New esters of carboxylic acids cyclopropane comprising a polyhalogéné substituent, method of preparation and pesticides compositions.

The invention objot novel esters of cyclopropane carboxylic acids bearing a substituent polyhalogcnisomores possible in all their forms, of the general formula I is T

(I-)

wherein X ^ represents hydrogen, fluorine, chlorine or bromine, the X₂ , identical or different, represents a fluorine, chlorine or bromine, ^ the X represents a chlorine, bromine or iodine, and R represents:

" T-bonzylo radical optionally substituted by one or more radicals selected from the group consisting of alkyls having from 1 to 4 carbon atoms, alkenyl radicals having from 2 to 6 carbon atoms, alkenyloxy radicals having from 2 to 6 carbon atoms, the radicals having from 4 to 8 alcadiénylcs carbon atoms, methylene dioxyle, the benzyl radical, halogen atoms,

- Either a group:

in ' which the substituent R ^. represents a hydrogen atom or a methyl radical and the R substituent₂ a monocyclic aryl or a group:

millimeters

and in particular a group 5 benzyl 3-furyl-methyl,

the R: Either a group :•

wherein R represents an aliphatic organic radical conduct as, as confectioneries 2 of 6 carbon atoms and one or more carbon-carbon insaturationg, -^: :::, and especially the vinyl radical, propen-l-yl, -buta L, 3 a-diënyle or butenoate L-ylç,

wherein R ^ represents a hydrogen atom, a group:

THE N==- C.

or a group:

α ≡ ≡ α ΐ -

R_ and represents a chlorine atom or a methyl radical and n

D

represents a number equal to 0, 1 or 2, and particularly the group 3-phenoxy benzyl, O-^ a cyano - 3-phenoxy benzyl or&(ethynyl - 3-phenoxy benzyl,

- Either a group:

wherein the substituentsR_C. , R_, R.₀ and R_Q represent

o/o therein

hydrogen, a chlorine atom or a methyl radical and wherein the symbol s/i indicates an aromatic ring or a like cycle, dihydro or tetrahydro tetrahydro.

By convention, in the coupling the alcoholic esters of formula I, when n is 50, the core of the supported<substituent R - then represents a benzene ring.

The esters of formula I can exist in many forms isomers. Indeed, the cyclopropane carboxylic acids forming the coupling the acid esters of formula I have, in general, asymmetric carbons 3, namely, the asymmetric carbons in position 1 and 3 cycle cyclopropane and the asymmetric carbon at position 1' of the side chain of poly - ethyl

halogenated fixed in position 3.

In the case where the three substituents X ^, the X ^ ' ^ and X " are different from each other, an additional asymmetric carbon may exist in position 2' the polyhalogenated ethyl side chain.

Furthermore, the alcohol R-OH coupling the products constituting the alcoholic esters of formula I may have one or more asymmetric carbons and/or one or more double bonds giving rise 5 e/z isomerism.

The esters of formula I, object of the invention, include, for a given resolution substituents, Χ ^, and R, all compounds derived from the combination of an isomer (racemic or optically active) resulting from the existence of different asymmetric carbons of the acid portion of the molecule with an isomer (racemic or optically active) corresponding to the coupling the alcoholic.

In the case where the substituents and X ^ are identical, for a steric configuration determined of the asymmetric carbons in position 1 and 3 cycle cyclopropane, and for a given structure of the alcoholic portion (which may herself have one or more asymmetric carbons and/or one or more double bonds resulting isomerism. e/z), two diastereoisomeric forms esters (I-) or acids (K.) corresponding, due to the presence of asymmetric carbon in 1', may exist and be effectively characterized in particular by their spectrum of an nmr or their migration rate of thin layer chromatography. These isomers can be, in general, separate and isolated in pure form, in particular by chromatography. These two diastereoisomers are termed herein and in the following, isomers (has) and (d).

Among esters of I, object of the invention, examples more particularly, those in which the cyclopropane carboxylic acids (K.), forming the coupling the acid of these esters, are structural (Ir, cis-) or (IR-, trans-) and the names of which follow:

2.2-dimethyl 3 - acids - (2 ', 2' a-bromo 1 ', 2'-dichloro-ethyl) cyclopropane-l carboxylic;

'2.2-dimethyl 3 - acids - (L-', 2 ', 2', 2' to-tétrachlorp ethyl) propan-l-carboxylic ring;¹

•2.2-dimethyl 3 - acids - (2¹ , 2 'difluoro 1 2' ',-dichloro-ethyl) cyclop ^ WCPFC and 1 a-carboxylignes ii

; 2.2-dimethyl 3 - acids - (2 ', 2' dichloride 1 ', 2' a-bromo ethyl) cycidpropane L-carboxylic acids;

'2.2-dimethyl 3 - acids - (2 ', 2 'difluoro 1 ', 2' a-bromo ethyl) cycldpropane L-carboxylic acids;

Y Acids 2.2-dimethyl (1 ', 2 ',', 2 2' a-tetrabromo éthylfcytîo-to-ptopahe L-carboxylic acids;

I-acids 2.2-dimethyl 3 - (2 ', 2' difluoro 2 ',l' a-diodo ethyl) cyclopropane-l carboxylic;

the j - 2.2-dimethyl 3 - acids (2 ', 2' - dichlorophenyl 2 ',l' a-diodo ethyl)

'•1 sec.

lÿclopropane L-carboxylic ;

^V. - ii acids 2.2-dimethyl 3 - (2¹ , 2 'a-bromo 2 ',l ' a-diodo ethyl) Syclopiropane L-carboxylic acids;

2.2-dimethyl 3 - acids - (1^{the R} , 2 ', 2' a-tribromo ethyl) cyclôpropa-to-bound L-ccirboxylic ;.

•2.2-dimethyl 3 - acids - (1 ', 2' dichloride 2' bromo-ethyl)-cycle pfopane^WITH the L-carboxylic acids;

- Acids 2.2-dimethyl (1 ', 2 ', 2' 4N-trichloro ethyl) cyclopropane group 1 a-sarboxylic;

2.2-dimethyl 3 - acids - (1 ', 2' a-bromo 2'-chloro-ethyl) cycloaliphatic ".

propan-l-carboxylic acids;

- Acids 2.2-dimethyl (1 ', 2dichloro 2' fluoro ethyl)* cycloolefin propan-l-carboxylic acids;

- Acids 2.2-dimethyl (1, 2 'a-dibrômo 2'-fluoro-ethyl) - cycloaliphatic.

propane 1-carboxylic acids ;.

2.2-dimethyl 3 - acids - (2 'fluoro 2 ',l 'a-dicdo ethyl) or cyclopropane - 1 a-carboxyliqu AE ;'.

. - Acids. 2.2-to-substituted dimethyl 3 - (2 'a-chioro 2 ',l ' a-diodo ethyl) cyclopropane-l carboxylic;

2.2-dimethyl 3 - acids - (2 'bromo-2 ',l ' a-diodo ethyl) cyclopropane-l carboxylic;

- Acids, 2.2-dimethyl 3 - (L-', 2 ', 2 '4N-trichloro 2' fluoro ethyl) cycDopr WCPFC-to-1 ii carboxy liquesi

2.2-dimethyl 3 - acids - (1 ', 2' a-bromo 2 '-chloro-2' fluoro ethyl) cyclopropane-l carboxylic;

2.2-dimethyl 3 - acids - (1 ', 2 ', 2 '4N-trichloro 2' bromo-ethyl) cyclopropane-l carboxylic;

2.2-dimethyl 3 - acids - (1 ', 2 ', 2 'a-tribromo 2'-chloro-ethyl) cycloprcyclopr.opane L-carboxylic ;

2.2-dimethyl 3 - acids - (2' fluoro 1¹ , 2¹ , 2¹ - tribromo ethyl)••cyclopropanc-to-1-carboxylic acids

2.2-dimethyl 3 - acids - (2 * - the bromo 2 'fluoro 1 ', 2'-dichloro-ethyl) cyclopropane-l carboxylic;

2.2-dimethyl 3 - acids - (2 'fluoro 2'-chloro-2 ',l' a-diodo ethyl) cyclopropane-l carboxylic;

2.2-dimethyl 3 - acids - (2 'fluoro 2' bromo-2 ',l' a-diodo ethyl) cyclopropane-l carboxylic;

2.2-dimethyl 3 - acids - (2 '-chloro-2' bromo-2 ',l' a-diodo ethyl) cyclopropane-l carboxylic acids.

Of course I-esters, object of the invention, may also be derived from carboxylic acid ester (K.) structure (the LS, cis-) or (the LS, trans-). Similarly these esters I can be derived either from cyclopropane carboxylic acids (K.) structural DL-cis (mixture of ëquimoléculaire (Ir, cis-) and.

(the LS, cis-)) or dl-trans-(mixture ëquimoléculaire of (Ir, trans-) and (the LS, trans-)), or mixtures of acids of structure DL cis and acids of dl-trans-structure.

The invention more specifically relates to the compounds of general formula I, characterized in that the coupling the acid has the structure of these esters (Ir, cis-) or (Ir, trans-), as well as the compounds of general formula I, characterized in that the coupling the acid of these esters is structural DL cis-or DL-trans and that the compounds of general formula I, characterized in that they consist of a mixture of esters having the structure coupling the acid is dl-alpha-cis-or dl-trans-.

Among alcohols constituting the coupling the alcoholic esters, object of the present invention, this included the benzyl alcohol, the alcohol 2.5-dimethyl 4-allyl-benzyl, the 5 benzyl 3-furyl-methanol, the 5 - (hydroxypropyn-a 2 'yl) 2-methyl 3-furyl-methanol (or kikuthrol), the 5 - (hydroxypropyn-a 2' yl) 2-furyl-methanol (or prothrol), the 1 oxo 2-allyl-3-methyl and cyclopent-to-2-ene 4-ol-(or alléthrolone), the 2 - 1 oxo (2 ', 4' a-pentadienyl) 3-methyl and cyclopent-to-2-ene 4-ol-, the 1 - 2 - oxocyclohexyl ·•(2'-butenyl) 3-methyl and cyclopent-to-2-ene 4-ol-, benzyl alcohol 3 a-phênoxy, alcohol-O(-_Cyano 3-phenoxy benzyl, - ethynyl alcohol<^ 3-phenoxy benzyl, alcohol 3, 4, 5, 6 tetrahydro phthalimido methyl and especially the optically active forms of those of these alcohols which have an asymmetric carbon

Among the compounds of general formula I, examples including those characterized in that X. ^ represents fluorine, chlorine or bromine, the X ^ is identical to X and represents fluorine, chlorine or bromine, and retain and P.

are as defined above, those characterized ·℮η that

represents hydrogen, fluorine, chlorine or bromine, is different from and represents a fluorine, chlorine or bromine, and X ^ and H retain the meanings set forth above, those characterized in that Χ ^, ^ ^ retain the X and X are as defined above and R represents a residue of 5 benzyl alcohol 3-furyl-methyl, a remainder 1 oxo 2-allyl-3-methyl cydopent-to-2-in 4-yl, an alcohol residue of 3-phenoxy benzyl, an alcohol residue of a cyano - 3-phenoxy benzyl, these alcohols which may be racemic or optically active, and those characterized in that represents fluorine, chlorine or bromine, identical to X ^ ^ the X represents a fluorine atom, chlorine or. bromine, represents a chlorine, bromine or iodine and R represents a residue of 5 benzyl alcohol 3-furyl-methyl, a remainder 1 oxo 2-allyl-3-methyl and cyclopent-to-2-in 4-yl, an alcohol residue of 3-phenoxy benzyl, an alcohol residue of hr-cyano-benzyl 3-phenoxy, these alcohols which may be racemic or optically active.

•the compounds of formula I, in the form of isomers (has), in the form of isomers (d), due to the existence of asymmetric carbon

1 · position of formula I, or a mixture of these isomers sousforme, the names of which follow:

LR - CIUs #2 #2 a-HD "ôthyl 3 - (1 * #2 '" 2' " 2' - tétr ABRs omo ethyl) cyclopropane 1-carboxylate (O)O-(cyano-benzyl - 3 a-phënoxy;

•LelR, 2 CLAs, ^ ^ Μ · 2 - 4 3 3 - (2 '* 2'-dichloro-I-¹_# 2' a-bromo ethyl cycloprepaneiTcarhoxylste ^ (e) of the c (a cyano - 3-phenoxy benzyl,

pre feel of particular interest.

The composed OD fërimilo•probe apparatus, D-form " isomers

(Has), in the form of isomers (β), due to the existence of the carbon .1 ii. - ' j. VBE1 1 asymmetric in the P position of In formula X. or as a mixture of isomers LOC "mentioned further in the examples are also composed preferred *_ a j - I .ν.. - ;, VBE1 - -4 F. R." the I "• the L'V^{the R}I-J. '**' ""

The invention relates to the compounds OD netwinent formula X as a mixture OD stereoisomers OD cis form and structural trans at any propertiens *

Among them "in Classroom" more particularly those

which consist of a mixture of stereoisomers of cis form and OD stnicturè-^:iitààà in proportions by weight 20/s0 loé, 50/50 or '80/20 *'¹

,, L.¹ a method for preparing compounds of formula, I " characterized in that

"'¹ 9.ï♦/ to i-j VBE1 - ' I-t * r• > ; üvi * v-VBE1<. 9.ï ' ll.j ' J. J-Xv frames. XVBE1••.' react on a redundantable T-ester of general formula

(ii)

-,, e - 9.ï^! has, -■lil-to-TCLs; :, }r_.I-•(R. , l. .

wherein. X "X and R are as defined above * said ester wherein xx is, spua any of its isomeric forms * a chlorinating agent", bromination or d'iodinating likely

secure Cl " brr or X. on ' the double bond of the side chain■^{the R} 't-! ., V-R: ¾ ;■,>i - g -.; '.^; '■■■■cyclopropane carboxylic acid.

The method hereinafter deeeus 0 method is calledC."

As a halogenating agent esters II which, used in particular chlorine, bromine or iodine, and 1' halogenation esters II is then performed within an organic solvent which does not react with chlorine, bromine or iodine, such as acetic acid, carbon tetrachloride, chloroform, methylene chloride. *,

' The invention also relates to a process for preparing the compounds of general formula I, characterized. in. what is reacted with an acid of the general formula III:

(III)

wherein X and X₂ retain the meanings set forth above, said acid III being under any one of its isomeric forms a chlorinating agent, brominating or iodinating can bind LC₂ , Brr₂ or I₂ on the. side chain acid-III, and then reacting the resulting acid of general formula /" VI:

wherein, X is₂ and X ^ retain are as defined above or one of its functional derivatives, with an alcohol ROH or one of its functional derivatives, R retaining the abovementioned meaning. "

. The method above is called method

As a halogenating agent upon acids lll, used in particular chlorine, bromine or iodine, and 1' halogenation acids III is then performed within - of Iin organic solvent which does not react with the chlorine, bromine or iodine web, such as acetic acid, carbon tetrachloride, chloroform, methylene chloride.

The derivative. functional acid. VI, used to perform the esterification with alcohol ROH or with a functional derivative of this alcçol, . .. is particularly the chloride, the anhydride, a mixed anhydride, lower alkyl ester, a metal salt or a salt based organic. ill .de acid.., the functional derivative of the alcohol be μη chloride, bromide or a sulfonate ' of this alcohol. ^ -

An alternative method of preparation of β compounds of general formula I, another object of the invention, is characterized in. that is reacted on a functional derivative of an acid of general formula III:

in which formula and retain the meanings set forth above, said functional derivative of the acid III being under any one of its isomeric forms, a chlorinating agent, brominating or iodinating can bind LC₂ , ^ Brr or I₂ The side chain of the _sur functional derivative of the acid-III, and then reacting the resulting functional derivative of the acid of IV:

(IV)

wherein, ^ ^ retain the X and X are as defined above with a₄ alcohol ROH or one of its functional derivatives, R retaining the abovementioned meaning.

The above method is called method

The agent, used to perform 1' halogenation of the derivative withers tee members corresponding acid-III, is, preferably, chlorine, bromine

a ft

or iodine, and the halogenation is then performed within a ground -

efore organic does not react with chlorine, bromine or iodine, such as acetic acid, carbon tetrachloride, chloroform, methylene chloride.

For ' to obtain the compounds ii.à from acids IV or functional derivatives of acids IV according to the methods β and K of the invention, acid is reacted IV or one of its functional derivatives on the alcohol ROH or a functional derivative of this alcohol.

For example, pages may be esterification by action of the acid VI, chloride, anhydride or mixed anhydride of this acid IV over 1' alcohol ROH. May also be used the method of trans esterification by reacting a lower alcohol ester de .1 ' acid IV with the alcohol ROH, especially in the presence of a basic catalyst. May also be reacting a salt of the acid IV enzyme, e.g., an alkali metal salt, silver or triethylamine on a functional derivative of the alcohol ROH, such as a chloride, a bromide or a sulfonate.

One may also use other conventional methods of esterification of the acid IV or a functional derivative thereof with the alcohol ROH or a functional derivative thereof without departing from the scope of the invention.

An advantageous embodiment of the method of the invention ^ confectioneries for use as functional derivative of the acid of IV, the acid chloride.

An advantageous embodiment of the method (f. of the invention is used as functional derivative of the acid III and as functional derivative of the acid of IV, chlorides of these acids.

The esterification of the acid chloride IV by the alcohol ROH is then suitably conducted in the presence of a tertiary base, such as pyridine or triethylamine.

In general, the II esters, acids III and the

functional derivatives of acids II, used as starting materials are methods of the invention, are described ' in particular in French patents no. 2,185 612 and 2,240 914 or may be prepared by methods analogous to those described in these patents.

In the case where the radicals X and X represent 1 - 2

halogen, X-being different from X ^ ^, the II esters, acids IJI

and functional derivatives thereof are described in the thesis

of helical Gordon's Brownian (Erickson, a Texas) of December 1974, entitled "construction - activity consisted of studies of halation pyrethroids" or can be prepared by methods analogous to those described in of course, esters II inhibitor, the method originally used

of the present invention, exist in many forms isomers, these isomeric forms from the existence of the asymmetric carbons at positions 1 and 3 of the cycle cyclopropane, as well as any fault in the alcoholic, either of one or more asymmetric carbons, or more double bonds resulting e/z isomerism.

Similarly, acids III or their functional derivatives, originally used methods β and ^ of the invention, also exist in various isomeric forms from carbons asymétri * er in positions L and 3 a-cycle cyclopropane.

The compounds do of general formula I are endowed with remarkable insecticidal properties, in particular, kill of extremely loud and NOU very good stability against atmospheric agents (heat, light, moisture).

These compounds are particularly well adapted for application to the insect control in agriculture. For example, they allow effective against aphids, the cabbage, Coleoptera.

They are then used, of préférencc, at doses between 1 g and 100 g of active material per hectare. By their speed of action, the compounds can also be used as insecticides in household.

The insecticidal activity of the compounds of the invention can be demonstrated in particular by tests on houseflies, on Spodoptera littoralis Littoralis, as well as larvae Varivestris frontalis, on weevil Sitophilus Granarius and Tribolium castaneum on BlatellaGerrnanica.

These tests are described below in the experimental part * the invention also relates to the insecticidal compositions, characterized in that they contain, as active ingredient, at least one of compounds of general formula I, as defined above, and more especially the insecticidal compositions, characterized in that they contain, as active ingredient, at least one of compounds, of the general formula I, in the form of isomers (has), in the form of isomers (b.), due to the existence of the asymmetric carbon at position 1' of the formula I, or as a mixture of isomers with cos, whose names are mentioned,

1

THE T 2

The active materials may 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 baits or other preparations traditionally employed 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 can be a liquid, such

that water, alcohol, or other organic solvents the hvdrocarbures, mineral oil, animal or vegetable, a powder, such as talc, clays, silicates, kieselguhr or a solid fuel, such as tabu powder (or grounds pyrethrum).

To enhance the insecticidal activity of the compounds of the invention, it is possible to sum them up with synergists employed conventional in such a case, such as 1 - (2, 5, 8 a-trioxa dodecyl 2 propyl 4.5 to-methylenedioxy) benzene - (or piperonyl butoxide), n - (2-ethyl hepyl) bicyclo-/ 2.2 L / - 5-heptene-to-2.3-dicarboximide derivatives, the piperonyl-bis 2 - (2' n-butoxy-ethoxy) ethyl acetal (or tropital).

. , These insecticidal compositions contain, preferably, between 0,005 °fi and 10 ^{the P} the O / by weight of active material.

The invention thus has an aim the insecticidal compositions as defined above, characterized in that they contain in addition to the active ingredient, an agent synergisant and especially as synergisant piperonyl butoxide,

The compounds of formula I, as defined above additionally have interesting properties and acaricidal néinaticides,

Tests given hereinafter on Tétranychus authorisation of and on DitylenchusMyceliophagus demonstrated.

The invention thus also relates to acaricidal compositions characterized in that they contain as active material, at least one, in all their possible isomeric forms, compounds of general formula I as defined above, and more particularly those containing at least one compound having the following names ii

05761 " TO

- isomers and b of 1r, cis-2.2-dimethyl 3~(1¹ j2¹ , 2 ', 2 < tétrabromoothyl) - 6α-to-1 cax' of (e) boxylato c6 c-yano 3 a-pliénoxy benzyl,

- isomers and b of 1r, cis-2.2-dimethyl 3 - (2 ', 2' a-dichioro 1 ', 2' a-dibromoéthyl) cyclopropanc-to-1-carboxylate (e) ^, a cyano - benzyl 3 a-phcnoxy; and the nematicidal compositions characterized in that they contain as active ingredient a at least, in all possible isomeric forms of the compounds of general formula I as defined above and especially those that contain. at least one of compounds having the following names {

- isomers and b of 1r, cis-2.2-dimethyl 3 - 0^F. >2 ', 2 * j2'-to-tee trabromoé. the Thyl) - cyclopropanecarboxylic 1-carboxylate (e) a cyano - 3-phenoxy benzyl,

- isomers and b of 1r, cis-2.2-dimethyl 3 - (2 ', 2' dichloride 1 ', 2' a-dibromoéthyl) cyclopropane 1 a-carboxylato of (e) a cyano - ^ 3-phenoxy benzyl_I

As the insecticidal compositions above, acaricidal and nematicidal compositions may be added optionally one or more other pesticidal agents. acaricidos and nematicidal compositions can be in the form of powder, granules, suspension, emulsions, solutions for use acarielde, are a preferred wettable powders, for foliar spray containing 1 to 80 weight percent of active ingredient or back liquids for foliar spray containing 1 to 500 g/l of active ingredient.

There can further be used for powder-containing 0.05 to 3 foliar powderings weight percent of active material.

For use néraaticide, preferably liquids used for soil treatment containing 300 to 500 g/l of active material.

Acaricidal compounds and nematicidal according

the present invention are used, preferably, at doses between 1 and 100 g of active material per hectare.

The properties against mites to compounds of formula I, as defined above * also allow products are useful as pharmaceutical compositions for veterinary use, in combating mites parasitic on animals and particularly against the the Ixodidae

and the sarcoptide ^ e■animal pests.

Back test data, further in the experimental part show the activity of a compound formula I on RhipicephalusSanguineus OD in dogs.

The compounds of formula I can be used in animals

5 for fighting all kinds OD gall, fabrics that

the scabies, scabies psoroptiquo and scab chorioptic, compounds formula I OD still permit combat all kinds OD tick species such as Boophilus, Hyalomnia species, the species and the species AmblyomaRhipicephalus,

lo and the I "'invention therefore also' im-preparation process this" 'pharmaceutical compositions to use, veterinary, characterized in that, as active principle, at least one of the compounds of formula I, in a form suitable àà.l' therapeutic use.

The compositions can be used externally,

5 but also parenterally or gut,

Compositions can. - also be advantageously added agent synergisant pyrethroids,

Such an agent has been defined previously. These compositions are prepared according to the usual methods *

The O finally, it can be convenient for veterinary use the compounds I in mixture with food compounds balanced animal.

It will be possible, for example, employ compound feedstuff containing of 0,002 to 0.4 ^C. the O / by weight of 1r, 2 cis 1, 2 -

^ 3r substituted dimethyl - (2 ', 2 *, 1 ', 1' a-tétrabromoéthyl) cyclopropane 1-carboxylate_L i-a cyano - 3-phenoxy benzylc,

The compositions intended for animal feed are characterized in that they are composed of a compound feed, balanced, animal and they further contain a at

0 least compounds of general formula I,

Furthermore, the compounds of formulae

corresponding to the formula I,

wherein is hydrogen, fluorine, chlorine or bromine OD, the X ", the same as or different from X, represents a fluorine, chlorine or bromine and represents a chlorine atom, bromine or iodine atom OD, and especially the 1r, cis-2.2-dimethyl 3~(2 ', 2', 2', 1¹ (Rs)- tétrabromoéthyl) cyclopropane 1-carboxylate (e)Tg-cyano-3-phenoxy benzylc and

1r lG, cis-2.2-dimethyl (2 ', 2' - dichlorophenyl 2 ·, 1 · (SRV) dibxOmo-ethyl) cyclopropane 1-carboxylate (e) pp-cyano-benzyl 3-phenoxy have excellent antifungal properties, for their use in agriculture for combating fongi plant pathogens.

The antifungal activity of the compounds of formula can be illustrated particularly by tests on the Fusarium Rosoum, Dotrytis cinerea on Phoma cf Specus, Penicillium Roqueforti, provided hereinafter.

1.' invention also relates to the antifungal compositions characterized in that they contain as active ingredient at least one of the compounds of formula 1^as defined above and in particular fungal compositions characterized in that they contain as active ingredient at least one

compounds named above.

In the antifungal compositions, the active ingredients may be added optionally one or more other pesticidal agents. These compositions may be in form of powders, granules, suspension, emulsion, solution, solutions for aerosols or other preparations used conventionally for the use OD OD compounds such "

In addition to the active ingredient, the compositions comprise, in general, a vehicle and/or a surfactant, nonionic, providing, further, NOU uniform dispersion of substances that make up the mixture. The vehicle can be a liquid, such as water, alcohol, hydrocarbons or other organic solvents, mineral oil, animal or vegetable or NOU powder, such as talc, clays, silicates or kieselguhr,

The antifungal compositions preferably contain, for_O the powders for spraying to 95 $25, by weight of active material, for powders or spray liquidos for 10 to 30 ground OD % by weight of active material "

The invention further provides novel following the LOS acids in all their possible isomeric forms, the I of the general formula IV

REARWARD IY

wherein X₁ represents hydrogen, fluorine, chlorine or bromine, xgidentic or different, represents a fluorine, chlorine or bromine and X ^ represents a chlorine atom, of b ' rone or iodine, as well as functional derivatives thereof and especially their chlorides "

a TES new products are obtained temporarily during the implementation of the invention "

The following examples illustrate the invention without however limiting same.

05761

Example 1 : (ir, cis-) 2.2-dimethyl 3 - (1¹ , 2¹ , 2¹ , 2' a-tetrabromo chloroethyl) cyclopropane-l carboxvlate of (e) C. (a cyano - 3-phenoxy benzyls(Isomer) and (b-isomer)

In 100 cm3 of carbon tetrachloride, is dissolved

7.57 g of (L-R, cis-) 2.2-dimethyl 3 - (2 ', 2' a-bromo vinylaromatic) cyclopropane-l carboxylate (O)O-(a cyano - 3-phenoxy benzyl, added 2.4 g bromine in solution in 15 cm3 of carbon tetrachloride stirred for 45 minutes at 20 °c, concentrated to dry under reduced pressure, separates the constituents of the residue (10 grams) by silica gel chromatography; obtained by elution with a mixture of benzene and petroleum ether (eb. 35 - 75 degrees) (1 - 1), firstly the isomer (has) (4.12 grams), then the isomer (d) (4 grams) of the (L-R, cis-) 2.2-dimethyl 3 - (1 ', 2 ', 2 ', 2' a-tetrabromo ethyl) cyclopropane-l carboxylate (e) the O(a cyano - 3-phenoxy benzyl.

The isomer has has the following characteristics:

THE M/_{the O} -=(c=0.5%, benzene) 53°

Analysis :^C.₂ 2^H i9^Brr 4^NR °3 (665,037)

Calculated; C.% 39.73% 2.88% 2.11% 48.06 brr H-n-

Found 39.9 2.9 48.2 2.1

R-I spectrum. (Chloroform)

Absorption at 1740 cm¹ (esters), absorptions to 1615, 1588, 1573 and 1488 cm "* assigned to the aromatic rings"

Peaks to 1.25 - 1.33 P P m (hydrogens methyl radicals in position 2 cyclopropane); peaks of 1.75 confectioneries 2.17 P P m (hydrogens in positions 1 and 3 cyclopropane); peaks to 5, 19 - -

5.55 p P m (hydrogen in position 1' of the side chain);

6.38 picpic.à P P m (hvdroqëne benzyl); peaks 6.91 to 7.59 e. e. m corresponding hydrogens aromatic rings

The isomer (has) is most mobile in thin layer chromatography/

Circular dichroism (dioxan)

WITH =T- 3 - confectioneries 224 nm;

4.5 to - 237 nm;

. GBP - ^=0.05 to 290 nm.

The isomer (b.) has the following characteristics:

ο / (+ / ^=1.11^I (c=0.6%, benzene)

Analyzed: c__II. brr, no. (565,037)

^WITH 22, 19 4, 3

Calculates: c-I-H-n-39.73% 2.88% 2.11% 48.06 brr

Found 39.8 3.0 48,1 - 2.0

R-I spectrum, (chloroform)

Absorption l743 ο π Τ¹ (esters), absorptions to 1615, 1588, 1573 and 1488 Cntf¹ assigned to the aromatic rings.

Peaks to 1.24 - 1.40 P P m (hydrogènesdes methyl radicals in position 2 cyclopropane); peaks of 1.83 to 2.25 P P m (hydrogens in positions 1 and 2 cyclopropane); peaks to 3.98 -

5.20 p P m (hydrogen in position 1' of the side chain);

peak at 6.39 w, P m (benzylic hydrogen); peaks of 6.92 to 7.52 e. e. m corresponding hydrogens aromatic rings

(D)- isomer is the least mobile in thin layer chromatography.

Circular dichroism (dioxan)

Has the £=+ 4.7 to 223 nm;

Has [=+ 4.2 to 247 nm.

Example 2 : (ir, cis-) 2.2-dimethyl 3 - (2^{the R} , 2 'dichloride 1', 2' to-dibroro ethyl) cycloprooane L-carboxylate (e) the K-cyano-3 a-phénoxv berber.zyle (Isomer) and (b-isomer)

In 200 cm3 of carbon tetrachloride, is dissolved

17.06 g of (L-R, cis-) 2.2-to-dimêthyl 3 - (2 ', 2'-dichloro-vinyl-)' cyclopropane-l carboxylate (e) C. (a cyano - 3-phenoxy benzyl, introduced the EH 6.55 g bromine solution in 20 cm3 of carbon tetrachloride in 10 minutes, stirred for 48 hours at 20 °c, concentrated to dryness by distillation under reduced pressure and separates the constituents of the crude residue (23.8 grams) by silica gel chromatography eluting with a mixture of benzene and cyclohexane (. 7 - 3) and obtains 10.4 g of isomer (has) (the more mobile in thin layer chromatography *) and 10 g of isomer (3) (the less displaced

thin-layer chromatography) of the (L-R, cis-) 2.2-dimethyl 3 - (2 ', 2' dichloride 1 ', 2' a-bromo ethyl) cyclopropane-l carboxylate (O) c->(a cyano - 3-phenoxy benzyl.

The isomer has has the following characteristics:

^ / / C._D -=(c=0.5%, benzene) 61°•

Analysis : ^ ^ C-ii₉ Brr₂ LC₂ N0₃ (576,125)

Calculated: C.^? 45.85% 27.74% 3.3 hr'd % 12.3% 2.4 n-Cl or brr found: 45.8 3.3. 27.7 12.3 2.3 β 1 057

R-I spectrum. (Chloroform)

Absorption at 1738 cm in~^ (esters), absorptions to 1485, 1585 and 1610 cm " ^ due to aromatic rings.

Peaks to 1.29 - 1.37 P P m (geminal methyl cyclopropane hydrogènesdes); peak at about 2.05 P P m (hydrogènesen at positions 1 and 3 cyclopropane); peaks to 5.20 - 5,29 - 5.37 5.45 P P m (hydrogen attached to the asymmetric carbon of the side chain); peak at 6.45 P P m (benzylic hydrogen);

7.0 to 7.6 peaks P P m assigned hydrogens aromatic rings.

Circular Dichroîsme (dioxan)

gBP - δ=8 to 221 nm (inflection);

+ 0.14 to 289 nm (MAX).

The isomer (b.) has the following characteristics:

ο / (ρ=+ / 119° (c=1% in benzene)

Analysis : C. ^} ^₉ Brr₂ LC₂ N0₃ (576,125)

Calculated: C.% 45.86% 27.7% 12.3% 3.3 hr n-Cl or brr % 2.4 Found: 46.2 3.4 27.6 12.2 2.3 R-I spectrum.

Absorption at 1740 cm^-1 (esters); absorptions to 1610, 1585 and.. 1485 cm (aromatic rings).

Peaks to 1.25 - 1.38 P P m (hydrogens of geminal methyl cyclopropane); peaks of 1.87 to 2.3 P P m (hydrogènesen at positions 2 and 3 cyclopropane); peaks to 4.97 - 5.01 - 5, P P m it 5.16 (fixed hydrogen on the asymmetric carbon of the side chain); peak at 6.46 P P m (benzylic hydrogen) ;. 7 peaks to 7.67 e. e. m assigned hydrogens aromatic rings.

Circular Dichroîsme (dioxan)

AF-=+ 9 to 220 - 221 nm (MAX)

Has the £=289 nm to + 0.23 (MAX).

Example 3 : (1R, SLE) 2.2-to-dlméthyl 3 - (1¹ , 2', 2¹ , 2¹ - tetrabromo Chloroethyl)cyclopropanc L-carboxylate (O)O-( - a cyano 3 a-phcnoxybenzvle Patent: JlR acid, cis-)_ _ 2^2 a-substituted dimethyl /_ _ 3 a-GJs, 2.¹ 2/ytétrabromoéthy_l) _cycloDropane and _ 1 processes or boxy lic:

In 150 cm3 of carbon tetrachloride, is introduced

19.4 g acid (L-R, cis-) 2.2-dimethyl 3 - (2¹ , 2' a-bromo vinylaromatic) cyclopropane-l carboxylic, 10.4 g of bromine are added - in. 22 cm3 solution in carbon tetrachloride, stirred for one hour at 20 °c, concentrated to dryness by distillation under reduced pressure and obtains 31.4 g of crude product (f=145 °c). The crude product is recrystallized in 110 cm3 of carbon tetrachloride and obtained 22.12 g acid (L-R, cis-) 2.2-to-dimêthyl 3 - (1 ', 2', 2 ', 2' tetrabromo ethyl) cyclopropane-l carboxylic. F=150 °C.

This product is a mixture of two isomers (has) and (b.) which are highlighted by the spectrum of an nmr indeed, the spectrum of an nmr identifies a compound (corresponding to about 2/3 of the mixture) at peaks of 1.31 -

1.43 e. e. m corresponding hydrogens methyls gemini, and peak of 5.33 to 5.66 e. e. m corresponding to fixed hydrogen on the asymmetric carbon monobromo and another compound (corresponding to about 1/3 of the mixture) at peaks of 1.28 - 1.48 e. e. m corresponding hydrogens methyls

•gemini and peak of 4.24 to 5.34 e. e. m corresponding to fixed hydrogen on the monobromo asymmetric carbon.

In the mixture, is detectable, moreover, peaks at 1.67 e 2.17 P P m (hydrogens in positions 1 and 3 cyclopropane) and a peak P P m to 11.25 (mobile hydrogen of the acid function).

Analyzing the obtained mixture (f=150 °c) is as follows:

. C₈H₁₀ Brr₄ 0₂ (457,804)

Calculated: C. % 20.99% 2.20% 69.82 Brr of H

Found. : - 20.9 2.2 70.2

Step b: the £hlorure_de ii.lr acid; the £ls)_ 2_{the I} 2ydi_L 3y mémé .thyl _ü'y tee 2/2 T-R has brr omo_é T-hly]_ cyclopropaneylyearboxyligue:

In 179 cm3 of petroleum ether (to EB. 35 - 75 Degrees), dimethyl formamide with 0.2 cm3 introduced, 8.5 cm3 thionyl chloride, carries the mixture at reflux, introduced 35.76 g acid (L-R, cis-) 2.2-dimethyl 3 - (1 ', 2 ', 2 ', 2' a-tetrabromo ethyl) cyclopropane-l carboxylic in 150 cm3 of methylene chloride, stirred for 2 hours at reflux "cools" dry concentrate by distillation, rflinnfpfnlnènorhi. 5 pflnfonfronpmmsii= tower proliferation 4 - ΐ - ν=νΐ Λΐ ℮ ΐ 1, 1=(- ΐ. Λη reduced pressure and obtains 38 g of crude acid chloride

(P f=88 °c) used as such for the next step.

Step c: _ (the R 1, the cis) 2 _ _, 2 a-substituted dimethyl 2, 2'. ^ tetrabromo ethyl) cyclopropane-l carboxyI-to-atejde Js in) the j ^ ^~cyano_ 3 a-phénoxy_benzyle:

In a solution of 18.4 g of (e) a cyano - ^ C. 3-phenoxy benzyl in 100 cm3 benzene, pyridine 7.5 cm3 is introduced, and then, to + 10 °c, under an inert atmosphere, the 38 g of the crude acid chloride obtained in step b, stirred for 15 hours at 20 °c, adding water, stirred, the organic phase is separated by settling, extract to benzene, benzene phases are washed with water, at-sodium bicarbonate, water, the normal hydrochloric acid, then with water, dried, concentrated to dryness by distillation under reduced pressure, the residue is purified by silica gel chromatography and obtains the (L-R, cis-) 2.2-dimethyl 3 - (1¹ , 2 ', 2', 2' - tëtrabromo ethyl) cyclopropane 1-carboxylate (O) OC1 - 3 a-phênoxy ^ a cyano benzyl in the form of a mixture of isomer (has) and isomer (d).

Analogously to the previous examples, we prepared the compounds described in the following examples.

Example 4 : (ir, trans-) 2.2-dimethyl 3 - (1 ', 2', 2¹ , 2' a-tetrabromo ethyl) cyclopropane-l carboxylate (R) ^ I-a cyano - 3-phenoxy benzyl

This compound is obtained by the action of bromine on the (L-R, trans-) 2r2-dimethyl 3 - (2 ', 2' a-bromo vinylaromatic) cyclopropane 1-carboxylate (SRV) degrees (one cyano - 3-phenoxy benzyl, isomer mixture (has) and (d).

R-I spectrum. (Chloroform)

Absorptions to 1740, 1586 and 1485 cm "*¹ .

Peaks to 1.20 - 1.26 - 1.35 P P m (hydrogens methyls in 2 cyclopropane); peaks to 4.3 - 4.48 - 4.67 P P m (hydrogen in 1' chain cyclopropane ethyl alcohol to 3); peak at 6.48 P P'm.

(hydrogen attached to the same carbon that the CEEN.); 7.17 to 6.3, 7 peaks P P m (hydrogènesdes aromatic rings).

Example 5 : (ir, trans-) 2.2-dimethyl 3 - (2 '2 ', dichloride 1', 2¹ - dibrono ethyl) cyclopropane-l carboxylate (R) ^ a V-cyano-benzyl 3 a-phënoxv

This compound was obtained by brominating the (L-R, trans-) 2.2-to-dimé -.

the Thyl 3 - (2 ', 2'-dichloro-vinyl-) cyclopropane-l carboxylate (R) ^ (a cyano - 3-phenoxy benzyl, isomer mixture (has) and (d).

R-I spectrum. (Mth Chlorofox *)

Absorptions to 1743 cm¹_/ 1588 cm¹ , 1487 cm¹ .

SPEsthe CTre asi R M N.

Peaks to 1.20 - 1.26 - 1.32 - 1.35 P P m (hydrogen? methyls in position 2 cyclopropane; peaks to 1.68 - 1.77 e. ρ. m (water gene in] cyclopropane); P-peaks to 1.95 - 2.42, P m (3 hydrogen-cyclopropane); 4.23 - 4.25 - 4.40 - 4.42 - 4.57 pp.p.rn chisel. (hydrogen in 1' of the chain ëthyle cyclopropane in 3); peak

to 6.4, 8 P P m (hydrogen fixed on the same carbon than c=m-Ξ) -, peaks of 7.0 to 1.67 P P m (hydrogènesdes aromatic rings).

Example 6 : (l-R~, yryears) 2.2 d-iméthyl 3 a-cl¹ , 2 ', 2', 2¹ - tetrabromo ethyl) çyçlopropaac -1-carboxylate (e) 1 oxo 2 a-allvl 3 methyl-and cyclopent-to-2-in 4-yl

Step a: acid. (1 The R, trans-)_ 2j. 2 a-substituted dimethyl 3~_ jj.l'" O-tétrabror. 6thy_l) _cyc_looropane L _-carboxylic acid:

This compound is obtained by brominating acid (infrared, trans-) 2.2-dimethyl 3 - (2¹ , 2' a-bromo vinylaromatic) cyclopropane-l carboxylic, isomer mixture (has) and (d).

Spectrum of Dr. R. M. M.,

1.30 To 1.40 peaks P P m (hydrogènesdes methyls in 2 cyclopropane); peaks to 1.65 - 1.74 and 1.97 P P m has 2.37 (hydrogens is 1 and 3 cyclopropane); peaks to 4.30 - 4.47 - 4.47 and

4.65 p P m (hydrogen in 1' ethyl)? 9.63 e. e. the m peak.

(hydrogen of the carboxyl).

Step b: Chlorure_de acid (1r, trans-)_ _ 2_GJS 2-dimethyl 3~_ _ (1 _ (_, 2

2¹ the Thyl - tetrabromo|.) ^ _cclo£ropane L _-carboxylic :

By the action of thionyl chloride on the acid (infrared, trans-) 2.2-dimethyl 3 - (1', 2¹ -, 2 ', 2' a-tetrabromo ethyl) cyelopropane L-carboxylic acid obtained in step a, the acid chloride is used as such for the next step.

R-I spectrum. (Chloroform)

Absorption at 1778 cm " *.

Step c: JlR, 2 fcransj __{the X} 2-dimethyl 3 - _, 2 _ _^2 * 'détrabromo ethyl.) cy £loprooanc2licarboxylate_de j_S|__ L-oxo, 2~3, a-rné ally thyl_cyclor NC. t 2 - en_42yla ■

By action (in the presence of pyridine) of the (e) 1 oxo 2-allyl-

3 - methyl and cyclopent-to-2-in 4-ol-on the previous acid chloride, there is obtained the (IR-, trans-) 2.2-dimethyl 3 - (1¹ , 2 ', 2', 2¹ - tetrabromo ethyl) cyclopropane-l carboxylate (e) 1 oxo 2-allyl-3-methyl cyclopenu-to-2-in 4-yl, isomer mixture (has) and (d).

R-X spectrum. (Chloroform)

/ absorptions to 1725 cm ^, 918 cm VBE1 1710 cm 1655 cm 1638 cm 99, 5 cm^-1 .

Spectre of R. M N.

Peaks to 1.30 - 1.32 - 1.36 ρ ρ.. m (hydrogens methyls in 2 cyclopropane); chisel 1.98 - 2.05 e. e. FFI. (methyl hydrogen in 1 of 3¹alléthrolone); peaks to 4.83 - 5.25 P P'm.

(hydrogens of the terminal methylene of the allyl chain of 1' alléthrolone); peaks to 4.30 - 4.48 and à,4.48 - 4/67 P P m (1 hydrogens¹ the ethyl side-chain in 3 of the cyclopropane ring)? peaks to 5.33 - 6.17 P P m (hydrogen in position 2 'of the allyl chain of 1' alléthrolone.

Example 7 ; (ir, cis-) 2.2-dimethyl 3 - (1¹ , 2¹ , 2¹ , 2¹ - tetrabromo ethyl) cyclopropane 1 carboxylate 5 benzyl methyl 3 a-fury1

By esterification, in. the presence of pyridine, acid chloride obtained in step b of example 3 by the 5 benzyl 3 a-fury1 methanol, is obtained:

has) The isomer (has) the (L-R, cis-) 2, 3 - 2 a-diraëthyl (12',2¹ , 2' a-tetrabromo ethyl) cyclopropane-l carboxylate 5 benzyl 3-furyl-methyl.

the O / (/_D -=(c=0.5%, benzene) 104°. The more mobile isomer in thin layer chromatography.

P P m peaks to 1.23 - 1.37 (hydrogens methyls in 2 cyclopropane); peaks to 1.65 - 2.03 P P m (hydrogens 1 and 3 cyclopropane); peak at 3.92 w, P m (benzyl methylene hydrogens); peak at 4.92 P P m (methylene hydrogens c0₂ HM~₂ ); peaks to 5.27 - 5.67 P P m (1 hydrogen in¹ chain 3 in ethyl cyclopropane); peak at 5.96 P P m (hydrogen in 4 of the furyl); peak at 7.25 P P m (hydrogens of the phenyl);

peak confectioneries 7.33 P P m (hydrogen in 2 of the furyl).

Circular dichroism (dioxan)

Λ 1=- 6.5 to 2.17 nm.

b.) The isomer (b.) the (L-R, cis-) 2.2-to-dimêthyl 3 - (1¹ , 2 ',', 2 2' a-tetrabromo ethyl) cyclopropane-l carboxylate 5 benzyl 3-furyl-methyl.

6 / (+ / ρ=(c=0.5%, benzene) 84°.

Peaks to 1.20 - 1.42 P P m (hydrogens methyls in 2 cyclopropane); peaks of 1.67 to 2.17 P P m (hydrogens 1 and 3 cyclopropane); peak at 3.92 P P m (methylene hydrogens of the bcrbcr.zyic); peak has!, ? 5 e. e. m fKvrlrnrroneiq DNs nipfhvl PDAs of the ^ - ^ c0 HM); peaks of 4.95 to 5.18 P P m (hydrogen in 1' of the chain ethyl cyclopropane in 3); peak at 7.25 P P m (hydrogens of the aromatic ring of the benzyl); i. e. m peak confectioneries 7.33 (hydrogen in position 2 of the furyl).

Circular Dlchroïsme (dioxan)

247 nm to + 4.30.

Example 8 : (l-R_F. lCOS) 2.2-dimethyl 3 - (1¹ , 2¹ , 2¹ , 2' a-tetrabromo ëthyl) cyclopropane]-carboxylate (e) 1 oxo 2-allyl-3-methyl - T-cycloper.2-in 4-yl (isomers and b)

(E) by esterification of 1 oxo 2-allyl-3-methyl and cyclopent-to-2-in 4-ol derivatives, in the presence of pyridine, by acid chloride (Ir, cis-) 2.2-dimethyl 3 - (1¹ , 2 ',', 2 2' a-tetrabromo ëthyl) obtained at the cyclopropane 1-carboxylic¹ step b of example 3, is obtained:

has) The isomer (has) the (L-R, cis-) 2.2-dimethyl 3 - (* 1, 2¹ , 2', 2 tetrabromo ëthyl) cyclopropane-l carboxylate (e) 1 oxo 2-allyl-3-methyl and cyclopent-to-2-in 4-yl.

/ σ (/ ρ '=- 56° (c=0.6%, benzene).•R. spectrum M N.

Peaks to 1.28 - 1.39 P-P, m (hydrogens methyls in 2 cyclopropane); peak confectioneries 1.96 P P m (methyl hydrogen in 3 of 1' alléthrolone); i. e. m peaks confectioneries 4.83 - 5.16 (hydrogens of the terminal methylene of the allyl chain); peaks of 5.33 confectioneries 6.16 P P m (1 hydrogen in¹ the chain in position 3 ethyl cyclopropane and hydrogen in the 2' of the allyl chain).

Circular dichroism (dioxan)

Has the £=1.84 to 332 nm +?

Has [+=2.06 to 320 nm;

to 225 nm - 19.

The isomer (has) is most mobile in thin layer chromatography.

b.) The isomer (b.) the (L-R_{the R} the cis) 2.2-dimethyl 3 - (1 ', 2', 2 ', 2' - tetra bromo-ethyl) cyclopropane-l carboxylate (e) 1 oxo 2-allyl-3-methyl and cyclopent-to-2-in 4-yl. F=110 °C. "/ b-( /_D =+ 8l degrees (c=0.6%, benzene).

Peaks to 1.27 - 1.47 P P m (hydrogens methyls in 2 cyclopropane); peak at 2.07 P P m '(methyl hydrogen in 3 of 1' alléthrolone); peaks of 4.83 to 5.33 P P m (hydrogen in 1 'of the side chain 3 cyclopropane and hydrogen methylene in 2' of the allyl chain); peaks to 5.5 - 5.16 e. e. hr.■(hydrogens 2' of the allyl chain); peak at 5.15 e. e. naked (1 of 4 hydrogens¹alléthrolone).

Circular Dichroîsme (dioxan)

δ u + 2.46 to 332 nm;

THE L - + Λ 2.76 to 320 nm;

+ 3.79 to 250 nm;

- 14.7 225 nm confectioneries.

Example 9 : (l-R_F. the cis) 2.2-dimethyl 3 - (1¹ , * 2, * 2, 2' a-tetrabromo Chloroethyl) cyclopropane-l carboxylate 3-phenoxy benzyl (isomers and b)

By esterification in the presence of pyridine, acid chloride (Ir, cis-) 2.2-dimethyl 3 - (1 ', 2', 2¹ , 2' a-tetrabromo ethyl) cyclopropane-l carboxylic by alcohol 3-phenoxy benzyl, is obtained:

has) The isomer (has) the (L-R, cis-) 2.2-dimethyl 3 - (1 ', 2', 2 ', 2' -

•tetrabromo ethyl) cyclopropane-l carboxylate 3 a-phênoxy benzyl.

F. ≈ 90 °C.

the Q / (/_{the O} ~~ (C=0.5%, benzene) 106°.

Peaks to 0.92 - 1.37 P P m (hydrogens methyls in 2 cyclopropane); i. e. m peaks confectioneries 1.67 - 2.08 (hydrogens in positions 1 and 3 cyclopropane); peak at 5.08 P P m (hydrogens methylene CO ^ ^ HC); peaks to 5.38 - 5.56 P P m (hydrogen in. location 1' ethyl cyclopropane attached in 3); peaks of 6.67 confectioneries 7.58 P P m (hydrogens of the aromatic ring).

Circular Dichroîsme (dioxan)

GBP - 10=<4. to 218 nm.

The isomer (has) is most mobile in thin layer chromatography.

b.) The isomer (b.) the (L-R, cis-) 2.2-dimethyl 3 - (1 ', · 2', 2 ', 2' tetrabromo ethyl) cyclopropane-l carboxylate 3-phenoxy benzyl.

with d=/ / VBE1 K.⁺ 61.5 Degrees (c=2.3%, benzene).

Peaks to 1.22 - 1.42 P P m (hydrogens methyls in 2 cyclopropane); 2.08 to 1.67 peaks P P m (hydrogens 1 and 3 cyclopropane); peaks P P m 5.33 has 4.93 (hydrogen in 1' ethyl cyclopropane in 3); peak at 5.15 P P m (methylene hydrogens of the c0₂ HM₂ ); peaks of 6.75 to 7.58 P P m (hydrogens of the aromatic ring).

Circular Dichroîsme (dioxan)

Has the R .. , ..., "

^^H r ° The £■•<=*" ' juu.

Example 10 : (! The R, tràns) 2.2-dimethyl 3 - (2 ', 2'-dichloro-l', 2' a-bromo ethyl) cycJopropanc L-carboxylate-OD(e) 1 oxo - 3 2-allyl-born thy a I-C.ycjopent-to-2-in 4-yl

Step a: an AC IDs grams j_I R., trans-) _2j32-to-substituted dimethyl. 3 - _ (_ 2j, 2'l_ _* - dichlorophenyl r_2j_dibr οΐ α ο Chloroethyl.) 1 Ο _cyc g PO year ℮ - Iy carboxylmethyl rívetted I-I:

By the action of bromine on acid (L-R, trans-) 2.2-dimethyl 3 - (2', 2¹ in vinyl - dichlorophenyl) cyclopropane-l carboxylic, obtained acid (infrared, trans-) 2.2-dimethyl 3 - (22 'a-dichloride 1', 2¹ - dibronoëthyl) cyclopropane-l carboxylic, isomer mixture (has) and (d).

P P m peaks to 1.17 - 1.37 (hydrogens methyls in 2 cyclopropane); 1.65 - 1.73 peaks P P P P the m to m 1.93 - 2.03.

(1 hydrogens cyclopropane); 4.23 - 4.45 4.45 4.62 and peaks to P P m (hydrogen in 1' ethyl cyclopropane in 3).

Step b: Chlorure_de .1 ' acid (1r, trans_)_ _ 2_gJs 2 a-diraéthy 1 2 - {2 ^, 2' ^ dichloro_l_, _ 2¹pdibromo_éthyl) cyclopropane _; ylycarboxy_liqu 00:

By the action of thionyl chloride on the acid prepared in step a previous, obtained acid chloride (Ir, trans-) 2.2-to-dimêthyl 3 - (2¹ , 2¹ - dichlorophenyl ', 1 2' a-bromo ethyl) cyclopropane-l carboxylic.

R-I spectrum. (Chloroform)

Absorption at 1777 cm ^.

Step c: J_lR_F. the trans) 2 _ ^ 2-dimethyl 3 a-j2 ^ _, _ 2 '^ dichlorophenyl 1' 2 /Jydibromo ethyl) _cycloDropane L₁ (e)- carboxvlatede_ _ ly ° .xo_2yallyl_32méthyi.

and cyclopent-to-2 _ a-en_ 4 yl_: i:

By esterification in the presence of pyridine, the previously prepared acid chloride in step (e) by the 1 oxo 2-allyl-3-methyl and cyclopent-to-2-in 4-ol-, obtained the (IR-, trans-) 2.2-dimethyl 3 - (2 ', 2' dichloride 1 ', 2' a-bromo ethyl) cyclopropane-l carboxylate (e) 1 oxo 2-allyl-3-methyl and cyclopent-to-2-in 4-yl as a mixture of isomers (has) and (d).

Peaks of 1.30 to 1.34 P P m (hydrogens methyls in 2 cyclopropane); peaks of 1.63 to 3.0 P P m (hydrogens I and 3 cyclopropane); peak confectioneries 2.05 P P m (methyl hydrogen in 3' of 1¹alléthrolone); peaks to 1.95 - 3.03 P P m (1 in methylene hydrogens¹ of the allyl chain); peaks to 4.25 - 4.43 4.61 P P m (hydrogen in 1' of_% the cyclopropane in ethyl 3);

peak of 4.25 P P m (hydrogens of the methylene chain terminating allyl); peaks of 4.83 confectioneries 5.41 P P m (hydregene in position 2' of the allyl chain); peak at 5.83 P P'm.

(hydrogens 4 of 1' alléthrolone).

Example 11 : (ir, cis-) 2.2-to-dimethy1 3 - (2', 2¹ 1 - bromo¹ , 2' - dichlorophenyl ethyl) cyclonropane-to-1-carboxylate (SRV) 7 α-cyano 3 a-phénoxv Bas zylc

Step a: j.1r acid, cis-)" substituted dimethyl 'ydÿbromo_l 2 _' ydÿchj °ro_éthvll_. the £çyclopropaneylycarboxyli UEs^:

30 Cm3 in carbon tetrachloride, introduced by bubbling s - 15 °c, 11.8 ' g of chlorine, then slowly added to

- 10 °c, 24 g of an acid solution (Ir, cis-) 2.2-dimethyl 3 - (2 ', 2' a-bromo vinylaromatic) cyclopropane-l carboxylic in '37 cm3 of methylene chloride, stirred for one hour and 30 minutes to 2 hours and during 0 °c confectioneries 25' °C, concentrated under reduced pressure, purified by crystallization in carbon tetrachloride and obtains 7.4 g acid (L-R, cis-) 2.2-dimethyl 3 - (2¹ , 2 'a-bromo 2' 1 ',-dichloro-Chloroethyl) cyclopropane-l carboxyligue. F=134 °c (mixture of isomers (has) and (d)).

Peaks to 1.32 - 1.44 confectioneries and 1.28 - 1.48 P P m (hydrogens methyls in 2 cyclopropane); peaks to 5.08 - 5.45 and to 4.67 5.0 P P m (hydrogen in 1' of the chain ethyl cyclopropane in position 3); peak confectioneries 10.1 P P m (hydrogen of the carboxyl).

Step b: Chlorure_de 1' acid_e j_1r, cis-)_ _ 2_{the I} _ 2-dimethyl-bromo 1 ' 1 / _ j-di çhjLoro_é the Thyl]_ cyc1oprooane-a 1 a-carboxy1 unterstanding of I:

By the action of thionyl chloride in the presence of pyridine on the acid obtained in step a previous, obtained acid chloride (Ir, cis-) 2.2-dimethyl 3 - (2 ', 2' a-bromo l', 2'-dichloro-ethyl) cyclopropane-l carboxylic, used as such for the next step.

Step c: _ (1r, IC e)_ 2_{the I} 3y 2ydiméthyJL _ (2, 2¹ydÿbrono_l_|_, 2 ' polyethylene resins of £ichloroyd) _cycl_cycl.opropane and 3_L - carboxyl_atede_ (RSs|_ 7 ycyano_3yphénoxy benzyl:

By esterifying alcohol (R) DEGREES ( a cyano - 3-phenoxy benzyl in the presence of pyridine by the acid chloride obtained in step b above, obtained the (L-R, cis-) 2.2-dimethyl 3 - (2 ', 2'-bromo 1 ', 2'-dichloro-ethyl) cyclopropane-l carboxylate (R)- cyano-the c ^ 3-phenoxy benzyl, isomer mixture (has) and (d).

Chisel 1.23 - 1.52 P P m (hydrogens methyls in 2 cyclopropane); 2.11 has peaks of 1.77. w, - m-P(R ogeneshvr3 in 1 and 3 of the rvnlnnrnnaiiûl•nor the n WITH 70 / - 5 £∩ û4 - 0 - m-m-m-ζ 01 drogcne in 1' OD the ethyl side chain at position 3 cyclopropane); peaks 6.40 to 6.43 P P m (hydrogen, carried by the same carbon than c - ΞΞΤΝ); peaks of 6.94 to 7.66 P P'm.

(hydrogens aromatic rings).

Example] 2 : (Infrared, LC e) 2.2-dimethyl 3 - (2¹ , 2¹ 1 - bromo¹ , 2¹ dl - ch-lore ethyl) DEYE oprooanc] and 1-carboxylate (e) 1 oxo 2-allyl-3-methyl and cyclopent -? - in 4-yl

By esterification of the acid chloride obtained in step b of example] 1, (e) by the 1 oxo 2-allyl-3-methyl 4 - and cyclopent-to-2~en ο 1, is obtained (Ir, cis-) 2.2-to-dimôthyl - 3 (22 'a-bromo the, 2' Chloroethyl dichlorophenyl) cyclcpropane-to-1-carboxylate (e) 1 oxo 2-allyl-3-methyl and cyclopent-to-2-in 4 ℮ ^ 1, isomer mixture (has) and (d).

Peaks to 1.25 - 1.45 1.29 - 1.40 and P P m (hydrogens of methods for the ' nyles in 2 cyclopropane); peak at 1.96 P P m (methyl hydrogen in 1 of 3¹alléthrolone); peaks to 2.96 - 3.03 P P'm.

(hydrogens methylene in 1 'of the allyl chain); peaks to 4.83 - 5.16 P P m (hydrogens of the terminal methylene of the allyl chain); peaks to 5.25 - 5.36 P P m (hydrogen in 1' chain 3 in ethyl cyclopropane); peaks of 5.5 to

6.0 p P m (hydrogens 4 of 1 'alléthrolone and hydrogen in the 2' of the allyl chain).

Example 13 : (ir, trans-) 2.2-dimethyl 3 - (2¹ , 2¹ 1 - bromo¹ , 2' a-dichlceR ethyl) cyclopropane-l carboxylate (R)- cyano-3 a-phérphér.oxy ^ benzyl

By action of chlorine on acid (L-R, trans-) 2.2-dimethyl 3 - (2¹ , 2¹ in vinyl-bromo -) cyclopropane-l carboxyligue, obtained acid (L-R, trans-) 2.2-dimethyl 3 - (2¹ , 2¹ 1 - bromo¹ , 2¹ - dichloro-ethyl) cyclopropane 1-carboxylic acid which is converted into the acid chloride by the action of thionyl chloride, and then esterified as previously by alcohol (R) the O{a cyano - 3-phenoxy benzyl and obtains the (L-R, trans-) 2.2-dimethyl 3 - (2¹ , 2' a-bromo-L¹ , 2'-dichloro-ethyl) cyclopropane-l carboxylate (R)- cyano-3-phenoxy benzyl, isomer mixture (has) and (d).

Peaks to 1.22 - 1.27 - 1.37 - 1.4 - 1.45 P P m (hydrogens methyls in 2 cyclopropane); peaks P P m to 2.5 to 1.67.

(hydrogens 1 and 3 cyclopropane); peaks pp.p.n 3.67 to 4.5.

(hydrogen in M M * chain ethyl cyclopropane in 3);

6.52 confectioneries peak P-P, m (hydrogen carried by the same carbon that the CSN)? peaks of 7.0 sec 7.67 ρ ρ.. m (hydrogenated aromatic rings).

Example 14 : (Infrared, trans-) 2.2-dimethyl 3 - (2', 2¹ -difluoro - 2 'l', dithe bromo ethyl) cyclopropane-l carboxvlate of (e) 1 oxo - 2-allyl-3rodthylcÿclopent-to-2-in 4 a-TLV

Stade_A_: acid (infrared, trans-) of £, 2^_ di £sthyl_3 - (2 '- 2 ^ ^ DIFs luoro_l GBP, .2' éthyl_-bromo) _cvc_lo£ropane L _ a-carbox ^ lic:

Similarly to those described previously by action of bromine on acid (infrared, trans-) 2.2-dimethyl 3 - (2', 2¹ in vinyl-difluoro -) cyclopropane-l carboxylic, but by operation at - 60 °c, obtained acid (infrared, trans-) 2.2-dimethyl 3 - (2 '2 ', difluoro 1¹ , 2¹ bromo ethyl) cyclopropane-l carboxylic. F=122 °c (mixture of isomers (has) and (d)).

Peaks of 1.33 to 1.36 P P m (hydrogens methyls in 3 cyclopropane); peaks of 1.60 to 2.23 P P m (hydrogens 1 and 3 cyclopropane); peaks of 3.75 to 4.37 P P m (hydrogen in 1' of the chain ethyl cyclopropane in 3); peak at 10.96 P P m (hydrogen of the carboxyl).

Step b: Chlorure_de _ 1 '1 R-J_ acid, trans-) _j_ _ 2 2 d-imqthy __ 1 - 3 (2j _, luoro_l_ DIFs) _, 2_'p_dibromo_éthyl)_ cyclopropane-l carboxylic:

By the action of thionyl chloride on the acid obtained in step a previous, obtained acid chloride (infrared, trans-) 2.2-dimethyl 3 - (2 ', 2' difluoro 1 *, 2' a-bromo ethyl) cyclopropane 1-carboxylic acid used as such for the next step.

Step c: _ (1 the R, trans-) _j_ _ 2 2 a-substituted dimethyl 2~_ (.2j ^, 2'l_-difluoro - ' _j_ _ 2)_ a-bromo ethyl) _cyclo£ropane-to-a-carboxylate (e) de__lpoxo_ 2 a-ally1_ 3-methyl and cyclopent-a 2 and 4 en_-yl:

By esterification of the acid chloride obtained in step b above, (e) by the 1 oxo 2-allyl-3-methyl and cyclopent-to-2-in 4-ol-in the presence of pyridine, to give the (IR-, trans-) 2.2-dimethyl 3 - (2 ', 2' difluoro 1 ', 2' a-bromo ethyl) cyclopropane-l carboxylate (e) 1 oxo 2-allyl-3-methyl and cyclopent-to-2-in 4-yl, isomer mixture (has) and (d).

Peak at 1.32 P P m (hydrogens' methyls in 2 cyclopropane);

peaks of 3.26 to 1.68 and 1.73 to 2.19 P P m (hydrogens I-cyclopropane); peak at 1.20 P P m (methyl hydrogen in 3 of 1 'alléthrolone); 2.93 peaks P P m has 3.05 (hydrogen methylene 1' of the allyl chain); peaks, of 4.83 to

5.25 ρ ρ.. m (hydrogenated terminal methylene of the allyl chain); 3.58 to 4.3 3 P-peaks. p m (hydrogen 'in 1' of the chain ethyl cyclopropane in position 3); peaks of 4.83 to 5.25 P P m (hydrogen in 2' of the allyl chain); peak confectioneries

5, 5.83 p P m (hydrogens 4 of 1' alléthrolone).

Example 15 : (ir, cis-) 2.2-dimethyl 3 - (2¹ , 2' - dichloro-1¹ , 2' a-dibrordibror.o ethyl) cyclopropane-l carboxylate (SRV) pj is a cyano - 3 a-phëno: Bas<thereinzyle

Step a: acid _ (1 _ the R, cisJ_2yd thy a PLA 2 ^ 1. 2¹ " dichlorophenyl!_¹j2 '_ -

o-O-dibrorr. éthyJL) - carboxylic Iy _cyclojoropane:

By the action of bromine on acid (L-R, cis-) 2.2-dimethyl 3 - (2 ', 2'-dichloro-vinyl-) cyclopropane-l carboxylic, obtained acid (L-R, cis-) 2.2-dimethyl 3 - (22¹ 1 - dichlorophenyl¹ , 2' a-bromo ethyl) cyclopropane-l carboxylic, isomer mixture (has) and (d).

1.26 - 1.30 Confectioneries peaks and 1.41 - 1.42 P P m (hydrogens methyls in 3 cyclopropane); peaks to 1.83 - 2.17 e. e. the Ra. (hydrogens 1 and 3 cyclopropane); peaks of 4.83 5.58 m-P to P.

(hydrogen; in 1¹ ethyl 3 in cyclopropane); peak at

8.17 p P m (hydrogen of the carboxyl).

Step b: HM] _orure_de the J acid (SR, çis)_ 2_{the X} 2-dimethyl 3y _ (2 ^, ^ 2 'ydichloro_l_, 2 _' thy a 1 yd TONI omo_é]_ which yc ARs boxy_1ique çyclopropaney 1:

It is obtained by the action of thionyl chloride on the acid obtained in step a above.

: 5 Step c: _ (_ 1r, CYI)_ _ 2_{the I} 1 __ _2ydimëthy 3 - _ (, 2¹ydichloro]_¹ tONI orrorr.o ethyl) _cyclopropane-to-lycarboxvlatede_ (RSs]_ ^ ^ ycyanoSyphénoxy benzyl:

It is obtained by esterification in the presence of pyridine,

acid chloride obtained in step b above, by alcohol

50 (SRV) C.>{a cyano - 3-phenoxy benzyl, isomer mixture (has) and (d).

1 £•1r * T-for example, the cis 2, 3~2 a-substituted dimethyl (2 *, 2 *, 2^! , 1¹ - tee trahromoéthyl) cyclopropane 1 carboxylate OD RSs; 6-cyano-benzyl 3-phenoxy " of £Stade_A_ _* 1r acid chloride^{c.; the I} -^O 2.2-dimethyl 3 - ^ ^ ^ ^ 2 2 2 ν tee trnbroraoéthyl2cyclopropane-to-1-carboxylic acid,

40 Cm3>5 in a mixture of petroleum ether (to EB_O 35 AND 70°),

10 cm3 and thionyl chloride, 8.9 grams of d is introduced^F. aci.de (infrared, cis-) Z-, 3 2-dimethyl - (2 *, 2¹ , 2 *, V-¹ - tétrabromoéthyl) cyclopropane 1 - carboxyliquo, refluxes, maintains the 3 hours under reflux for, üliiüine ether oil and OD 1 * excès thionylc chloride by distilling and obtains the OD 1r acid chloride, IC e 2.2-to-substituted dimethyl - 3 · (2^{the R} , 2 ', 2', 1 * - tétrabromoéthyl) cyclopropane 1 a-cnrboxyliquo raw "

¹ ; ^¹ 11¹ ^~tee trabromoéthvlEE2E2 basing the I 00 00' 2 £llz^C. 2r^{bo is} the R ^ '* -^has ^^G-C. * ^ ^ 3 HS for GBP ℮ - ℮ α ηο 3-phenoxy benzyl.

In a mixture of benzene and 10 cm3 5 cm3 pyridine, 7 g of alcohol is introduced ated-cyano-benzyl 3 a-phéuoxy, adds to 0 °c, in 15 minutes the crude acid chloride obtained in step a, in solution in 4 θ cm3 benzene, stirs to 20 °c, 16 hours during, acidified to pH 1 by a dilute aqueous solution of hydrochloric acid, extracted to benzene, washing of the organic phase to water, dried over magnesium sulfate and concentrated solution is dry benzene j. chromatography the residue on silica gel eluting with benzene and obtains 1r 7s 33 g, 2.2-dimethyl 3 - cis-(2 ', 2', 2. ', 1" - tétrabromoéthyl) cyclopropane 1 a-carboxylato of R, O // a cyano - 3 a-phénox3^{the R} benzyl.

/malyse : C. i ^ ^ ^ O-n-brr,₊ (665.05)

Calculated C #39.73 hr with fo 2.88 D #2.10 brr ^C. the O / 48.06

Found e 39.7 3 2.2 47.4 " IR spectrum Rougo (chloroform)

Absorption at 1743 cm ""¹ , characteristic of the carbonyl ii absorptions to 1613, 1588, 1477 cm, features the ACS aromatic rings,

Uu.y spectrum. (ethanol)

Inflection to 230 nm (ε=194|) J.

Inflection to 270 nm (ε=|36) 5

Maximum at 278 nm (ε=|37),

Inflection to 2s5 nm. (I|=28)"

- NMR spectrum (deuterochloroform)

1, 23 - 1, 5 P-peaks, P-" the m, characteristics hydrogens methyls gemini J.

p-peaks to 1, 83 - 2, 16 "w" the m, characteristics of the hydrogens of the cyclopropyl;

peaks to the P * 4, 82 - 5, 5 p.m., characteristics of hydrogen in position 1' OD ethyl substituted side chain,

p-peaks to 6, 37 - 6, 42" p * m; characteristics of 1' hydrogen attached to lo and Laddie carbon - CHNs quo to the group,

oD peaks 6, 83 - 7, 58 ppm characteristics back hydrogens of 1r acid, 3 - cis-2.2 a-substituted dimethyl (2 *, 2 ", 2", 1' a-tétrabromoéthyl) cyclopropane 1-carboxylic acid used in step OD can be prepared as follows:

30 Cm3 in carbon tetrachloride, introduced 5 grams

the d * 1r acid, 3 - cis-2.2-dimethyl (2 ', 2' a-dibromovinyl) cyclopropane 1-carboxylic, tee has j centimeters, in 30 minutes approximately ., a solution of 0.9 cm3 die bromine in 10 cm3 of carbon tetrachloride, stirred for one hour and 30, min, concentrated to dry under reduced pressure and obtains an IR 8.9 g acid, cis-2.2-dimethyl 3 - (2 ', 2', 2 *, 1" - tétrabromoéthyl) cyclopropane 1-carboxylic crude.

Example 17: infrared, trans-2.2-dimethyl 3 - (2 ** 2 ', 2', T tetrabromoéthyl) cyclopropane 1 carboxylate 3-phenoxy benzyl"

20 Cm3 in benzene, is dissolved 5 grams - IR-acid chloride, 3 - 2.2-dimethyl-trans (2 ', 2 *, 2 ', 1 'a-tétrabromoéthyl) cyclopropane-l earboxylic, 2.4 g of alcohol 3-phenoxy benzyl, cooled to 0 °c, introduced progressively 4 cm3 pyridine, stirred for 48 hours at 20 °c, pouring the reaction mixture into an aqueous solution of hydrochloric acid, extracted to benzene, washed with sodium bicarbonate, water, dried on sodium sulfate and concentrated to dryness by distillation under reduced pressure "is obtained 6, 2g of residue that silica gel chromatography by eluting ^ ith a mixture of petroleum ether (to EB, 35 and 75 degrees Celsius) and ethyl ether (9/l) and collects and 3.68 g of 1r, trans-2.2-dimethyl 3" * (2', 2 ', 2', 1' - tétrabromoéthyl) cyclopropane 1 carboxylate 3-phenoxy benzyl (isomer mixture a and b),

Analysis c ^ ^ ^ ^ O-O brr (640.03)

Calculated: # C. 39.41 hr % 3.15 Brr % 49.94

Found: 39, 9 3.2 50.2 "

Spectrum An IR (chloroform)

Absorption at 1728 cm ", characteristic of the carbonyl, 1615 - 1590 -1490 cm to characteristics of absorptions ** aromatic rings

NMR spectrum (deuterochloroform)

To peaks 1, 26 - 1, 29 - 1, 35 p * p " the m, geminal methyl hydrogens of characteristics;

peaks to the P "w" of m 2, 00 - 2, 33, characteristics of hydrogen in position 1 of the cyclopropyl;

peaks to the P 1, 70 - 1, 79" p * m, characteristics of hydrogen in position 3 of the cyclopropyl,

peaks to 4, 31 - 4, 48 - 4 * 50 - 4,67 w, p.m., characteristics of hydrogen in position 1' of the substituted ethyl side chain;

5 peaks " 17 - 5, 20 p.p.m., characteristics of methylene hydrogens of the benzyl moiety,

peaks to 6, 92 - 7, 58 p.p.m., characteristics of the hydrogens of the aromatic rings.

Chloride 1 'Ir acid, 3 - traas 2.2-dimethyl (2 *, 2", 2 *, 1' tétrabromoéthyl) cyclopropane 1-carboxylic used at the start of the present example can be obtained as follows:

' i-² the I *² the Thyl ^ * of £tetrabromo - cyclopropane-l earboxylic.

Act 1 * acide 1r on bromine, trans-2.2-dimethyl 3 - (2 *, 2 Udibrbmovinyl) cyclopropane 1-carboxylic acid analogously to that used in 1 '1 example έ℮ΐ obtains 1" 1r acid, trans-2.2-dimethyl 3 - (2', 2 *, 2 *, 1' a-tétrabromoéthyl) cyclopropane 1-carboxylic acid (isomer mixture a and b).

NMR spectrum (deuterochloroform)

1.30 To 1.40 peaks P p.m (hydrogens methyls in 2 cyclopropyl) J.

peaks to ^ 1, 65 - 1, 7 and¹ " 97 - 2, 37 P.p.m., 1 and 3 hydrogens cyclopropyl;

4, 30 - 4, 47 to peaks and 4, 47 - 4, 65 p.p.m., (hydrogen in 1' ethyl);

peak at 9" 83 P p.m (hydrogen of the carboxyl),

E ^ tade_B_ chloride * 1" 1' a-tétrabromoéthyl) cyclopropane 1-carboxylic acid.

By the action of thionyl chloride on the acid obtained in step a, similarly to glue 1 'example 56, obtained chloride the acidél 1r, 2.2-dimethyl-trans - 3 (2', 2 ', 2', 1' tétrabromoéthyl) cyclopropane 1-carboxylic acid.

Example 13 ii 1r, cis-2.2-dimethyl 3 - (2 ', 2', 2 *, 1' a-tétrachloroéthyl) cyclopropane 1 carboxylate 3-phenoxy benzyl,

Stade_A 9.ï ^ ^ 2 cis-IR-acid 2 a-dimcthvl of £2 - 3¹ ethyl) cyclopropane 1-carboxylic acid.

30 Cm3 mainly in carbon tetrachloride, chlorine is bubbled up to saturation (dissolved 11.8 g of chlorine), introduced in 30 minutes a solution of 16.7 S 1r acid, 3 - cis-2.2-dimethyl (2 ', 2' a-dichlorovinyl) cyclopropane-T-carboxylic in 4o. cm3 of methylene chloride, at a temperature below 0 °c, 24 hours at 0 °c stirred pepdant, causes the temperature of the " j-j ii 1 the X,otîor " the n r-e -** - THE X -. temperature, eliminates excess chlorine by bubbling nitrogen, dry concentrate by distillation, under reduced pressure, the residue is purified by chromatography on silica gel by eluting with a mixture of cyclohexane and OD/ethyl acetate (8f2)_T- crystallizes in the éthcVde oil (to EB, °0 35 - 75) and obtains 3.14 1r g acid, 3 - cis-2.2-to-dimlxthyl (2 ', 2 *, 2', * .1 - tétrachloroéthyl) cyclopropane 1-carboxylic F. ≈ 144 °c.

Analysis: ^ ^ ^ LC hCG Ρ 27, 98)

Calculated ii C. lo 3 ^, 3 HR /* the O 3.6 LC with fo 50.6

Found: 34.4 3.7 50.3,

nMR spectrum (deuterochloroform)

1, 26 - 1, 42 P-peaks, P-₀ m and 1, 30 - 1, 42 P p.m characteristics hydrogens gemini methyls;

7 4.67 - 5, ΐ peaks ρ·ρ·ηΐ and 5.08 to 5, 43 P p.m characteristics has hydrogen 1' of the substituted ethyl side chain;

peaks of 1.67 to 2.0 m-pp.p *, characteristics of the hydrogens of the cyclopropyl ;

peak at 10.2 p.p.m., characteristic of 1 * hydroxyde carboxyl.

The £Stade_B__Chlorure_de__lacidei ^_{_} 1_5i, £i £_2 ^ ^ ^ I-L-diméth 3 - 2 ^ ^ '^ 2' 2 '^ 1' î'2îïl2.2^: gBP GBP i22ï22S22zIz22ilk2il2Ziïi2ï2éiîï!: SZiîS^uEs •

In a mixture of 60 cm3 of petroleum ether (to EB. 35 and 70 degrees centigrade) and 8.7 cm3 thionyl chloride, 6.75 g acid introduced 1r, cis-2.2-dimethyl 3 - (2 ', 2 ', 2 ', 1' a-tétrachloroéthyl) cyclopropane 1-carboxylic, carries the reaction mixture at reflux, kept there 4 hours and 30 mins, concentrated to dryness by distillation under reduced pressure, adds benzene, concentrated to dry and obtains 1r acid chloride, 3 - cis-2.2-dimethyl (2 ', 2 ', 2 ', 1' a-tétrachloroéthyl) cyclopropane 1-carboxylic crude used as such for the next step *

3 thvl " _ (_ 2^2', 2 ^ - ^ 1 * tétrachloroéthyl) 22 2 2 Σ ΐ Ξ ^ 1 2222 ΐ ΐ; Ξΐ 22⁰ ^ ^ ^⁶ 3^2" phén°xy benzyl.

Dissolving the crude acid chloride in benzene θ cm3 6, 'introduced at 75 °c, 5.2 g of alcohol 3-phenoxy benzyl in solution in 50 cm3 of benzene, pyridine and then 2.6 cm3, stirred for 16 hours at 20 °c, the reaction mixture is poured into a mixture of water and hydrochloric acid, extracted with ethyl ether, and after concentrating to dryness of the ethereal solution, 11 g of residue obtained is chromatographed on silica gel eluting with a mixture of benzene and cyclohexane (1/1), crystallizes in ether and obtains a first fraction OD 4.6 g of 1r, cis-2.2-dimethyl 3 - (2', 2', 2^! , 1' - tétrachloroéthyl) cyclopropane 1 carboxylate 3-phenoxy benzyl f=86 °c, !Û<- ^ Q- -86.5 Degrees (0.5 c/o=00, benzene).

Analysis : C, (462.20)

C calculated iF 54.56 HR the I 4.36 LC iF 30.68

Found: 54.9 4.5 30.3 *

Ultraviolet spectrum (ethanol)

I ^ j=228 226 nm to inflection,

I ^=36 inflection à - 266 nm,

1

Most ee.j 271 nm=41,

Maximum at 277 nm Ε=θ ^ 4.

RKM spectrum (deuterochloroform)

Peaks to 1, 27 - 1, 4 p.p.m., characteristics hydrogens methyls geminal isomer has j

5.13 ρ·Ρ· π ΐ to peak, characteristic of hydrogen group

- C 0chl - isomer to•

0

peaks to 5, 27 - 5, 43 p.p.m., characteristics of hydrogen in position 1 * of the side chain of the ethyl isomer has,

1, 23 - 1, 40 p.p.m. to peaks, features methyls geminal hydrogens of the isomer B,

peak at 5.18 p.p.m., characteristic of hydrogen group

C OCEL - b-isomer,

iF

peaks to 4, 83 - 5, 17 p.p.m., characteristics has hydrogen '1' of the side chain of the ethyl isomer B, peaks 1, 61 - 2, 03 p.p.m., characteristics of hydrogen c3 '^,clopropyle,

peaks to 6, 92 - 7, 58 p.p.m., characteristics of the hydrogens of the aromatic rings "

This NMR spectrum shows that the compound contains about 9/10 of isomer A and isomer B of 1/10.

. By further chromatography is obtained, after crystallization from ether in the second fraction of 3.3 S of 1r, the cis 2, 3 2-dimethyl - (2 *, 2 ', 2 ', 1' a-tétrachloroethyl) cyclopropane 1 carboxylate 3-phenoxy benzyl, F. ≈ 62 °C // THE X ^=DEGREES -9 DEGREES (00=1 flt benzene).

IR spectrum (chloroform)

-1

Characteristic of the carbonyl absorption at 1725 cm, 1615 - 159 q -, 1490 cirf absorptions to ^ characteristics hydrogens aromatic rings "

Spectrum - RîlH■■( - doutérochlorof elm)

Peaks to 1.23 - 1, 4 ΐ w, w, w characteristics methyls geminal hydrogens of the isomer B;

4, 83 - 5, 17 p-peaks, P-" m-characteristics has hydrogen 1v ' of the side chain of the ethyl isomer B;

peak at 5.2 w_I p.m characteristic hydrogens of the array:

- More O-O clip - b-isomer.

O

1, 28 - 1, 4 peaks ç. p.m characteristics hydrogens methyls geminal isomer has;

5, 27 - 5, 43 p * p to peaks " m-characteristics of hydrogen in position 1' of the side chain of the ethyl isomer has j

peak at 5.13 w " w, m-characteristic of hydrogen group:

- jji-O-CHP-isomer has j

peaks to 1.58 - 2^08 w. p.m characteristics hydrogens of the cyclopropyl;

6, 9 - 7, 16 p-peaks, P-" m-characteristics of the hydrogens of the aromatic rings.

This spectrum of rii-and shows that the compound contains about 3/5 of isomer b and 2/5 of isomer has,

Example43 ; 1R, cis-2.2-dimethyl 3 - (2 ".2", 2 ', 1' a-tétrachloroéthyi) cyclopropane 1 carboxylate of R, Sgé-to-evano 3-phenoxy benzyl " Patent: irir.cis acid chloride 3 - 2.2 to-diméthvl (2 ', 2', 2 ', 1' - ^ ^ ^ c-L-tétrachloroéthclogrogane L-carboxliajaee ^

5 Is used, ^ g acid 1r, corresponding cis-and it is carried out in a manner similar to that used in step b of example i8 " step b ii IRje.⁰¹ ' -³ 2^2-dimethyl 3 - (2 '^ 2' 2 '1 ^' ^ - ^ c-tétrachloroéthvl2 cloprogane-to-1 carboxylate ^ ^ ^ - ^ C. RjjS anogenital 3 a-phénox£_benzyle dissolving the acid chloride obtained in step a of the present example in 50 cm3 of benzene, introduced at 4 - 5 °c, a solution of 4.6 g of alcohol R, O ^ a cyano - 3-phenoxy benzyl, 30 cm3 in benzene, pyridine and then 2.2 cm3, stirred for 48 hours at room temperature, the reaction mixture is poured into a mixture of water and hydrochloric acid, extracted with ether, dry ethereal solution is concentrated, the residue gel chromatography on silicàvecéîuant in a mixture of benzene and cyclohexane (l/2) and obtains 4.7 g of 1r, cis-2.2-dimethyl 3 - (2 ', 2 ', 2 ', 1' a-tétrachloroéthyl) or cyclopropane - 1 carboxylate (the R, e) a Ti-cyano-benzylidene-to-1r 3-phenoxy "/ /, / 6? = . (i VBE1 - cl.h the s-n ^<hr ànp).

Analysis : ^ ^ ^ H-c-c-n->LC₃ (487.22)

Calculated; C. The O/degrees 54.23 HR ^C. the O / 3.93 LC ^C. the O / 29.11 N. ^C. the O / 2.87 Found: 54.3 3" 8, 29.0 2.8.

UfV spectrum. (ethanol.)

Inflection to 227 nm (≈ 225 JE) J.

Inflexion at 268 nm (ε=35|) ii

Inflexion at 272 nm (ε=|38)?

Maximum at 278 nm (ε=|43) the j.

Inflection confectioneries 284 nm (W *=33)"

mR spectrum>T- (deuterochloroform)

Peaks to 1, 22 - 1, 43 pp.p₀ the m, geminal methyl hydrogens of characteristics;

to peaks 1, 67 - 2, 08 p.p.m., characteristics of the hydrogens of the cyclopropyl;

peaks 4, 83 - 6, 47 to PEP's " in-, characteristics of hydrogen in position 1 * OD ethyl substituted side chain;

peaks to 6, 38 - 6, 46 p.p.m., characteristics of hydrogen carried by the same carbon that the Cn $

peaks to 6, 92 - 7, 58 p.p.m., characteristics of the hydrogens of the aromatic rings.

Example 20 ii an IR, the OIS 2.2 dimethyl 3 - (2 ', 2', 2^F. , 1 * - tetrachloroéthvl) cvclonronane-to-1 carboxylate of FRS) alléthrolonc,

3 ** i-²¹ j.,^2; * T- 1' - tétrachloroéthyl) cyclopropane 1 - carboxvlique.

Is prepared as in step b of example) 3 starting with 7 g acid 1r, corresponding cis-"

Step b: 1r, cis-2.2-dimethyl 3~(2 ', 2', 2 '" 1' a-tétrachloroéthvl) GBP £z £i2s £2 £™ III 22ZiSi ^ e 00 00^I . -,^of (^Rallethrolone .SL "

Dissolving the acid chloride obtained in step a of the present example in 20 cm3 of benzene, introduced to * 5 °c, a solution of 4 g of allethrolone 15 cm3 in benzene, pyridine and then 2.55 cm3, stirred for 18 hours at 20 °c, poured into a mixture of water and hydrochloric acid, extracted with ether, dry cthérée solution is concentrated, the residue chromatographed on silica gel, eluting with a mixture of cyclohexane and ethyl acetate (9/1) and obtains 8 g of 1r, cis-_F. 2.2-dimethyl 3 - (2 ", 2 ', 2', 1" tétrachloroéthyl) cyclopropane 1-carboxylate (SRV) alléthrolone^ ^~/ YF -54.7 Degrees (≈ 0.5 c_vBE1 i° chloroform)

Analysis : ^ ^ ^ II-c-LC(4 ΐ 4, 15)

Calculated: C. ^C. the P 4 - 9, 30 Η °p 4.87 34.24# LC

Found: 49.5 4.9 34.1.

U-spectrum, V.<, (ethanol)

Most 227 nm (Ε ^=334).

Spoctre of R? 1n (deuterochloroform)

1, 31 - 1, 42 P-peaks to_I p.m., characteristics of the hydrogens of the mth -

thyles gemini e,

to peaks 1, 67 - 2, 17 P p.m, characteristics of the hydrogens of the cyclopropyl;

peaks to 4, 83 - 6, 17 p.p.m., characteristics has hydrogen -1 ' side chain-ethyl substituted *

Example 2/1: 1r, 3 - trans-2.2-to-diraéthyl (2 ', 2 ',', 1 2' a-tétrachloroéthyl) cyclopropane 1 (R)- carboxylaterestorativee/a cyano - 3-phenoxy benzyl " Stadium _A_: c-c-d-I-T-R-year _R __ 1 _ 2 sec._? _ 2 - mth T-dl of HY * ^ ^ 3 - £2 1 2 2 ^ "•- tétrachloroé WFQ 1 £cycloproaane - _ 1 a-carboxviic"

In 30 cm3 of carbon tetrachloride, is dissolved to -10 °c, 13.25 g of chlorine, added in 15 minutes approximately 18.8 g acid 1r, trans-2.2-dimethyl 3 - (2 '2 ', above dichlorovinyl) cyclopropane 1-carboxylic acid in solution in 30 cm3 of methylene chloride, the reaction vessel being surmounted by a refrigerant circulating a pre - 6o °C to condense the unreacted chlorine, stirred for one hour and 30 minutes to -10 °c, and then for one hour and 30 minutes at 0 °c, removes chlorine or excess, to 20 °c, by bubbling nitrogen, concentrated to dry under reduced pressure, the residue is purified by chromatography on silica gel by eluting with a mixture of cyclohexane and ethyl acetate (7/3) and obtains 23 g acid 1r, 2.2-dimethyl-trans - 3 (2 ', 2', 2 ', 1' tétrachloroéthyl) cyclopropane 1-carboxylic acid used as such for the next step:

Step b; IR-acid chloride, 3 - 2.2-dimethyl-trans (2 ', 2', 2 ', 1' a-tétrachloroéthyl) cyclopropane 1-carboxylic acid.

In a mixture of 30 cm3 of Cther of petroleum (eb.35 above 75 degrees Celsius) and 16 cm3 thionyl chloride, is introduced 12,276 g acid obtained in step a, and refluxes, maintains the reflux for 4 hours and 30 mins, concentrated to dryness by distillation under reduced pressure, adds benzene, concentrated again

a plowshare and obtains an IR chloride acid, trans-2" 3 2-dimethyl - (2 *, 2 ', 2', 1 * - tee trachloroc polyethylene resins) or cyclopropane - 1 carboxylic acid, used as such for the next step ii

Step g I-1r, ARTnsec 2, 2 a-substituted dimethyl 3 - (2 ', 2', 2', 1' - teetrachlorocthryl) cyc 1 opropane L-carboxylate (SRV) szee cyano 3 a-phénox3^{the R} b.enzyle.

Added to the acid chloride obtained above in step b, 25 cm3 OD benzene " adds to + 5 °c, a solution of 10.5 quickly g of (R) to RF-cyano-benzyli 3-phenoxy_that 20 cm3 in benzene, pyridine•quickly into 4.5 cm3, stirred for 16 hours at 20 °c, the reaction mixture is poured into a mixture of water, ice and hydrochloric acid, extracted with ethyl ether, washed with water éthcrées phases, the dry, the concentrate to dryness by distillation under reduced pressure, chromatography the residue on silica gel eluting with a mixture of cyclohexane and ethyl acetate (9 θ / ΐ θ) and obtains 14.18 g of 1r, trans-2.2-dimethyl 3 - (2 ', 2', 2', 1" - tétrachloroéthyl) cyclopropane 1-carboxylate (R) ^ 7 α-cyano 3-phenoxy-benzyl=-22.5 degrees (≈ 0.5 / ό c_, benzene).

Analysis : ^ ^ ^ C-H-R-IC 0₃ (487.21)

Calculated: C. with fo 54.2 HR ## N-3.9. 2.9

Found ii 54.0 4.0 2.7

Spectrum I " the R, (chloroform)

Absorption at 1742 cm, characteristic of the carbonyl

LC ^C./₀

29.1

29, σ.

1484

cms

1■

characteristics of the cores absorptions to 1610, 1584,

aromatic.

Uu.y spectrum. (ethanol)

Inflection to 230 nm (ε ≈ 23 θ ^);

Inflection to 267 nm (I|≈ 41) grams

Inflection to 271 nm (ε=|44);

Maximum at 277 nm (I ^ j=49) }

Inflection to 283 nm (ε=|37)?

Inflection to 305 nm (ε=|4).

NMR spectrum (deuterochloroform)

Peaks 1,22 - 1.42 p.p.m., hydrogens of the methyl group characteristics,

1.50 to 2.50 pp.pftin peaks, features a CB hydrogens $cyclopropyl

peaks of 3.66 p * p_I m to 4.4 1 w_I w, thein_F. characteristics. 1 * hydrogène in position 1' of the side chain,

peak at 6.5 w " w_I the m, characteristic of hydrogen carried by the carbon in the - D. the - c-n,

peaks of 7.00 to 7.66 p * p_I the m, characteristics of the hydrogens of the aromatic rings "

Example 22. : Irir.trans 2.2-dimethyl 3 - (2 ', 2 ', 2 ', 1' a-tétrachloroéthyl) cyclopropane 1 carboxylate 3-phenoxy benzyl.

Step a: 1r acid chloride, trans-2^2 a-diraéthyl3 - ^ 2 * 2 ', 1' a-tétrachloroéthyl) cyclopropane 1-carboxylic₀

It is prepared as in 1' g. % HAS at the start of 10.4 g of acid, the acid chloride obtained dissolved in 30 cm3 of benzèn and obtains 37.2 cm3 of benzene solution of acid chloride,

the L ^ ^ tracloroé MC) £ï2i°eîl2 £2b £.2l"£ ielk2' ££ iâ ££"ç * 2,_.3~: £hén^{the O} the XY bonzyle.

In 18.6 cm3 of the solution of acid chloride obtained above, introduced to 0 °c, 4 g of alcohol 3-phenoxy bonzylic 15 cm3 in solution in benzene, adds 2 cm3 of ' pyridin, stirred for 18 hours at 20 °c, the reaction mixture is poured into a mixture of water, ice and hydrochloric acid, extracted with ethyl ether, the organic phase washed with water, dried over magnesium sulfate, filter and concentrated to dryness by distillation under reduced pressure. The residue (8.6 grams) is purified by chromatography on silica gel by eluting with a mixture of cyclohexane and ethyl acetate (95/5) and then cyclohexane and benzene (5/5)•

Analysis ; ^ ^ ^ H-c-LC(462.20)

lo 54.6 Hr # T-,

55.2 4.5

Spectrum I, R.<, (chloroform)

"." " ii

Absorption at 1728 cm, characteristic of CrO,

absorptions to 1615 - 1587 cms VBE1 characteristics are aromatic hydrogens

U-spectrum " V.<, (ethanol)

Inflection to 227 NHS (≈ 245 JE) %

Inflection to 266 nm (I ^=36) J.

Maximum at 272 nm (ε=|42) J.

Calculated: C. The O/degrees 54.6 HR ^C. the O / 4.4

T-found

LC The O/degrees 30.7

29.4.

Maximum at 277 nm (JE has 4 θ),

NMR spectrum (deuterochloroform)

Peaks to 1 * 19 - 1.33 p.p.m., characteristics hydrogens methyls gemini,

peaks 1, 66 - 2, 25 p.p.m., characteristics back hydrogens cyclopropyl,

peaks 4, 0 - 4, 41 P p.m characteristics has hydrogen 1 * of the chain ethyl substituted side;

peak at 5.18 p.p.m., characteristic of the methylene of the benzyl moiety;

peaks to 6, 83 - 7, 67 p.p.m., characteristics of the hydrogens of the aromatic rings.

ExampleZî : 2.2 To-diméthvl irir.trans 3 - (2 '.2', 2', 1 * - tetrachloroethyl) cyclopropane 1 a-carboxylato OD (e) alléthrolone.

Stage a_2_ £blorure_de_M_l2_{the I} acid_> __{the I} 15, 00!. i-âBâ "SASz-to-iS2iî} Rl" 2zISJj2I. "

2^{the R}_WITH 1' - tétrachloroéthyljcyclogropane-to-jî-to-carboxyliguo.

It is prepared as in step b of example 2 HAS. at the start of 10.4 g acid 1r, corresponding trans.

Stage) cyclopropane 1 carboxylate ^ ^ ^ of throlone Sj the expedition.

Dissolving the acid chloride obtained in step a in 30 cm3 benzene and 37.2 cm3 obtained a solution of acid chloride (solution),

In 18.6 cm3 solution (has), cooled to 5 °c +, 3.2 g of introduced (e) 15 cm3 alléthrolone in solution in benzene, agitates, adds 2 cm3 pyridine, stirred for 16 hours at 20 °c, the reaction mixture is poured into a mixture of water, ice and hydrochloric acid, extracted with ether, concentrated to dryness by distillation under reduced pressure, the residue purified by chromatography on silica in pearl cluant by a mixture of cyclohexane and ethyl acetate (8 θ / ΐ θ) and obtains 4.56 grams OD 1r, trans-2.2-dimethyl 3 - (2 ', 2', 2 ', 1' a-tétrachloroéthyl) cyclopropane 1 carboxylate OD (e) alléthrolone p=85 °c, '.

Analysis ^ ^ c-ii ^ ^ O-H-QCIs(4 ΐ 4, 6 ΐ)

C #4 - 9 calculated, the II 3 ^C. the O / 4.8 LC ^C. , the O 34.2

Found ii 4 · 9, 0, 4.8 35.5 *

IR spectrum (chloroform)'

Absorptions to 1710 cm ""¹ and 1730 cm "¹ , characteristics of c ^ Û;

Absorptions to 1655, and 1538 cm "¹ , cAI-to-actéristiqucs of c=c {

-•- " the j - 1 rtrrn_

UoV spectrumthe O (ethanol production)

Most to 227 - 228 nm (Ε ^=357)?

Maximum 2 γ 8 ran (Ε=^ 8)}

SnMR pectre (deuterochloroform)

Peaks to 1, 32 - 1, 37 p * p " the m, characteristics hydrogens methyls gemini,

peak at 2.08 w " POMs, characteristic of hydrogen methyl in position 2 of 1 * $allethrolone

2, 98 - 3, 08 to P-peaks_I p.m., characteristics of the hydrogenated methylene chain allyl 1" alléthrolone, contiguous to

ring;

4, 12 - 4, 23 and 4, 28 - 4, 39 P-peaks to_I the P_I the m, characteristics of hydrogen in position 1 * of the side chain ethyl substituted 4, 83 - 5, 25 P-j-peaks, P-" the m, characteristics of the terminal methylene of the allyl chain of 1' alléthrolone;

5 * 5 peaks to 6.17 w "w" the m, characteristics of the hydrogen attached to the carbon in position 1 'of 1 * alléthrolone, and hydrogèxpositionde * carbon in the chain allyl 1' alléthrolone " example jl4: 1r, cis-2.2-dimethyl 3 - (2 '1 ',-a-bromo 2 2 ',',-to-dichloroéthyl) cyclopropane 1 carboxyl3~phénoxy ATE bcnzyle " in EMT 4.65 g of solution of the acid chloride 1r, cis-

2 -. ,2-dimethyl 3- ( 1 ' " 2 ' -dibromo 2' ,2 '-dichloroéthyl)cyclopropnne-1-cai'boxylique et de 2,4θ g d'alcool 3-phénoxy benzylique dans 20 cm3 de benzène, on introduit à 0°C, progressivement 4 cm3 de pyridine, agite pendant 17 heures, verse le mélange réactionnel dans une solution aqueuse d'acide chlorhydrique, extrait au benzène, lave la phase organique avec une solution saturée de bicarbonate de sodium, à l'eau, sèche sur sulfate de magnésium et concentre à sec par distillation sous pression réduite"

The residue is chromatographed on silica gel eluting with a mixture of petroleum ether (to EB " 35 and 75 degrees Celsius) and ethyl ether (9/1) and obtains 2.37 grams of 1r, cis-2.2-dimethyl 3 - (1 '" 2' a-bromo 2 *, 2' a-dichloroethyl) cyclopropane 1 carboxylate 3-phenoxy benzyl (isomer mixture a and b)* f=75 °c

Analysis: ^ ^ ^ H-c-LC. ^ brr (551.11)

Calculated ii C. with fo 45.76 HR lo 3.65 Brr #29.0 LC ^C. the O / 12.86 Found % 45.8 3.6 28.5 12.9 * IR spectrum (chloroform)

Absorption at 1725 cm "¹ , j-carbonyl characteristic absorptions to 1615 - 1590 -1492~cm. VBE1 features aromatic rings "

NMR spectrum (deuterochloroform)

Peaks to 1, 25 - 1, 37 and 1, 22 - 1, 39 pp.p " the m, characteristics hydrogens methyls gemini,

1, 75 - 2, 17 p-peaks, P-, M., characteristics of the hydrogens of the cyclopropyl ;

peaks to 5.1 - 3.16 poPoin, characteristics of methylene hydrogens of the benzyl moiety,

peaks to 5, 0 - 5, 42 and 5, 35 - 5, 53 p.p.m., characteristics of hydrogen in position 1 * ethyl substituted side chain;

peaks to 6, 83 - 7, 59 p.p.m., characteristics of the hydrogens of the aromatic rings.

The NMR spectrum shows that the compound is made up of 2/3 of isomcre 1/3 of a and b-isomer. /', 2 2' a-oichlcrc. 1R acid chloride, 3 - cis-2.2-dimethyl (1^F. , 2' a-bromo/

." the Thyl) cyclopropane 1 a-carboxyliqtie further described in example 15, can be prepared in the manner described in example 16, initially 1r acid, 3 - cis-2.2-dimethyl (22 * - dichlorovinyl) or cyclopropane - 1-carboxylic acid.

Example 15• The IR, cis-2.2-dimethyl 3 - (1 '.2' a-dibrcmo 2 ', 2'-dichloro-ethyl) cyclopropane 1-carboxylate (e) alléthrolonc.

i. 2 a-dimé MC ^ L-3 a-£l ' _L 2 ' - dibro-to-njO and 2^2 ^ - dichloroéthyl2^C. therein^C. the L⁰ the PR^{the O} panel^I -1 - carboxylic.

It is prepared in a manner similar to that used in the example 2 Λ departure of 3.6 g acid 1r, cis-2.2-dimethyl 3 - (the, 2 '22' a-dichloroethyl-bromo) cyclopropane 1-carboxylic and obtains 4 g of acid chloride,

§î£-to-GBP-to-.5-to-.i_ 25i .£î£_ " jlsléi^{TIMING FACTOR} THE £III ^ 3 GBP - 1', 2^! * ^ 2 - bromo 2' - dichlorophenyl £} Zi2_ GBP £I-Z-00 00 00 ï22 FIA £2 ^ I-2l2 00 00 00 00 _l_ë the I^O 2 alléthrolone.

40 Cm3 in benzene, 4 g of dissolved acid chloride obtained in step a and 1.75 g of (e) throlone expedition, introduced at 0 °c₅ 2 Cm3■a mixture of pyridine and 2 cm3 of benzene, stirred for 2:00 hours, to 20 °c, the reaction mixture poured

in a mixture of water, ice and hydrochloric acid, extracted to benzene, washing of the organic phase with an aqueous solution saturated with sodium bicarbonate, water, dried on sodium sulfate and ^ d|Parsing to dryness by distillation under reduced pressure " esVpurifié/the residue by chromatography on silica gel

eluent by a mixture of benzene and ethyl acetate (97/3) and /is

4.25 g / obtains 1r, cis-2.2-dimethyl 3 - (1 ', 2' a-bromo 2 ', 2' dicliloroé the Thyl) cyclopropane 1~carboxylate of (e) alléthrolone " analysis: c, ^ - ^ ^ ^ I-b-LC(503.07)

Calculated C #40.58 hr ^C. the O / 4.0 Brr The O/degrees 31.76 LC $ 14.09 Found ii 41.3 4.1 31.0 14.2.

IR spectrum (chloroform)

Absorption characteristic c=0|1y18 VBE1 cm.

Absorptions to 1655 "1638 cm" * VBE1 - characteristics of c=c;

Absorptions to 918 - 997 cm "" VBE1 characteristics - HM=Gil₂NMR spectrum (deuterochloroform)

1, 25 - 1, 28 to peaks 1, 39 - 1, 42 P-P p.m and₀ the P_I the m, geminal methyl hydrogens of characteristics;

peaks to 1, 95 - 2, 07 p.p.m., methyl hydrogen characteristics in 3 * of - 1' throlone expedition;

peaks to 4, 83 - 6, 17 p.p.m., characteristics of the terminal methylene hydrogens of the side chain allyl alléthrolone;

peaks to 4.83 - 6, 17 P-"w" the m, characteristics of hydrogen in position 1 * ethyl substituted side chain;

peak at 5.75 "w" m-P-., characteristic has hydrogen 4 'of 1' alléthrolone.

Example■[!GBP!] 1r, cis-2_F. the Thyl 3 - 2 a-dimé (* 2, 2' - dichloro-1¹ , 2' - bromo ethyl-) cyclopropane 1 a-carboxyXate of 5 benzyl 3-furyl-methyl.

Patent îchlorure 1r acid, cis-2 ^ ^ 2-dimethyl 3 - 2 '2' to-dichlo ro_2li ^ * ;!" dibroraoéthyl) cyclopropane 1 - carboxylic_I

It is prepared in a manner similar to that used in the example 14, starting with 10 grams of d¹ 1r acid, 3 - cis-2.2 a-substituted dimethyl (2 ', 2' 1 dichlorophenyl¹ , 2' a-dibromoéthyl) cyclopropane 1-carboxylic®

2^2 a-dimé the Thyl 3 - (2' , 2 '1' ^ 2' - di-chloro-bromo - ^ - ^ cthyl cyclopropane-l-carboxyl ATE 5~benzyl 3-furyl-methyl.

Dissolving the acid chloride obtained in step a previous, in dtî benzene and obtains 27 cm3 of acid chloride solution (solution),

In Uno solution of 2.9 OD grams 5 benzyl alcohol 3 a-fury1 15 cm3 in methyl benzene, 12 cm3 introduced OD solution has acid chloride, cooled to 0 °c, introduced 3 cm3 pyridine, stirred for 48 hours at 20 °c, poured over a mixture of water, ice and hydrochloric acid, extracted benzene and then, after s usual treatments, concentrated to dry by distillation. The residue is purified by chroraatogx-to-'aphie on silica gel by eluting with a mixture of petroleum ether (to EB. 35 and 75 degrees Celsius) and ether (95/5)" and then with petroleum ether (to EB. 35 - 75 °c) and ether (2.2 g of 9/0 and obtains 1r, cis-2.2-dimethyl 3 - (2 *, 2 * - dichlorophenyl 1 ', 2'~dibromoéthyl) cyclopropane 1 carboxylate 5 benzyl 3-furyl-mth. thyle.

/<V._D =-57.5 degrees (00=0.4 $0, benzene)

Analysis: (539, θ 1 4)

Calculated: ## C. 44.56 hr 3.7 ^ brr ^C. with fo 29.04 LC the I 13.15 Found: 44.9 3.8 29.1 13.3.

Spectrum of liquids. (ethanol)

Inflection to 252 nm (ε=20 *)

Inflexion at 258 nm (ε=|15)

Inflection to 264 nm (ε=|11)

Inflexion at 268 nm (ε=|9).

I.R. spectrum. (chloroform)

Absorption at 1720 cm VBE1 characteristic of the carbonyl, absorptions to 1600, 1522.1493 cm, the c=this - characteristics of the aromatic ring.

NMR spectrum (deuterochloroform)

1, 23 - 1, 35 To peaks 1, 20 - 1, 38 and w. p.m characteristics hydrogens methyls in position 2 of the cyclopropyl;

to peaks 1, 67 - 2, 17 P p.m characteristics of hydrogen

- cyclopropyl;

peak at 3.93 p.p.m., characteristic of methylene hydrogens of the benzyl moiety;

peaks to 4, 93 - 5, 0 p.p.m., characteristics of hydrogens carried by the carbon adjacent to the carboxyl;

6, 02 - 6, 1 pp.p peaks_C. the m, characteristics of hydrogen in position 3 of the furan ring;

peaks to 4, 83 - 5, 16 - 5, 33 - 5, 58 p.p.m., characteristics of hydrogen on earth. + - nriQ-to-ii T 1 "|R._{the n} 1~~ & - i-j of _.'

peak at 7 "3 P-" p.m characteristic hydrogens of the radical phcnyle;

7>37 to peaks pp.p " the m, characteristic of hydrogen in position 5 of the core furanno,

Example 27: 1r, cis-2" 2 a-substituted dimethyl 3 - (2 ', 2' dichloride 1', 2 * - dibronto ethyl) cyclopropane 1 carboxylate 3, 4.5 > 6 a-tetrahydrophthalimido methyl "

Stade_A: ^ ^ ^ chloride of the L '^ ^ 2 cis-IR-acid 2-dimethyl 3 - 2 ^' ^ 2' - dichlorophenyl 1•dibromoé thth.vl] ^ _cclopropane-a 1 - carboxylic;

It is prepared in a manner similar to that used in the example 2k, starting with 10 g of 1r acid, 3 - cis-2.2-dimethyl (2 ', 2' dichlorophenyl 1', 2 * -. dibromoéthyl) cyclopropane 1-carboxylic "

Step b: 3" (2 ', 2 ^ - di-chloro-1' ^ 2' - dibromoéttrrl) cyclopropane 1 carboxylate ά℮ ^ ^ 3 methyl 4, 5, 6 a-tetrahydrophthalimido *

Dissolving the acid chloride obtained in step ' Λ in benzene and obtains 27 cm3 of benzene solution (solution) in a solution of 1.4 g of 3, 4, 5 " 6 a-tetrahydrophthalimido mcthyliquc 15 cm3 in benzene, is introduced. 7>5 cm3 of solution of acid chloride, and then 0 °c, 2 cm3 pyridine, 36 hours at 20 °c stirred churning, pouring the reaction mixture on a mixture of water ice and hydrochloric acid, benzene extract, washing of the organic phase with an aqueous solution saturated with sodium bicarbonate, then with water, dried over sodium sulfate and concentrated to dryness by distillation under reduced pressure. The residue is purified by silica gel chromatography, eluting with a mixture of benzene and ethyl acetate (9/l)" 1.89 g of 1r is obtained, the cis 3 - 2.2 to-dimétlayl (2 ', 2' to-dicliloro 1 ', 2' dibromoé the Thyl) c3^{the R}clopropane-1 - carboxylate 3, 4, 5, 6 tetrahydro - phthalimido methyl,

/ / - 'A d°⁼ " 53 VBE1 5° (c_=0.98 with fo, benzene)

^ ^ Îc analysis H-b-c-n-^ ^ ^ 0 (532.07)

Calculated ii C. $ 38.37 HR oF 3.6 NR # 2.63 Brr ^enjoying the O / 30.03# LC 13.32 Found; 39 "0, 3" 6, 2.6 28.3 12.7 IR spectrum (chloroform)

Absorptions to 1778 cm "- 1735 ^" ^ 1723 cm carbonyl characteristics:

absorption at 1665 cm - de - c=c ^ characteristic

NMR Spectrc (deuterochloroform)

Magpies to 1.21 - 1 * 22 - 1,39 w " p * m_T features hydrogens methyls gemini,

to peaks 1, 67 - 1, 83 p.p.m., characteristics hydrogens cyclopropyl and back methylenes in yields~j-c=c

peak at 2.37 p.p.m., characteristic of the methylenes in de - c=c - / -, peaks to 5, 0 - 5, 5 p.p.m., L-OD characteristics^F. hydrogen in 1"

the ethyl side chain;

5, 5 - 5, 75 to peaks of P " P-₀ the m, characteristics of methylene hydrogens in custom the carboxyl "

Example 28; DL cis or trans 3 - 2.2 to-dxméthyl (2 ', 2' - dichloro-the, 2' dibromoéthyl) cyclopropane 1 a-carboxvlate of R, O - 6 and the cyan-O 3~phénoxy benzylo.

Used dl-cis or trans 3 - 2.2-dimethyl (2', 2 * - dichlorovinyl) cyclopropane 1 carboxylate of R, e 06 cyano 3-phenoxy benzyie whose characteristics are the following:

7 U-spectrum., (cthanol)

Inflexion at 226 nm (ej=522)

Inflection to 267 nm (ε=|43)

Inflexion at 272 nm (ε=|47)

Maximum at 278 nm (I|≈ 52)

NMR spectrum OD (deuterochloroform)

1.20 To 1.30 pep.m peaks, features hydrogens groups mth thyle}

peaks at 5, 60 - 5, 75 p.p.m., characteristics of hydrogen in position 1 * of the chain dichlorovinyl, corresponding to the trans isomer,

peaks to 6, 20 - 6, 31 p.p.m., characteristics of hydrogen in position 1 * of the chain dichlorovinyl, corresponding to the cis isomer,

6, 41 - 6, 46 to peaks P p.m characteristics of hydrogen carried by the carbon in the " I of the function -0 ≤ Ν 5

peaks of 7.0 to 7.66 p.p.pm characteristics of the hydrogens of the aromatic rings.

30 Cm3 in carbon tetrachloride, introduced 6.7 S dL cis or trans 3 - 2.2-dimethyl (2 ', 2' a-dichlorovinyl) cyclopropane 1 a-carboxylato of R, e 06 cyano 3-phenoxy benzyl whose characteristics have been given above, introduced in an hour a solution of 0.85 cm3 OD bromine in 10 cm3 of carbon tetrachloride, stirred 2 hours at 20 °c churning, concentrated to dry under reduced pressure and obtains 10 grams crude product that silica gel chromatography eluting with a mixture of cyclo hexane and ethyl acetate (9/0 and obtains 7.5 g of DL-cis or trans 3 - 2.2-dimethyl (2 *, 2⁵ 1 - dichlorophenyl¹ , 2' a-dibromoéthylCyclopropane - 1 carboxylate (R., sjij ^ a cyano - 3-phenoxy benzyl_I Analysis: ^ ^ brr or Cl

Calculated the IC^C. , ' the O 45.86 HR $ 3.32 D 5° 2.43 LC #12.30 brr #27.7 ½ found: 46.2 3.6 2.4 12.5 27.5 " XlgV spectrumthe O (ethanol)

Inflection to 267 (I ^ j=34) um in

Inflexion at 272 nm (I]=35)

Maximum at 277 nm (I]=38)

NMR spectrum (deuterochloroform)

P-peaks to 1, 20 - 1, 44_I the P₀ the m, characteristics hydrogens mth thyle e groups,

peaks of 1.54 to 2, 4 P-θ_I w, M.₍ characteristics of the hydrogens in positions 1 and 3 of the cyclopropane ring;

peaks of 4.21 to 4.51 ΡοΡ· γ π, characteristics of hydrogen in position 1' of the chain dichlorovinyl and corresponding to the trans isomer;

to 4.97 peaks 5A DEGREES W "w" the m, characteristics of hydrogen is at position 1' of the each dichlorovinyl and corresponding to the j-cis isomer

peaks of 6.42 to 6.50 pap.m, characteristics of hydrogen carried by the carbon in the WCT of the array - costs CZK;

peaks of 7.0 to 7.55 w_I w, w, characteristics of hydrogen nuclei an Aroma tick e "

Example 29: 1r, trans-2.2-dimethyl 3 - (2 '2 ',-dichloro-', 1 2' a-dibromocthyl) cyclopropane 1 carboxylate 5 benzyl 3 a-furyl methyle in 30 cm3 of benzene, is introduced J, 6 g chloride IR-acid, trans-2.2-dimethyl 3 "(2 ', 2' dichloride 1 ', 2' a-dibromoéthyl) cyclopropane 1-carboxylic, 3.2 g of 5 benzyl 3-furyl-methyl, added dropwise 5 cm3 pyridine, stirred for 48 hours at 20 °c, adding water, separated by decanting the organic phase, extract the aqueous phase to benzene, joins the organic phases dried, the concentrate to dryness by distillation under reduced pressure, chromatography of the residue on pearl silico by eluting with a mixture of benzene and cyclohexane (7/3) and 'obtains 6.1 g of 1r, trans-2.2-dimethyl 3 - (2 *, 2' dichloride 1 ',' 2" dibromoéthyl) cyclopropaue-to-1 carboxylate

oD 5 benzyl methyl 3 a-fury1 *

//V-p°=-19 degrees (=0.5 c_ benzole)

Analysis:^C 2o^{the n} 20^Brr 2^LC 2 °3(539, 09)

Calculates : C. ##44.56 Η 3.74 29.65 brr

Found: 44.2 3.7 29.4

IR spectrum *

Absorption at 1725 CRAs " VBE1 characteristic of the

absorptions to 1555, 1540, 1498, 1495 cm VBE1

- C=c - and aromatic rings "

U * v spectrum, (ethanol)

Inflection to 216 nm (I ^=265)

Inflection to 251 nm (Ε ^=10.5)

Maximum at 257 nm (I! j=8.5)

Inflection to 26 ΐ nm. (b-j-≈ 7!)

Inflexion at 263 nm (ii ^=6)

Maximum at 268 nm (I ^ j=4.5)*

LC #13.15

13.5 *

carbonyl;

characteristics

of

NMR spectrum (deuterochloroform)

Peaks to 1, 22 - 1, 25 - 1, 28 pp.p_I the m, geminal methyl hydrogens of characteristics;

m is 1, 6 - 2, 32 to peaks pp.p *, characteristics of the hydrogens of the cyclopropyl;

peak at 3.93 p.p.m., characteristic of methylene hydrogens of the benzyl moiety;

p-peaks to 4, 25 - 4, 37 - 4, 54, the P " m-characteristics of hydrogen in position 1^{the R} ethyl substituted side chain,

peaks 4, 95 - 4, 97 to p.m and 6, 0 - 6, 05 P-P₀ p.m characteristics of hydrogen méthy3 " ene ^ bontigu at carboxyl;

peak at 7.33 p.p.m., characteristic of hydrogen in position 4 of the core furylo;

peak at 7.25 w. p.m characteristic hydrogens of the phenyl.

The L *>th acid chloride used at the start of the present example, also described in the example 10, may be prepared in example 16 presented here mannered, initially 1r acid, 2.2-dimethyl-trans - 3 (2', 2 f dichlorbvinyl) cyclopropane 1-carboxylic acid.

ExemplepO: 1r, trans-2.2-dimethyl 3~(1¹ , * 2 - bromo 2', * 2 - dichlorophenylethyl) cyclopropane 1 carboxylate 3~~phénoxy bcnzyle.

In a solution of 9 grams of d * 3-phenoxy benzyl alcohol in a mixture of $0 10 cm3 cm3 of benzene and pyridine, is intra-5 bro dropwise, NOU solution 19 "35 g of acid chloride 1r, trans-2.2-dimethyl 3" (1¹ "* 2' a-bromo 2, 2 - dichloroethenyl *) or cyclopropane - 1-carboxylic, stirred for 18 hours at 20 °c, the reaction mixture is poured into water, extracted to benzene, dried over magnesium sulfate, concentrated to dry by distillation. The residue is purified by chromatography on i0 silica gel by eluting with a mixture. de petroleum ether (to EB, 35" 75 °c) and ethyl ether (95/5) and obtains 8.1 g of 1r, trans-2.2-dimethyl 3 - (1^{the R} , 2 'a-bromo 2 ', 2' a-dichloroethyl) cyclopropane 1 carboxylate 3-phenoxy benzyls.

5 ΛΥ β degrees!=- 20.5 degrees (c=0.6 <OF, benzene).

Analytical^C 21^II 20^Brr 2^C '^I ' 2⁰ 3 (551, 1l)

Calculated: C. ^C. the O / 45.17 HR tM 3.66 Brr #29.0 LC ^C. the O / 12.87

Found: 45.7 3.7 28.5 13.0.

I.R. spectrum" (chloroform)

) ∩ absorption at 1730 cm "¹ characteristic of the absorptions to carbonyl|1618.1590 cm characteristics hydrogens<e aromatic nuclei,

Spectrum of liquids(ethanol).

228 Nm inflection (W¹ =216)

>5 Inflection 267 nm (ε=|34)

Most ' 272 nm (ε=37.5|)

Maximum at 278 nm (ε=| 36)"

NMR spectrum (deuterochloroform)

Peaks topPftPj-1.29 e. p.ra characteristics hydrogens of the geminal méthy-to-30 $

peaks to the P 1, 66 - 1, 75" p * m 1, 92 - 2, 13 and p.p.m., characteristics of hydrogen in position 1 of the 3>cycloprop the j

peak at 1, 92 - 2, 33 p.p.m., characteristic of hydrogen in position 3 of the j-cyclopropyl

35 peaks to 4, 22 - 4, 38 and 4, 38 - 4, 57 e. p.m characteristics has hydrogen 1•side chain-ethyl substituted 5, 12 - 5, 13 P j of peaks to methylene hydrogens p.m characteristics of the benzyl moiety Y

peaks 6, 83 - 7, 53 to the P " P-<Qn ., characteristics of the hydrogens of the aromatic rings "

Example 31:3 - 2.2 to-dimcthyi irir.trans (* 1" 2¹ bromo - 2', 2¹ the Thyl - dichloroé) cyclopropane 1 - carhoxyl3 aTE, hr, 5.6, methyl - tétrahydrophtallmiüo "

20 Cm3 in benzene, is dissolved 2 g chloride acid 1r, 2.2-dimethyl-trans - 3 (1¹ , * 2 * 2 - bromo, 2 'a-dichloroethyl) - carboxylic cycloprcpane-a 1 and 3 g of 0,930, hr, 5.6 and tétraJiydrophtalimido be methanol, added dropwise 2.5 cm3 pyridine, stirred for ^ 8:00 EURES to 20 °c, adding water, decanted, benzene is extracted, concentrated to dry, the residue chromatography on silica gel by eluting with a mixture of benzene and ethyl acetate (9/1) and obtains 2.17 g of 1r, trans-2.2-dimethyl 3 - (the, 2'-bromo 2 ', 2' a-dichloroethyl) cyclopropane 1 carboxylate of j, hr, 5.6 and 1étrahydrophtalimido mth thylethyle.f=117 °c,

=-6.5 degrees (je=0.9 The O/degrees, benzene)

Analysis : ^ ^ ^ H-b-c-ClgN 0 ^ (532,066)

Calculated: C jth 38.38 hr #3.60 brr $30, The OH LC #13.32

Found

THE K #2.63

C<■* 38.5

2.5

# HR 3.5

Brr ^ 29.9

LC #13, hr

NR

Spectrum I, R.<, (chloroform)

. Absorption at 1783 cm "' * characteristic c=0;

absorptions to 1728 cm "and 1750 cm *" * c=0 characteristics

and the ester function,

absorption characteristic 1669 cm * c=0.

U-spectrum " V., (ethanol)

Most 223 nm (ε=|30l);

most 229 - 230 nm (b.?=293) J.

* - j.

Inflexion at 236 nm (I ^=172);

inflexion at 272 nm (ε=8 *)_I

Example 52/ ; Infrared, trans-2.2-dimethyl 3 - (2', 2¹ bromo - 1 ', 2' a-dichloroethyl) cyclopropane Icarboxylatc OD 3 a-phcnox3 " bcnzyle.

Step a: chloride acid 3 - (2',2'dibromo__1 irir.trans 2.2-to-diméthvl '^ 2' - dichloroethyl ^ cyclopropane-l carboxylic.

Operations are carried out in process like the example 1étau starting of 4.5 g acid 1r, trans-2.2-dimethyl 3 - (2 ', 2' a-bromo 1 ', 2'~dichlorocthyl) 6α-to-1-carboxylic and obtains the OD acid chloride 1r trans-2.2-dimethyl 3" - (2 ', 2' - bromo 1 ', 2' - dichloroé the Thyl) cyclopropane 1-carboxylic,

B-Stndc; ^ ^ 2 trans-rpm 2-dimethyl 3 - 2 ^ '^ ^ 2 - bromo-I' ^ ^ e ' a-dichlorocthylcyclopropanc-L-to-carboxylatc ^ ^ ^ - DCs ghcnoxvbenzylc..

In a solution of 2.7 S d. 3 a-phcnoxy benzylic alcohol * 7 cm3 in benzene, introduced to 0 °c, the solution is obtained by dissolving the acid chloride obtained in step 7 cm3 in benzene, pyridine 1.5 cm3 added, stirred for 16 hours at 20 °c, the reaction mixture is poured into a mixture of oau, ice and hydrochloric acid, extracted with ethyl ether, washing of the organic phase to water, dried over magnesium sulfate and concentrated to dryness by distillation under reduced pressure. The residue (6.37 grams) is purified by silica gel chromatography, eluting with a mixture of cyclohexane and ethyl acetate (9 θ / ΐ θ) and obtained 2.09 g of an IR, hafnium 2.2-dimethyl 3 - (2 *, 2¹ - dibromo 1 ', 2' a-dichloroethyl) cyclopropane 1 carboxylate 3 - phenoxy benzylco

WITHnalyse O^C. ? i-^H 20^Brr 2^C1 2 °3 (551.12)

Calculated; C. 45.7 Π ## 3_F. 6 Brr #29 # LC 12.8

Found e 46.0 3.8 29.4 12.6 .,

IR spectrum (chloroform)

Absorption at 1730 cm VBE1 characteristic c=0,

absorptions to 1615 -■1590 cm, characteristics of the aromatic rings.

CSectreUoV. (ethanol)

Inflection to 220 nm (I! j=205) J.

Inflection to 6 nm in 2 β (I|=33) J.

Most 271 - 272 nm (ε=|36);

Maximum at 278 nm (ε=|34) of £

Spectrum OHR (deuterochloroform)

Peaks to 1, 25 - 1, 28 - 1, 33 P p.m, characteristics hydrogens methyls gemini $

1, 7 - 2, 42 p.p.m. chisel, characteristics of hydrogen cyclopropylei

peaks to 3, 98 - 4, 35 PoPom, characteristics of hydrogen in position 1' side chain-substituted ethyl ;

6, 85 - 7, 5 pop.m peaks, caractéristiqties hydrogens aromatic rings J.

peak at 5.13 w₀ the P_{the O} the m, characteristic of methylene hydrogens of the benzyl moiety<,

1R acid, 3 - 2.2 to-substituted dimethyl-trans (2 ', 2' - dibronio 1 ', 2' a-dichloroethyl) cyclopropane 1-carboxylic acid may be prepared in the following manner:

In a mixture of 20 cm3 of carbon tetrachloride and 20, 5 cm3 of methylene chloride, is introduced 24 g acid 1r, 2.2-dimethyl-trans - 3 (2 ', 2' - dibromovinyl) cyclopropane 1-carboxylic, fact. bubbling to~10 °C, chlorine in the reaction solution by adapting to the vessel, reaction, which circulate a refrigerant in methanol at -60 °c, stirred for two hours and 30 Ni 10 nutes to -10 °c, for one hour and 30 minutes to + 10 °c, evaporated excess chlorine, the solvents removed by distillation under reduced pressure, the residue is purified by chromatography on silica gel eluent by the tan mixture of cyclohexane, ethyl acetate and acetic acid (75/25 / *!) and then cyclohexane

15 ethyl acetate and acetic acid (θ / θ / ΐ 8 2) and obtains 16.3 g acid 1r, trans-2.2 d-iméthyl 3 - (2', 2 - dibrono * 1¹ , 2' - dichloroethyl) cyclopropane 1-carboxylic "

NMR spectrum (deuterochloroform)

1, 33 - 1, 56 To peaks pp.p.rn, characteristics of hydrogens

2o geminal methyl,

1, 7 - 12, 25 p * p peaks " the m, characteristics of the hydrogens of the cyclopropyl;

4, 11 - 4, 37 p-peaks "w" meters. characteristics of hydrogen in position 1' stxbstituée ethyl side chain;

2^peak at 10.8 p.p.m., characteristic of hydrogen from the carboxylc "

1 Βχο π τη ο 33; 1r " trans-2.2-dimethyl 3 - (2 ', 2' - dibrono 1 ', 2' - dlchloroéthyl) cyclopx'cyclopx' onano L-carboxylate (e) throlone expedition " e ^ ado_A_î__chloruro__> of the L ^ ^ toto acide__ir_{the I}trans__Y 2_{the I} 2 a-diméthvl_ 3 a-£2 ^2^^iîie £2 £_lii. £izëi. £îïi £^: I-I 00 00 ii: t's._ I 00 00 00 00 00 2S2 I2 which I; ll; i£EEk£S-to-ii2e2i

30 Operation is carried out analogously to the previous examples initially * of 4.5 g acid 1r, trans-2.2-dimethyl 3 - (2', 2¹ - dibrono

1 ', 2' a-dichloroethyl) cyclopropane 1-carboxylic and obtains 1r acid chloride, 3 - 2.2-dimethyl-trans (2 ', 2' a-dibrono 1 ', 2'~dichloroethenyl) cyclopropane 1-carboxylic "

33 Step b: 1r, trans-2.2-dimethyl 3 - 2 ^ '^ 2' a-bromo * 1, 2 - dichloroethenyl ^ ^ cyclopropanc-to-ll.gcarboxyiato dé_ (_s2_alléthrolone_has

In tone service solution of 2.05 S s-allctlirolono in 7 cm3/of benzèno, introduced to 0 °c, a solution of acid chloride in step 6 hr btenu, 7 cm3 in benzene, pyridine 1.5 cm3 added, stirred for 16 hours at 20 °c, the reaction mixture is poured into a mixture of water, ice and hydrochloric acid, extracted with ether, washing of the organic phase to water, dry on suifosuifo.te magnesium and concentrated to dry by distillation " the residue (5.15 grams) is purified by chromatography on silica gel by eluting with a mixture of cyclohexane and OD acctate 'ethyl (8/2 θ θ), crystallizes in isopropyl ether and obtains 1,s6 1it g of, trans-2.2-dimethyl 3 - (2 ', 2 'a-bromo 1', 2' dichloroethyl) cyclopropane 1 carboxylate s-alléthrolone

F=126^Q C..

IR spectrum (chloroform)

Absorption at 1713 - 1730 cm in~^ c=0 characteristic, absorptions to de - c=c - 1658 - 1642 cm in characteristics;

absorptions to 923 - 995 cm - HM=CIî characteristics_{the n} " UV spectrum (ethanol)

Most to 229 is NRa (I ^=315)

Inflection to 300 nm (ej=1)

RHTi spectrum (deuterochloroform)

Peaks 1,32 - 1,35 - 1>38 to the P, P-_I the m, geminal methyl hydrogens of characteristics;

peaks to 4, 23 - 4, 4 P pp.p p.ra 4, 1 - 4, 27 "w characteristics has hydrogen 1 'of the side chain ethyl substituted, peaks to pp.p 2, 08 - 2, 15" w, characteristics methyl hydrogen in position 3 of 1' alléthrolone,

2, 98 - 3, 08 to P-peaks_I p.m., characteristics of the methylene 5 of 1' alléthrolone;

4, 83 - 5, 25 p-peaks "w" the m features of methylene hydrogens terminal 1' alléthrolone J.

5, 5 - 6, 17 p * p to peaks " m-characteristics has hydrogen β the allyl radical of 1' alléthrolone J.

peak at 5.83 pp.p " m-characteristic has hydrogen 4 'of 1' alléthrolonee

Example 34; 1r, 3 - cis-2.2-to-dimcthyl (2 ', 2' a-bromo 1 ', 2' a-dichloroethyl) cyclopropane 1 a-carboxylato of 3-phenoxy bonzyle "

Step a: ACI chlorideD.e - an IR, iCe 2.2-dimethyl 3~(2 ', 2'-bromo ', 1 2' a-dichloroethyl) cyclopropspeed bumps and 1 a-carboxylithat "

In a mixture - of 30 cm3, e ^ Her2neu petroleum (BE. 35 and 70° Celsius) OD and 10 cm3 thionylo chloride, acid amides 5 introduced 1r, cis-2.2-dimethyl 3 - ('2', 2 '- bromo 1, 2' - dichloroethyl) cyclo proprmc-to-1~carboxylique, carries the reaction mixture at reflux, kept there 4 hours, concentrated to dryness by distillation under reduced pressure, adds benzene, concentrated again to share by distillation under reduced pressure and obtains 5, 4 grams OD chloride 1 '1r acid, 3 - cis-2.2-dimethyl (2 ', 2' a-bromo 1·,2·dichloroéthyl) cyclopropane 1-carboxylic acid.

", VBE1 '

Stapreferably10 b.: 1r, cis-2.2-to-dlméthvl 3~(2¹ " 2' a-bromo 1 * 2.¹ - d.ichloroéthyl) cyclopropane 1 - carboxylate 3-phenoxy benzylc,

With 3.2 g of alcohol 3-phenoxy bonzylic, added 5.4 S acid chloride obtained in step a previous_F. 38 cm3 benzene, and then sequentially to + 8 °c, 4.35 g of pyridine derivatives,_is solution in 10 cm3 bensene OD, stirred for 17 hours at 20 °c, poured into a mixture of water and ice, extracted to benzene, dry on sxilfate magnesium and concentrated to dry the solution benzéniq ' aw, the residue purified by chromatography on silica gel by eluting with a mixture of benzene and ethyl (7/3) aectate, crystallizes in petroleum ether (the BB_C. 35 And 70 degrees centigrade) and obtains 4.7 g of 1r, cis-2.2-dimethyl 3 - (2 ', 2' a-bromo 1 ', 2' a-dichloroethyl) cyclopropane 1 carboxylate 3-phenoxy benzyl " f=68 °c,

^ · / ρ=degrees / -34 °c (c_=1 ^C. the I /, chloroform);

Analysis ii C.₂ (551.20)

Calculated: C. £45.76 hr $3.66 Brr $29.00 LC £12.86 Troxivé: 46.0 3.6 29.3 12.7.

IR spectrum (chloroform)

Absorption at 1725 cm¹ characteristic of the carbonyl;

absorptions 1615 - 1588 cm and 1490 cm ^ characteristics of

•aromatic rings,

- Titi.v spectrum, (ethanol)

Inflection to 22J ran (I|=214)

■inflexion at 266 nm (I ^ j=33)

Maximum at 272 nm (I ^ j=35)

Maximum at 278 nm (ε=|36),

. NMR spectrum (deuterochloroform)

P-chisel 1, 22 - 1, 39, p * m and 1, 26 - 1, 42 ρ, ρ, ΐη characteristics hydrogens gemini methyls;

chisel 1, 66 - 2, 08 e. p.m characteristics of hydrogen cyclepropyle, *

4, 8 - 5, 37 p-peaks " p.m characteristics back hydrogen - group

c OCIL centeredly -

it

0

peaks to 6.83"7"5s w. p.m ristiristi.ques Elements hydrogens aromatic rings "

5 1R acid, cis-2₅ 2-dimethyl 3 - (2 ', 2' a-bromo 1 ', 2' a-dichlorocthyl) cyclopropane 1 a-carboxydLiquo, used in step Λ of the present

•example is prepared in step a of example 11 above_I

Ex-DMC55 c.: 1r, cis-_ 2, R.the Thyl dimc - 3 - (2 ', 2' - T-fluoro, 2' a-PlantFume Nicotineo-ethyl) Cy ofclopropane " 1-carboxylate (e) alléthrolone.

I0 a_i_açidc_1r stage_{the I} 2 cis_ __T- 2_;; diméthyl_3_:; [2 ^_{the X} 25-to-difluoro_ 15_{the X} 2 - ^ _ dihroInoéthyl2c · yclonropan ℮ g1_z ¾~2 of £^: 2 ^ XiiSlli^,

In 120 cm3 ., OD methylene chloride, 17 g acid is introduced

1R, cis-2.2-dimethyl 3 - (2 ', 2' - difluorovinyl j-cyclopropane 1 - carboxylic, introduced to -65 °c, in about two hours, 15.2 g of

15 bromine in solution in carbon tetrachloride 40 cm3 OD, stirred for 30 minutes to two hours and -65 °c, raising the temperature to 20 °c leaves, concentrated to dryness by distillation under reduced pressure, the residue dissolved, hot, in 50 cm3 of carbon tetrachloride, cooled to 0 °c, stirred at that temperature for

45 Minute îo, eliminates the insoluble by filtration, the filtrate concentrated to dryness by distillation under reduced pressure, the residue dissolved in 4 θ cm3 of carbon tetrachloride, stirred for 30 minutes to -10 °c, eliminates the insoluble by filtration, the filtrate concentrated to dryness by distillation under reduced pressure, the residue is purified by chromatography on>5 silica gel cluant by a mixture of cyclohexane and ethyl acetate (75/25)* D., crystallizes in 1 'petroleum ether (to EB, 25 and 75 degrees Celsius) and obtains 1,465 1r g acid, 3 - cis-2.2-dimethyl (2', 2 '- fluoro 1', 2 '- dibro' mocthyl) cyclopropane 1-carboxylic p=124 °c "

50 NMR spectrum~ (deuterochloroform)

1, 28 - 1, 38 * P-peaks to p.m characteristics back hydrogens methyls gemini,

peaks 1, 67 - 2, 0 P p.m characteristics hydrogens of the cyclopropyl;

55 - 4, 67 - 5, 33 * p-peaks to p.m characteristics of hydrogen OD the ethyl side chain substituted F.

Step b; chlorothe Ure asI 1r acid_C. iCe 2.2-dimethyl 3 - (2 '', 2 difluoro 1 *, 2' a-dibromoéthyl) cyclopropane 1 a-carboxyliquc.

Dane-15 cm3 of éthor OD oil (eb. 35"75 °c), 1.43 g of acid introduced 1r, 3 - 2.2~diméthyl-cis (2 ', 2' - fluoro 1 ', 2 * - dibromoéthyl) cyclopropane 1-carboxylic, adds 2.5 cm3 thionyl chloride, refluxes, lo and reflux for 4 hours holds and 30 min, the excess thionyl chloride and LO solvent by distillation under reduced pressure, adds benzene residue ., concentrated to dryness by distillation under reduced pressure, and obtains the âcide chloride 3 - 2.2 to-dimcthyl 1r, c ± s (2', 2 *~-difluoro 1 *, 2' a-dibromoéthyl) cyclopropane 1-carboxylic raw lo and used as such for next stage.

Step c: Ir, the cis 3 - 2.2 to-dimé polyethylene resins (2 ', 2" - fluoro 1', 2' -bromo ethyl) cyclopropane~l-to-carb'carb' oxylate of (e) allcthrolone. _

To a solution of the acid chloride 1r, cis-obtained in step b, 10 cm3 in OD benzene, introduced to + 2 °c, 0.7 g of (e) in solution in 5 cm3 allcthrolone benzene, pyridine 0.5 cm3 added, stirred for 16 hours at 20° g, pouring the reaction mixture into a mixture of water, ice and hydrochloric acid, extracted with 1 * ethyl ether, washed the phase-gall ganic water, dried over magnesium sulfate and concentrated to dry. Obtained crude ester 2.02 g of purified by chromatogranliie eluent is a mixture of c3^{the R}clohoxane and ethyl acetate (θ / 8 2 θ), obtained 1,224 1r g, 2.2 and a Dime polyethylene resins of cis 3 - (2 ', 2 * 12' a-dibromoéthyl-difluoro) cyclopropane 1-carboxylate (e) alléthrolone,

Analysis ii C.₁ ^ ^ ^ o-Yh-brr (θ 47, 62 ΐ)

Calculated: C. ' 0 43.4 Hr #4.3 brr 34.0 w % 8.1

Found 43.2 4.4 33.7 8.1.

Spectrum of liquids, (ethanol)

Most to 227 - 228 nm (ε=| 3 ^ 8)

Spectrum ' NMR (deutérochloroformo)

Peaks to 1, 25 - 1, 36 w. p.m characteristics back hydrogens methyls gemini,

p-peaks to 2, 0 - 2, 06 "w" the m features methyl hydrogen in position. 2 of the alléthrolone;

4, 83 - 5, 25 p-peaks_I w, m-characteristics of the terminal methylene hydrogens do of the side chain of 1' alléthrolone;

5.5 oD peaks to 6.17 pp.poin characteristics of hydrogen/>are performed by positioning of the side chain of 1 'alléthrolone and hydrogen carried by the carbon in position 1 OD 1' alléthi 'olonc, peaks P-OD 4, 83 - 6, 17' " w, m-characteristics of hydrogen into a partnership is * 1 except ethyl substituted side chain;

oD 1, 67 - 2, 16 P-peaks, P-, m-characteristics of hydrogen cyclopropylc;

peaks to P 2, 95 - 3, 05 p.m characteristics of the methylene hydrogens of OC the side chain of OD 1 * throlone expedition;

peaks 1, 67 - to 3.17 w. p.m characteristics of methylene cycle OD 1' alléthrolone "

Example 36; 1r, cis-thy a 2.2 to-dimé|. 3 - (2 ', 2' - dIFs luoi 'O-', 1 2 'a-bromo cthyl) c3 'clopropan.e-to-1~carboxylate of (the R, O) ^ c a cyano 3 a-pheno::; -. bonzyle. ~~

Stage Xl: 1 * acide 1r chloride, 3 - cis-2.2-dimethyl (2 ', 2' fluoro 1¹ , 2^F. - dibromoéthyl) cyclopropane 1 a-carbox3^, The j - IQ UEs.

In 15 enq) OD petroleum ether (to EB, 35 and 75 degrees Celsius), introduced 2.5 grams 1r acid, cis-obtained in step a of example 3?, 7 cm3 added thionyl chloride, refluxes, maintains the reflux for 13 hours and 30 min, concentrated to dryness by distillation under reduced pressure, adds benzene, concentrated to dry and obtains acid chloride 1r, cis-2.2-dimethyl 3 - (2 '', 2 a-difluoxo 1¹ , 2' a-dibromoéthyl) cyclopropane 1-carboxylic crude, used as such for the next step.

Stage _b: 1_ri 5 2 _ j_ 2 a-dimé the Thyl 3 - (2 * 2 * ^ DIFs - fluoro 1¹ , 2' - dibromoéthyl) cyclopropane 1 - carbox 3^{the R} eTL of (the R, O)~3 a-phénoxv cvacva.no - good

Dissolving the acid chloride obtained in step 15 cm3 in benzene, adds to + 2 °c, 1,995 grams alcohol (R)- cyano-^ 3-phenoxy benzyl in solution in 10 cm3 benzene, 1 cm3 introduced pyridino, stirred for 16 hours at 20 °c, the reaction mixture is poured into a mixture of water, ice, and hydrochloric acid, extracted with ether, concentrated to share by distillation, the residue is purified by silica gel chromatography eluting with a same OD mixture of cyclohexane acetate (90/10) and ctbyle * obtains 1,972 1r g of, 3 - cis-2.2-to-dimcthyl (2", 2 'difluoro 1', 2' - dibromoéthyl) cyclopropane 1 - carbox 3^{the R} eTL of (the R, O) f6 cyano 3-phenoxy benz3^, - the "

Analysis : O ^ C.₁ The O ^ ^ brr (543.22) 'calculated C cs 48.6 hr ^ 3.5' brr #29.4 P-n-$ 0, 7.0 2.6 found: 48.9 3.5, 29.6 7.1 2.5.

FXR spectrum (chloroform)

Absorption at 1735 cm "¹ , characteristic of c=0;

absorptions to 1588 - 1610 centimeters "¹ and 1487 cm "¹ , characteristics of the aromatic rings.

The NV spectrum (éthanolj

Inflection to 230 nrn (I¹ =208)

Inflexion at 268 nm (I ^=34)

Inflection to 273 nm (I¹ =' 37)

Maximum at 278 nm (I a-j^has 4 θ)

Inflexion at 285 nm (I ^ = 29)"

NMR spectrum (deutérochlorof elm)

Peaks of 1.03 to 1.45 w "w" the m features hydrogens methyls gemini J.

peaks 1, 75 - 2, 0 w " w, m-characteristics of the hydrogens of the cycle

propyl;

peaks 4, 42 - 5, 17 P p.m characteristics has hydrogen 1' side chain-j-ethyl

6, 4 - 6, 47 to peaks of P, p * m features of the hydrogen in the λ ℮ 0 ≡ Ν;

6, 92 - 7, 67 oD peaks P p.m characteristics back hydrogens back core?: s at an Aroma tick,

The Exe3 could become? ; Infrared, trans-2,^ substituted dimethyl - 3 - (2 '2 ', di1 fluorine¹ , 2•dibromoéthyl) cyclopropane 1 carboxylate 3-phenoxy-Benzyl, Step a; 1r, tr acid chlorideyears 2.2 diusesa HYan L - 3(2 ', 2' dIFs fluoro 1 ', 2' to-PlantFume Nicotinethe Oethyl) cyclopropane 1-carboxylic ,

In the d 40 cm3¹ petroleum ether (Ebo35-to-75⁰ C), introduced 11, 1r acid, trans-2.2-to-dimcthyl 3~(2 ', 2' - difluoi~4 O 12 'a-dibromoéthyl) or cyclopropane - 1 carboxylic acid, thionyl chloride 10 cm3 adds OD, carries the reaction mixture at reflux, kept there 4 hours, the excess thionyl chloride and solvent by distillation under reduced pressure, adds benzene, concentrated again to dry and obtains acid chloride 1r, 3 - trans-2.2-to-dimcthyl (2', 2 * - fluoro 1 *, 2' a-dibromoéthyl) cyclopropane 1-carboxylic what you used for the following step.

Step b T- 1 The R, 3 - 2.2-dimethyl-trans (2'₁ 2 _' dIFs -luorthe O 1 2 ' -bromoethyl) cyclopropane 1 a-carboxylato OD 3 a-phcnoxy benzyl.

Dissolving the acid chloride obtained in step a in ipo cm3'd bonzene and obtains, 56 cm3 OD a solution (solution),

In 18.5 cm3 OD solution has, introduced to + 2 °c, 2.4 grams of LQ -

T-

murray 3-phenoxy benzyl in solution in 2.5 cm3 OD benzene,

1 cm3 adds OD pyridin, stirred for 16 hours at 20 °c, the reaction mixture is poured into a mixture of water, ice and OD of hydrochloric acid, extracted with ether, washing of the organic phase with water, sèclae over magnesium sulfate, concentrated to dry, the residue purified by chromatography on silica gel by eluting with a mixture of cyclohexane and benzene (95/5) and obtains 3.20 - 1 g of 1r, trans-2.2-dimethyl 3 - {2', 2' difluoro ', 1 2' a-dibromoethyl) cyclopropane 1 carboxylate 3-phenoxy benzylc.

Analysis:^C.₂^^{the LL} Z0^Brr 2^F 2 °3 (518,206)

Calculated: C. tM 48.7 Hr $3.9 brr ##7.3 30.9 F.

Finds: 48.9 3.9 31.0 7.1,

Spectrum TJT (1 ethano)

Inflection to 225 nm<th]=225);

Inflection to 265 nm (Ε ^=33)

Most to 271 nm (I ^=37)

Maximum at 277 nm (I]=36)

NMR spectrum (dcutérochloroforme)

Peak at 1.27 w. p.m characteristic geminal hydrogens methyls,

1, 58 - 2, 17 p-peaks to " p * m caractci ' gamble hydrogens of the cyclopropyl;

3, 67 - 4, 33 to peaks pp.p.n characteristics has hydrogen 1' of the substituted ethyl side chain;

peak at 5.13 pp.p " m-characteristic of the endu methylene carboxyl;

peaks OD 7, 58 - 7, 75 P p.m characteristics hydrogens of core?: aromatic.

1R acid, the TX * 2.2-dimethyl 3 - year (2 ', 2' - fluoro 1 ', 2' - dibromoethyl) cyclopropane 1-carboxylic acid used in step a of the present example can be prepared in the following manner:

In 150 cm3 of methylene chloride, is dissolved 26.4 g acid 1r, 'trans-2.2-to-dimcthyl 3~(2', 2 '- fluoro vinyl-) cyclopropane 1 carbdxylic, introduced into the resulting solution to -60 °c, in one hour and 30 minutes, a solution of 24 g of bromine in 50 CMY carbon tetrachloride stirred for 3 hours at $-60 °c, causes the temperature of the reaction medium at 20 °c, a plowshare concentrated by distillation under reduced pressure, crystallizes in ether EP' trole and obtains 14.09 g acid 1r, 2.2 and climétrnns the Thyl 3 - (2 *, 2 * - fluoro 1 *, 2 * - dibromoéthyl) cyclopropane 1 a-carboxyliquc F. ≈ 116 °c.

Analysis:^C 3^{THE II}₁₀^Brr 2^F 2⁰ 2 (535.98)

Calculated ii C. #28.6 With fo the K 3.0 Dr. '^C. the O /¹ 17.6 F. ^C. the O / 11.3

Finds: 28.8 3.1 47.7 11.5.

Spectrum OD and Fe O 'T (deuterochloroform)

Peak at 1.33 ρ ρ.. π characteristic geminal hydrogens methyls;

1, 5 - 2, 33 p-peaks to " w * nor characteristics of hydrogens of the cyclopropyl;

peaks of 3.67 to 4.41 w. p.m characteristics has hydrogen 1' of the substituted ethyl side chain;

peak at 10.9 w. p.m characteristic hydrogen from the OD carboxylc "

39 Lxcmnlo: 1r, 2.2~diméthyl-trans 3 - (2 '2 ', difluoro

1¹ , 2' a-dibromocthyl) cyclopropane 1-carboxylate (R)- cyano-^ 3-phenoxy benzyl *

Prepared acid chloride 1r, trans-2.2-dimethyl 3~(2 ', 2' difluoro 1 ', 2' a-dibromoéthyl) cyclopropane~1-to-carboxyliquo starting with 11 g acid, as exemplified by gold, and dissolves the acid chloride resulting in 50 cm3 of benzene, hereby 56 cm3 OD acid chloride solution (solution)₀ In 37.5 cm3 of solution, is introduced, to 0 °c, 5.4 g of alcohol (/ - 3 a-pbcnoxy. a cyano benzyl in solution in 5 cm3 benzene, pyridine 2 cm3 added, stirred for 16 hours at 20 °c, the reaction mixture is poured into a mixture of water, ice and hydrochloric acid, extracted with ethyl ether and after the treatments usual dry concentrated by distillation under reduced pressure " the residue is purified by chromatography on silica gel by eluting with a mixture OD c3^{the R}clohoxane and ethyl acetate (9 θ / ΐ θ) 0 ο 5.46 g of 1r η obtains, trans-2.2-dimethyl 3 - (2 ', 2' difluoro 1 ', 2' a-dibromoéthyl) cyclopropane 1~carboxylate of (R)AC-cyano-benzyl * 3-phenoxy

Analysis ; C. ^ - hr, ^ ^ n-degrees brr₃ (543.22)

Calculated 9.ï C. ^C. the O / 48.6 HR lo 3, 5 - Brr #29.4 n-sze 2.6 F. 7 found: 49.1 3.5 28.8 2.5 6.7.

IR spectrum (chloroform)

*** ^ t-VBE1

Absorption characteristic of the carbonyl $1745 cm

1

absorptions to 1590 cm in~16î5 characteristics are aromatic hydrogens *

UV spectrum (ethanol production)

Inflection to 230 nm (Ε=1 ^ ^ 2)

Inflection to 269 TEV (Ε ^=34)

Inflection to 273 nm (I ^=36)*

Maximum at 278 nm (I ^ j=39)

Inflection to 305 nm (ε=|■1!)"

NMR spectrum OD (deuterochloroform

Peaks to 1.2 - 1 * 33 ρ, ρ, ΐη characteristics back hydrogens back méthy~the gemini,

1, 9 - 2, 25 p-peaks " p.m characteristics hydrogens of the cyclopropyl;

peaks to 3i66-to-4.33 w "w" m-characteristics of hydrogen in position 1' of the substituted ethyl side chain;

peak at 6.45 of PVP " m-characteristic of hydrogen carried by the same carbon covering joint that radical,

peaks to 6, 91 - 7, 58 P p.m characteristics are aromatic hydrogens *

Example 39: 1r, cis-2.2-dimethyl 3 - (2¹ (Rs)- 2'-chloro-flouro 1',2'd ± bromoéthyl) cyclopropane 1 a-carboxYlatc of 3-phenoxy benzyl (isomer A and isomer B),

Step a; 1r acid, 3 - cis-2.2-dimethyl (2 '- flouro (SRV)' e-chloro-1', 2¹ - dibromocthyl) cyclopropane 1-carboxylic *

100 Cm3 in carbon tetrachloride, 8.9 g acid is dissolved 1r, cis-2.2-dimethyl 3 - (2 '-chloro-2' a-Fluoro) cyclopropanc-to-1-carboxylic (e * z isomer mixture), adds to -10 °c, in 30 minutes, 2.4 cm3 bromine in solution dodo.ns 20 cm3 of tcti 'achlorure carbon, stirred for 4 hours at + 10 °c, concentrated to dryness by distillation under reduced pressure, chromatography the residue on silica gel by eluting with ethyl acetate and obtains 1r 13.7 g acid, cis-2.2-dimethyl' 3 - (2 '- flouro (R) 2'-chloro-1^{the R} , 2'~dibromoéthyl) cyclopropanc~1-carboxylic " IR spectrum (chloroform)

Absorption at 1710 cm, c=0 characteristic,

-1

353, 0 cm absorption, 011 OD characteristic,

NMR spectrum (deuterochloroform)

Peaks 1, 30 - 1, 32 - 1 * 42 to the P, P-" the m features of hydroGcnes. gemini methyls;

p-peaks to 1, 75 - 2, 08" characteristics of hydrogen cyclopronylo p.m;

4, 67 - 5, 50 p-peaks " p.ra characteristics of hydrogen in position 1¹ ethyl substituted side chain;

peak at 10.75 pp.p " m-characteristic of hydrogen from the carboxylc.

Step b : 1R, cis-2.2-to-diméth3~-yl (2 '(R) fluorine~2' - chlor - 1 '.2'dibroraoéthyl) cyclopropane - 1 carboxylate 3 - 1 ΐ℮ηοχτ benxyle ρ "Mixed 3" 5 S iR-acid/2.2-dimethyl 3 - cis-(2 '(R)- flouro 2 * - chlor 1', 2 - dlbromoéthyl *) - cyclopropane 1-carboxylic acid obtained in step Λ, 3.5 g of 3~phénoxy benzyliquo, 3.5 g of dimethyl formamide with acétainéopontyliquo, 35 cm3 benzene, carries the reaction mixture to 50 °c " holds the graft during 17 hours at such tempéx-to-ature, cools, a plowshare concentrated by distillation under reduced pressure, chromatography the residue on silica gel eluent is a mixture of benzene and cyclohexane (1/1) and obtains, on the one hand, 1,050 g of isomer Λ of the 1r, 2.2 a-substituted dimethyl 3 - cis-(2 '(R)- flouro 2'-chloro-1 ', 2 * - dibromocthyl) cyclopropane 1 a-cnrboxylatc of 3-phenoxy benzj' the, the P= 50 °C *

Analysis ii C.₂₁H_{? ()} Brr₂ LC (534.65) ^ 0 F.

Calculated■: P L 47.17 hr ^{the R} , the O 3.77 LC #6.63 F. 3.55 brr 29.83 found ii -47.4 3.8 7.2 3.7 29.4, Rpm spectrum (chloroform)

Absorption at 1735 cm ^ characteristic 0=0,

Absorptions to 1675 and 1590 to-i4p0 cm7, càractéris ticks of core:: aromatic.

Spectrum OD TIR? (nitroaniline)

Tic to 1, 23 - 1, 39 w " w, m-characteristics back hydrogens : back, geminal methyl;

peaks to 1, 73 - 2, 01 pp.p_I the m characteristics of hydrogen. i.' clopropyle;

peak at 5.08 w. p.m methylene hydrogens back feature

of the radical bonzyle J.

5 peaks, δ - 5 0, 50 w, w, w characteristics 1 'hydrogen in position 1' OD étîiyliquc substituted side chain;

6, 83 - 7, 58 p-peaks, P-, M., back hydrogens of core features:: aromatic. On the other hand is collected 0.62 g of isomer B, AnaIvs ο

Calculates C 9' 47.17 Η % 3.77 LC ^{the R} the O / 6.03 F. $ 3.55 Dr. 9' 29.8? Is 47.5 3.8 6.2 3.6 20.6.

IR spectrum (chloroform)

Identical to that of the isomer has " · ·

NMR spectrum OD (deuterochloroform)

'Peaks to 1, 22 - 1, 34' p * p, m-characteristics hydrogens to des-méthy -

The gemini•;

chisel 1, 73 - 2, 0 pop.m characteristics back hydrogens cyclo ' propyl;

peak at 5.12 pp.p_I the m characteristic hydrogens methylene of the benzyl radical;

foot of the 4.83 to 5.33 pp.p " m-characteristics of hydrogen in position 1' éthyliqrie substituted side chain;

peaks of 5.83 to 7.5 ' w, w₀ the m features back hydrogens of core:; aromatic.

1R acid, 3 - cis-2.2-dimethyl (2 '-chloro-2 "- Fluoro) or cyclopropane - 1 - carboxylic acid used in step a can switched prepared - of NOU similarly to that used by d, BROUR in its thesis 197' L-, entitled construction activity consisted of studies of halopyrcthrolds, published in 1976, by the" Scanners University in microfilm ANNs, boron concentrations has_F. Mich u * s, has, pages 27 to 29, for preparing DL Tra-: ls corresponding, but by using the Z, 2-dimethyl 3s fofo.rmyl~ the cyclopropane - 1r-to-carboxylatc T-butyl instead of the 2.2 and diméthydiméthy.l 3Ds-formyl-cyclopi-to-WCPFC-to-SRI-carboxylate t-butyl "

Example 40: study of insecticidal nropriétés isomers (has) and (d) of the (irir.c.is) 2.2-dimethyl 3 - (1', 2¹ , 2 ', 2' a-tetrabromo Chloroethyl) cyclopropane 1-carboxylate (e) "with" 3 a-Phcnoxvcyoaobonsvie (Y, and Y,,), insecticidal properties isomers

(Has) and (d) of the (L-R, cis-) 2.2-dimethyl 3 - (2 '', 2 a-dishloro 1 ', 2'bromo ethyl) eyclooropane-to-1-carboxylate (e)- C. ΔΨ ^ year O 3 a-nhénoxybenzylo♦(Y₀ and Y,,) as well as of the following compounds; ^{the R,, W.} '"^{the R} '■" J-. ". n-ft /, ..,,. -, . , ... in-... - n-■■■■■■■■dl-cis or trans 3 - 2.2-dimethyl (2 ', 2' - dichloro-1 ', 2' to-dibromoéthyl) cyclopropane 1 carboxylate of RS o6~cyano 3~phénoxy benzyl

(compound Y ^) j of the 1r, 3 - trans-2.2-to-dimcthyl (1¹ , 2'_therein 2 ', 2" tétrabromoéthyl) cyclopropane 1 carboxylate OD (RSs), ^ 3 para-cyano - benzyl (compound I HS); the 1r, c ± s 2.2-dimethyl 3 - (2', 2 'a-bromo 1', 2 '- dichlorocthyl) cyclopropane 1-carboxylate (R)- Cy-/' anogenital 3-phenoxy benzyl (compound Υ γ) ; the 1r, trans-2.2-dimethyl 3p (2 ', 2' dichloride 1 ', 2' a-dibromoéthyl) cyclopropane-a 1 - (R)P-OD carboxylatc<3~phénoxy bcnsylo a cyano - 00

(compound I HS) j. 1g 1r, cis-2_} 2-dimethyl 3 - (ΐ ^, 2 ·, 2^2 · tetrabromoethyl) cyclopropane 1~carboxylate OD 5 a-bonzyl 3-furyl-métliyl (compound Y ^)®

THE O• Study D.the O y-back activity^ . Y₀₁Y grams and Y ^.

The LOS insect tests are flies domestic female elderly OD 4 days. It is performed by topical application of 1 jJl solution acctoniquo on dorsal thorax insects by the micro-manipulator of Arnold. Used 50 individuals per treatment. We monitor mortality twenty-four hours

after processing.

The assays are performed without or with the addition of synergist piperonyl butoxide (10 parts of synergist for 1 part of compound has testing).

Experimental results, summarized in the following table, are expressed DL 50 or dose (in nanograms) necessary to kill 50% of the insects:

(

(

₍

(

(.

(

(

(

(without synergist

(

(with synergist

(

LD 50 in nanograms

)) 1 Compound Y,)

*)

(Isomer B))

)) 0.60)

) 0.46)

)

Concluding :

The compounds, YYg and according to the invention have lethal, on housefly, extremely high. This activity is enhanced by addition of piperonyl butoxide.

•2) Study of the activity of the compoundTHEREIN "

The conditions of the experiment are the kids as above, .

The results were the following:

B.) Study de_lj_ef F. et_létal_sur_larves willwill de__spodoptgra littoralis:

WITHJ assays are performed by topical application of an acetone solution by the micro-manipulator of Arnold on dorsal thorax larvae. 10 To 15 is 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 treatment, the individuals are placed on a nutrient medium

. artificial (Poitoit medium).

We monitor 48 hours after treatment of mortality.

The experimental results are summarized in the following table:

()

(9.Ï>L to 50 in nanograms)

)

(•

(Compound y

(¹

((Isomer)

(-

(

(0.68

Compound Y₀ }

^)

(Isomer B))

)

)

0.32)

)

Concluding :

The compounds Y and Y₂ of the invention are endowed with extremely high lethal activity on larvae of Spodoptera littoralis,

l) Study oD the insecticidal activity tracked Spodop ODa Tera Littoralis a mixture approximately équimoléculairo OD compound Y^and OD conrposc , a mixture substantiallyéquivnoléculaire of compound Υ ^ and COMthe Pdared therein^, the compound d e of the C. the OMPdared c the assays are performed by topical application. Deposited L of a 1/i<acetone solution of the product to be tested on dorsal thorax of each individual. Used 15 Spodoptera Littoralis caterpillars at 4ème larval stage, for each dose employed.

After treatment, the individuals are placed on an artificial diet (Poitoit medium), we monitor of officacity (percentage mortality taking into consideration a untreated control) 24 hours and 48 hours after treatment and determining the lethal dose 50 (LD ^ Q-) in nanogranmes by track.

The experimental results are summarized in lo and following table Compound

' llélango substantially equimolar of: ο π ρο - 50 therein (Λ isomer)

and

compound (isomer B)

Substantially equimolar mixture of compound Y_ (Λ isomer)

d e OD ^

compound yii (isomer B)

0,125

49.3: 20.0

2.5

: 100

('

1.25

: 66.6

7

0,625

KCS.

0,312

: ^ ο, ο

Compound Ythe P

1

0.75

: 93.2

; 66.6

0.50

: 46.6

0.25

: 13.3

0.51 0.51

Witness; zero mortality

Concluding:

The test compounds have insecticidal activity very high lability towards willwill spoddptera littoraüsc 05761

C) study of £de_lj_activ_ité_c_chocmouchejdomestiqu on. I:

Insects tests are flies domestic female âgëes of 4 days. It is performed by direct spraying in chamber Kearns and market by using as solvent a mixture in equal volumes of acetone and kéronëse (amount of solution used 2 x 0, 2 cm3). Uses about 50 insects per treatment. Checks are carried out every minute to 10 min, and then 15 minutes and 1' is' determines the KT 50 by the usual methods.

Experimental results obtained are summarized in the following table:

__

(KT is 50 minutes (for a concentration of 1 g/l) (- -•) (compound Y₁ (¹ Compound y2 compound HS compound Y) ')

The K. ENU Time 50 T 50 denotes the time needed for 50% kill insects with a fixed dose of product to be tested.

This time is inversely proportional to the speed of action of the product.

Concluding :

The compounds therein, and Y ^ ^ agonists of the invention have activity on flies shock interest.

t-σ ( isomer B) , THEREIN^ , HS, on larvae Epilachnhas Yarivcstris"

The LOS assays are performed by topical application in a manner similar to that used for the larvae of Spodoptera "are used larvos penultimate larval stage and after processing the larvae are fed by of bean plants" we monitor mortality 7' - hr after treatment " experimental results are summarized in the following table:

05761 γ υ

E) study of the insecticidal activity toto suir if tophus read GranariustDC TriboliunCastaneun, a mixture is equimolar amount of compound sensiblcncnt Υ ^ (isomors Λ) and OD compound Y, (b-isomer), and a mixture in proportion to louse near cquinoléculaire OD compound Y ^ (isomer Λ) and OD compound Y ^ (isomer B) testing is performed by direct spraying toto sxir infested wheat. 5 Ml of acetone solution is sprayed OD 0.1 cm3 TDC test product water on 100 g of wheat content in a flash vessel 1 liter of a rotary évaporatcur (moving)® is artificial infestation by 50 individuals (weevil Sitophilus or beetle), for each doso, OD the percentage mortality is determined after 7 days in consideration of a untreated control and performing NOU moycrmo over 100 individuals and the concentrations are determined lethal $0 (5 DEGREES OF CL)•

The LOS results, experimental obtained are summarized in the following table;

5 Witness natural mortality: Sitopliilus 1.0

4.0 Beetle ^C. , d₉

Concluding:

The mixtures tested are have potent insecticidal activity on beetle Castanoum,

ο their activity on a louse SitopliilusGranarius is lower.

F.)Study of the insecticidal activity on BlatellaGormanica (adul -

a TES male) D.^F. a mixture in roughly équimoléculairc compound (isomer Λ) and compound Y₀ (isomer B) and a mixture in proportion to louse near compound therein cquimoléculairc 5 ^ (isomer) and compound YZj. (isomer B).

The test performed is a tost by film on glass. Deposited back in petri dishes of 154 cm2, OD 2 cm3/acetone solution to 10 mg L of product to be tested, and then left to evaporate acetone; the film formed corresponds to 1.3 mg of active substance per

ο m2. The LOS insects are placed onto the film_I Is the count back insects slaughtered after 5 min, 10 min, 15 min, 20 min, 25 min, 30 min, 40 min,

50 min, θ min 6. Removes the insect of the box, and the Petri specimen in jars own " checks are performed mortality after 24 hours OD, 48 hours and 72 hours (the percentages of insects slaughtered and insect

5' dead are determined in consideration of an untreated control.

The LOS experimental results are summarized in the following table:

Concluding: the LOS mixtures is sputtering louse Catherines équimoléculairos ratios of the compound and d VBE1 ii compound Y₀ , as well as the mclanccs in quantities approximately cquimoléculaires of compound Y

and compound therein, are endowed with insecticidal activity romnrnuablo, reefing screw OD ^J

hr

BlatcllaGernanica -,

1

5 p-χο π ;the Li è1 •

Study OD the acaricidal activity of compound Y_lo a mixture OD compound (isomer) TDC of compound (d-isomer) and d¹ a mixture OD compound Y ^ (isomer) and compound Y ^ (isomer 13) has) Activity on the authorisation Tétranychus.

1 aryicido_ovicido and test.

Leaves are used OD bean infested with 10 female Tétranychus authorisation of foil-coated of Glu at their periphery; allowed females lay for twenty-four hours, and removed and distribute the sheets thus infested eggs in two groups "

a) a first group is treated with the compound to be tested; it is carried out by spraying an aqueous solution of 0.5 cm3 on each sheet using back concentration and OD 50 -25 g of test compound per hectare.

b) a second group of sheets is not treated and serves as a control group.

Enumeration live eggs and live larvae occurs nine days after start of treatment * results expressed in percent mortality of eggs and larvae in subsystem summarized in the following table (taking into account the untreated control)"

The experimental results are summarized in the following table the j

Concluding ii the compounds of therein₀ and Y and Y ^ ^ processed well ovicidal activity and larvicidal to screw the authorisation Tétranychus "

5 B.) Activity on the UL Panonychusmid₀

The test was performed with the compound Y₀ on grapevine cultivar of "SHIAH" " it has 4 repeats for each dose, the method blocks selo_C. An untreated control is introduced into each block *

5 Elemental each parcel is composed of 10 vines.

Single treatment is performed, on the basis of 1000 liters of slurry per hectare, using a van puivérisaïomrvfeij at constant pressure.

The monitoring is carried out 7 days_O 16 days, and then 26 days,

>. after processing. Count is calculated mobile (larvae and adults) present on 15 sheets, harvesting by brushing and the results are expressed relative to the untreated control.

Experimental results obtained are summarized in lo and

1 following table:

Number of mobile on 15 sheets:

The compound has acaricidal activity on the net NOU adultos and larvae Panonychus ulmi "

■Example 42the I

Study of the activity nematicide DitylenchusMyceliopliagus

D.¹ the Un-mixture OD compound THE Y ^ (isomer) and of COMthe PmonosaccharideY₀(p-isomer) and a mixture of compound Y" (isomer) and compound Y ^ (isomer B)"

In a pill containing 10 ml aqueous acaricidal solution

•testing, 0.5 ml of water is deposited containing about 2,000 nematodes. Mortality checks are performed to the binocular loupe twenty-four hours after treatment and on three repeats each corresponding to a sample OD 1 ml of the test solution *

Experimental results obtained are summarized in the following table (results expressed in percent mortality) in view D.^{the L} an untreated control *

Concluding ii

The LOS approved mixtures are endowed with interesting nematicidal activity screw to Screw DitylenchusMyeeliophag-to-U.S.*

\

The ex3 'i env :

Study of the activity of a mixture ixodicidal équimolécula-to-ii'ii' e of compound and compound Y₀ ,

The cos for performing assays, we used a solution, of which the preparation is further explained below to the example 29",

This solution to 0.5 percent active ingredient is diluted at the time of use in 50 times its volume of water which causes a concentration of ΐ / ΐ 0, 000,

A) in vitro testing in vitro

Of the genus ^ tiqtxesRlxipicephalusSanguineus " were obtained on. dogs, They were contacted during 30 minutes with the preparation containing ΐ / ΐ 0, 000 of active ingredient. It has been found that at " OD tip 30 min, tick remover are moving alternately incoordonnés and 4 hours later,

they OS cyle dead (while removers witnesses are undamaged)*

B.) Test on dogs

Was used 2 dogs infested Ixodes genus RliipicophalusSanguineus; the tiquos are attached primarily to the wagering; on the RO-to-eilles, neck and chest_I

Soaked body of each animal with a solution containing ΐ / ΐ 0, 000 PI ' incipe active (2.5 liters per dog).

The premises where livestock is sprayed with the residual solution having served the traitor,

It is found, after 24 hours that ticks are still attached and still have movements.

After 72 hours, the tiqxies further attached but died,

The local and general tolerance is excellent, the animals being observed during 8 days after treatment.

The ex44 env; study antifongiq activitythe UEs 1r, 2 cis 1, 2 -dimethyl 3~(1¹ , 2 ', 2', 2' (R)~tétrabromoéthyl) cyclopx^> nAFO and 1 carboxylate SF) çg cyano 3~phénoxy benz3^{the R} the (* compounds therein₀ or A) and 1r, cis-2.2-to-dimcmC3 - yl derivatives (2 *, 2' a-dichloeR 1 ', 2'(SRV) bromo~éthvl) c.yclopropane-a 1 - CARB SCMthe Otyre treadhasthe Tc(E)- j6 __dea cyano 3 a-Phenoxy b.enzyle (C.the OMPbold Y2_QïlJB)"

Is fungistatic study the efficacy of the test compound by introducing 0.5 cm3 of solution of the compound and 0.5 cm3 of spore suspension of the fungus to combat adjusted to about 100,000 spores per cm3 in 4 cm3 nutritive media STARON.

The readout is performed, after 7 days of incubation, by visually monitoring the development of the fungus or its absence of development (0% or 100% efficiency).

The nutritive media STARON to the following composition:

- water amount sufficient to 1 liter.

A) T-is on PusariumRosemn "

En. operative procedure using the previously given, is troixve that thresholds fungistatic compounds a and 13 are between 25 and 50 p.p.m..

B.) Test on Botryt innovative advanced cinerea on

The thresholds fungistatic compounds a and b are between 25 and 50 w "Gunnar"

C.) Test on Phoma cf species and

The threshold, F. ongistatic. the compound a is between 25 and 50 w " p.m and that of the compound b is between 10 and 25 w, p.m " D.) Test on Penicillium Roquefort cheese!

The threshold fungistatic of compound b is between 150 and 200 p.p.m.*

E) concluding:

The compounds a and b are endowed with d^F. nOU interesting antifungal activity against fungi tested.

Example h5 ? Preparation of⁽ a suitableC.iabloénulslf entered,

Mixed homogeneously of ii

(Has)- isomer of (LU, cis-) 2.2-to-substituted dimethyl 3 - (1 *, 2 ", 2', 2" - tétrabrono ethyl) cyclopropane 1 a-carboxylacarboxyla.te of (e) an O (a cyano - 3-phenoxy benzyl 0.25 grams ii

- Piperonyl butoxide 1 grams;

The Tween 80 . 0.25 grams *;

- 0.1 Grams Topanol has;

•98.4 g of water.

Example * RG is preparing an emulsifiable concentrate

Intimately mixed:

The isomer (has) (Ir, cis-) 2.2-dimethyl 3 - (1', 2 *, 2¹ , / - 2 tëtrabromo ethyl) cyclopropane-l carboxylate (O) c-^ a cyano - 3-phenoxy benzyl 0,015 grams

- Butoxide pipêronyle 0.5 grams;

- 0.1 Grams Topanol has;

' - Xylene 99,385 grams. Example Ml. : Preparation of an emulsifiable concentrate

Homogeneous mixture of wine is carried out:

- Isomer (has) the (L-R, cis-) 2.2-dimethyl 3 - {1¹ , 2 ', 21, 2' - tetrabromo ethyl) cyclopropane-l carboxylate (e) ^ (a cyano - 3-phenoxy benzyl ' 1.5 grams?

The Tween - 80:; 20 g;

- 0.1 Grams Topanol has;

- 78.4 G of xylene.

Mixed homogeneously:

- Isomer (has) the (L-R, cis-) 2.2-dimethyl 3 - (1¹ , 2', 2¹ , 2' a-tetrabromo ethyl) cyclopropane-l carboxylate (O) c-{a cyano - 3-phenoxy benzyl 0.25 grams;

i - tabu powder 25 grams;

- Cedar leaf powder..' 40 grams;

Pine wood powder -... 33.75 grams;

Brilliant green - 0.5 grams;

- p-nitrophenol '. 0.5 grams.

Example ^ 3; the composition, insecticidal containing a compound of fx-ormule :

Performing a mixture;

the cis-trans~LID, 2.2 and dimctliyl 3 - (2 ¹ , 2 ' dicliloro - 1^F. , 2' - dibronoethyl) eyclopropano~t-to-carboxylato % OD of RS - cyano group. 3 a-phph.cnoxy benzyl -

1 gm

- butoxide pipêronyle e grams

- tvveen OS ., 1 gm

Λ Topanol -,,,. 0.1 80 _F. 9 OJ.?: T-ISO ii.l. the O .50 : Suitable ' is the ACAR posltû. I-c-c-OD 1 year T-O-N T a compound OD i-fonnulo"

We prepared an emulsifiable concentrate containing by weight,

20 percent OD 1r, cis-2.2-dimethyl 3~(2 ', 2', 2¹ , 1 'a-tétrabromoétliyl) cyclopropane 1 OD (e)- carboxylato■•>a cyano - 3-phenoxy bonzyle, 6.5 POMs: percent, by weight of Atiox 4851 (triglyceride oxyethylenated combined with sulfonate, acid value 1.5) "3.3 pwi' cone Atiox I-|s55 (triglyceride oxyethylenated combined with sulfonate, acid value: 3 and 70.2 percent OD xylene"

E51 xemple : nematicidal composition containing a compound of fi-ormule,

An emulsifiable concentrate prepared for soil treatment containing by weight, 45 percent of 1r, cis-2.2-dimethyl 3~(2 ', 2', 2 ', 1' - tétrabromoéthyl) cyclopropancyclopropan.e-to-1~carboxylate (e) do of the L-cyano-benzyl 3-phenoxy, 6.4 percent of Atiox 4s51 (triglyceride oxyethylenated combined with sulfonate) acid value 1.5), 3.2 percent of 45.4 percent Atiox 4855 and xylene.

We prepared a solution whose composition is as follows:

THE O•0 * ""

0.5 grams 10 grams

C. C. 0000000 ℮· ℮· 00000000000 0 0" 0

0OC00000O00000

000000 * 00460

0 *••0 O-O

25 grams

1 G 100 ml.

equimolar mixture of compound Y ^ and c "

"""" 80th polysorbat """"""""""""""""""""" " """"""""""

as Triton, the X """" 100 """"""""""""""""""""" " """""""""""""

^ d-tocopherol acetate " .,

ethanol q * s * p.

This solution is used for external use after dilution in 50 times its volume of water "

Example 53; a composition containing ixodicidal

We prepared an injection solution containing a mixture of compounds 1 .j and Y the P c. """"""" * """"""""""""""""""""" "" "*" * "" 2 grams

- purpose oxide pyperonyle, T-""""""""""""""""""""" "". """" * 6, 6p grams

- c-O T of at T O th'T-O-O-O pH of gold LO """"""""""""""""""""". """ "•"" 0, has 3 grams

- q-oil vehicle, . O " P-. 100 yAC.

This oily vehicle is composed of 29 g of benzyl benzoate and peanut oil in sufficient quantity to obtain 100 cm3 URs voluine total "

Example 54 -: compound feed

containing a compound of I-_formule.

Used as balanced food base, a alimeiit-rad U-as-loading in the but, the luisemdoshydratée ©, wheat straw, palm kernel meal molasses, OD urea, a condiment mineral vitaminiqueo

TOC food c have T-ion and, at minimum 11 ^C. the O /protéiaues materials

5 raw (whose 2.8 provides by urea); 2.5 percent fat and not more than 15 percent of cellulosic materials, 6 percent of mineral matter and 13 percent moisture•

The food used corresponds to 82 imitated forage for 100) kilograms; and contains, for 100 kilograms; 910 * 000 U-shaped, I-, vitamin a, 910q0'd, the I " vitamin 156 mg vitamin e 150 and its g of vitamin c_I rt. incorporates the animal feed, 0, 0:00 1r kg, 3 - cis-2.2~dimcthyi (2 ·, 2 ', 2', 1'~téîrabromoétliyl) cyciopropane~1 carboxylate D.¹ the cyan-O 3-phenoxy benzylo (mixture of Y and Y ^ ^).

Residuthe 35' Antifungal composition"

We prepared a solution containing;

1R, cis-2.2 a-substituted dimethyl 3~(1^F. , 2 '>2', 2' - (PVS are) tôtrabromoéthyl) cycling breaded and 1-carboxylate (e) Go cyancbennyle 3-phenoxy_I " ** 50 grams

1 - O-H-I-cml _? I 00 5i 0 hr """""""""""<"1" I " I c-c-P-T- < >""" I 80 grams

- * - * Aa.y 1ox1g c e c-th. the FR-E "" d e 0♦p and O-β *•"P-T-•0"•"•th P-C.•**" s * e t * t " e 8/0 grams * mixture of calcium salt alcoylo benzene sulfonate (anionic portion) and d * polyoxyethylene ethers (part nonionic)_I

? Example 5 β-I The composition antifongramsigue_I

A wettable powder prepared whose composition is as follows;

2.2-to-substituted dimethyl 3 - irfirf.cis (* 2, 2' - dichloro-1¹ , 2' " RSs dibromoé thythy.l) cyclopropane 1 carboxy ETL (O)- therein of a cyano 3-phenoxy benzyl, .20 B 3 Ekapersol "e" (I) 15 5 (2) 0 Brecolane atomsnis, 39 (3)* Zeosil39₁ WormcosylE (hr) 25 grams (1) condensation product of naphthalene sulfonate,

5 (2) alkyl naplitalene sodium sulfonate,

(3) synthetic hydrated silica obtained by precipitation,

(hr) colloidal clay.