butyl ester,
22.8 g of IR tert-butyl ether, 2-dimethyl-3- (2,2-dibromovinyl) diclopropanecarboxylic acid, 250 cm tetrahydrofuran, and then at -60 ° C-55 cm 20% solution are introduced butyl lithium in cyclohexane. Maintained at -65 C for 1
h and at
-65 ° C is introduced over a period of 15 minutes to 8 cm of propyl chloride of chloroic acid. The mixture is kept under stirring for 1 hour at -65 ° C, allowed to rise to room temperature over 1 hour, and stirred again at room temperature. The mixture is poured onto a saturated aqueous solution of primary sodium phosphate, stirred, extracted with ether and washed with water. The mixture is dried and brought to dryness under reduced pressure. 19.5 oils are obtained, which are purified by chromatography on silica, eluting with a mixture of cyclohexane and ethyl acetate (9: 1). 1155 g Tseo 1 o product are obtained.
NMR spectrum (CDCl,), ppm: 1.17 and 1.37 (protons of methyls in position 2 of cyclopropane); 1.72 (protons in position 1 and 3 of cyclopropane); 1.44 (protons of tert-butyl); 4.0 - 4.12 - 4.23 (the methylene proton in position 1 is propoxycarbonyl); 0.83 - 0.95 - 1.06 (protons of methyl propoxycarbonyl).
Stage B. FlR cis D tert-butyl ester, 2-dimethyl-3- (3-propoxy-3 oxo-1-cropenyl) cyclopropanacarboxylic acid.






7 g of IE cis 2,2-dimethyl-3- (n-propoxy-3-oxo-1 -propynyl) cyclopropanecarboxylic acid tert-buty ester IE in 140 cm acetic acid ethyl ester is hydrogenated in the presence of 1.4 g of palladium hydroxide (10%) on barium sulfate and 1.4 cm quinoline. The filtrate is washed with 2N hydrochloric acid solution and then with water, dried and brought to dryness under reduced pressure. 7.2 g of product are obtained which is chromatographed on silica, eluted with a mixture of cyclohexane and ethyl acetate (95: 5). 6.1 g of the expected product are obtained.
26
NMR spectrum (CDCl 1), h, / mpn: 1.2 and 1.29 (the proton is methyl in position 2 of cyclopropane); 1.5 - 2.03 (carbon proton 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 bound to cyclopropane); 5.82-6.0 (proton of ethylene carbon bearing the propoxycarbonyl group); 4.02 - 4.12 - 4.23 (the methylene proton in position 1 of the propoxycarbonyl group); 0.86 - 0.98 - 1.1 (proton of the propoxycarbonyl moiety).
Stage B, IR cis, d, 2-Dimethyl-3- (3-propoxy-3-oxo-1-propenyl) cyclopropanecarboxylic acid.
5.8 g of the product obtained in stage B, 200 mg of hydrated para-toluenesulfonic acid and 60 cm of toluene are heated under reflux for 1 h. The argument is dry under.
reduced pressure and get 5 g of the product, which is chromatographed on silica, eluting with a mixture of cyclohexane - ethyl acetate - acetic acid (70: 29: 1),
4.2 g of the expected product are obtained.
NMR spectrum (CDC.lj), ppm: 1.27 and, 29 (P methyls in position 2 of cyclopropane); 1.86-2 (n methyls in position 1 of cyclopropane); -
3.45 (n of 3 cyclopropane); 5.8-6 (n ethylene carbon bearing the grouping CO, CH, CH2CH5); 6.4 - 6j56 - 6.59. (H ethylene carbon combined with cyclopropane); 3.98 - 4.08 - 4.18 (n methylene in position I of the propoxycarbonyl group); 0.83 - 0.95 - 1.06 (H methyl groups of propoxycarbonyl).
Example 84, IR cis, &, 2-Dimethyl-3- (3-1-methylethoxy-3-oxo-1-propenyl) cyclopropanecarboxylic. acid.
Stage A. 1R cis, D, 2-dimethyl-3- (hydroxy-3-oxo-1-propenyl) cyclopropanecarboxylic acid tert-butyl ester,
2 g of tert-butyl ether lRcis - -2,2 dimethyl-3- (3-hydroxy-3-oxo-l- -propynyl) cyclopropanecarboxylic acid
lots in 40 cm of ethyl eff) and acetic acid are hydrogenated in the presence of 0.38 g of palladium hydroxide (10%) on barium sulfate and 0.4 cm of quinoline. Filter out
27
the filtrate is washed with 0.5N hydrochloric acid and then with water until neutral, dried, concentrated to dryness under reduced pressure, and 2 g of the expected product is obtained, melting at.
Stage B, iR cis t-butyl ester, & s-2,2-dimethyl-3- 3- (1-methyl-ethoxy) -3-oxo-1-propenyl 3 cyclopropanecarboxylic acid.
2.7 g of IR tert-butyl ester, 2-dimethyl-3-g - (3- -hydroxy-3-oxo-1-propenyl) cyclopropanecarboxylic acid in 10 cm ethyl acetate are mixed, then 2 g are added o-isopropyl-I, H - -diisopropylisourea and stirred for 1 h at room temperature. The mixture is heated with reflux for 1.5 hours to 20 ° C, the insoluble matter is filtered off and the filtrate is brought to dryness under reduced pressure. 3.5 g of oil are obtained, which is chromatographed on silica using a benzene-cyclohexane mixture (7: 3). Get 1 h of the target product, which is used in the next stage.
Stage B. IR cis, 2-Dimethyl-3-H- (1-methylethoxy) -3-windows-1-propenyl cyclopropanecarboxylic acid.
While stirring for 2.5 hours, the mixture containing 1.4 g of tert-butyl ester iR cis, dGS-2,2-dimesh1-3-3- (1-methylethoxy) -3-oxo-1 is heated to 120 ° C. -propenyl cyclopropencanoic acid, 100 mg of para-toluene sulfonic acid and 14 cm of toluene. Reduce to dry under reduced pressure. A residue is obtained which is recrystallized in isopropyl ether. Ice N t, sucked off, dried and norf emit 900 mg of the desired product, melting at 98 C.
Example 85. IR cis, L -2,2-Dimethyl-3- (3-cyclobutyloxy-3-oxo-1-propenyl) cyclopropylcarboxylic acid.
Stage A. IR cis, t-butyl ester, 2-dimethyl-3- (3-cyclo-butyl-hydroxy-3-oxo-1-propenyl) cyclopropanecarboxylic acid.
4 g of IR cis t-butyl ester, 2-dimethyl-3- (3-hydroxy-3-oxy-1-propyl) cyclopropancarboxylic acid is dissolved in 20 ml of methylene chloride, and then added
 ,
-,
240828
1.7 mg cyclobutane. The temperature is lowered to O + 5 ° C, 3.45 g of dicyclohexylcarbodiimide, 28 mg of dimethylaminopyridine and 20 mg of methylene chloride are added and kept under stirring for 2 hours at 5 ° C and 2 hours at room temperature. The resulting dicyclohexylmoxide is removed.
Q Chevina, the filtrate is concentrated to dryness and chromatographed on silica, eluting with n-hexane: isopropyl ether (9: 1). 2.3 g of the expected product are obtained.
15 Stage B. iR cis, L, 2-Dimethyl-3- (3-cyclobutyloxy-3-oxo-1-propyl) cyclobate opancarboxylic acid. Within 15 minutes, 2.3 g of the obtained product is heated with reflux.
2Q ta, 25 cm of toluene and 250 mg of para-toluenesulfonic acid, cooled and stirred for 2 hours at 0/45 C. Insoluble matter is filtered off and the filtrate is concentrated to dryness
25 FOR 1.8 g of the target product.
G-spectrum: - OH: acid 3500 cm, -: acid 1733 + ester 1702 pairs. di Me: 1390 cm and -1380 cm.
30 Example 86. IR cis, D -2,2-dimethyl-3- (3-RS I-methylpropyl-hydroxy-3-oxo-1-propenyl cyclopropanecarboxylic acid.
Stage A. 1R cis -2,2-dimethyl-3- (3-RS -1-methyl-propyloxy-3-oxo-1-pro-pinyl) cyclopropanecarboxylic acid tert-butyl ester.
35
4 g of t-butyl ester is mixed
DR, 2-dimethyl-3- (3-hydroxy-3-oxo-1-propynyl) cyclopropanecarboxylic acid, 40 cm of methylene chloride and 6 mg of 4-dimethylaminopyridine, and then 3.4 g of dicyclic
logexilcarbodiimide. After 30 minutes of movement in an inert atmosphere, 2 cm of 1-methylpropanol and 2 cm of methylene chloride are added over 5 minutes and kept under stirring.
Research institutes for 3 hours at room temperature. The dicyclohexyl urea formed is filtered off, the filtrate is concentrated to dryness under reduced pressure and the residue is chromatographed
on silica, eluting with K-hexane-isopropyl ether (8: 2). 3.5 g of the expected product are obtained.
Step B. Tert-butyl ether iR qi c, & Z - 2,2-dimethyl-3 (3 - RS -1 -me29
tyl-propyloxy-3-oxo-1-propenyl) cyclopropanecarboxylic acid.
3 g of the product obtained above is subjected to hydrogenation as in Example 84. Chromatographing is carried out on silica, eluting with hexane-isopropyl ether (9: 1), and 2.5 g of the expected product is obtained.
Stage B, IR cis, & Z1-2,2-Dimethyl-3 (3-RS-i-methylpropyloxy-3-oxo-1-propenyl) -cyclopropanecarboxylic acid.
Stir. 3 g obtained above. product with 250 mg of para-toluenesulfonic acid in 25 cm of toluene. Heated with reflux until gas evolution ceases. It is concentrated to dryness under reduced pressure, the residue is chromatographed on silica, eluting with a mixture of cyclohexane and ethyl acetate (acetic acid (70: 30: 1)). 1.85 g of the expected product is obtained.
IR spectrum (СНС1,). - OH: acid 3510 cm-; - acid 1735 ester 1170 cm 5 concom. 1637 cm; guys di me see
Example 87. IR dis, -2 5 2-Dimethyl-3 3-oxo-3- (cyclopropyl-methoxy) propynylcyclopropane 1-carboxylic acid.
Stage A. iR cis, t-butyl ester, 2-dimesh-1-3 Z-oxo-3-cyclopropylmethoxy) propenyl cyclopropan-1 - carboxylic acid.
In 150 cm of methylene chloride, 20 g of iR cis, b, 2-dimethyl-3- (3-hydroxy-3-oxo-opyl) cyclopropane-1-carboxylic acid tert-butyl ester are introduced and 6.2 g of cyclopropyl carbinol, add 2 g of dimethylaminopyridine and 17.5 g of dicyclohexylcarbodiimide in 60 cm of honey chloride, ice and sodium bicarbonate.
stirred for 2 hours at 20 ° C, prepared to prepare the insoluble material formed, concentrated to dryness by distillation under reduced pressure, the residue chromatographed on silica, eluted with hexane-isopropyl mixture
50
extracted with ethyl ether, washed with water, acidified with aqueous layers, extracted with ether, washed with water the combined organic layers, concentrated to dryness by distillation under reduced pressure, the residue is chromatographed on silica, eluting with a mixture of cyclohexane: ethyl acetate (6: 4 ),
Saw ether (9: 1), and get 12.32 g
iR cis tert-butyl ester, 2-dimethyl 3- (3-oxo-3-cycloprop 1-gg containing% acetic acid, semimethoxy) propynylcyclopropan-1-carboxylate 6.8 g of iR methyl ester, 2- dimesh-1- (3-oxo-3-hydroxypropy.
pinyl). cyclopropane-1-carboxylic acid
new acid.
Stage B, IR cis, L, 2-, dime-3 (3-oxo-3-cyclopropylmethoxy)
lots.
.

34240830.
propenylcyclopropanecarboxylic acid.
about
12.32 g of tert-butyl ether IR cis, -2,2-dimethyl-3- (3-oxo-3-cyclopropyl-methoxy) propynylcyclopropane-1-carboxylic acid, 0.6 g are introduced into 120 cm of toluene. para-toluenesulfonic acid, heated with reflux, reflux suppressed for 45 min, cooled, concentrated to dryness by distillation under reduced pressure, the residue is chromatographed on silica, eluted with a mixture of hexane and ethyl acetate of acetic acid (7: 3) containing 1% acetic acid, and get 8.94 g of Sh cis, b, 2-dimethyl-3- (3-cyclopropylmethoxy) propenyl-cyclopropane-1-carboxylic acid . M.p. 106 ° C.
ten
20
25
thirty
35
40
NMR spectrum (CDC1,), ppm: 1.29 - 1.31 (protons of paired methyl); 1.13 (proton —CH—); 1.85-2 (proton in position 1 of cyclopropane); 3,9-4 {proton in O - CH, -); 5.82 - 6.01 and 6.52 - 6.77 (protons, ethylene Cys).
Example 88. 1R cis, -i, 2-Dimethyl-3- (3-oxo-3-tert-butoxy-propenyl) cyclopropanecarboxylic acid.
Step A, iR, -2,2-dimesh1-3- (3-oxo-3-hydroxypro- pinch) methyl ester, cyclopropane-1-carboxylic acid,
36.5 g of iR, 2-dimethyl-3- (2,2-dibromoethenyl) cyclo-g-propane-1-carboxylic acid methyl ester are introduced into 360 cm of tetrahydrofuran at -70 ° C at 100 ° C. suspensions butyl lithium in cyclohexane, stirred for 10 minutes, allow carbon dioxide to pass through for 30 minutes, allow the temperature to rise to -20 ° C, pour the reaction mixture into the mixture
Water, ice and sodium bicarbonate.
50
extracted with ethyl ether, washed with water, acidified with aqueous layers, extracted with ether, washed with water the combined organic layers, concentrated to dryness by distillation under reduced pressure, the residue is chromatographed on silica, eluting with a mixture of cyclohexane: ethyl acetate (6: 4 ),
gg containing% acetic acid, poluloty.
Step B. Methyl 1R, -2,2-dimethyl-3- (3-oxo-3-tert-butoxy-propynyl) cyclopropane-1-carboxylic acid.
6.8 g of IR, 2-dimethyl-3- (3-oxo-3-hydroxypropynyl) cyclopropane-1-carboxylic acid methyl ester is added to 10 cm of ethyl acetate; 1% is added at + 15 ° C. 13.5 g of 0-tert-butyl-K, to -di-isopropyl urea, stirred for 2 hours, removed by filtration of the insoluble material formed, the filtrate was concentrated to dryness, the residue was chromatographed on silica, eluted with a mixture of cyclohexane and ethyl acetate. acids (85: 15), and get 7 g of methyl ester of qi (G -2,2-dimethyl-3- (3-oxo-3-tert-butoxypropinyl) cyclopropane-1-carboxylic acid.
Stage B. 1R cis, 2-dimethyl-3- (3-oxo-3-tert-butoxy-1-propenyl) cyclopropane-1-carboxylic acid methyl ester.
7 g of IR cis-2,2-dimethyl-3- (3-oxo-3-tert-butoxypropynyl) cyclopropane-1-carboxylic acid methyl ester in 149 cm of ethyl acetate are hydrogenated at 20 ° C in the presence of 10 % hydroxide palladium on sulfuric acid and then at 0 ° C add 2.8 g of dicyclohexylcarbodiimide and 30 mg of dimethyl shnopyridine (dissolved in 10 cm of chloride, methylene), a fracture of barium and 1.4 cm of quinoline. The filter is stirred for 16 h at, washed off, the filtrate is washed with 1N. . insoluble matter is filtered,
concentrated to dryness by distillation under reduced pressure, the residue is chromatographed on silica, eluted with a mixture of cyclohexane - isopropyl ether (9: 1), to obtain 2.1 g of tert-butyl ether iR cis, A Zj- -2,2- dimethyl-3- (3-5Izo-butoxy-3-oxo--1-propenyl) cyclopropane-1-carboxylic acid.
45 Stage B. iR cis, &, 2-flHMe-mn1-3- (isobutoxy-3-oxo-1-propenyl) cyclopropane-1-carboxylic acid. 1 g of a aqueous solution of caustic soda injected with 2.5 g of methyl ester, ygZ-2,2-dimethyl-3- (3-oxo-3-tert-bu-§0 toxy-1-propenyl) cyclopropane-1-carboxylic acid, stirred for 3 hours at 50 ° C, cooled to -75 ° C, poured the reaction mixture into water, extracted with ethyl ether, acidification for 20 minutes, concentrated to dryness. poured the aqueous layer to pH 1 hydrochloric acid by distillation under reduced pressure, with a lot, extracted with ether, concentrated on silica dioxide and then with water, dried, and concentrated to dryness by distillation under reduced pressure. 5.8 g of iR cis, -2,2-dimethyl-3- (3-oxo-3-tert-butoxy-1-propenyl) -cyclopropane-1-carboxylic acid methyl ester are obtained.
Step G. IR cis, 2-flHMe-tyl-3- (3-oxo-3-tert-butoxy-1-propenyl) cyclopropane-1-carboxylic acid.
33
in a mixture of 25 cm of methanol and 9.8 cm
2.1 g of tert-butyl ester iR cis, U z3-2,2-dimetsI-3- (3-isobutyce-3-oxo-1-propenyl) cyclopropane-1-carboxylic acid and 0.1 •; toluene sulfonic acid is introduced into 20 cm of toluene, heated under reflux and allowed to reflux, organic extracts are allowed to dry until dry by distillation under reduced pressure.
chromatographic of the residue on silica, eluting with a mixture of cyclohexane and ethyl acetate (7: 3),
containing 1% acetic acid, and get 1,576 g of iR cis, 2-dimethyl-3- (3-oxo-3-tert-butoxypropanol) cyclopropane-1-carboxylic acid.
IR spectrum (СНС1,), cm: 3500 (HE acid; monomer + dimer); 17300 and 1695 (acids and esters); 1628 (corresponding to conjugate) -, 1390 and 1377 (paired methyls); 1368
(t. Bu),
Example 89. IR cis, -2,2-Dimethyl-3- (3-iso-butyloxy-3-α-oxo-1-propenyl) cyclopropane-1-carboxylic acid.
Step A. Tetbutyl ester iR cis, 2-dimethyl-3- (3-isobutoxy-3-oxo-1-propenyl) cyclopropane-1-carboxylic acid,
4 g obtained according to example 84
(Stage A) iR cis tert-butyl ester, U, 2-dimethyl-3- (3-hydroxy-3-oxo-1-propenyl) cyclopropane-1-carboxylic acid is introduced into 10 cm of methylene chloride and 1 Isobutanol,
and then at 0 ° C, 2.8 g of dicyclohexylcarbodiimide and 30 mg of dimethyl shnopyridine (dissolved in 10 cm of chloride, methylene) are added, stirred for 16 hours at, the insoluble matter is filtered off,
 Stage B. iR cis, &, 2-flHMe-tn1-3- (isobutoxy-3-oxo-1-propenyl) cyclopropane-1-carboxylic acid. 20 min, concentrated to dryness. By distillation under reduced pressure, chromatographed on silica dioxide 2, 1 g of tert-butyl ether iR cis, U z3-2,2-dimethyl-3- (3-iso-botoxy-3- oxo-1-propenyl) cyclopropane-1-carboxylic acid and 0.1 g; para-toluenesulfonic acid is introduced into 20 cm of toluene, heated under reflux and refluxed for a period of elution with a mixture of hexane and ethyl ether acetic acid (7: 3) containing 331342408
1% cis, y7.7-2,2-dnmethyl-3- (3rd-3-butoxy-3-oxo-1-propenyl) cyclopropane-1-carboxylic acid.
IR spectrum (chloroform), 3300 (OH acids); 1730, 1706, 1694 (acids and the conjugate ester); 1630 (, Z);. 390, 1380 (paired methyls).
Example 90 „1R cis, U -2,2-Dimethyl-3- (3-n-butoxy-3-oxo-1 propene1) cyclopropanecarboxylic acid.
ten
34,
Step B. 1R cyo, i, 2-Dimethyl-3- (3 H-butoxy-3-oxo-1-propenyl) cyclopropanecarboxylic acid.
3.3 g of the product obtained above are mixed with 350 ml of para-toluene sulfonic acid in 40 cm of toluene. The mixture is heated under reflux until the end of the gas elimination of isobutylene, i.e. about 40 min Concentrated to dryness under reduced pressure, chromatographic of the residue on silica, eluting with a mixture of C1-1kohexane-ethyl acetate
Stage A, iR Tert-Butyl Ester, 15 Acids - Acetic Acid 75: 25: 1. , 2-dimethyl-3- (3-I-butoxy-3- 2 g of the expected product are obtained.
NMR (CDC1,), ppm: 1.26 and 1.3
25
-oxo-1-propynyl) hclclopropanecarboxylic acid.
Eat 4 g of tert-butyl ether.
ra IR, 2-dimethyl-3- (3-hydro-20 si-3-oxo-1-propynyl) cyclopropanecarboxylic acid, 40 cm of methylene chloride and 6 mg of 4 diethylaminopyridine, and then 3.4 g dicyclohexylcarbodiimide. After 30 minutes of stirring in an inert atmosphere, 4 cm of a mixture (1: 1) of n-butanol and methylene chloride are added over 5 minutes and kept under stirring for 3 hours at room temperature. The formed dicyclohexyl urea is filtered off, the filtrate is concentrated to dryness under reduced pressure and the residue is chromatographed on silica, eluting with cyclohexane ethyl acetate (9: 1). 4.7 g of the expected product are obtained.
Stage B, iR cis, b, 2-dimethyl-3- (3 H-butoxy-3-oxo-propenyl) cyclopropanecarboxylic acid Tert-butyl ester
For 15 minutes, 800 mg of palladium hydroxide in barium sulfate are stirred in a hydrogen atmosphere.
(protons of methyls in position 2 of cyclopropane) ;. 1.85 - 1.99 (proton in position 1 of cyclopropane); 3.13 - 3.47 (proton at positions 3 of cyclopropane); 6.4 - 6.57 and 6.59 - 6.75 (proton in the 1st allylla chain); 5.8-5.99 (proton in the 2nd allyl chain). Example 91, 1R cis, and -2,2-Dimethyl-3- (3-cyclopentoxy-3-ox-1-propenyl) cyclopropane-1-carboxylic acid.
Stage A. 30 IR cis t-butyl ester, & , 2-dimethyl-3- (3-cyclo-pentoxy-3-oxo-1-propenyl) cyclopropane-1-carboxylic acid.
4 g of tert-butyl ester lRcic, & , 2-dimethyl-3- (hydroxy-3-oxo- - 1-propenyl) cyclopropane-1-carboxylic acid and 1.43 g of cyclopentanol are introduced into 15 cm of methylene chloride, and 3.43 g of cyclohexane are added at 0 ° C.
silcarbodiimide, 40 mg dimethylamino-
about
4Q pyridine in 10 cm methylene chloride, stir the suspension at 20 ° C for 17 hours to remove the insoluble matter by filtration, concentrate the filtrate to dryness by distillation
g under reduced pressure, chromatographic of the residue on silica, eluting with a mixture of cyclohexane-isopropyl ether (9: 1), to obtain 1.38 g of tert-butyl ether, iR cis, D -2,2-dimethyl-3- (3-cyclopentoxy -3- -oxo-1-propenyl) cyclopropane-1-carboxylic acid. T, pl. 57 ° C.
20 cm of ethyl acetate, and then 4.7 g of the product obtained is added to 50 cm of ethyl acetate and 0.8 cm of quinoline and left under hydrogen atmosphere for 30 minutes. Filter, wash the filtrate with 1N. hydrochloric acid and then with water, dried, concentrated to dryness under reduced pressure, and the residue is chromatographed on silica, e: wide, with a mixture of cyclohexane and ethyl acetate (95: 5). 3.4 g of the expected product are obtained.
0
34,
Step B. 1R cyo, i, 2-Dimethyl-3- (3 H-butoxy-3-oxo-1-propenyl) cyclopropanecarboxylic acid.
3.3 g of the product obtained above are mixed with 350 ml of para-toluene sulfonic acid in 40 cm of toluene. The mixture is heated under reflux until the end of the gas elimination of isobutylene, i.e. about 40 min The concentrate
(protons of methyls in position 2 of cyclopropane) ;. 1.85 - 1.99 (proton in position 1 of cyclopropane); 3.13 - 3.47 (proton at positions 3 of cyclopropane); 6.4 - 6.57 and 6.59 - 6.75 (proton in the 1st allylla chain); 5.8-5.99 (proton in the 2nd allyl chain). Example 91, 1R cis, and -2,2-Dimethyl-3- (3-cyclopentoxy-3-ox-1-propenyl) cyclopropane-1-carboxylic acid.
Stage A. IR cis t-butyl ether, & , 2-dimethyl-3- (3-cyclo-pentoxy-3-oxo-1-propenyl) cyclopropane-1-carboxylic acid.
4 g of tert-butyl ester lRcic, & , 2-dimethyl-3- (hydroxy-3-oxo- - 1-propenyl) cyclopropane-1-carboxylic acid and 1.43 g of cyclopentanol are introduced into 15 cm of methylene chloride, and 3.43 g of cyclohecate is added at 0 ° C.
silcarbodiimide, 40 mg dimethylamino-
about
pyridine in 10 cm of methylene chloride, the suspension is stirred at 20 ° C for 17 hours, the insoluble matter is removed by filtration, the filtrate is concentrated by distillation to dryness
with reduced pressure, the residue is chromatographed on silica, eluting with a mixture of cyclohexane-isopropyl ether (9: 1), 1.38 g of tert-butyl ether, iR cis, D -2,2-dimethyl-3- (3-cyclopentoxy- 3-oxo-1-propenyl) cyclopropane-1-carboxylic acid. T, pl. 57 ° C.
Stage B. IR cis,, thyl-3- (3-cyclopentoxy-3-oxo-1-propyl) cyclopropanecarboxylic. acid.
2.54 g of cis tert-butyl ester, D -2.2 dimethyl-3- (3-cyclo pentoxy-3-oxo-1-propenyl) cyclopropane-1-car are introduced into 25 cm of toluene
boven acid, 0.1 g of para-toluene sulfonic acid, heated under reflux, kept reflux for 20 minutes, concentrated by dry distillation under reduced pressure, chromatographed on silica, eluted with hexane-ethyl acetate (7: 3) containing 1% acetic acid and receive 1.82 g of iR cis, 2-dimethyl-3- (3-cyclopentoxy-3 oxo-1-propenyl) cyclopropan-1 -carboxylic acid.
IR spectrum (chloroform), 3510 (he acid); 1735, 1702 (acids and conjugated esters); 1632 (corresponding to the conjugate); 1380 (paired methyl).
Example 92. IR trans, l -2,2-Dimethyl-3-3- (1-methylethoxy) 3-oxo-1-propenyl cyclopropanecarboxylic acid.
Stage A. IR trans -2,2-dimethyl-3- (3-hydroxy-3-oxo-1-propynyl) cyclopropanecarboxylic acid tert-butyl ester.
The procedure is as indicated in Example 82 (step A), starting from 40 g of IR trans -2,2-dimethyl-3- (2,2-dibromovinyl) cyclopropane carboxylic acid tert-butyl ester. After chromatography on silica of the crude product (eluantgcyclohexane - ethyl acetate - acetic acid, acid (6: 4: 0.2), 19.2% of the expected product is obtained.
Step B. Tert-butyl ether IR Tpand -2, 2-dimethyl-3- (3-1-methyl-to-si-3-oxo-propynyl) cyclopropanecarboxylic acid.
3.6 g of the product obtained according to the above method are mixed with 20 cm of ethyl acetate, 3 g of 0-isopropyl-N, N-diisopropylisourea are added and the mixture is refluxed for 16 hours. After reaching room temperature, it is filtered, the filtrate is concentrated to dryness under reduced pressure, and 2.7 g of the expected product are obtained.
Stage B. IR trans, 6,, 2-dimethyl-3-C3- (1- -methylethoxy) -3-oxo-1-propenyl cyclopropanecarboxylic acid tert-butyl ester.

2.7 g of the product obtained in the predush; the product of 50 cm of ethyl acetate is hydrogenated in the presence of 0.55 g
0
25
10% palladium hydroxide on barium sulfate and 0.55 cm of quinoline. Filter, wash the filtrate with 1 and a saline COC., And then with water until neutral, dry and concentrate to dryness under reduced pressure. 2.18 g of the expected product are obtained.
Step G. 1R trans, L, 2-Dimethyl-3-Z- (1-methylethoxy) -3-oxo-1 - -propenyl cyclopropanecarboxylic acid.
2.18 g of the product obtained in the previous stage, 20 cm of toluene and 0.2 g of para-toluene and sulfonic acid are heated with reflux. After returning to room temperature, the typeype is washed with water and the organic layer is dried, and Q is concentrated to dryness under reduced pressure. 1.6 g of the expected product are obtained.
Example 93. .3 Phenoxy-O6-hydroxybenzeneethanethioamide.
In a solution of 20 g of ei-cyano-3-phenoxy-benzyl alcohol in 200 cm of toluene
2
And 4.5 cm of triethylamine is bubbled with hydrogen sulfide for 22 hours, the reaction mixture is poured onto 1 kg of water. A 3Q hydrochloric acid is separated, the organic layer is separated by decantation, rinsed with water, dried, concentrated to dryness under reduced pressure, chromatographed residue on silica, eluting with benzene-ethyl mixture
35
40
Acetic acid ester (8: 2) is crystallized in isopropyl ether and 18.5 g of 3-phenoxy-o-hydroxybenzenethanethioamide are obtained. M.p. 70 C,
IR spectrum (chloroform), cm: 3600 (corresponds to free OH and combined OH); 3478 (-NH); . 1670, 1578, 1477 (aromatic cores and -C - W /).
45 s
NMR spectrum (CDCI,): peaks at 3.97 - 4.03 h, / mPc, corresponding to hydrogen hydroxyl; peaks at 5.18 - 5.25 h / min, the corresponding hydrogen
50 on carbon; peaks at 6.92 7.58 ppm, corresponding to aromatic hydrogen peaks at 7.5 ppm, corresponding to hydrogen - Hj ,.
55
Example 94, (2-phenoxy-5
-tyaz OLYL) methanol.
Stage A. 2-phenoxy-thiazole-5-carboxylic acid ethyl ester.
371
Mix 2 g of ethyl 2- chloro-thiazole-5-carboxylic ester, 50 cm of dimethylformamide, 2.5 cm
1.5
hexamethylphosphorotriamide and sodium iodide, heated to the reaction mixture, maintained at this temperature for 1 hour, cooled to 20 ° C, introduced in portions of 1.32 g of potassium phenol, heated the reaction mixture with reflux for 1.5 hours, added , 66 g of potassium phenol, maintain reflux for 1.5 hours, cool, add water and ethyl acetate, extract with ethyl acetate, wash the organic layers with water, concentrate them to dryness, chromatograph the residue on silica, eluting with hexane-isoprop mixture sulphate is triethylamine (7: 3: 1) and 1.08 g of 2-phenoxy-thiazole-5-carboxylic acid ethyl ester is obtained. M.p. 67 C.
Stage B. (2-phenoxy-5-thiazolyl) methanol,
In a solution of 12 g of ethyl 2- -phenoxythiazole-5-carboxylic ester in 60 cm of toluene is slowly added at -10 C-54 cm, a toluene solution of sodium aluminum-diethyl hydride containing 2 mol / l is stirred for 1 h at -5 ° C, 80 cm 2 of a hydrochloric acid aqueous solution are introduced at -20 ° C and then water, the resulting insoluble material is filtered off, the filtrate is decanted, the organic layer is washed with water, then with 2N aqueous sodium hydroxide solution and again concentrated dry, chromatograph the residue on silica, heat the mixture with chloride etilen - ethyl acetate (8: 2 to give 8.15 g of (2-phenoxy-5-thiazyl lil) methanol.
IR (chloroform), 3590 (hydroxyl); 155), 1530, 1503, 1486 (aromatic core and thiazole); 690 (phenyl, deformation).
NMR spectrum (CDC1): peak at 4.5 ppm, hydrogen corresponding to peak at 3.5 ppm, corresponding to -OH hydrogen; peak at 6j66 ppm, corresponding to thiazolic hydrogen; peaks at 7.10 - 7.50 h, ppm, corresponding to aromatic hydrogens.
Example 95 RS-Cyano (2-enoxy-5-thiazolyl) methanol.




eight
38
(2-phenoxy-5-thiazolyl)
Stadium A. Methanal.
19.1 g of manganese dioxide are introduced into a solution of 4.6 g (2-phenoxy-5-thia. Zolyl) methane, stirred for 17 h at 40 ° G, and then for 3 h at 60 ° C, the insoluble is filtered off , the substance is concentrated to dryness, the filtrate is under reduced pressure, the residue is chromatographed on silica, eluting with methylene chloride-ethyl acetate (8: 2), and 2.6 g (2-phenoxy-.5-thiazolyl) methanol are obtained. M.p. 63 ° C.
Stage B. RS ct -Ciano (2-phenoxy-5-thiaz olyl) meth anol.
In a solution of 0.85 g of sodium cyanide in 5 cm of water. At a temperature of + 10 ° C, 2.4 g (2-phenoxy-5-thiazolyl) methane, dissolved in 10 cm of ether, are mixed with Yumin, added dropwise at 0 ° C, a mixture of 2 cm of a concentrated aqueous solution of sulfuric acid and 3 cm of water is stirred for 2 hours at 0 ° C, the organic layer is separated by decanting, washed with water, dried, concentrated to dryness under reduced pressure, isopropyl is added to the residue ether, the precipitate is filtered off with suction, dried, and 2.28 g of RS-cyano (2-phenoxy-5-thiazolyl) methanol are obtained.
IR spectrum (chloroform), cm: 3580 (hydroxyl); 3550 (combined hydroxyl); 1590, 1504, 1487 (aromatic core and thiazole).
NMR spectrum, (SBSI3): peak at 4.08 ppm, corresponding to -OH hydrogen; peak at 5.41 ppm, corresponding to hydrogen of CH-OHj peak at 7.33 ppm, corresponding to phenyl hydrogens; peak at 7.0 ppm, corresponding to thiazole hydrogen.
Investigation of the activity of the proposed compounds.
Example 96. Study of the lethal effect of the compounds of examples 1-8 on mosquitoes.
The insects under study are female breed mosquitoes, sensitive to pyrethrinoids, released at 22–23 ° C and 60–65% relative humidity, aged 4–5 days. They act by topical application of an acetone solution on the dorsal thorax of insects with the help of the micromanipule torus Arnold. Use 50 individuals per dose of the studied product. Mortality control is done 24 hours after treatment.
Products have been found to exhibit good lethal activity.
Example 97. The study of the lethal effect of the compounds of examples 1-8 on. larvae of Spodoptera littoralis.
Topical application of the acetone solution was performed using an Arnold micromanipulator on the dorsal thorax of the larvae. Investigate 15 larvae per dose of the studied product (larvae of the fourth stage, i.e. at the age of about 10 days, hatching at 24 ° C and 65% relative humidity). After the treatment, the larvae are placed on an artificial nutrient medium - the environment of Poitou.
Mortality control is done 48 hours after treatment.
Products have been found to exhibit good lethal activity.
Example 98. Investigation of the activity of products of winners 1-8 on the larvae of Epilachna Varivestzis.
Samples are topically applied, as for flies and Spodoptera larvae.
The larvae of the penultimate larval stage are used, after treatment the larvae feed on bean seedlings. Mortality control is done 72 hours after treatment.
It has been established that in the consumed sample the products show good lethal activity.
Example 99. Study of the activity of shock on houseflies.
The insects under study are domestic flies (females aged 4-5 days). Operate by direct spraying in a cylinder of Cairns and Marsh, using a mixture of acetone (5%) and isopair L (petroleum solvent) as solvent, the amount of solvent used is 2 np in l-c. 50 insects per dose are used. The control is made every minute for 10 minutes, and then after 15 minutes, CT 50 (the time required to kill 50% of the used insects) is determined by conventional methods.
It was found that the products exhibit good activity, the most effective is the product of Example 1, since its QT 50 is equal to 0.4 min.
five
0
five
0
five
0
five
0
five
1.26 min and 2.02 min for respective concentrations of 1, 0.5 and 0.25 g / l.
Example 00. Activity on Tetranychus Urticae.
The trial of the destruction of adults.
Two-leaf bean seedlings are treated with the various products studied using a Fisher pistol. After drying, these seedlings infect with 25 females of Tetranychus breed per sheet and are kept at 22–23 ° C, 60–65% relative humidity (constant and artificial). Live and dead ticks are counted 24 and 48 hours after treatment.
The products of Examples 1-8 exhibit good activity against adult insects.
Example 101. A study of the insecticidal activity on the Culex pipiens mosquitoes of the compound of Example 1 used as a smoke-forming serpentine.
The neutral carriers of smoke-forming serpentines are impregnated with the active substance dissolved in acetone. In a closed glass cylinder with a capacity of 13.00 cm, 20 mosquitoes at the age of 4-5 days are admitted and smoke-forming serpentine is introduced for 2 minutes, which smolders at one end. The knock-down control is performed. every minute and stop the sample after 5 min after all insects were knocked off.
I
At a dose of 0.60% of the active substance per weight of serpentine CT 50 is equal to 5.42 min; at this dose, the lethal effect is 98.3%.
Example 102. Studying the lethal effect on a home fly.
The insect pests tested are female flies domesticated at the age of 4-5 days.
Topical application of 1 µl of acetone solution is made to the dorsal thorax using an Arnold micromanipulator. 50 flies are used for each treatment. Mortality control is carried out 24 hours after treatment.
The results, expressed in DLjo, are presented below:
Connection example DL 50,
ng / insect 525.7
911,4
Example 103, Explore a lethal effect on cockroaches.
At the bottom of the Petri dish, pipette acetone solutions of the tested substances of different concentrations. The effect of the drugs is tested when insects come in contact with the film obtained on the stack.
Are determined; lethal concentration of 50 (CLjo).
The results of the experiments are presented below:
CL connection
Example 5 9 Prime
so
mg / m
104
20
25
thirty
35
1.95 3.1
The study of the destroying effect on the home fly.
The pest insects tested are female house flies (it will take 4 days). The test is carried out by direct spraying of the preparation with an concentration of 0.25 g / l in the chamber of Cairns and Marsh using an acetone (5%) mixture of isopar L (the amount of solvent used is 2 ml / s) as a solvent. For each treatment, 50 insects are used. Every minute control is exercised. first up to 10 minutes, then up to 15 minutes and the CT 50 is determined.
The results of the experiments are presented below:
Connection CT 50, min example
11.64
472.22
Example 105. Study of the deadly effects on Spodop-Q tera littoralis larvae.
Tests are carried out by topically applying an acetone solution of this compound using an Arnold micromanipulator to the dorsal chest of the larvae. 15 larvae per dose of the product to be tested are used (the larvae of the fourth larval stage, i.e., about 10 days old, developed at 24 ° C and 65% relative humidity). After processing, the chinks are placed in an artificially created nutrient medium. Control of mortality of the larvae is carried out 48 hours after the treatment.
The results of the experiments are presented below;
50
1Q
i5
45
55
DLj, mg / nesCompound by
as an example
five . 5.0
O4,64
Example 106. Study of the lethal effect on Acanthocelide sobtuctus (bean weevil).
Topical application of 1 µl of the acetone solution of the product to be tested on the insect's chest is carried out. Determine
The results of the experiments are given below:
DL compound.,. Mg / insect example
57.54
ABOUT . 4.2
five
0
five
Q
Example 107, The study of the home-destroying action of a fly.
The insects tested are female flies at 4 days old. The tests are carried out by direct spraying of the drug at a concentration of 0.25 g / l in the chamber of Cairns and Marsh, using a mixture of acetone (5%) and isopair L (the amount of solvent is 2 ml per second) as a solvent. 50 insects are used for each treatment. Every minute control is carried out up to 10 minutes, then up to 1.5 minutes and CT 50 is determined by conventional methods. The results are expressed in units of the relative strength of the LDS CT 50 (reference pro, product); . CT 50 (product tested) (P.R),.
Results obtained: Compound for P, R, with respect to the example. to bioallethrin
0
five
five
one
2 3 4 5 6
7 8
9
14 17
6,271 2,794 1,369 3,455 2,828 1,065
2,655 9,223
1,666 1,289
4.261
The method of obtaining cyclopropanecarboxylic acid derivatives of general formula I
H ROoC
H
COOA
PR and mer 108. Study of the lethal effect on the larvae of Epilachpa .Varivest.
The tests are carried out by topical application of an acetone solution of the drug to the dorsal chest of the larvae using an Armanold micromanimeter. G 15 larvae per dose of product to be tested are used. After processing, the larvae are placed in an artificially obtained nutrient medium.
Control of mortality of the larvae is carried out 48 hours after treatment. Results are expressed in units of relative strength of action (P.R.).
The obtained experimental results:
Connection P.R. in relation to deltamethrin
9,362 1,712 2,024
example 4 9
21 67
1,175
five
0
five
0
five
0
five
0
where the double bond has a geometry Z; A- - 3-phenoxybenz1, 5-benzyl-3- -furylmethyl, -Z-4 enylmethyl-3-α-furanylmethyl, l-thioamido-3-phenoxybenzyl, 3 phenoxyphenylethyl-, (2-phenoxy-5- thiazolyl) methyl, 3-benzoyl benzyl, 3-fenoksifenilpropi- RL, fenoksiftorbenzil-3, 3-fenoksiftorfensh1etil, benzyl, nile ftorfenoksifenilpropi-, fenilkarbonilbenzil, tsiayo-3-phenoxy-4-fluorobenzyl, pentaftorbenzil; cyanopentafluorobenzyl, cyanobenzoylbenzyl, cyano-3-bromophenoxybenzyl, 4-oxo-4 (H) -pyranyl, 2- -propinyl -2,4-dioxo-imidazolidine-methyl, hexahydro-1,3-dioxo-2H α-isoindolylmethyl, 2-methyl-4-oxopropenylcyclopentenyl, cyanophenoxypyri dilmethyl, phenoxypyridylmethyl, phenoxypyridylethyl, cyano-phenoxy-5-thiaz olylmethyl, phenoxypyridylpropinyl; R is linear or branched, C, -C5-alksh1, or C4-C5-cycloalkyl, or C -C-alkylcycloalkyl,
in the form of their racemates or optically active antipodes, characterized in that the acid of general formula II
HO-GII About
Have
SNS SNT
n
55
where the double bond has a geometry Z,
R has the indicated meanings, is reacted with an alcohol of the general formula III
. AND HE,
where A is as defined, in the presence of dicyclohexylcarbody 5, 1342408
imide and pyridine or dimel-shamino from the interaction with total forridine alcohol in chlorinated aliphatic mule III in the presence of pyridine in a solvent at C or aromatic hydrocarbon chloride solution of an acid of general formula II is subjected to a solvent at 0-20 ° C.
Compiled by S. Polkova Editor L Veselovska Tehred M. Khodanych Proofreader V, But ha
Order 5725 Circulation 372 Subscription
BNII1SH State Committee of the USSR
but in the matters of inventions and discoveries 1130355 Moscow, Zh-355 Raushsk nab., d ,, 4/5
Production and printing company, Uzhgorod, uLo Proektnad, 4

权利要求:
Claims (2)
[1]
Claim
274,210
28 13,266
297,900
302,898
31 10,081
372,034
38 2,608 42 2,883 44 1.351 fifteen 47 7,354 48 6,635 fifty 2,825 20 58 3,271 62 13,280 64 2,096 25 65 5,157 66 2,298 70 4,932 75 2,332 thirty
Example 108. The study of the lethal effect on the larvae of Epilachna Varivest.
Tests are carried out by ³⁵ local application of an acetone solution of the drug on the dorsal chest of larvae using an Arnold micromanilator. Used (15 larvae per dose of the product to be tested. After processing, the larvae are placed in an artificially obtained nutrient medium.
Control of mortality of larvae is carried out 48 hours after treatment. Results are expressed in units of relative strength (P.R.K
The obtained experimental results:
Connection by P.R. in relation an example to deltamethrin 4 9,362 9 1,712 21 2,024 67 1,175
A method of obtaining derivatives of cyclopropanecarboxylic acid of General formula I where the double bond has a geometry Ζ;
A- - 3 — phenoxybenzyl, 5 — benzyl — 3—-furylmethyl, 5-phenylmethyl-3 — furanylmethyl, os — thioamido-3-phenoxybenzyl, 3 — phenoxy-phenylethyl-1 ', (2-phenoxy-5-thiazolyl ) -methyl, 3-benzoylbenzyl, 3-phenoxyphenylpropynyl, 3-phenoxyfluorobenzyl,
3-phenoxyfluorophenylethyl, benzyl, fluorophenoxyphenylpropynyl, phenylcarbonylbenzyl, cyano-3-phenoxy-4-fluorobenzyl, pentafluorobenzyl; cyanopenta - fluorobenzyl, cyanobenzoylbenzyl, cyano-3-bromophenoxybenzyl, 4-oxo-4 (H) -pyranyl, 2— propynyl -2,4-dioxoimidazolidinylmethyl, hexahydro-1,3-dioxo-2H-isoindolylmethyl,
[2]
2 — methyl — 4 — oxopropenylcyclopentenyl, cyanophenoxypyridylmethyl, phenoxypyridylmethyl, phenoxypyridylethyl, cyanophenoxy-5-thiazolipmethyl, phenoxypyridylpropinyl;
R is linear or branched, C ₍ —C ^-alkyl, or C ₄ -cycloalkyl, or C ₄ ~ C ₅ -alkylcyclo-alkyl, in the form of their racemates or optically active antipodes, characterized in that it is an acid of the general formula II where the double bond has the geometry Ζ, R has the indicated meanings, is reacted with alcohol _{55 of the} general formula III
A - OH, where A - has the indicated meanings, in the presence of dicyclohexylcarbodi45
1342408 imide and pyridine or dimethylaminopyridine in a chlorinated aliphatic solvent at 0-20 ° C or an acid chloride of general formula II is reacted with an alcohol of general formula III in the presence of pyridine in an aromatic hydrocarbon solvent at 0-20 C.
S. Polyakova
Proofreader V. Butyaga

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JP4488765B2|2004-02-26|2010-06-23|大日本除蟲菊株式会社|Aerosol insecticide|

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EP1877377A2|2005-04-29|2008-01-16|Wyeth|Process for preparing 3,3-disubstituted oxindoles and thio-oxindoles|

法律状态:

优先权:

---

申请号 | 申请日 | 专利标题

---

FR8011569A|FR2482955B1|1980-05-23|1980-05-23|

---