SU1558301A3 - Method of producing esters of cyclopropane carbonic acids and unsaturated aliphatic alcohols - Google Patents

Abstract

The invention relates, in all their stereoisomeric forms, to the compounds of general formula I: <IMAGE> in which Y denotes a hydrogen, fluorine, chlorine or bromine atom, Z denotes an oxygen or sulphur atom, R1 denotes either an optionally substituted alkyl radical or an optionally substituted aryl group or an optionally substituted heterocyclic radical, R2 denotes a hydrogen atom, a fluorine, chlorine or bromine atom, a -C IDENTICAL N group or a -C IDENTICAL CH group and R3, R4 and R5, which are identical or different, denote a hydrogen atom, an optionally substituted alkyl radical, an alkenyl radical or an alkynyl radical.

Description

Q1 ЈЈ

This invention relates to a process for the preparation of esters of cyclopropanecarboxylic acids and unsaturated aliphatic alcohols of the general formula

n3s ss R R

R

-COO-CH-C C-R5

where Y is H, F;

T ° v

I / RiO — C — C — CH — 1 — R — C, —C — alkyl; E. - H, -CsN, -CaCH; R, - F, CH3; R4 is H, CH3;

K5 - H, lower alkyl, Denotes the E or Z configuration, with insecticidal activity.

The compounds of formula (i) exhibit properties that allow their use in the control of parasites, for example, the control of parasites of plants, premises and warm-blooded animals. Thus, compounds of formula (l) can be used in the fight against insects, nematodes and ticks, which are parasites of plants and animals.

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In particular, the products of formula (l) may be used in the fight against insects in the agricultural field, in the fight against, for example, against aphids, lepidopteran and coleopteran larvae. These products are applied in doses between 10 and 300 g of active substance per hectare.

The products of formula (I) can also be used in the fight against insects in buildings, in particular against flies, mosquitoes and cockroaches, as well as in the fight against insects that are parasites of animals, such as lice, in particular in cattle, sheep and poultry. The products of formula (l) can also be used in the fight against ticks and nematodes, which are plant parasites.

The products of formula (l) can still be used in the fight against ticks that are animal parasites, for example, in the fight against ticks of the breed Boophilus, Hyalomnia, Amblyomnia and Rhipicephalus, or in the fight against all varieties of scabies and, in particular, against tick mange, lichen lichen

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weave and chorioptic scabies. These products can also be consumed against worms.

In particular, the products of formula (l) may be used to prepare insecticidal compositions.

The compounds of formula (l) can be used as an active ingredient for the preparation of formulations intended for controlling parasites of plants, rooms and warm-blooded animals.

The compounds of formula (l) may also be used to prepare acaricidal compositions intended to combat ticks, plant parasites, as well as nematicidal compositions.

The compounds of formula (l) may also be used to prepare acaricidal compositions intended to combat the parasites of warm-blooded animals, in particular ticks and scabies.

Among the compositions, in particular insecticidal, it is possible to cite compositions containing the compounds described in the examples. These formulations are prepared by conventional methods known in the agrochemical industry. To these

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Formulations may be added — on request — one or more other pesticidal agents. The compositions may be in the form of powders, granules, suspensions, emulsions, solutions, solutions for aerosols, combustible tapes, baits or other preparations classically used for the use of such compounds.

In addition to the active principle, these compounds usually contain a carrier and / or a surfactant (non-ionic), which, in addition, ensure uniform dispersion of the mixture's compound substances. The carrier used may be a liquid, such as water, alcohol, hydrocarbons or other organic solvents, mineral, animal or vegetable oil, powder, such as talc, clays, silicates, kieselguhr, or a solid combustible substance.

Insecticidal compositions with compounds of formula (l) preferably contain 0, by weight of the active substance.

For use in premises, the proposed formulations are used in the form of smoke-generating compositions.

Then, compounds with compounds of the formula (l), with regard to the inactive part, may advantageously be composed of combustible serpentine, or else of a non-combustible fibrous substrate. In the latter case, after administration of the active substance, the resulting fumigant is placed on a heating apparatus.

When insecticidal serpentine is used, the inert carrier may consist, for example, of zhigunts, Taba powder (or Machilus Thumbergii leaf powder, igunum stem powder, cedar leaf powder, wood powder such as sawdust pine), starch and coconut shell powder. The amount of active substance, for example, may be in the range of 0.03-1% by weight.

When a non-combustible fibrous substrate is used, the dose of the active substance may be in the range of 0.03-25% by weight.

Compounds with compounds of the formula (l) for indoor use can also be obtained by preparing sprayed oil based on the active principle, and this oil

impregnate the wick of the lamp and it is subjected to burning.

The concentration of active ingredient introduced into the oil is preferably in the range of 0.03-25% by weight.

Acaricidal and nematicidal compositions can be in the form of powders, granules, suspensions, emulsions, solutions. One or more pesticides can be added to acaricidal and nematicidal compositions.

 For acaricidal use, wettable powders are preferably used for irrigating leaves containing 1 to 80% active principle or liquid for irrigating leaves containing 1-500 g / l of active principle. You can also use powders. for dusting leaves containing 0.05-3% active ingredient.

For nematicidal use, it is preferable to use soil treatment fluids containing 300 to 500 g / l of active principle.

The acaricidal and nematicidal compositions proposed are preferably used in doses ranging from 1 to 100 g of the active substance per hectare.

When it comes to the fight against ticks that are animal parasites, it is possible to introduce the products of formula (l) into food compositions in association with a nutrient mixture adapted for feeding animals. The nutritional mix may vary depending on the breed of the animal; it may contain cereals, sugars and grains, soybean cake, ground nut and sunflower, animal flour, such as fish meal, synthetic amino acids, mineral salts, vitamins and antioxidants.

Thus, the compounds of formula (l) can be used to prepare formulations intended for feeding animals and containing at least one of the products defined above as active principle.

When it comes to controlling ticks that are animal parasites, the proposed formulations can be administered externally by spraying, bathing shampoo} or smearing the spinal column in a manner called pour on. These compounds can

be also introduced through the digestive tract.

The compounds of the formula (T.) can also be used for the preparation of compositions having insecticidal, acaricidal or nematicidal activity, characterized in that they contain at least one of the compounds of general formula (I) as active substance, and also at least one of the pyrethrinoid esters selected in the group that includes alletholone esters, 3 ,, 5,6-tetrahydrophthalimido methyl alcohol, 5-benzyl-3-furyl methyl alcohol, 3-phenoxy benzyl alcohol and CB -cyano-3-phenoxy benzyl spi with chrysanthemum acids, 5-benzyl-3-furyl methyl alcohol esters with 2,2-dimethyl-3- (2-oxo-3-tetrahydrothiophenylidenemethyl) cyclopropane-1-carboxylic acids, 3 phenoxy benzyl esters alcohol and b-cyano-3-phenoxy benzyl alcohols with 2,2-dimethyl-3- (2, 2-dichlorovinyl) cyclopropane-1-carboxylic acids, esters of sy-cyano-3 phenoxy benzyl alcohols with 2 , 2-dimethyl-3- (2,2-dibromovinyl) cyclopropan-1 -carboxylic acids, esters of 3-phenoxy benzyl alcohols with 2-parachlorophenyl-2-isoprolyl acetic acids, are complex esters of allerolone, 6-tetrahydrophthalimido methyl alcohol, 5-benzyl-3-α-furyl methyl alcohol, 3-phenoxy benzyl alcohol, and oi-cyano-3-phenoxy benzoyl alcohol with 2,2-dimethyl-3 - (1 , 2,2,2-tetrahaloethyl) cyclopropane-1-carboxylic acids (where halo is a fluorine, chlorine or bromine atom), and the bonds between the acids and alcohols of pyrethrinoid esters can be in all possible stereoisomeric forms.

In order to excite the biological activity of the products of formula (l), it is possible to add to them the synergistic agents used in such 4 cases, such as 1- (2,5,8-trioxadodecyl} -2- -propyl-4,5-methylene dioxybenzene (or piperonyl butoxide) or M- (2-ethylheptyl) bicyclo (2,2,1) -5-heptene 2,3-di-carboximide or piperonyl bis-2- (-n-butoxyethoxy) ethyl acetate (or tropital ) „

The purpose of the invention is to develop a method for obtaining new compounds,

CH2CHS

peaks at 1.8-2.2 ppm, attributed to methylene ethyl hydrogens; peaks at 2.55-2.58 ppm, assigned to 4Q hydrogen ethynyl; peak at ppm, attributed to methyl methoxyl hydrogen; peaks at 5.6–5.9 ppm attributed to hydrogens

SS N

III / H-Сso

peaks at 5.9–6.1 parts per million and 6.5–6.9 parts per million attributed to hydrogens

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Example 2. (K8) ethynyl 2-me- (NE) pentavyl ester 1R, cis--2,2-dimethyl 3f (AZ) 3 oxo-3-tert-butoxygtropenyl cyclopropane carboxylic acid.

2.4 g of 1R, cis-2,2-dimethyl 3C (UZ) 3 oxo-3-tert-butoxy-propenyl cyclopropane carboxylic acid, 1.24 g of 4-methyl 4 (LE) -hepten-t - are mixed -in-3-ol, 50 cm3 of dichloromethane, 2.06 g of dicyclohexylcarbodiimide, 25 cm3 of dichloromethane and 0.1 g of 4-dimethylaminopyridine, stirred for 1 hour at + 10 ° C, and then for 16 hours at 20 ° C, filtered, the filtrate is concentrated to dryness by distillation under reduced pressure, the residue is chromatographed on silica, eluted with a mixture of hexane and isopropyl ether (9-1), and 2.42 g of the desired product is obtained.

NMR spectrum (deuterochloroform): peaks at 0.87-0.98 - 1.1 ppm, attributed to methyl ethyl ethyl; peaks at 1.29-1.33 ppm, attributed to paired methyl; peaks at 1.5 Li. per million, attributed to tert-butyl methyls; peaks at 1.75 ppm, attributed to methyl hydrogen

(SND) CH2CH3

peaks at 2.5-2.53 and 2.52-2.55 ppm, attributed to acetylene hydrogen; peaks at 5.6-6.0 ppm, attributed to hydrogens

®

1®

.-С-О-С х,

about

peaks at 6.4–6.8 m

I

C CH-j CH2CH

with

H

per million, attributed

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PRI me R 3. (RS) 1-cyano-2-fluoro-3 o or 2-butenyl ether 1R; cis--2,2-dimethyl 3 (AZ) 3- ° cco-3-methoxy-propynyl cyclopropane carboxylic acid.

Staci A. 1 Cyano-2-fluoro-3-methyl-35

-2-5yi gn

16.2 g of 3-methyl-2-fluoro-2-butenal, g cm3 of methanol, 90 cm3 of water, 22 cm3 of acetic acid are mixed, in small fractions at 0 ° C, 12.6 g of sodium cyanide are added, stirred for 5 min at 0 ° C, and then for 1 h at 20 ° C, extracted with ethyl ether, concentrated to dryness by distillation under reduced pressure and obtain 19.5 g of 1-cyano-2-fluoro-II-methyl-2-butenol.

Stage B. (RS) 1-Cyano-2-fluoro-3-methyl-2-butenyl ether 1R, cis-2,

1R 2-fluoro-3-methyl-2-butenyl ester, cis-2,2-dimethyl 3t (&amp; Z) 3-oxo-3-methoxypropenyl cyclopropane carboxylic acid;

1R 2-propenyl ester, cis-2,2-dimethyl 3 (AZ) 3-oxo-3-methoxypropenipic cyclopropane carboxylic acid;

o-2 methyl 2-propenyl ether 1R, cis-2,2-dimethyl (kZ) 3-methoxy-3-oxopropenyl cyclopropane carboxylic acid;

 -2-methyl-2-propenyl ester 1R, cis-2,2-dimethyl zO - (&amp; E) 3-ethoxy-3-oxo-2-fluoropropenyl Cyclopropane carboxylic acid;

C 2-methyl-2E-butenyl ester 1R, 45 cis-2,2-dimethyl 3S (A2) 3 oxo-3-methoxypropenyl cyclopropane carboxylic acid;

40

2E 1R butenyl ester, cis-2,2-di. t., .- ,, l methyl 3 (UZ) 3-oxo-3-methoxyprop-2-dimethyl 3 (UZ) 3-oxo-3-methoxypropion cyclopropane carboxylic acid; psyl cyclopropane carboxylic acid. 3,3-dichloropropane 1R ester, cis 2 g of 1R, cis-2,2-dimethyl 3 C (AZ) 3-oxo-3-methoxypropenyl cyclopropane carboxylic acid, 15 cm3 of methylene chloride, 1 , 4 g

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2 fluoro-3-methyl (RS) 1-cyano-2-butenol, AO mg 4-dimethylaminopyridine, at 0 ° C a solution of 2 g dicyc-2, 2-dimethyl 3 (AZ) -3-oxo-3- methoxypropenyl cyclopropane carboxylic acid;

2-fluoro-2. (Yg) butenyl ester IR., Cis-2,2-dimethyl (AZ) 3-methoxy-3-oxopropenyl cyclopropane carboxylic acid;

logexilcarbodiimide in 10 cm3 of methylene chloride, stirred at 20 ° C for 3 h, the filtrate is concentrated to dryness by distillation under reduced pressure, the residue is chromatographed on silica gel, eluted with hexane - ethyl acetate (85-15) j and get 2, k g target ester.

(et) + 84 ° (k 0.5%, chloroform).

Compounds whose properties are given in the table were obtained by the method of example 3

These compounds are as follows:

(RS) 1-cyano-2-fluoro-3-methyl-2-butene 1R, cis-2,2-dimethyl 3T

Ј (iZ) 3-oxo-3-tert-butoxypropenyl3g cyclopropane carboxylic acid;

3-Methyl-2-butenyl ether 1R, cis-2,2-dimethyl 3 C (&amp; Z) 3-oxo-3-metoxypropenyl cyclopropane carboxylic acid;

1R 2-ftrro-3-methyl-2-butenyl ester, cis-2,2-dimethyl 3 p (uZ) 3-oxo-3-tert-butoxypropenyl cyclopropane carboxylic acid;

1R 2-fluoro-3-methyl-2-butenyl ester, cis-2,2-dimethyl 3t (&amp; Z) 3-oxo-3-methoxypropenyl cyclopropane carboxylic acid;

1R 2-propenyl ester, cis-2,2-dimethyl 3 (AZ) 3-oxo-3-methoxypropenipic cyclopropane carboxylic acid;

o-2 methyl 2-propenyl ether 1R, cis-2,2-dimethyl (kZ) 3-methoxy-3-oxopropenyl cyclopropane carboxylic acid;

 -2-methyl-2-propenyl ester 1R, cis-2,2-dimethyl zO - (&amp; E) 3-ethoxy-3-oxo-2-fluoropropenyl Cyclopropane carboxylic acid;

C 2-methyl-2E-butenyl ester 1R, cis-2,2-dimethyl 3S (A2) 3 oxo-3-methoxypropenyl cyclopropane carboxylic acid;

HCG cyclopropane carboxylic acid; 3,3-dichloroprene 1R open ester, cis

-2,2-dimethyl 3 (AZ) -Z-oxo-3-methoxy-dipropenyl cyclopropane carboxylic acid;

2-fluoro-2. (Yg) butenyl ester IR., Cis-2,2-dimethyl (AZ) 3-methoxy-3-oxopropenyl cyclopropane carboxylic acid;

111558301

2-fluoro-2 - (& E) 1R, cis-2,2-dimethyl-3-1 (&amp; Z) 3-methoxy-3-oxopropenyl cyclopropane carboxylic acid butenyl ester;

(1K8) cyano-2-methyl 2 (E) 1R pentenyl ester, cis-2, -2-dimethyl 30 (&amp; 2) 3-methoxy-3-oXoaropenyl cyclopropane carboxylic acid;

1R 2-fluoro-3-methyl-2-buten-1-yl ester, cis-2,2-dimethyl 3 | CHS 2-fluoro-3-oxo-3-ethoxypropenylZcyclopropane carboxylic acid;

1-ethynyl-2-methyl LE penten-2-ylo12

(RS) 1R, cis-2,2-dimethyl 3 1 (3-ethoxy-3-oxo-1-propenyl cyclopropane carboxylic acid; 1-1-ethynyl-2-fluoro-3-methyl-2-butenyl ether;

(RS) 1-ethynyl-2-fluoro-3-methyl-2-butene 1R, cis-2,2-dimethyl 3 (DE) 3 methoxy-3-oxo-2-fluoro-1-propyl cyclopropane carboxylic acid;

(RS) 1-ethynyl-2-fluoro-3-methyl-2-bugenyl ether 1R, cis-2,2-dimethyl 3-L (fc, E) 3-ethoxy-3 oxo-2-fluoro-1 -propenylZcyclopropane carboxylic acid;

(1RS) 1-R-1-ethynyl-2-methyl-2-pentenyl ester, cis-2,2-dimethyl 3 L (k E) 1R 1R ester, cis-2,2-dimethyl)

2-fluoro-3-ethoxy-3-oxo-1-propenyl cyclopropane carboxylic acid (isomer A);

1.-ethynyl-2-methyl LE penthen-2-yl ester 1R, cis-2,2-dimethyl 3 (&amp; E) 2-fluoro-3-oxo-3-ethoxypropenyl cyclopropane carboxylic acid (isomer B) ;

(1 K8) ethynyl-2-methyl-hex-2 (& E) en-5 yl 1R ether, cis-2,2-dime 3-methoxy-3-oxo-2-bromo-1-propenyl - cyclopropane carboxylic acid;

(RS) 1-ethynyl-2-methyl-hex-2-en 5-ynyl eshir 1R, cis-2,2-dimethyl 3 20 XD 3 methoxy-3-oxo-2-bromo-1-propyl cyclopropane carbon acids

(1RS) 1R 1-ethynyl-2-methyl-2-pentenyl ester, cis-2,2-dimethyl 3Q &amp; E) 3-methoxy-3-oxo-2-chloro-1-propenyl tely) 3-oxo -3 gret-butoxyprop-25cyclopropane carboxylic acid; no cyclopropane carboxylic acid; (RS) 1-ethynyl-2-ma, thyl-hex-2-ene

(1RS) ethynyl-2-methyl-hex-2 (iE) 5-yl ether 1R, cis-2,2-dimethyl 3

1R en-5-ynyl ester, cis-2,2-dime- (AE) 3-methoxy-3-oxo-2-chloro-1-propyl-3 (E) 2-fluoro-3-oxo-3-ethoxypro -nil | cyclopropane carboxylic acid;

penyl cyclopropane carboxylic acid; thirty

(1RS) ethynyl-2-methyl-hex-2 (E) en-5-ynyl 1R ester, cis-2,2-dimethyl 3 f (kZ) 3 methoxy-3-oxo-1-propenyl} cyclopropane carbon acids; 2-fluoro 2 (&amp; Z) 1R butenyl ester, cis-2,2-dimethyl GP (&amp;) 3-ethoxy-3-oxy-2-fluoro-1-propenyl Cyclopropane carboxylic acid;

2-fluoro 2 (& E) 1R butenyl ester,

35

ORS) 1-ethynyl-2-methyl-2-pentenyl ester 1R, cis-2,2-dimethyl 3 G () 3-ethoxy-3-oxo-2-bromo-1-propenyl cyclopropane carboxylic acid;

(1RS) 1-ethynyl-2-methyl-hex-2-en 5-ynyl 1R ester, cis-2,2-dimethyl

3 Ј (DE) 3-ethoxy-3-oxo-2-bromo-1-pro-i penyl Cyclopropane carboxylic acid,

(1RS) 1R 1-ethynyl-2-methyl-2-pentenyl ester, cis-2,2-dimethyl 3

cis-2,2-dimethyl 3 (& E) 3-ethoxy-3-ca-40 G (LE) 3-ethoxy-3-oxo-2-chloro-1-propo-2-fluoro-1-propenyl Cyclopropane car - Nile cyclopropane carboxylic acid; side acid;

(RS) IR 2-methyl-2-pentyl ester, cis-2,2-dimethyl-3 (&amp; E) 2-fluoro-3-ox-3-ethoxypropenyl Cyclopropane car (1RS) 1-ethynyl-2- 1-methyl methyl-hex-2-ene 5-yl ester, cis-2,2-dimethyl 3-C (s) 3-ethoxy-3-oxo-2-chloro-1-propene 45 j cyclopropane carboxylic acid;

(1RS) 1R, 1-ethynyl-2-methyl-2-pentyl ester, cis-2,2-dimethyl 3Q &amp; E) 3-tert-butoxy-3-oxo-2-bromo-1-propylene | cyclopropane carboxylic acid; 5o (1RS) 1-ethynyl-2-methyl-2-pentenobonic acid;

(RS) 1R cyano-2-fluoro-3 methyl 2-butenyl ester, cis-2,2-dimethyl 3- (iE) 2-fluoro-3-oxo-3-ethoxypoopenyl cyclopropane carboxylic acid; amp-2-methyl-2E-butenyl ester 1R, cis-2,2-dimethyl 3 (&amp; E) 2-fluoro-3-ethoxy-3-oxo-1-propenyl cyclopropane carboxylic acid;

(RS) 1R, cis-2,2-dimethyl 3 (42) 3-methoxy-3-oxo-1-propenyl 3-cyclopropane carboxylic acid methyl 2-buranyl ether 1R, cis-2,2-dimethyl 3;

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(RS) 1R, cis-2,2-dimethyl 3 1 (3-ethoxy-3-oxo-1-propenyl cyclopropane carboxylic acid; 1-1-ethynyl-2-fluoro-3-methyl-2-butenyl ether;

(RS) 1-ethynyl-2-fluoro-3-methyl-2-butene 1R, cis-2,2-dimethyl 3 (DE) 3 methoxy-3-oxo-2-fluoro-1-propyl cyclopropane carboxylic acid;

(RS) 1-ethynyl-2-fluoro-3-methyl-2-bugenyl ether 1R, cis-2,2-dimethyl 3-L (fc, E) 3-ethoxy-3 oxo-2-fluoro-1 -propenylZcyclopropane carboxylic acid;

(1RS) 1-ethynyl-2-methyl-2-pentenyl ether 1R, cis-2,2-dimethyl)

Lovy ester 1R, CIS-2,2-dimethyl)

3-methoxy-3-oxo-2-bromo-1-propenyl - cyclopropane carboxylic acid;

(RS) 1-ethynyl-2-methyl-hex-2-en 5-ynyl eshir 1R, cis-2,2-dimethyl 3 XD 3 methoxy-3-oxo-2-bromo-1-propyl cyclopropane carboxylic acid

(1RS) 1-R 1-ethynyl-2-methyl-2-pentenyl ester, cis-2,2-dimethyl 3Q &amp; E) 3-methoxy-3-oxo-2-chloro-1-propenyl cyclopropane carboxylic acid; (RS) 1-ethynyl-2-ma, thyl-hex-2-ene

 cyclopropane carboxylic acid;

ORS) 1-ethynyl-2-methyl-2-pentenyl ester 1R, cis-2,2-dimethyl 3 G () 3-ethoxy-3-oxo-2-bromo-1-propenyl cyclopropane carboxylic acid;

(1RS) 1-ethynyl-2-methyl-hex-2-en 5-ynyl 1R ester, cis-2,2-dimethyl

3 Ј (DE) 3-ethoxy-3-oxo-2-bromo-1-pro-i penyl Cyclopropane carboxylic acid,

(1RS) 1R 1-ethynyl-2-methyl-2-pentenyl ester, cis-2,2-dimethyl 3

G (LU) 3-ethoxy-3-oxo-2-chloro-1-propenyl cyclopropane carboxylic acid;

G (LU) 3-ethoxy-3-oxo-2-chloro-1-propenyl cyclopropane carboxylic acid;

(1RS) 1-ethynyl-2-methyl-hex-2-en 5-ynyl 1R ester, cis-2,2-dimethyl 3-C (y) 3-ethoxy-3-oxo-2-chloro-1-prope - or jcyclopropane carboxylic acid;

(1RS) 1R, 1-ethynyl-2-methyl-2-pentyl ester, cis-2,2-dimethyl 3Q &amp; E) 3-tert-butoxy-3-oxo-2-bromo-1-propylene | cyclopropane carboxylic acid; (1RS) 1R, 1-ethynyl-2-methyl-2-petenyl ester 1R, cis-2,2-dimethyl 5C (AE) 3-tert-butoxy-3-oxo-2-chloro-1-propanoic cyclopropane carboxylic acid ;

(1RS) 1R 1-ethynyl-2-methyl-2-pentenyl ester, cis-2,2-dimethyl 5 (AE) 3-tert-butoxy-3-oxo-2-chloro-1-propenyl Cyclopropane Carboxylic acids;

(1RS) 1-ethynyl-2-methyl-hex-2-en 5-ynyl 1R ester, cis-2,2-dimethyl 3

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Ј (& E) 3 Tert-butoxy-3-oxo-2-bromo-1-si-3 oxo-1-propenyl cyclopropane car-propenyl cyclopropane carboxylic acid; lots;

. 1-methyl-2-E 1R peityl ester, cis-2,2-dimethyl-l-3- (DE) 3 ethoxy-3-ox-1-propenyl cyclopropane carboxylic acid;

1-ethynyl-2-methyl-2-E pentyl

ether) R, cis-2,2-dimethyl 30 & 2) 3 by this} about si-3 oxo-1-propenyl cyclopropane si-3-oxo-1-propenyl cyclopropane carboxylic acid; bonic acid;

1-ethynyl-2-methyl-2-E pentenyl ether 1R, cis-2,2-dimethyl 3 C (&amp; 2) 3-isopropoxy-3-oxo-1-propenyl cyclopropane 15, carboxylic acid; pan carboxylic acid; 2-methyl-2-E pentenyl ester 1R,

1R 2-methyl-2-propenyl ester, cis-2,2-dimethyl 3Q &amp; Z) 3 ethoxy-3-ox-1-propenyl cyclopropane carboxylic acid;

1R 2-methyl-2-propenyl ester, cis-2,2-dimethyl) 3 isopropo2-methyl-2-E 1R pentenyl ester, cis-2,2-dimethyl) 2-fluoro-3 isopropoxy-3-oxo -1-propenyl cycloprocis-2, 2-dimethyl 3 C (D) 3-isopropoxy-3-oxo-1-propenyl cyclopropane carboxylic acid;

1-ethynyl-2-methyl-2-E pentavyl ester 1 R, cis-2,2-dimethyl 3 (AZ) toxy-3-oxo-1-propenyl cyclopropane carboxylic acid;

1-ethyl-2-methyl-2-E pentenyl

2-methyl-2-E 1R pentenyl ester, cis-2,2-dimethyl 3 (L2) 3-ethenyl ox.

120 cm3 of ethinyl magnesium bromide suspension in tetrahydrofuran are added,

1R, cis-2,2-dimethyl 3 C (AZ) 3 ethoxy-3-oxo-1-propenyl cyclopropane karsi-3-oxo-1-propenyl cyclopropane carboxylic acid ester.

Bonoic acid; 25% 1-ethyl-2-fluoro-3-methyl ester 1R, cis-2,2-dimethyl 3 t (&amp; E ). 2-fluoro--2-butenol is prepared by the following sposo-3-ethoxy-3-oxo-1-propenyl cyclopropane carboxylic acid;

2-methyl-2-E pentenyl ether tR ,,.

cis-2,2-dimethyl 3 (UE) 2-fluoro-3 label-zo at 0 ° C. add a solution of 2.5 g of si-3-oxo-1-propenyl cyclopropane l-2-fluoropan 2 -bentene, stirred with boic acid; for 17 hours at 20 ° C, at C 2-methyl-2-E pentyl ester 1R, saturated aqueous Chlots-2, 2-dimethyl 3Q &amp; E) 2-fluoro Ammonium H-ether, extracted with ether, niloxy-3-oxo-1-propenyl cyclopropane 35 washed with water, the organic layer, carboxylic acid, concentrated to dryness, the residue is chromatographed on silica, hexane-ethyl ester -2-E pentile u Fir 1R, cis-2,2-dimethyl ZG (E) 2-fluoro-3-tert-butoxy-3-oxo-1-propenyl cyclopropane hydrochloric acid (1-1), and get carboxylic acid; 40 9 & 3 mg of the desired product.

(1RS) 1-ethynyl-2-methyl-hex-2-enIK spectrum (chloroform): absorption

1R 5-ylyl ester, cis-2,2-dimethyl 3-P &amp; E) 3 Tert-butoxy-3-oxo-2-chloro-1-propenyl cyclopropane carboxylic acid in 3990 cmn, assigned to -OH; absorption at 3300 and 3130CM, SnS (n) and.

attributed

lots;

2-methyl-2-E pentyl ester 1R, cis-2,2-dimethyl 3Ј (d2) 3-ethoxy-3-ox-1-propenyl cyclopropane carboxylic acid;

45

PRI me R 63. Preparation of soluble concentrate.

Produces homogeneous mixing of the following components, g: product at

1-ethynyl-2-methyl-2-E pentenyl 50mera 20 °, 25; piperonifer ether 1R, cis-2,2-dimethyl 3 (AE) la 1.00; tween 80 0.25; topanol A

2-fluoro-3-ethoxy-3-oxo-1-propenyl cyc- (2, -dimethyl-6-tert-butylphenol) 0.1;

lopropane carboxylic acid; water 98 ,.

 2-methyl-2-E pentenyl ether 1R, Example 64. Preparation

cis-2,2-dimethyl 3 (& Z) 3 methoxy-3 ca-55 emulsifiable concentrate, co-1-propenyl cyclopropane carboxylic The following compo-acids are well mixed; nenty, g: product of example 17 0.015 ;.

3-methyl-2-pentenyl ether 1R, piperonyl butoxide 0.5j topanol A

cis-2,2-dimethyl 3C (& E) 2-fluoro-3-ethoxy-0.1; twin 80 3,5; xylene 95.885.

 bonic acid;

 si-3 oxo-1-propenyl cyclopropane carboxylic acid;

1R 2-methyl-2-propenyl ester, cis-2,2-dimethyl 3Q &amp; Z) 3 ethoxy-3-ox-1-propenyl cyclopropane carboxylic acid;

2-methyl-2-propenyl ether 1R, cis-2,2-dimethyl) 3 isopropoxy-3 oxo-1-propenyl cyclopropane carboxylic acid;

 pan., carboxylic acid; 2-methyl-2-E pentenyl ether 1R,

2-methyl-2-E pentavyl ester 1R, cis-2,2-dimethyl) 2-fluoro-3 isopropoxy-3-oxo-1-propenyl cyclopropane., Carboxylic acid; 2-methyl-2-E pentenyl ether 1R,

cis-2,2-dimethyl 3 C (D) 3-isopropoxy-3-oxo-1-propenyl cyclopropane carboxylic acid;

2-methyl-2-E 1R pentenyl ester, cis-2,2-dimethyl 3 (L2) 3-ethenyl-hydroxy-3-oxo-1-propenyl cyclopropane carba.

120 cm3 of ethinyl magnesium bromide suspension in tetrahydrofuran are added,

1-ethynyl-2-fluoro-3-methyl--2-butenol is prepared as follows.

,

at 0 ° C, a solution of 2.5 g of tl-2-fluorop-2-butenol is added, stirred for 17 h at 20 ° C, at about 0 ° C the spectrum (chloroform):

at 3990 smn, attributed to pups at 3300 and 3130СМ, СНС (н) и.

PRI me R 63. Preparation of soluble concentrate.

Produces homogeneous mixing of the following components, g: product at15

Example 65. Preparation of emulsifiable concentrate.

Produces homogeneous mixing of components, g: gtrimer product 7 1.5 tween 80 20.00; topanol A 0.1; xylene 78.4.

PRI me R 66. Preparation of smoke-generating composition.

Uniformly mixed, g: product of example 6 0.25 j Taboo powder (powdered leaves of Machylus Thurabergii) 25.00; cedar leaf powder AO, 00; pine wood powder 33.75 brilliant green 0.5; p-nitrophenol 0.5.

Study of the insecticidal and acaricidal activities of compounds of the formula

(I).

The study of the lethal effect on the cockroach.

The experiments are conducted by touching the film by depositing a pipette of acetone solutions of different concentrations to the bottom

one

The study of the biological activity of the product And obtained in example 17, and comparing it with the activity of the product (product B) of the patent of the USSR

thirty

Petri dishes made of glass, the edges of which were previously talkirovany, that-25 No. 1210661 and with bioallethrin. would avoid escaping insects. The temperature at which the lethal concentration of 50 (CLgo) is sprayed is determined. The following results were obtained:

Connection example CL50, mg / m

63.27

270.9

530, V

The study of home flies.

Experienced insects are female flies at home for k days. They act by direct spraying at a concentration of 0.25 g / l in Kearns and Marsh cells, using a mixture of acetone (5%) and Isopara 4o L (petroleum solvent) as a solvent, 2 ml of solvent per second. 50 insects per treatment. Conduct control every minute to 10 mi35

The active substance in the ambient atmosphere exceeds 60 ° C, for example, it may be 80 - 120 ° C.

A priori, it would be possible to refuse to use high temperatures in order to avoid the risk of destruction of the active substance molecule and, consequently, a complete lack of effectiveness.

However, it turned out that product A can be brought to relatively high temperatures while maintaining efficiency.

The following biological test results clearly reveal the remarkable insecticidal properties of Product A, presented in the form of plates or discs intended for chickens, then in 15 minutes and the KT50 45 of the heating is determined by electric

devices, and, in particular, its preimage ways.

The following results were obtained:

Connection examples KT50, min 7h, 78

94.78

174.68

201.74

271.28

562.86

A study of the lethal effect on Aphis Cracivora.

Adult individuals at the age of 7 days and 10 Aphie are used on the use of -.

50

55

compared with bioallethrin.

i

PRI me R 67. Smoke coil. Use the following components, g: Powder Tabu40

Coconut flour 35 Pine Wood Powder10

Starch12.4

Perfume0,5

Salicylanilide1,3

Product A0.8

0116

my concentration. Use the touch-feeding method. The processing is carried out with a Fischer's pistol of a sheet of bean, which is placed in a plastic petri dish on a moistened paper circle. Processing lead 2 ml of acetone solution of the investigated product (1 ml on the side of the sheet). Insects are introduced after the sheet has been dried. The insects are kept in contact with the leaf for 1 hour, and then the insects are laid on untreated leaves and the mortality is checked after 2k hours. Determine, (mg / l).

The following results were obtained: Compound of Example CL50, mg / l 204.37

185,2k

223.26

The study of the biological activity of the product And obtained in example 17, and comparing it with the activity of the product (product B) of the patent of the USSR

No. 1210661 and with bioallethrin. The temperature at which the spray 0

about

35

The active substance in the ambient atmosphere exceeds 60 ° C, for example, it may be 80 - 120 ° C.

A priori, it would be possible to refuse to use high temperatures in order to avoid the risk of destruction of the active substance molecule and, consequently, a complete lack of effectiveness.

However, it turned out that product A can be brought to relatively high temperatures while maintaining efficiency.

The following biological test results clearly reveal the remarkable insecticidal properties of Product A, presented as a plastic

five

compared with bioallethrin.

i

PRI me R 67. Smoke coil. Use the following components, g: Powder Tabu40

Coconut flour 35 Pine Wood Powder10

Starch12.4

Perfume0,5

Salicylanilide1,3

Product A0.8

17

Example 68. Composition intended for electrical heating.

A solution of 0.6 g of product A is adsorbed in 5 cm3 of toluene on the surface of a fibrous inert piece of matter in the shape of a parallelepiped with dimensions of 2x2x XO, 8 cm. The piece is fixed on this piece of wool.

The activity of product A is 20 times higher than that of bioallethrin, while the product of the prior art is completely inactive.

The known substance X indicated in the tests below is 1R, cis-2,2-dimethyl-3- (2,2-dibromovilox material, the second piece of tannyl) cyclopropane-1-carboxylate of the same size. In this way, a smoke composition is obtained which is used by heating it on a plate with electrical resistance.

A comparative study of the activity with respect to Culex pipiens of product A and a commercial product, namely bioallethrin.

The test is carried out in a cubic aerosol chamber with a 3 m side, i.e. volume of 27 m3.

Mature Culex pipiens are placed in cylindrical plastic boxes with a diameter of 10 cm and a height of 3 cm. Both sides of these boxes are covered with a mesh.25 About 25 mature Culex pipiens are used per carton. K boxes are used in each trial, i.e. fourfold repetition of the experiment is carried out. The boxes are placed at a height of 60 cm from the ground at the four vertices of a square with a side of 1 m. The axis of the boxes is set horizontally.

The active substance is introduced in a coil made of inert substances, and a pipette is inserted into a predetermined amount of an acetone solution containing this active substance.

The coil is placed in the center of the aerosol chamber at a distance of 10 cm 4 from the ground. The insect lesions are checked every 2 minutes from the start of combustion 9 for 30 minutes.

Activity testing on mature Ci-Jex pipiens.45

Below are the results of tests of product A compared with biooallethrin and product (product B) of USSR patent No. 1210661, which are expressed in relative power of KT50 50 (knock time 50), mosquito coil). Product Concentration

0.15-ZP,

but-3-phenoxybenzyl.

The activity of substances is expressed in relative power (P).

For the effect of slap relative., Power (P) expresses the ratio between the time required to kill 50% of treated insects (KTgp) using substance X (known) and the time needed to kill 50% of insects treated with a new substance obtained by the proposed method (KJgo expressed in minutes).

Therefore, the relative power (P) determines whether a new substance is more active than the control substance (X). If the new substance is more active, this ratio (P) is -30 more than 1.

The effect of indoor flies Substance X6,370

The substance according to example 1 2.23 Relative power 2,852

Substance X6,370

Example 15, 680 Relative power 1.3 &amp; 1

Substance X8.20

Substance according to example 16 1,677 Relative power 5,021

Substance X7,381

The substance in example 18 1, Relative power, 238

Substance X7,381

The substance according to example 20 1,663 Relative power 4,37

35

Substance X2,821

Substance according to example 21 2,676 Relative power of 1.05 EXAMPLE 69. Comparative test of the activity with respect to Culex pipiens of product A, namely bioallethrin, and the product obtained in the USSR patent tf.

Relative power,% 20

one

ABOUT

5830113

The activity of product A is 20 times higher than that of bioallethrin, while the product of the prior art is completely inactive.

The known substance X indicated in the tests below is 1R, cis-2,2-dimethyl-3- (2,2-dibromvi

but-3-phenoxybenzyl.

The activity of substances is expressed in relative power (P).

For the effect of slap relative., Power (P) expresses the ratio between the time required to kill 50% of treated insects (KTgp) using substance X (known) and the time needed to kill 50% of insects treated with a new substance obtained by the proposed method (KJgo expressed in minutes).

Therefore, the relative power (P) determines whether a new substance is more active than the control substance (X). If the new substance is more active, this ratio (P) is greater than 1.

The effect of indoor flies Substance X6,370

The substance according to example 1 2.23 Relative power 2,852

Substance X6,370

Example 15, 680 Relative power 1.3 &amp; 1

Substance X8.20

Substance according to example 16 1,677 Relative power 5,021

Substance X7,381

The substance in example 18 1, Relative power, 238

Substance X7,381

The substance according to example 20 1,663 Relative power 4,37

Substance X2,821

Substance according to example 21 2,676 Relative power of 1.05 EXAMPLE 69. Comparative test of the activity with respect to Culex pipiens of product A, namely bioallethrin, and the product obtained in the USSR patent tf.

191558301

carried out in cubic (l but

This aerosol chamber with an edge of 3 m, therefore a volume of 27 m3.

Adult Culex pipiens are placed in plastic cylindrical boxes with a diameter of 10 cm and a height of 3 cm. The two sides of these boxes are covered with a net. Use about 25 adult Culex pipiens per box. In each trial, k boxes are used. The boxes are placed at a height of 60 cm from the floor at the four corners of the square with a side of 1 m. The axis of the boxes runs horizontally.

The active substance is contained in coils made of inert materials and in which a predetermined amount of acetone solution containing this active substance is pipetted.

The coil is located in the center of the aerosol chamber at a height of 1 cm, from the floor,

The insect knockout is controlled every 2 minutes and for 30 minutes.

Study of adult activity on Culex pipienso

Below are the results of tests of product A compared with bioalletrin and product (product B) under USSR patent No., which are expressed in relative power of CT50 (knock time, mosquito coil). Product concentration 0.15 30 g.

Product

Relative power,%

Products at-40

measure 17 or product A20 Bioallethrin 1 Product B on the patent

№ 13 0813,9

The activity of product A is 20 times higher than the activity of bioallethrin while the known product is clearly less active.

45

20

Thus, the compounds of formula (l) have a higher insecticidal activity compared with the known analogues.

Claims (1)

Invention Formula The method of obtaining esters of cyclopropanecarboxylic acids and unsaturated aliphatic alcohols of General Formula I Y RQ-C-C CH1 and O five where Y R -% - R5 R R 5 means o tl and h and r. p, g, C-C-alkyl; H, -CHN; F, CH3; H, SNE; H, lower alkyl, —CH —CsCHj E or Z configuration, u sh and so that the acid of general formula II R, 0-C- 0 one NSSN 2 soon where Y, R ,, have the indicated meanings, are reacted with an alcohol of the general formula III Where ReMO HO-CH-C C-R5 k Rs have the indicated meanings. in the presence of dimethylaminopyridine dicyclohexylcarbodiimide.