New esters of related acids cyclopropanecarboxylic to the acid pyrethric, their method of preparation and their application to the fight against the parasites.

T-

the present invention relates to novel willwill estera eyelopropanecarboxyliquee acid-related pyrethric acid, process for their preparation and their application to the pest control " the subject of the invention is composed of formula X

- X represents hydrogen, fluorine, chlorine bromine cm #

R represents an alkyl radical•rawifil # linear or cyclic saturated or unsaturated containing up to 8 carbon atoms optionally substituted, aryl having up to 14 carbon atoms

or an optionally substituted heterocyclic radical optionally

F.

substituted

- Z represents a hydrogen atom, CH radical ^_# c." m or o5ch # and

- Y represents a hydrogen atom # a hydroxy radical is linear alkyl # branched, saturated or unsaturated optionally substituted containing up to 8 carbon atoms a nitroxyl radical, a radical ** Q." alkyl, (HM₂ )_{the m} ~s-alkyl (HM₂ )_{the m} ~tMalkyle) ^ # wherein m represents

the number 0.1# 2, 3 or 4 and containing jusqü ' to 12 carbon atoms # a radical if (alkyl) ^, alkyl represents a linear or branched saturated # cms insaturê, optionally substituted with up to 8 Lenient carbon atoms, a radical-O-aryl or CCH₂ ) - aRs_therein le, aryl is an aryl radical having up to 14 carbon atoms in all forms possible stereoisomers, as well as mixtures of such stereoisomers.

When R represents alkyl saturated, linear or branched it is preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, n-pentyl, n hexyte, tertbutyl, tert-pentyl or neopentyl.

When R represents a cyclic radical, it is preferably of a cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl, an alkyl radical, linear or branched, or a cyclic radical carrying of a cyclopropyl, cyclobutyl, cyclopentyl or cyclohexvle radical substituted with one or more alkyls whose link to the group - C00 - is located on any of its vertices, for example, the radical 1 to-mêthylcyclobutyle, 1 a-methylcyclopentyl, 1 - ' methylcyclohexyl or 2, 2, 3, 3 a-têtraméthylcyclopropyle.

When R represents alkyl unsaturated, it is a radical containing ethylenic, as for example, a vinyl radical or 1.1 and dimethylallyl or radical acetytenic, as, for example, the radical ethynyl or propynyl.

When R is an alkyl radical substituted with one or more functional groups, is meant preferably by alkyl radical containing 1 to 8 carbon atoms, such as, for example, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl or tertbutyl.

When R is an alkyl radical substituted with one or more functional groups, is meant preferably by functional group, a halogen atom, a group OR or SR *' wherein R * represents a hydrogen atom or an alkyl radical containing 1 to 8 carbon atoms /, a group:

NAKED₂ . THE N -

wherein R "and R", identical or different, represent a hydrogen atom, or an alkyl radical containing 1 to 8 carbon atoms, a group - c=n, or Po SOjH ^ hi or a group - COalc -],

^ SOgalc, °u SOsalcs where has the - j-, alk₂ and alcj - nts

feel radicals containing from 1 to 18 alkylated carbon atoms.

R may also represent an alkyl radical substituted by an aryl radical as, for example, the benzyl radical or the radical phénêthyle, itself optionally substituted by one or more group - - OHyOalc or have 1 to 8 comprising carbon atoms, by one or more halogen or group - CFji, OCF31 -, or by a group - SCF31 (grams) 9.ï

R may also represent an alkyl radical substituted on two adjacent carbons by a group (^ grams);

0

0

/ VBE1

H

(E!)

substituted by a group

When R is an alkyl radical substituted with one or more functional groups include as preferred values of R radicals:

" (CHgjn c Hal3 wherein n is an integer of 1 to 3 and Hal a

halogen atom, for example the radical - Ch-DC - ^ T-CHjjCFj "

- CH3_- CH2_- CCl4 or - CH2₂ - HC₂ FS -₃ .

HM -<₂ )_{the n} i-ch-Hal--₂ wherein hal is as defined above and n-j is a number from 0 to 8, for example CH2 - group₂ - CHC1₂ ,

- HC₂ - CHF-₂ or - CHF-₂ the I

" (CH2>_{the n} Hal-wherein n and Hal are as defined above, for example the radical - CH2₂ - HC₂ Cl or - OH₂ - HC₂ F.,

- C lCHaljîj wherein hal is as defined above, by

example a radical - c FCL-to-jîj or

THE X,

FS,

FS - C.

AKT,

- C. ..._CHt

VBE1 FS,

..^FS 3

<- HM - C.₃

vBE1 HM₃

or - Cl

VBE1

, FS₃

- hC₃

- hC₂ - hC₃

SKC,

fS.₃ THE OB 806

The c - ' - HM, or CF₃Y

HM, ^hM 3

The c - - - CN or -<the c " - - NC

' ^ HC,

or " (HM₂ )_{the n} " NC, wherein η is as defined hereinbefore,

ExpressVu.

- Cil_CN

wherein hal is as defined above, for example by the radical

SKC,

c/c -;;

NR

- (^ ^ " OR1^, wherein n is defined as above and R¹ the d * represents hydrogen or a linear or branched alkyl, having from 1 to 8 carbon atoms, for example the radical

- HC₂ - 0CH3 ", - CH2 CH₂ - 0 CH₃ the I, - OH₂ - HC₂ - 0 CH₂ - HC₃ or

- hC₂ - hC₂ the OH -,

THE R '

THE N -:

wherein n and R¹ are as defined above and the two radicals r1 can be different between them, for example the radical

HM,

- hC₂ - hC₂ the n -

HM,, HC₃

- CH2 CH₂ - N or - ch2 Ch₂ THE N~^: ^ CHj•HM₂ - hC₃ *<CH₂ >_{the n} - CH-TO-CH₂

><

hr₃ the c ^ ^ HC₃

wherein n is as defined above, for example by the radical

- hC₂ hM - HM₂

hr₃ the c ^ ^ HC₃

•^(HM 2>the n " 2

OH

wherein n is defined as previously/for example by the radical

- hC₂ - ch ch-₂ the OH -

in vivo

■"(ch2) the n"

wherein n is defined as previously/for example the radical

- -|ch2 O ^ J or - shii-to-shii O

- №) η ^ - 3

as defined hereinbefore wherein nis/for example the benzyl or phenethyl radical/

- (cH2₂ )"

U

wherein n is defined as previously/for example the radical when R represents an optionally substituted aryl radical/it is preferably phenyl or phenyl substituted by one or more OH groups, containing 1 to Oale have 8 carbon atoms/or by halogen or - cf31 - ocf3^or

When R represents a heterocyclic radical/it is preferably pyridinyl, furanyl, thiophenyl, thiazolyl or oxazolyl.

In the definition of Y, in the case of alkyl radicals/it is preferably methyl ethyl // propyl, isopropyl, n-butyl or tertbutyl.

If Y is an unsaturated alkyl/it is an ethylenic group such as ethenyl, propenyl or propadiênyle or radical acetylinic éthynyleou the radical as for example propinyl.

When Y is an alkyl radical substituted with one or more functional groups is meant preferably/functional group by halogen, such as fluorine or bromine.

If Y is an 0-aryl or (CH2₂ )_{the m} aryl is understood to mean aryl preferably by the phenyl radical.

The invention more particularly relates to compounds in which X represents a fluorine atom, and among them, those in which the geometry of the double bond is e.

The invention also relates to the compounds of formula I, in which X represents a hydrogen atom, and among them, those in which the geometry of the double bond is Z.

Among the preferred compounds of the invention, include the compounds of formula I, in which R represents a linear or branched saturated alkyl radical containing up to 4 carbon atoms, as well as those in which Z represents a hydrogen atom and those wherein Y is a radical ch3, (- O-same çhg ^ ^ wherein m is 0 or 1ou noirbre HM₂ THE CH2=CH2 - *

. Among these may be mentioned more particularly have the aforementioned products in examples and particularly those having the following names:

the 1r Ialpha - /, / 3 α (Z-) 2.2-dimethyl 3 - (3 methoxy 3 oxo-1 a-propenyl) cyclopropane carboxylate of (4-methoxy 2, 3, 5, 0 and tétrâfluorophényl) methyl;

the 1r Ialpha - /, / 3 α (Ε) 2.2-dimethyl 3 - (2 fluoro-3 ethoxy 3 oxo-1 a-propenyl) cyclopropane carboxylate of (4-methyl 2, 3, 5, 6 a-tetrafluorophenyl) methyl);

the 1r/1alpha -, 3 α (I/>2.2-dimethyl 3 a-c3 - (1.1-dimethyl ethoxy) 3 oxo-2 fluoro-1 a-propenyl] cyclopropane carboxylate of (4-methyl 2, 3, 5, 6 a-tetrafluorophenyl) methyl;

- cLR, (pgc, 3 α) (I)] - 2.2-dimethyl 3 - (3-ethoxy 2 fluoro-3 oxo 1 a-propenyl) cyclopropane carboxylate of c4 - c2 - propênyl) methyl 2, 3, 5, 6-tetrafluoro phényU;

the 1r Ialpha / -, the alpha 3 (I)/3 / - 2.2 to-dimêthyl 2 fluoro - 3<1_# 1-dimethyl ethoxy-3 oxo-1 a-propênyl/cyclopropane carboxylate of (4-methoxy 2, 3, 5, 6 a-tetrafluorophenyl) methyl;

the 1r Ialpha / -, the alpha 3 (I)/2.2-dimethyl 3 - (2 fluoro-3 a-êthoxy-to-3 oxo-1 a-propenyl) cyclopropane carboxylate of (4 methoxy 2, 3, 5, 6 a-tetrafluorophenyl) methyl;

the ClRC1alpha -, 3 alpha-this)]] 2.2-dimethyl 3 - (2 fluoro-3 ethoxy 3 oxo-1 a-propenyl) cyclopropane carboxylate of the c (4 a-methoxymethyl-2, 3, 5, 6-tetrafluoro) phenyl] methyl;

- the [1RC1alpha, 3 alpha-this)]] 2.2-dimethyl 3 - 00 - 3 (1.1 to-diméthyléthoxy 2 fluoro-3 oxo-1 a-propenyl] cyclopropane carboxylate of the IC (4 a-methoxymethyl-2, 3, 5, 6-tetrafluoro) phenyl] methyl;

the ClRC1alpha -, 3 alpha-this)] 2.2-dimethyl 3 thereof [2 fluoro-3-methoxy-3 oxo-1 a-propenyl) cyclopropane carboxylate of cc4-methoxymethyl-a 2, 3, 5, 6-tetrafluoro) phenyl] methyl.

The compounds of formula I have valuable properties which enable their use in pest control. It may be for example of combating plant pests, parasites premises and parasites from warm-blooded animals.

It thereby can be used the products of the invention for combating insects, nematodes and parasitic mites of plants and animals.

The invention particularly relates to the use of compounds of formula I to the pesticides - plants, parasites premises and parasites from warm-blooded animals,

The products of formula I may thus be used especially for insect control in agriculture, to control for example, against aphids, the cabbage and beetles, as well as for insect control soil. They are used at doses between 10 g and 300 g of active material per hectare.

The products of formula I may also be used to control insects in the premises, for fighting a flies, mosquitoes and cockroaches.

The products of formula I are further photostable and are not toxic to mammals '.

All of these properties to products of formula I products θg $faithful to the requirements 1' modern agrochimiqgp industry: they provide privacy crops while preserving the environment.

The products of formula I may also be used to control mites and plant parasitic nematodes.

The comjbosés of formula I can also be used to combat the açafiens<animal pests, for example against the fight

•pques CD especially ticks of the species of Boophilus, those of the species Hyalorçnia, those of the species Amblyomnia and those of the species Rhipicephalus or to combat all sorts of gall and especially the scabies, the mange and scabies chorioptic.

The invention therefore also relates to pharmaceutical compositions for the control of parasites in warm-blooded animals, pests premises and plants, characterized in that they comprise at least one of the products of formula I defined above and particularly the products of formula I.

The invention has for its object the insecticidal compositions containing as active ingredient at least one of punching the above-defined products. ."

These compositions are prepared according to conventional methods for industry agrocjximic or veterinary or industry products for animal nutrition.

In these compositions for agricultural usage and premises, the active materials can be added optionally one or more other pesticidal agents. These compositions may be in form of powders, granules, suspension, emulsion, solution, solutions for aerosols, strips fuels, bait or other preparations used conventionally for the use of such compounds.

In addition to the active ingredient, the compositions comprise, in general,

a vehicle and/or a surfactant, nonionic, providing, further, a uniform dispersion of substances that make up the mixture. The vehicle used - may be a liquid, such as water, alcohol, hydrocarbons or other organic solvents, mineral oil, animal or vegetable/powder such as talc/clays/silicates/kieselguhr or solid fuel.

The insecticidal compositions according to the invention preferably contain de .0/005 X 10 X by weight of active material.

According to an advantageous procedure, for use in the premises, the compositions of the invention are used as compositions fumigantes.

The compositions of 1' invention may then advantageously be made, for the inactive portion, an insect coil (or coil) fuel, or a noncombustible fibrous substrate. In the latter case, the fumigant obtained after incorporation of the active material is placed on a heating apparatus such as a electrical emanator.

In the case of employing an insect coil, the inert support can be, for example, pyrethrum marc compound, Tabu powder (or MachilusThumbergii leaf powder), pyrethrum stem powder, cedar leaf powder, wood powder (such as pine sawdust) starch and powder of coconut shell.

The dose of active material can then be, for example, of 0.03 to 1% by weight.

In the case of employing a noncombustible fibrous carrier, the dose of active material can then be, for example, of 0.03 to 95% by weight.

The compositions of the invention for use in the premises may also be obtained by preparing a pulvêrisable oil based active ingredient, this oil soaking up the wick of a lamp and then being subjected to combustion.

The concentration of the active ingredient incorporated into the oil is, preferably, of 0.03 to 95 X in weight.

The insecticidal compositions according to the invention, since the compositions acaricides and nematicides, may be added optionally one or more other pesticidal agents. Acaricidal and nematicidal compositions can be in the form of powder, granules, suspension, emulsions, solution.

For use acaricidal, preferably used powders mouil-to-Labiés, for foliar spray, containing 1 to 80 X or liquids for foliar spray containing 1 to 500 g/l of active ingredient. There can further be used for powder-containing 0.05 to foliar powderings 3% of active material.

For use nematicide, preferably liquids used for soil treatment of 300 to 500 g/l conenant active principle.

And nematicidal acaricidal compounds of the invention are used, preferably, at doses between 1 and 100 g of active material per hectare th.

To enhance the biological activity of the products of 1 'may be made be admixed with synergists employed conventional in such a case as the 1 - (2, 5, 8 a-trioxadodecyl) 2 a-propyi 4.5 to-methylenedioxy benzene (or butoxide pipêronyte) or n - (2-ethyl hepyl) bicyclo-/ 2.2 - 1/5-heptene-to-2.3-dicarboximide derivatives, or the pipêronyl-bis 2 - (2' n-butyloxy êthoxy) êthylacêtal (or tropital).

The compounds of formula I exhibit excellent tolerance

general, and the invention therefore also relates to the products of formula I, for fighting against diseases caused by ticks and gall in humans and animals.

The products of the invention are particularly useful for control of the lice th preventive or curative as against scabies.

The products of the invention can be administered externally, by spraying, by shampoo, bath or by painting.

The products of the invention for veterinary use may also be administered by swabbing backbone according to the method designated method "for on earth".

Can also indicate that the products of the invention can

be used as biocides or growth regulators.

The invention also relates to the associations activity.in insecticidal, acaricidal or nematicidal, characterized in that they contain as active material, on the one hand at least one of compounds of general formula I, and on the other hand, at least one of ester pyrethroids selected from the group consisting of esters of allêthrolone, alcohol 3Æ ^ S, .6-to-têtrahydrophtalimido methylic, 5 benzyl alcohol 3-furyl-methylic, alcohols 3-phenoxy benzyl alcohols and alpha-cyano 3 a-phênoxy chrysanthemic benzylic acids, esters of alcohols 5 benzyl 3-furyl-methylic acids 2.2-dimethyl 3 - (2 - methyl οχο 3 a-tetrahydrothiophenylidene) cyclopropane 1-carboxylic acids, esters of benzyl alcohol 3 a-phênoxy and alpha-alcohols-cyano-benzyl of 3-phenoxy, acids 3 - 2.2 to-dimêthyl (2.2 above dichlorovinyl) cyclopropane 1-carboxylic acids, esters of alcohols perse alpha-cyano 3-phenoxy benzyliqufs " acid 2.2-dimethyl 3 - (2.2 to-dibromovinyl) cyclopropane 1 a-carboxyHques, esters of alcohols 3-phenoxy benzyl acids 2 to-parachlorophényl 2-isopropyl-acetic acids, esters by the ai * léthrolopes/alcohol 3, 4, 5, 6 a-tetrahydrophtalimidomethylic, 5 benzyl alcohol 3-furyl-methylic *, .'d ' alcohol 3 a-phênoxy benzylic alcohols and alpha-cyano 3-phenoxy benzylic acids 3 - 2.2 to-dimêthyl (2, 2, 2 a-tètrahaloèthyl 1>) cyclopropane 1-carboxylic acids, wherein "haloalkyl" represents a fluorine atom, chlorine or bromine/it being understood that the compounds (I-) may exist in all their stereoisomeric forms possible Copula model as well as the acids and alcohols esters pyrethrinoid above.

The invention also relates to a process for preparing the compounds of formula I characterized in that a acid of formula II;

the c / \ α=c .A_ difficulty HM₃ ■co2h year

RO2C

wherein a functional derivative of this acid in which. X and R retain their previous meaning/to the action of an alcohol of the formula III:

HO GH THEREIN (III-}

or a functional derivative of this alcohol wherein Y and Z retain their previous meaning to obtain the corresponding compound of formula I.

The compounds of formula II are known products described in the European patents 0038271, 0041021, 0048186, 0050534.

. The compounds of formula III in which Z represents hydrogen are generally known compounds; they can be prepared for example according to the methods described in the European Patent Application 0031199, in the patents Americans 4370346, 4405640, in the Patent or in British English 2171994 protective tube-conferencing pis NDA Desease 1986 on page 199.

The products of formula III wherein Z is not hydrogen are new products. They can be prepared according to the reaction scheme:

When it is desired to prepare a product of formula III in which Z represents a methyl radical VBE1/reacting the product of formula VI with URIs hâlogënuré methylmagnesium, for example methylmagnesium iodide.

When it is desired to prepare a product of formula III wherein Z is a radical c=n, reacting the product of formula III with an alkali metal cyanide such as sodium cyanide or potassium.

Some other products of formula III whose preparation is given below are also new products and are in themselves an object of the present invention.

The invention also relates to a variant due above method characterized in that a acid of formula IV:

wherein X, Y and Z retain their previous meaning, to the action of an alcohol of formula V:

WITH ROH (V.)

wherein R retains its previous meaning to obtain the corresponding compound of formula I.

The following examples illustrate the invention without however limiting same.

Example 1 : 1R Ialpha/(the R, O) 3 α (I? / 2.2-dimethyl 3 - (2 fluoro-3-ethoxy -3 a-οχο-a 1 a-propénylî cyclopropane carboxylate of 1 - (4 methyl 2, 3, 5, 6 -tetrafluoro-phenyl) ethyl

Introduced to ONC 950 mg of dicyclohexylcarbodiimide in a solution including " 1/g acid 1r Ialpha (the R, O) 3 (I)/alpha-2.2-dimethyl 3 c2 fluoro-3 ethoxy 3 oxo-1 a-propenyl) cyclopropanecarboxylic acid, 910 mg of alcohol alptia-to-mêthyl 4-methyl 2, 3, 5, 6 a-têtrafluoro benzyl, 20 cm3 of methylene chloride and 50 mg of e-dimethylaminopyridine. The reaction mixture was stirred for 5 hours at one derivatives, eliminates the formed precipitate by filtration_# and flush the solvent under reduced pressure. Obtained 2/12 g of a produitque is silica chromatography by eluting the mixture by hexane isopropyl ether (8 - 2). Obtained 1/6 g of desired product:

* + 41 "+ 1.5" CHCl ce=1%₃ ).

Examples 2 to 20 9.ï

By operating as to the example 1/by following the reaction scheme:

Having obtained the following products:

Example 2 ii 1R/1alpha CR39, e) in the alpha 3)/2.2-dimethyl 3 a-c2 fluoro-3 - (1, 1 -dimethyl ethoxy? 3 oxo-1 a-propényU cyclopropane carboxylate of 1 - (4-methyl 2/3/S/6~tétrafluorophényt) ethyl

alphaj)* +50/5 " as ha (1/3% Islanders CHCI3)

Example 3 : 1R/Ialpha (R._# S) the CZ-alpha 3)/2/2-dimethyl 3 a-c3-methoxy-3 oxo-1 -propenyl) cyclopropane carboxylate of 1 - (4 methyl-2/3/5/6 a-tetrafluorophenyl) ethyl

The alpha_D "+ 1"=+ 58 (1/2=C. %CHCI3)

Example 4 :an IR/dienophil (r/s) (W)/3 α / 2 3 2-dimethyl - (2 fluoro-3-ethoxy -3 oxo 1 a-propenyl) cyclopropane carboxylate of a cyano (4 a-méthyl~2, 3, 5, 6 ~tét the Rafluorophenyl) methyl

"+ 1" AlphaD ≈ +31/2 (c=1.3 XCHCI3)

Example e the Ilr/1alpha (R._# S) the alpha 3/2/(Z-) 2-dimethyl 3 - (5-methoxy-3 oxo-1 -propenyl) cyclopropane carboxylate of a cyano (4 methyl 2/3# 5/6-tetra-fluoro-phenyl) methyl

The alpha_D "^ 1/5"=+ 39 (c=0/85% CHCl₃ )

Example 6 : 1R Ialpha/(the R, O>3 alpha-this)/2_# 2-dimethyl 3 a-c2 fluoro-3 - (1_# 1 -dimethyl-ethoxy) - 3 oxo-1 a-propényll cyano-cyclopropane carboxylate (4 -methyl 2, 3, 5, 6 a-tetrafluorophenyl) methyl

The alpha_D + 19A + 1a=(X-c=1 CHCl₃ >

Example 7 ;1R Ialpha /, / 3 α (Z-) 2.2-dimethyl 3 - (3 methoxy 3 oxo-1 a-propenyl) cyclopropane carboxylate of (4 methyl 2, 3, 5, 6 a-tetrafluorophenyl~) methyl

The alpha_D n + 20b + ln (X-c=0.9 c13>H

Example 8 O1R/1alpha, 3 α ' (I)/2.2-dimethyl 3 - (2 fluoro-3 ethoxy 3 oxo -1 a-propényt) cyclopropane carboxylate of (4-methyl 2, 3, 5, 6 a-tetrafluorophenyl) methyl)

The alpha₀ + 4=" + 1n (c=0.95% CHCI3)

Example 9 ;1R/1alpha, the alpha 3 (I)/2.2-to-diméthyt - 3 b (1.1-dimethyl ethoxy) -3 oxo-2 fluoro-1 a-propényll cyclopropane carboxylate of (4-methyl 2, 3, 5, 6 -tetrafluorophenyl) methyl

AlphaD=19, 2a (c=1.3 XCHCI3)

Example 10 the Ilr/1alpha, 3 α (Z-)/2.2-to-dimethyl 3 - (3 a-méth0xy-to-3 oxo-1 a-propenyl) cyclopropane carboxylate of (4-methoxy 2, 3, 5, 6 a-tetrafluorophenyl) methyl :

Alphajj + 17=π + 1a (c=0.75 %CHCI3)

Example 11 ;1R/Ialpha, 3 α (W)// - 2.2 to-diwëthyl 3% 3 - flouro - (1, 1 -dimethyl ethoxy) - 3 oxo-1 a-propényl7 cyclopropane carboxylate of (4-methoxy 2, 3, 5, 6 a-tetrafluorophenyl) methyl

F=76ac alfa_D 13=π + 1, 5a + (X-c=0.8 CHCI3)

Example 12 :1R/Ialpha, the alpha 3 (I)/2.2-to-dimethyl 3 a-c2 fluoro-3 ethoxy 3 -oxo 1 a-propenyl) cyclopropane carboxylate of (2, 3, 5, 6-tetrafluoro 4-methoxyphenyl) methyl

The alpha_D =- 1, 5a + 1, 5a (CHCl3 was X-e=0.75)

Example 13 ;1R/Ialpha, the alpha 3 (I)/2.2-to-àinéthyl 3 a-c3~(1.1 to-diffléthyl ethoxy) -3 oxo-2 fluoro-1 a-propényl3 cyclopropane carboxylate of 2, 3, 5, 6-tetrafluorophenyl methyl

The Alphajj=+ 22, 5a (c=1 X-ch-LC 3)

Example 14 ;1R/Ialpha, Salpha (Z-)/2.2-to-dimethyl 3 - (3 - οχο 3 a-inéthoxy-a 1 -propenyl) cyclopropane carboxylate of methyl 2, 3, 5, 6 a-tetrafluorophenyl âlpha 50ac F._D (C=0.9% CHCI3)=+ 27a + 1a

Example 15 ;1R/Ialpha, 3 α (W) 3 7 2.2-to-dimethyl - (3 - οχο 3-ethoxy - 2fluoro 1 a-propenyl) cyclopropane carboxylate of 2, 3, 5, 6 a-tetrafluorophenyl methyl

Α=π ℮ 50 F._D =- 21n + 1, 5a (c=0.7 X-CHCl₃ )

Example 16 ;lr/2alpha, 3 α (Z-)/2.2-to-dimethyl 3 - (3 oxo-3-methoxy-1 -propenyl) cyclopropane carboxylate of 4 a-d1méthylarino 2, 3, 5, 6 a-tétnf fluoro " phenyl methyl

The alpha_D (C=0.7% HCC 3) ≈ + 14b + 1, 5a

Example 17 :1R/Ialpha, the alpha 3 (I)/2.2-dimethyl 3 a-c3 -<1.1-dimethyl ethoxy) -2 fluoro-3 oxo-1 a-propényUcarfaoxylate cyclopropane derivatives of 4 a-diméthylaBinomethyl 2, 3, 5, 6 a-tetrafluorophenyl

The alpha_D =+ 9a + 1, 5a (_C.CHCI3=0.4%)

Example 18 ;1R/1alpha, 3 α (I? / 2.2-dimethyl 3 a-c2 fluoro - 3 oxo 3ethoxy-1 a-propenyl) cyclopropane carboxylate of 4-dimethylamino - 2, 3, 5, 6tetrafluorophenyl methyl

A - 2, 5a + 2a AlphaD (c=0.6 %CHCl₃ >

Example 19 ;1R/Ialpha, the alpha 3 (I)/2.2-dimethyl 3 a-d - (1.1-dimethyl ethoxy)

- 2 fluoro-3 oxo-1 a-propenyl) cyclopropane carboxylate of 4 - (2 a-propenyl) 2, 3, 5, 6 a-tetrafluorophenyl methyl

The alpha_D =+ 16a + 1a (c has 1% CHCl₃ >

Example 20 ;1R/Ialpha, 5 α (Z-)/2.2-dimethyl 3 - (3 - οχο 3-methoxy 1" propenyl) cyclopropane carboxylate of 4 - (2 a-propenyl) 2, 3, 5, 6 a-tetrafluorophenyl methyl

The alpha_D s + 6, 5a as ha (=C. Π CHCI3)

Example 21 : 1R Ialpha /, / 3 α (Z-) 2.2-dimethyl 3 - / 3 - (1.1-dimethyl ethoxy)

3 - 1 - propenyl - οχό - cyclopropane carboxylate of //(4-methoxy 2_< 3_J .5_J 6. - " tétrafluoro)/phenyl methyl

Λ / 60nc F.

The alpha_D 1N=a T + 27a (c=1% CHCI3)

Example 22 : 1R/1alpha, 5 alfa (I)/2.2-dimethyl 3~/ 2 f/2, 2, 2 - fluoro - 3(-trifluoro methyl) ethoxy/3 oxo-1 a-propenyl/cyclopropane carboxylate of/(4" 2, 3, 5, 6-tetrafluoro methoxy) phenyl/methyl

=π ℮ 69 F.

The alpha_D =- 2a + 1a (c has 1% CHCI3

Example 23 : 1R Ialpha /, / 3 α (Z-) 2.2-dimethyl 3 - / 5 - (2, 2, 2 a-triflouromethyl 1 - methyl-trifluoro</? / ethoxy 5 a-οχο-a 1 a-propenyl/cyclopropane carboxylate of/c4-methoxy 2, 3, 5, 6-tetrafluoro)/phenyl methyl

F=78ac

The alpha_D 5, 5A + 1a +=(_C. has 1% CHCI3

Example 24 : 1R/Ialpha, the alpha 3 (I)/2.2-dimethyl 3 a-à2 fluoro 3-methoxy - 3oxo 1 a-propényU cyclopropane carboxylate of //(4-methoxy 2, 3, 5, 6-tetrafluoro) /phenyl methyl

The alpha_D a + 5" + 2a (c=0.7% CHCI3

Example 25 : 1R/Ialpha, the alpha 3 (I)/2.2-dimethyl 3 - / 3 - (1.1-dimethyl ethoxy) 2 fluoro - 3 (1 a-propenyl) οχο / cyclopropane carboxylate of 4-ethoxy/2, 3, 5, 6 -08806

-tétrâfluoro/phenyl methyl

The alpha_D Ψ=24, 5 η of £2a (c=0.5 %CHCI3)

Example 26 O tr/1alpha, 3 alpha-this)/2.2-dimethyl 3 - / 2 fluoro 3-methoxy 3 tert-propenyl qxocyclopropanecarfaoxylate of // 4 ethoxy 2, 3, 5, 6 ...tétrafluoro/phenyl methyl

The alpha_D e ·Η 2a<c * 0.4 ¾ CHCI3 β + 7)

Example 27%1R/1 α, α (W) 3/2.2-dimethyl 3 - (2 fluoro - 3 3-methoxyoxo 1 a-propenyl) cyclopropane carboxylate of (2, 3, 5, 6 - 4-methylthiotétrafLuorophênyl) methyl

Alphap=+ 1b + 2a (c=0.5 %CHCI3)

Example 28 : 1R/Ialpha, 3 alpha-this)/2.2-dimethyl 3 - (2 fluoro-3-ethoxy - 3oxo 1 a-propenyl) cyclopropane carboxylate of (2, 3, 5, 6 - 4-methylthiotêtrafluorophênyl) methyl

Atphâ_D 2 Π + ≈ + 4, 5a _ (c=0.6 %CHCI3)

Example 29 : lr/1alpha, the alpha 3 (I)/2.2-dimethyl 3 - 3<2 fluoro) - (Τ, 1 -dimethyl ethoxy) 5 oxo-1 a-propênyt) cyclopropane carboxylate of (4-methylthio 2.3.5.6 tétrafluorophênyl -? methyl

The alpha_D =+ 5a + 2a (c=0.5 %CHCI3)

Example 30 9.ï 1R/Ialpha, the alpha 3 (I)/2.2-dimethyl 3 - (2 fluoro-3-methoxy-3 the oxo 1 a-propenyl) cyclopropane-de/4 - (difluoromethoxy) carfaoxylate 2, 3, 5, 6 -tFWs rafluorophênyl) methyl

The alpha_D 20:00 + 1 +® " ce=1 ' %' chçl₃ ) -

Example 31 ; 1R/Ialpha, the alpha 3 (I)/2.2-dimethyl 3 - / 3lc1, 1-dimethyl ethoxy) 2 fluoro-3 oxo 1 a-propenyl // of the cyclopropane carfaoxylate4jCdifluorométhoxy) 2, 3, 5, 6, a-TFWs inducable luorophênyl) methyl

Alphap + 22=" + the (_C. 1% - CHCl₃ )*

Example 32 5 lr/1alpha, 3 alpha-this)/2.2-dimethyl 3 - 3 are different, 1-dimethyl ethoxy) 2 fluoro-3 oxo 1 a-propenyl or cyclopropane carfaoxylate/de/4 - (bromod1fluoromèthoxy)/phenyl methyl 2, 3, 5, 6 a-tètrafluoro

AlphaD=1 + ό, 5 π + 2a (c - 0.5% CHGI3)

Example 33 O 1R/Ialpha, 3 alpha-this)/2, 2 - (3 - fimèthyl (2 fluoro 3-methoxy - 3the oxo 1 a-propenyl)-cyclopropane carboxylate (bromodifluoro methoxy) - de/4 - tetrafluoro phenyl methyl/2.3.5.6

The Alphap=+ + 7a CHCI3 ce=1%).•

Example 34 : 1R/1alpha, 3 alpha-this)/2.2-dimethyl 3 - / 2 fluoro 3-ethoxy 3 oxo 1 a-propênyl // cyclopropane carboxylate of (methyl 2, 3, 5, 6 - 4 to-mêthoxytetrafluoro)/phenyl methyl

Η + 1 has 5 s + 7, AlphapCHCI3 ce=1%) -

Example 35 O 1R/1alpha, α (Z-) 3/3 / - 2.2 to-dimêthyl 5-methoxy 1 - 3 oxo , /* propenyl or cyclopropane carfaoxylate of/(4-methoxy methyl 2.3>5, 6 -tétraftuoro) phenyl /" ethyl

Α,, ≈ + 23n + 1" (≈ 1 C. CHCl3 was 9.ï)

36 Exewple O lr/1alpha, α (W) 3/3 / - 2.2 to-diwéthyl - 3 (1.1 to-diwéthyl ethoxy) 2 fluoro 3 oxo 1 a-propényt cyclopropane carboxylate of //(4 a-wéthoxywéthyl2, 3, 5, 6-tetrafluoro)/phenyl methyl

(C=1% CHCI3) ≈ + 19, 5n + 1:00 alpha

37 Exewple : 1R/Ialpha, the alpha 3 (I)/2.2-to-diwéthyl 3 and 72 fluoro - 3 a-wéthoxy 3the oxo-L-propenyl // cyclopropane carboxylate of (2, 3, 5, 6 - 4 to-mèthoxywéthyltetrafluoro) phenyl/wéthyle

Α,,=+ 7b + 2a (c=0.5 %CHCI3)

38 Exewple : 1R/1alpha, α (W) 3/3 / - 2.2 to-diwéthyl 3-ethoxy 2 fluoro 3 oxo 1 a-propenyl-cyclopropane carboxylate/de/4 (2 a-propenyl) 2, 5, 5, 6-tetrafluoro /phenyl methyl

Α,, ^ 2 + a + 11, 5a " (c=0.5 % toluene)

39 Exewple 9.ï 1R/Ialpha, 3 α (Z-)// - 2.2 to-diwéthyl 3/3 - 2, 2, 2 a-triUupro-a 1 -(trifluorowéthyl) èthoxy / - 3 oxo-cyclopropane carboxylate 1 a-propenyl/de/4 (2 -propényt) phenyl 2, 3, 5, 6/wéthyletétraftuoro

F=58bc

Α,,=+ 5, 5a 1a (_C.CHCI3=1%)

40 Exewple 9.ï 1R Ialpha /, / 3 α (I) 3 - 2.2 to-diwéthyl/2 fluoro 3 - (1, 1 -diwéthylèthoxy? 3 oxo-cyclopropane carboxylate 1 a-propenyl/de/4 (2 a-propynyl) 2, 3, 5, 6-tetrafluoro phenyl/wéthyle

Α,,=+ 16.5 " + 1a (c=1% CHCI3)

41 Exewple O 1R Ialpha /, / 3 α (I) 3 - 2.2 to-diwéthyl/2 fluoro-3 a-inéthoxy - 3the oxo-cyclopropane carboxylate 1 a-propenyl/de/4 (2 a-propynyl) - 2, 3, 5, 6tetrafluoro/phenyl methyl

Α,,=+ + 8b (c=1% CHCI3) the

42 Exewple : 1R Ialpha /, / 3 α (I) 3 - 2.2 to-diwéthyl/2 a-ftuoro and 3 - (1, 1 -diwéthylèthoxy) 3 oxo-cyclopropane carboxylate 1 a-propenyl/de/4 (1, 2 -propadienyl)/methyl 2, 3, 5, 6-tetrafluoro phenyl

Α,,=+ 9, 5 β + 1n (c=1% CHCl3 was)

43 Exewple : 1R Ialpha /, / 3 α (I) 3 - 2.2 to-diwéthyl/2 fluoro - 3 a-wéthoxy 3' 1 a-propenyl substituted oxo-cyclopropane carboxylate/de/4 (1.2 to-propadienyt) 2,, 3, 5, 6 -tétraftuoro/phenyl methyl

Α,,=+ 2n + 1a (_C. THE X 1=CHCI3)

44 Exewple : 1R/1alpha, the alpha 3 (I)/2.2-dimethyl 5 - / 2 fluoro - 3 a-wéthoxy 3the oxo 1 a-propenyl cyclopropane carboxylate of // / tétraftuoro phenyl 2, 3, 5, 6 wéthyle

F=83" C.

AlphaD _ +_{19/5 n} (c=1 X-toluene)

, 3. a alpha (Ε)/2.2 di "éthrt-a 3 - / 3 cm-to-dî" ethyl ethoxy) cyclopropane carboxylate of (4 cyano 2, 3, 5, 6 -

: 87:00 THES - F.

ÂtphâB=+ + 14 ¾ 1st '. (c=1%

Example O 1R/1alpha, 3 α (I) ^ 1/2.2 π ΐ℮ΐΗ γ-L 3 - / 2 to-ΐluoro 3-methoxy-3 oxo-tert-propenyl/cyclopropane carboxylate of (4 cyano - 2, 5, 5, 6 a-tfetrafluoro

Α ^=ψ CHCI3 13 X-β + 1a ce=1)

47 the g ' 1R/Ialpha, 5 alpha-this)/2.2-dimethyl 3/3-ethoxy - 2 fluoro - 3 - propenyl / οχο cyclopropane carboxylate of 4/4 a-phényt methyl 2, 3, 5, 6 a-tetrafluorophenyl

F€ 50 C.

Α ^="+ 2" -12 CHCI3 ce=0.5%)

Example 4 β O 1R/1alpha, 3 alpha-<th? / 2.2-dimethyl 3/<1~3^1 a-diwéthyl ethoxy) 2 fluoro 3-oxo-propenyl-cyclopropane carboxylate/m-phenyl 2, 3, 5, 6 a-tétrafluorophényl methyl

r=90bc

The alpha_D "+ 1"=-5.5 (_C. =1 %CHCI3)

Example 49%1R/Ialpha, 3 α (i.e.(internal excitation)/2.2-dimethyl 3 - / 2 fluoro 3-methoxy 3 oxo-1 a-propenyl/de/4~-cyclopropane carboxylate (phenylmethyl)/methyl 2, 3, 5, 6 a-tétrafluorophényl

Alphap + 5="JH are 1" CHCI3 ce=0.8%)

Example OS grams 1R/Ialpha, the alpha 3 (I)/2.2-dimethyl 3 - / 5 (1.1-dimethyl ethoxy 2 fluoro 3 oxo-1 a-propenyl // cyclopropane carboxylate of 4 a-Cphénylméthyl) I ^ ^ e/e-to-tetrafluorophenyl methyl

F - 108" C.

The alpha₀ 7 ψ π ^ 5 sec. + 1:00 (c.. 1 - %CHCl₃ >

Example 51 grams lr/1alpha, 3 α (Z-)/2.2-dimethyl 3 - / 3 - (2, 2, 2 trifluoro-1 --trifluoro - methyl? ethoxy/5 a-οχο-a 1 a-propenyl/cyclopropane carboxylate of/ACmethyl 2, 3, 5, 6-tetrafluoro) phènyl/methyl

¢ 50 Β℮ F.

8 Ψ alpha=η + 1" (c=1% CHCl3 was)

Example 52 : an IR/talpha, 3 α (I? / 2.2-dimethyl 3 - / 2 fluoro-~3 ~méthoxy-a 3 -oxo 1 a-propenyl/cyclopropane carboxylate of/(4-methyl 2, 3, 5, 6-tetrafluoro) phènyl/methyl

Âlpha_D ; e + 4 "+ 2" ' (c=0.7% CHCI3)*

Example 53 - O iRnalpha, 3 alpha-this)// 3 - 2.2 to-dimethyl 2 fluoro-3-butoxy 3 -_{the Ox} ^₃ "' dd.■, w_{^ CENTS} the P_{the L} §_{the n}yj [cyclopropane carboxylate of //(4-methyl 2, 3, 5, 6-tetrafluoro) Step a

1R/Ialpha, the alpha 3 (I)/2.2-dimethyl 3 - / 3-hydroxy 3 oxo-1 a-propenyl/cyclopropane carboxylate of/(4-methyl 2, 3, 5, 6-tetrafluoro) phênyl/methyl is heated to 130 π ℮ during 1 hour 3/83 g of product prepared as in example 9 in ^ 38/5 cm in toluene in the presence of paratoluene sulfonic acid 0/385 g of. Allowed to return to ambient temperature/washed with water/dry and the solvents removed under reduced pressure/3/75 and obtains f2 * 90 - 95oc expected g of product.

1R/Ialpha, the alpha 3 (I)/2/3/2-dimethyl - 3 hydroxy-3 oxo-1 a-propênyl cyclopropane carboxylate of //<4-methyl 2, 3, 5, 6-tetrafluoro)/phenyl methyl by processing step a by butanol in methylene chloride in the presence of dicyclohexyl carbodimide and/dimethylaminopyridine to give the desired product.

AlphaD." - 32/50 + 2o (_C. The X=CHCl 0/5₃ >

By operating in the same manner/using the appropriate alcohol/prepared the following products.

Example 54 : 1R/1alpha, the alpha 3 (I)/2 3/2-dimethyl - (2 fluoro-3-butoxy-a 3 -oxo 1 a-propenyl/cyclopropane carboxylate of/(4-methyl 2, 3, 5, 6-tetrafluoro) /phenyl methyl

The alpha_D 19 - / 5=π + 2o (c=0.4% CHClj)

Example 55 : The alpha 1 r/1,, the alpha 3 (I)/2.2-dimethyl 3 - / 2 fluoro-3 a-c1-methyl)êthoxy-to-3 oxo-1 a-propenyl // cyclopropane carboxylate of (2, 3, 5, 6 - 4-methyltetrafluoro)/phenyl methyl

Α))=- 4o + 2n (_C.CHCI3=0.6%)

Example 56 : 1R/Ialpha, the alpha 3 (I)/2.2-dimethyl 3 - / 3-ethoxy - 2 fluoro-3oxo 1 a-propenyl/cyclopropane carboxylate of (4 hydroxy 2.3_# 5/6-tetrafluoro phenyl) methyl

1R/Ialpha, 3 alpha-<th)/2.2-dimethyl 3/3 ethoxy 2 fluoro-3 oxo-1 a-propenyl-cyclopropane carboxylate/de/4 - (dimethyl (1.1-dimethyl) silyloxy groups/2/3 ethyl, 5/6-tetrafluoro/phenyl methyl.

a operates as corresponding to example 1 from the acid and alcohol and relevant ' obtains the desired product.

IR spectrum (CHCI3)

Aromatic 1656 - 1515 - 1497 cm "¹

C=0 1727 cm "¹

1R/Ialpha, the alpha 3 (I)/2.2-dimethyl 3/3-ethoxy - 2 fluoro-3 oxo-1 a-propênyl/cyclopropane carboxylate of (4 hydroxy-methyl/phenyl 2, 3, 5, 6-tetrafluoro

4®C. is cooled to 1.8 g of the product obtained in step a in 5 cm³ of têtrahydrofuranne and adds in 5 minutes to 3.5 cm³ a solution of fluoride in the têtrahydrofurannetêtrabutylammonium (MI). Was stirred 30 min, is poured onto a frozen aqueous solution of ammonium chloride, extracted êther, washed with water, and removing the solvent under reduced pressure. After chromatography on if running (eluent hexane ethyl acetate 1 - 1) to give the desired product.

The alpha_D Ψ=5, 5 θ + 1:00 tee " CHCI3 0.8%)

Preparation 1s alcohol aIpha-to-méthy1-a 2, 3, 5, 6-tetrafluoro benzyligue

3.2 Cm 30 min is introduced in³ methyl iodide in a suspension containing 1 g of magnesium and 30 cm³ ethyl ether and stirred for 30 minutes at left.

0 ≈ 0 R4II cools at 30 min and introduces into 4 g of 4-methyl 2, 3, 5, 6 a-têtrafluorobenzaldêhyde and ' 100 cm³ ethyl ether,

The reaction mixture was stirred for 1 hour to one and poured in 150 cm³ of an aqueous solution saturated with ammonium chloride. Extracted I-ether, dry the phases éthérêes and causes dry under reduced pressure.

The crude product obtained is chromatographed on silica by eluting the mixture hexane isopropyl ether (8 - 2). 3.85 G of product is obtained the RF sought^O 0.10.•

Preparation 2 e alpftâ cyano alcohol 4 a-methyl 2, 3, 5, 6 a-têtrafluorobenzyligue

1.66 Is introduced. - g of sodium cyanide in a mixture containing

4 g of 2, 3, 5, 6 a-têtrafluorobenzaldêhydemêthyl 4, 70 cm³ methyl alcohol and 20 in? water, cools to one derivatives.

The reaction mixture was stirred for 1 hour to ONC and poured in water. Extracted with ether, dry the phases éthérêes and causes dry under reduced pressure. "

4.54 G of product is obtained desired melts at 124" C..

Preparations; 4 - 2, 3, 5, 6 a-têtrafluoro (hydroxyl mlthyl) benzonitrile are Step a

2, 3, 5, 6 a-têtrafluoro~4 //(tetrahydropyran-to-2 yl) alkyloxy // methyl benzaldehyde.

=60:00 C. is cooled to 13 g of 2 / - (2, 3, 5, 6-tetrafluoro-phenyl) mêthoxyîétrahydropyranne in 200 in? of têtrahydrofuranne and added dropwise in 30 min 35.1 cm³ of butyl lithium (1, 6 Μ) in hexane, stirred 1 hour to -55 ≈ 0, 5 min 5 cm added³ of dimêthylformamide in solution.

■2•' -.

in 10 of Tet rahydrofuranne PLI, agitates T-half hours at this temperature adds 50 cm³ die aqueous solution saturated with sodium chloride, to extract 1' isopropyl ether, dried and the solvents removed under reduced pressure. Collected 14, .4 g of expected product, used as such for the next step.

4 2, 3, 5, 6-tetrafluoro - (hydroxy methyl) benzonitrile are

Is dissolved in 100 cm in methanol ^ 11/7 g of aldehyde obtained above and 6/8 g of sodium acetate trihydrate and then adds 4/2 g ammonium chloride. Poured into water/isopropanol to extract, dry and the solvents removed under reduced pressure. Recovered 13/6 grams oxime F. 13qnc. 4 Hours at reflux is heated in 400 cm in ^ acêtonitrile of presence of 1/6 g of cuprous acetate/cools to 4qbc, dry concentrate, resumes with 300 centimeters ^ isopropanol/washed with water and then the salt water/dry and the solvents removed under reduced pressure. Collected a tertiary 11/3 g of product. G acid added 0/625 paratoluêne sulfonic 12/5 g of the product prepared as above in methanol/62/5 cms ^ stirred 1 hour at room temperature/poured into ice water/isopropanol/to extract washed with water/salt water/dry and the solvents removed under reduced pressure.

Collected 11/5 g of desired product F. { 50 *" C..

Preparation 4 I-alcohol 4 a-c (1.1 to-diaéthyl ethyl) dimethyl siloxy group] 2,3/5 6-tetrafluoro benzyl

1 / - (tetrahydro 2h pyran 2 yl) alkyloxy/2/3/5/6-tetrafluoro - 4 [(2 a-tetrahydropyranyloxy) mêthyl] phenol

8/4 G of potassium hydroxide is added in a solution comprising 15/3 g of the alcohol derivative pyranylé pentafluorobenzylic in 140 cm. and heats of terbutanol are^4 and one-half hours at reflux. Allowed to return to ambient temperature adds an aqueous solution saturated with sodium acid phosphate ice extract with ethyl acetate/washed with water and salt-water/dry and the solvents removed under reduced pressure. 16 G of the obtained crude product is chromatographed on silica Cêluant hexane acêtate ethyl 7 - 3) and obtains 10/78 g of desired product F.^O 90nc.

2 A-cc4 - (1/1-dimethyl ethyl) dimethyl siloxy group] 2, 3, 5, 6 a-TFWs inducable luorophényl] methoxy] tetrahydropyran

Is cooled to + 4nc 2/8 g of the product obtained above in solution in tetrahydrofurane^14 cm., adds 1/7 of triêthylaminecrrr *) and then adds in 15 min a solution of 1/8 g of chloride 6 cms ^ terbutyldiméthylsilyle in tetrahydrofuran. Was stirred 40 min/filter/and removes the solvent resumes the residue in isopropanol, filter and collects 4 g of desired product.

Step c

Alcohol 4 a-c (1.1-dimethyl ethyl) dimethyl siloxy group] 2, 3/5.6-tetrafluoro benzyl

Added 0.1 g of ambient temperature paratoluene sulfonic acid in a solution comprising 2 g of the product obtained in step b in 10 cm from ^ stirred 1 hour of mêthanola, poured into ice water, extracted with ether, and the solvents removed under reduced pressure. After chromatography of the residue on silica (eluent methylene chloride) 1.16 g of product is obtained expected

Preparation?; the 2 a-CiC2, 3, 5, 6 ~tétrafluoro - 4 (1.2~propa " - dienyl) phénylHBiêtbosty /. têtrafoydropyranneschéaa is prepared according to the following reaction:

Mixed homogeneously of:

Insects tests are flies domestic female 4 days of age. It is performed by direct spraying 0/25 g/l concentration in chamber Kearns and market by using as solvent a mixture of acetone (5%) and the L Isopar (petroleum solvent) (amount of the solvent used in a second 2 ml). Used 50 insects per treatment. Checks are carried out every minute until th 10 min, and then 15 minutes and it is determined the KT 50 by the usual methods.

Experimental results obtained are summarized in the following table:

5 days " process is performed by topical application of 1 L solution acetonic on dorsal thorax insects by the micro-manipulator of Arnold. Used 50 individuals per treatment. We monitor mortality twenty-four hours after treatment.

The results obtained expressed DL ^ Q or dosage (in nanograms) by individual required to kill 50% of the insects, are as follows :■

The tests are performed by contact on film on glass, by depositing to the pipette, acetone solutions of different concentrations on the bottom of the petri-dish glass whose edges have been previously chalked to prevent escape. Lethal concentration is determined (IC 50) 50.

Experimental results obtained are summarized in the following table e

Degrees) study of the lethal effect on larvae of Spodoptera Littoralis

The assays are performed by topical application of an acetone solution by the micro-manipulator of Arnold on dorsal thorax larvae. 15 Used larvae per dose of product to be tested. The larvae used are larvae of the fourth larval stage, it is to say is approximately 10 days when grown to 24" c and 65% relative humidity. After processing the individuals are placed on artificial diet (Poitout medium).

We monitor 48 hours after treatment of mortality.

Experimental results obtained are summarized in the following table:

|compounds|LD 50 in ng by insect|

8|11.5|g.

Used after 7 days and adults employed 10 USDA APHIS by concentration used. Method is used contact in a contact device. The treatment is carried out at gun Fisher bean of a sheet which is placed in a plastic petri dish on a paper washer moistened. The treatment is carried out using 2 ml of acetone solution of product to be tested (1 ml per side of sheet), insect infestation is carried out after drying of the sheet. Insects are maintained in contact with the sheet for one hour. Placing insects on sheets not treated and control mortality after 24 hours.

Experimental results obtained are summarized in the following table:

Plants are used bean having 2 sheets, infested with 25 female Tetranychus urticae by sheet and placed under cap aerated under ceiling light in constant light. The plants are processed at gun Fisher: 4 ml solution of toxic plant of an equal volume of a mixture of water and acetone. Allowed to dry during 12 hours followed by the infestation. The checks are performed 80 hours after death. The dose used in each test is 5 g of product by H U-lethal concentration is determined 50 (LC 50).

The experimental results are as follows: