DD202284A5 - PROCESS FOR PREPARING NEW DERIVATIVES OF CYCLOPROPAN CARBOXYLSAEURE - Google Patents

Abstract

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

Description

Berlin, 11.12.1981

O * 7 Ο 5 ~ ^ " AP C 07 C / 231 372/5

59 416/11

Process for the preparation of new derivatives of cyclopropane-carboxylic acid

Field of application of the invention

The invention relates to a process for the preparation of novel derivatives of cyclopropane-carboxylic acid for use in agriculture, in the hygiene and veterinary sector and for the protection of material and stored products for controlling plant and animal parasites »

Characteristic of the known technical solutions

No information is available on which compounds have hitherto been used for the control of plant and animal parasites. No information is available on processes for the preparation of cyclopropane-carboxylic acid derivatives.

Object of the invention

The aim of the invention is to provide novel compounds with excellent insecticidal, acaricidal and nematicidal activity and favorable plant and warm-blooded toxicity _β

statement _i the essence of the invention

The invention has for its object to find new compounds with the desired properties and processes for their preparation.

9

11,12.1981

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/ Z D-2-59 415/11

According to the invention, compounds of the formula (I ¹ ) are prepared and all possible isomeric forms or mixtures thereof

- CH

in the A * represents

either an alkyl radical having 1 to 18 carbon atoms

or a benzyl radical, optionally substituted by one or more radicals selected in the amount formed by the alkyl radicals containing from 1 to 4 carbon atoms, alkene radicals containing from 2 to 6 carbon atoms, alkeneoxy radicals containing from 2 to 6 carbon atoms, Alkadienyl radicals containing 4 to 8 carbon atoms, the methanol dioxy radical and the halogen atoms,

- or a group

-cn ιμ v \

~ / Γ y- ^CH 2 ^R 2 *

^R l

in which the substituent R _{1 represents} a hydrogen atom or a methyl radical and the substituent R ₂ denotes a monocyclic aryl or a group -CHp-C 1 -CH and in particular a group 5-benzyl-3-furyl-methyl,

- or a group

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in which a represents a hydrogen atom or a methyl radical and R_ an organic acyclic radical containing from 2 to 6 carbon atoms and one or more unsaturated carbon-carbon and especially the radical

-CH ₂ ^ CH = CH ₂ , -CH ₂ -CH = CH-CH, -CH ₂ -CH = CH-CH = CH ₂ I -CH ₂ -CH = CH-CH ₂ -CH, _.

- or a group

in which a represents a hydrogen atom or a methyl radical. R 'retains the same meaning as before, R ¹ and R * ₂ , identically or differently, represent a hydrogen atom, a halogenonitrile, an alkyl radical of 6 to 10 carbon atoms, a Alkyloxycarbonyl group having 2 to 5 carbon atoms or a cyano group,

or a group

231372 5 -

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in which B represents an oxygen atom or sulfur or a group

II

j-, R. represents a hydrogen atom,

-C- or -

a radical -C Ξ N, a methyl radical; a radical -CONH ₂ V is a radical -CSNH ₂ or a radical -CΞCH, R ₅ represents a halogen atom or a methyl radical γ and η represents a number equal to 0, 1 or 2 and in particular the group 3 ~ phenoxybenzyl, £ -cyan 3-phenoxybenzyl, ^ -thynyl-3-phenoxybenzyl / 3 <-benzoyl-benzyl, 1- (3-phenoxyphenyl) -ethyl or oi-thioatid-3-phenoxybenzyl ,

** or a group

- or a group

231372 5-

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in which the substituents R _ß y ^R

a hydrogen

atom, a chloratora or a methyl radical and in which S / I symbolizes an aromatic ring or a dihydro or tetrahydro analogous cycle,

- or a group

~ or a group

- ^C - ^C1H

Rio

-CH

11

12

wherein R ^ _{0 represents} a hydrogen atom or a CN radical, R ^ ₂ represents a radical - OU - or an oxygen atom, R ₁ ^ represents a thiazolyl or thiadiazolyl radical, its compound with R ₁₀ on

-CH-any of the available positions,

2 313 7 2 5-

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R _{12 is} bonded to R ₁₁ by the carbon atom between the sulfur atom and the nitrogen atom,

or a group

- or a group

-CH

in which R _{1 represents} a hydrogen atom or a CN radical,

or a group

^R 13

I CH-

in which R ₁₃ is defined as above and the benzoyl radical is in position 3 or 4,

or a group

231372 5 -

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16

15

in which R _{14 represents} a hydrogen atom, a methyl, ethyl or cyano radical, and R. _ς and R -, -, different; »represent a hydrogen-v fluorine or bromine atom,

- or a group

wherein R ₁₄ is defined as above, each of R ₁₇ independently represents an alkyl group having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms ¹ , alkylthip having 1 to 4 carbon atoms; Alkyl sulfonyl of 1 to 4 carbon atoms, trifluoromethyl, 3,4-methylene-dioxy, chlorine, fluorine or bromine, ρ represents a number equal to O, 1 or 2, B * represents an oxygen atom or a sulfur atom, and R represents Alkyl radical of 1 to 18 carbon atoms substituted by one or more identical or different functional groups, or an aryl group of 6 to 14 carbon atoms, optionally substituted by one or more identical or different functional groups, or a heterocyclic radical, eventually

11.12.1981 AP C 07 C / 231 372/5 23137 2 δ " ⁸ " 59 416/11.

substituted by one or more identical or different functional groups, compounds in which the double bond has the geometry Z or E.

The compounds of formula (I *) may exist in many stereoisomeric forms: they actually have two asymmetric carbons in 1 and in 3 of cyclopropane; they also represent an isomerism E / Z at the double bond level, they may also represent one or more asymmetric centers in part A as in part R *

When A represents an alkyl radical, it is preferably a methyl, ethyl ,; n-propyl, isopropyl, h-butyl, isobutyl or tert, butyl radical.

When A represents a benzyl radical substituted by one or more alkyl radicals, it is preferably methyl or ethyl radicals »

When A represents a benzyl radical substituted by one or more alkenyl radicals, it is preferably vinyl, allyl, 2-methylallyl or isobutenyl radicals,

When A represents a benzyl radical substituted by one or more halogen atoms, it is preferably chloro; Bromine or fluorine atoms »

When R represents an alkyl radical substituted by one or more functional groups, alkyl is preferably understood as meaning a radical having 1 to 8 carbon atoms,

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231372 5 - ⁹ - ^{59 4l5 / i1}

like ζ. Β »methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl or tert -butyl radical *

When R represents an alkyl radical substituted by one or more functional groups, functional group is preferably taken to mean a halogenator, an OH or SH group, an OR * or SR 'group in which R ^{4 is} an alkyl radical having 1 to 8 carbon atoms represents

a group NO ₂ or N> in the R "and R" !, identical

or different, represent a hydrogen atom or an alkyl radical having 1 to 8 carbon atoms, a group C = N> SO H or PO ₄ H ₃ or a group COalc *, S0 ₂ alc ₂ or SO alc_, in the alc ,, * alc ₂ and alc_ represent alkyl radicals having 1 to 18 carbon atoms »

R can also represent an alkyl radical "substituted by an aryl radical. such as the benzyl radical or phenetyl radical, this itself may be substituted by one or more OH groups, OaIc or alc of 1 to 8 carbon atoms, by one or more groups CF ₃ , ^0CF 3i ^SCP 3 ^or by a group (G):

(G)

R may also represent an alkyl radical substituted by two adjacent carbons through a group (G ₁ )

3 1 3 / ^ - 5 - ¹⁰ - ⁵⁹ 416/11

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AP C 07 C / 231 372/5

OH

or substituted by a group -0

When R represents an alkyl radical substituted by one or more functional groups, the preferred values of R may be called the radicals:

- (CHp) <-CHal ,, where η is a whole from 1 to S and Hal is a halogen atom, for example the radical -CH ₂ -CCl ₃ , -CHp-CF, -CH ₂ -CH ₂ -CCl ₃ or - CH ₂ -CH ₂ -CF ₃ ,, - (CH ₀ ) -CHHaIp where Hai is determined as above and n

Number from O to 8, for example the radical -CH ₂ -CH ₂ -CHF ₂ or -

₂ pi where η and Hai are determined as above, for example the radical -CH ₂ -CH ₂ Cl or -CH ₂ -CH F; -C- (CHaI-) ν where Hai is as defined above, for example

OO

the radical -C- (CF,) - or -C CF,, -C CH, y

CCl ₃ ^ CF ₃

_CF, CF-

3 S * 3 ^ 3

CH- or -C-CH, -C-CH- or

3 V _n 3 \ 3

CH ₃ ^ CH ₂ -CH ₃ H

^CF 3 / ^CH 3 = ^H 3

-C - CF, -C CN, -C CW or - (CH ₀₎ -CN, where

s. ο ν. ν. ^v 2 'η

^ H CH ₃ H

η as previously determined,

231372 5- ¹¹ -

11 * 12.1981

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Chai,

/ ³

-C-CN, where Hal is determined as before,

for example, the radical -C - CN

- (CH ₀ ) -OR ¹ , where η is as previously determined and R * is

^v 2 ' η

Represents a hydrogen atom or a linear or branched alkyl radical containing from 1 to 8 carbon atoms, for example the radical -CH ₂ -OCH,; -CH ₂ -CH ₂ -O-CH, -CH ₂ -CH ₂ -O-CH ₂ -CH ₃ or -CH ₂ -CH ₂ -OH,

^ R '- (CHp) -N, where η and R' are as previously determined

and the two radicals R * may be different among themselves, Pu

for example, the radical -CH ₀ -CH ₀ -N,

* ^A ^ H

² ' ² ~ ^ ^CH 3 ° ^he " ² ~ ² ~ ^ ^CH 2 ^CH 3 - (CH ₀ ) -CH CH ₀ , where η is determined as before,

⁰ X ⁰

CH ₃

for example the radical -CH ₀ -CH CH ₀

² I i ²

H ₃ C ^^ CH

231372 5 -

2 η ι Υ «

OH OH

11/12/1981

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where η is determined as before,

for example the radical -CH ₂ -CH-CH ₂ -OH

where η is determined as before,

for example the radical -CH ₂ -

or

CH "- <

.- ° -r ° ^ - < ^CH ₂ ) _n

where η is determined as

before, for example, the benzyl or Phenetylradikal

where η is determined as before, to

Example the radical

When R represents an aryl radical, optionally substituted, it is preferably a phenyl radical or a phenyl radical substituted by one or more OH groups, OaIc or alc having from 1 to 8 carbon atoms or by a group CF, OCF or SCF _Φ

12/11/1931

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23137 2 5 ¹³ - ^59416/11

When R represents a heterocyclic radical, it is preferably a pyridinyl, furanyl ,; Thiophenyl, oxazolyl or thiazolyl radical »

The invention relates in particular to a process for the preparation of the compounds of the formula (I *) as defined above, corresponding to formula (I):

RO ₂ C - CH = CH ^ / \ ^ CO ^ A (I),

in the A represents ** either an alkyl radical having 1 to 18 carbon atoms - or a benzyl radical "possibly substituted * as well as

previously defined "* or a group

CH,

in which the substituents R ₁ and R _{2 are} as previously defined, - or a group

where a and R are as previously defined, or a group

23 13 72 5 - "-

11 '12.1981

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59 416/11

R.

RV R *.

in the a, R ¹ . y R ' ₂ ^unc * ^R · * ^wi · ^{8 are} previously defined, or a group

in which B represents an oxygen atom, a group 0

- C- or -CH ₂ -, R is defined as before ·, R ₅ represents a Chbratom or a methyl radical, and η represents a number equal to 0, 1 or 2 and in particular the group 3-Phehoxy-Benzyl _t -äji- Cyan-S benzyl or ^ -thynyl-3-phenoxy-benzyl, or a group

- or a group

2 313 7 2 5 -μ-

11.12 · 1981

AP C 07 C / 231 372/5 59 416/11

or a group

N-CH ₂ -

in which the substituents R '»R ₇ V ^R ₈ * are previously defined, or a group

and S / I like

N-CH ₂ -CsCH

and R is defined as before »

The invention has in particular as its object a process for the preparation of the compounds of the formula (I, ')> for which the double bond has the geometry Z.

Among the preferred compounds obtained by the process of the present invention, mention may be made of the compounds for which the coupling is cyclopropanoic acid of the IR-cis or IR-trans structure, and more particularly those for which the cyclopropanoic acid coupling of the Structure IR-cis is »

11:12 "1981

-> 1 Q 1 OC ^{AP c 07 c / 231 372/5}

JI J / Z .O - 16 - 59 416/11.

The invention relates in particular to a process for the preparation of the compounds of the formula (I ¹ ) ·, as defined above, where A * represents a group o <-cyan-3 * -phenoxybenzyl in the form of S, R or RS and in which A ₁ * is a group 2-methyl-4-oxo-3 <- (2-propenyl) -2-cyclopenten-1-ylene in the form S ,. R or RS represents *

In particular, the invention provides a process for the preparation of the compounds of formula (I ')> wherein R represents an alkyl radical of 1 to 18 carbon atoms substituted by one or more functional groups and more particularly those in which R represents an alkyl radical substituted by one or more halogen atoms, for example one or more fluorine atoms. As an example of the alkyl radical, substituted by one or more halogen atoms, one can especially call the radical -CH-CF- «

Among the compounds of the formula (I *) # which can be prepared according to the invention, the compounds of Examples 1, 2, 23,. 26, 29, 30 and 35 call *

The compounds of formula (I * ·) offer interesting properties that allow their use in the fight against parasites »It may be, for example, the fight against plant parasites, the local parasites and the animal parasites of warm-blooded animals * So you can the products of the invention use for the control of insects, nematodes and mite parasites of plants and animals,

11.12,1981

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72 5- ^{17-59416 /} "

The invention therefore also relates to the use of the compounds of the formula (I ') in the fight against plant parasites, local parasites and animal parasites of warm-blooded animals,

The products of the formula (I *) can therefore be used in particular for controlling insects in the agricultural sector, for example for controlling aphids, butterfly and beetle larvae, they are used in amounts of between 10 g and 300 g of active matter per hectare *

The products of formula (Γ) can also be used to control insects such as flies, mosquitoes and cockroaches.

The compound of Example 1 is a remarkable product, as the results of the following tests show, it has excellent lethal ability and a large knock-down capability. "

The products of formula (I ') are very photostable and are not toxic to mammals »

The totality of these properties makes from the products of the formula (I *) products that perfectly meet the requirements of the modern agrochemical industry: they enable the protection of crops taking into account the protection of the environment »

The products of formula (I *) can also be used in the fight against mite and nematode parasites of plants.

11.12.1981 AP C 07 C / 231 372/5 231372 Β " ¹⁸ " ⁵⁹ 416/11

The compounds of formula (IV) can also be used in the fight against mite parasites of animals, for example in the fight against ticks and especially ticks of the species Boophilus, the species Hyalomnia, the species Rhipicephalus or in the fight against all types of mange "and especially mite mange, psoroptic mange, and chorioptic mange,

The compounds of the formula (I *) can therefore be used to prepare the compositions intended for combating animal parasites of warm-blooded animals, plant parasites and local parasites with one or more compounds of the formula (I *) as active component,

The compounds of the formula (I *) can be used in particular for the preparation of insecticidal compositions »

Among the preferred compositions obtained ,, according to the invention, one can particularly the compositions (IR-cis) - 2,2-dimethyl-3 - / (Z) -3- (2,2 ₁ 2-trifluoroethoxy) -3- 0xo-1-propenyl / cyclopropane carboxylate of (S) <x. -Zyan-3-phenoxy-benzyl,

(LR-cis) -2,2-dimethyl ~ 3 - / (Z) -3 ~ 0XO-3- (2- (1,1,1,3,3 "3-hexafluoro) propoxy) -l-propenyl / -Cyclopropane carboxylate of

(S) oi -cyan-3-phenoxybenzyl,

(IR-cis) -2,2-dimethyl-3 - / (Z) -3-0xo-3- (2 _i 2,2-trifluoro-ethoxy) ~ l-propenyl / -Zyklopropan-carboxylate of (R) * <ethynyl-3-phenoxy-benzyl

(lR-cis) -2,2-dimethyl-3 ~ / (Z) ~ 3 ~ 0xo-3 ~ (2,2,2-trifluoro-ethoxy) -1-propenyl / -cyclopropane carboxylate of (RS) - cyan-6-phenoxy-2-pyridyl-methyl,

231372 5

11.12.1931 AP G 07 C / 231 372/5 - 19 - 59 416/11

(1R-cis) -2,2-dimethyl-3 - / (Z) -3-oxo-3- (2-fluoro-ethoxy) -l-propenylZ-cyclopropane carboxylate of (S) i * cyan-3 Phenoxybenzyl ,

(IR-cis) -2,2-D-imethyl-3 - / (Z) -3-oxo-3 - (2,2,2.-trifluoro-ethoxy) -1-propenyl / -cyclopropane carboxylate of (3 -propargyl-2,5-dioxoimidazolidinyl} -methyl,

(1R-cis) -2,2-dimethyl-3 - / (Z) -3-oxo-3- (2,2,2-trifluoroethoxy) -1-propenyl / cyclopropane carboxylate of (IS) - Call 2-methyl-4-oxo-3- (2-propenyl) -2-cyclopenten-1-ylene »

These compositions are prepared according to the methods used in the agrochemical industry or the viniferous industry or the industry of products intended for animal nutrition.

In these compositions intended for agricultural use and local use, the active component (s) may eventually be supplemented with one or more other pesticidal substances. These compositions may be present in powdered formulated granules , Emulsions, solutions, solutions for aerosols ^ flammable strips, baits or other preparations, classically used for the use of this type of compounds »

In addition to the active principle, these compositions generally contain a binder and / or surfactant, nonionic, which, inter alia, assures a uniform dispersion of the constituent substances of the mixture. The binder used may be a liquid such as water, alcohol, hydrocarbons or others organic solvents, a mineral oil, an animal

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or vegetable oil, a powder such as talc, clay, silicates, kieselguhr or a combustible solid *

The insecticidal compositions according to the invention preferably contain from 0.005 to 10 % by weight of active compartments *.

According to an advantageous method of use in the locations, the compositions according to the invention are used in the form of smoke compositions *

The compositions according to the invention may thus be advantageously formed, for the non-active part, from a snake insecticide (or coil) combustible or else a fibrous incombustible substrate. In this last case, the smoke obtained after mixing the active matter is placed on a heater just like an electromosquito destroyer *

In the case of using a snake insecticide, for example, the inert carrier may be composed of pyrethrum pomace, tabu powder (or Machilus thumbergii leaves), powder of pyrethrum stielsi powder of cedar leaf, wood powder (such as pine sawdust) / starch and powder Powder of cup of coconut,

The dose of the active component may thus be, for example, from 0.03 to 1 % by weight. "

For example, in the case where a fibrous nonflammable vehicle is used, the dose of the active component may be from 0.03 to 95 % by weight. "

11 * 12.1981

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3 13 7 2 5 - ²¹ - ^{59 41S} '"

The compositions according to the invention for use in the places (premises) can also be obtained by preparing a pulverizable oil on the basis of the active principle ,, this oil soaks the wick of a lamp, so it undergoes combustion *

The concentration of the active principle mixed in the oil is preferably 0.03 to 95 % by weight »

The insecticidal compositions according to the invention, such as the acaricidal and nematicidal compositions, may optionally be supplemented with one or more other pesticidal agents. The acaricidal and nematicidal compositions may occur especially in the form of powders, granules, suspensions, emulsions, solutions.

For acaricidal use preferably wettable powders are used, for foliated pulverization with 1 to 80 % or liquids for pulverization with 1 to 500 g / l active principle. It is also possible to use powder for foliated sputtering with 0> 05 to 3 % active matter.

For nematocidal use it is preferred to use liquids for soil treatment with 300 to 500 g / l active principle *

The acaricidal and nematicidal compositions according to the invention are preferably used at dosages between 1 and 100 g of active matter per hectare,

In order to increase the biological activity of the products of the invention, they can be supplemented with synergists.

11.12 * 1981 AP C 07 C / 231 372/5 - 22 - 59 416/11

similar type used in such a case as 1- (2,5, S ~ trioxadodecyl) -2-propyl-4,5-methylenedioxy-benzene (or butoxide of piperonyl) or N- (2-ethyl-heptyl) -8icyclo - / 2,2-l / -5-heptene-2,3-di-carboximide or piperonyl-bis-2- (2'-n-butoxy-ethoxy) -ethyl acetal (or tropite 1).

When it comes to fighting the mite parasites of the animals, it is common to incorporate the products of the invention in the nutritional compositions in conjunction with a nutrient mixture adapted to animal nutrition. The nutrient mixture may vary according to animal species, it may include cereals, sugars and grains, soybean presscrops, peanut and sunflower, animal-derived flour, for example fishmeal, synthetic amino acids, mineral salts, vitamins and antioxidants.

The compounds of the formula (I ¹ ) can therefore be used for the preparation of compositions intended for animal nutrition »

The compounds of the formula (I ¹ ) show an excellent general tolerance / and they can be used in warm-blooded animals, in particular for the control of diseases caused by ticks and mange, as well as for controlling lice with preventive or curative property.

The compounds (I ') according to the invention can be administered by the external route, by spraying, by shampoo, by bath or brush,

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The compounds (I *) according to the invention can also be administered by brushing the backbone of the animals according to the so-called "pour on" method. They may also be administered by digestive and peranteral routes.

The compounds of the formula (I *) can therefore be used for the preparation of pharmaceutical compositions containing as active component at least one of the compounds according to the invention.

The products of the invention may further be used as biocides or as adjuvants.

The invention also makes it possible to prepare compositions having insecticidal activity, acaricidal or nematicidal activity, characterized in that they contain on the one hand at least one of the compounds of the general formula (I ') as active component and on the other hand at least one of the pyrethinoid esters selected from the group formed by the esters of allethrolone, alcohol 3,4,5,6-tetrahydrophthalimide-methyl, alcohol 5-benzyl-3-furyl-methyl, alcohol 3-phenoxy-benzyl and alcohol <* l-cyano 3-phenoxy-benzyl of chrysanthemum acids, through which esters of the alcohol 5 ~ benzyl-3 ~ furyl-methyl of the acids 2,2-dimethyl-3- (2-oxo-3-tetrahydrothiophenyl-methyl) -cyclopropane-l Carboxyl, by the esters of the alcohol 3-phenoxy-3-benzyl and the alcohol i5> t-cyano-3-phenoxy-benzyl of the acids 2,2-dimethyl-3- ( _2f 2 -dichlorovinyl) -cyclopropane-1-carboxyl, by the esters of the alcohol ot-cyan-3-phenoxy-benzyl of the acids 2,2-dimethyl-3- (2,2-Dibromv ynyl) -Zyklopropan-l-carboxyl,

11.12.1981 AP C 07 C / 231 372/5 313 7 2 5 - 24 - 59 415/11

by the esters of the alcohol 3-phenoxy-benzyl, the acids 2-parachlorophenyl-2-isopropyl-acetic acid, by the esters of allethrolone, by alcohol 3,4,5,6-tetrahydrophthalimide-methylj alcohol 5-benzyl-3-furyl -Methyl, Alcohol 3-Phenoxybenzyl and Alcohol <?--Cyan-S-Phenoxy-Benzyl of the acids 2,2-Dimethyl-3- (1,2,2-Tetrahydro) -cyclopropane-l-Ca rboxyl ', in which "halo" represents a fluorine, chlorine or bromine atom, it is understood that the compounds (I * j can exist in all their possible stereoisomeric forms as well as the acid couplings and alcohols of the esters,

The o.a "compositions according to the invention allow either the control, by the polyvalence of their action, a series of parasites or in certain cases a synergy effect»

The process for the preparation of the compounds of formula (I ¹ ), object of the invention, is characterized by reacting an acid of formula (II):

("J V

where R has the same meaning as before or a functional derivative of this acid, with an alcohol of formula (III)

A * OH

where A, *, has the same meaning as before to give the corresponding compound of formula (I *) *

231 372 5 -

11.12,1981

AP C 07 C / 231 372/5

The functional derivative of the acid used is preferably an acid chloride,

When reacting the acid of formula (II) with the alcohol of formula (HI) ₁ , it is preferable to proceed in the presence of a dicyclohexylcarbodiimide '.

The invention also has as its object a process for the preparation as defined above, characterized in that the compound of formula (II) is prepared by bringing a compound of formula (B ₁ ) into contact with an organic solvent>

O = C

in the form of trans or in the form of lactone eis, a compound of formula (B ^)

= P - CH - C - OR

where R retains the previous meaning to yield the corresponding compound of formula (II)

RO ₂ OCH = CH _χ / '\ _y CO ₀ H (H)

in the form of a mixture of isomers E and Z, which are separated, if desired, into each of the isomers,

313 7 2 5 - ²⁶ -

11 * 12 * 1981

AP C 07 C / 231 372/5

In the preferred embodiment, the solvent used is selected from the group consisting of ethyl ether, dimethyl sulfoxide, dimethylformamide, tetrahydrofuran, dimethoxyethane, alkanols, monomethyl ether of diethylene glycol and diethyl ether of diethylene glycol.

The compound of the formula (B ₂ ) is prepared by the action of a compound of the formula

(φ) = P-CH ₂ -CO ₂ R, shark

Hai represents a halogen salt anion on a strong base * For example, a strong base can be a hydride, an amide or an alkaline alkoxide or an alkyllithium *

The invention has also as its object a process of preparation as defined above, characterized in that the compound of formula (II) is prepared by reacting a compound of formula (IV)

Hal Hai

C0 ₂ alc

in which Hal represents a halogen atom and alc an alkyl radical of 1 to 20 carbon atoms, first with an alkaline agent capable of tearing out the halogen atoms, then in the second phase

2 313 7 2 5

11/12/1981

AP C 07 C / 231 372/5 59 416/11

"*" either with an agent capable of introducing the carboxyl group to obtain the compound of formula (V)

HO ₂ CC = C / \. C0 ₂ alc (V),

which is subjected to the action of an esterifying agent to obtain a compound of formula (VI)

RO ₂ CC SC / \ CO ₂ alc (VI),

where R has the same meaning as before, or with a derivative of the formula

Hal-CO ₂ -R,.

where Hal represents a halogen atom and R has the same meaning as before to directly obtain the compound of the formula (VI)

RO ₂ CC = C _v / C0, alc (VI),

then subjects the compound of formula (VI) to the action of a hydrogenating agent to obtain the compound of formula (VII)

11 * 12.1981 AP C 07 C / 231 372/5 - 28 - 59 416/11

C0 ₂ alc (VII),

in which the double bond has the geometry Z, which is subjected to the action of an acid hydrolysis reagent, capable of selectively cleaving the function of ester with carbon in 1 cyclopropane »to obtain the corresponding compound of formula (II) *

In the preferred production of the o, a »process

- Hai represents a bromine or chlorine atom>

alc is a tert-butyl or benzyl radical,

- the alkaline agent 'capable of' ripping out the vinyl halides is butyl lithium,

the agent capable of introducing the carboxyl group is carbon dioxide,

the hydrogenating agent is hydrogen in the presence of a catalyst such as palladium in the presence of traces of quinoline,

the acid hydrolysis agent capable of selectively cleaving the ester C0 ₂ alc function is a sulfonated-para-toluic acid.

The procedure also contains an evident variant for the chemist; in which the compound of formula (V) is first subjected to the action of a hydrogenation agent, then in a second phase of the action of a reducing agent *

11/12/1981

<> 1 O η 1 r ^{ΑΡ c} ° ^{7 c / 231 372/5}

J I J / Z D- 29- 59 416/11

The invention also has a process variant for object = as defined above, characterized in that the compound of formula (V) is first subjected to the action of a hydrogenating agent to obtain the compound of formula (VIII)

H ₂ OC-CH = CH / \ COaIc (VIII),

in which the double bond has the geometry Z which is subjected to the action of an esterification agent to obtain the corresponding compound of formula (VII)

RO ₂ OCH = CH _x / \ ^ CO ^ alc. (VII) ₁

in which R retains the previous meaning, then continues the synthesis as previously described *

The o »a» procedure contains a second evident variant in which the order of certain stages is changed »

The invention also relates to a process as defined above, characterized by reacting the compound of formula (VI)

231372 5 -

11,12.1981

AP C 07 C / 231 372/5 59 416/11

RO ₂ CC = C

C0 ₂ alc

in the ale is

in which R and A are as previously defined * undergoes the action of an acid hydrolysis reagent capable of selectively cleaving the function of ester in 1 cyclopropane to obtain the compound of formula (IX)

H., C CH

in which R is defined as before, which either undergoes , possibly in the form of a functional derivative, the action of an alcohol of the formula

(III)

AVOH

(HI)."

in the A 'has the same meaning as before to obtain the compound of formula (X)

H_C CH, 3/3

231372 5

11.12.1981 AP C 07 C / 231 372/5 - 31 - 59 416/11

in which R and A * retain the same meaning as before "subjected to the action of a hydrogenating agent to obtain the compound of formula (I *), or they are first subjected to the action of a hydrogenating agent to give the compound of formula ( II)

H H I

RO ₂ C -C = C / ^CO ₉ H (II>,

in which R is as previously defined and the double bond has the geometry Z, then, optionally in the form of a functional derivative, the action of an alcohol (III) to obtain the compound of formula (I *).

The preferred conditions of execution of the o.a * method are identical to those previously defined for analogous methods,

The invention likewise relates to a process for the preparation of the compounds of the formula (I *), characterized by "the compound of the formula (XI)

HO ₂ C-HC = CH

in which the double bond has the geometry Z, undergoes the action of an esterification agent to make the connection

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j I Ο / Ζ 0

corresponding to the formula (I ').

In a preferred mode of preparation of the o "a" process, the esterification is carried out with a functional derivative of the alcohol, namely a derivative of N, N'-diisopropyl urea of the formula

NH

I.

N C OR

The invention also relates to a process as defined above, characterized in that the product of formula (XI) is prepared by reacting an acid of formula (V)

HO ₂ C-CSC / \ CO ₂ SlO (V),

in.der alc represents an alkyl radical of 1 to 8 carbon atoms; the action of 24 _P ^; 2> 2-trichloroethanol to obtain the compound of formula (XII)

H_C CH_ 3 w 3

.C = C

CO ₂ CH ₂ CCl ₃

which is subjected to the action of an acid hydrolysis reagent to obtain the compound of the formula (XIII)

231372 5

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59 416/11

H_C CH, 3/3

(XIII)

CO ₂ CH ₂ CCl ₃

which is subjected to the action of an alcohol of formula (III)

A »OH

(III).

in the A ₁ ! maintains the same meaning as before to obtain the compound of formula (XIV)

H, C CH, ο / ο

(XIV)

CO ₂ CH ₂ CCl ₃

which is subjected to the action of an agent of cleavage of the function ester carried by acetylene carbon to obtain the compound of formula (XV)

CO ₂ H;

which is subjected to the action of a hydrogenation agent to obtain the compound of formula (XI) *

S ~

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AP C 07 C / 231 372/5

³⁴ ~ ⁵⁹

In the preferred embodiment of the method according to the invention ο »a _#

· - ale in the formula (V) represents a tert-butyl or benzyl radical;

the acid hydrolysis reagent is paratoluene sulphonic acid;

the esterification of the compound (XIII) is carried out by reaction of the compound (XIII) with the alcohol (III) in the presence of dicyclohexylcarbodiimide or diisopropylcarbodiimide;

the cleavage of ester (XIV) takes place using a metal powder, for example zinc powder in an acidic medium;

the hydrogenating agent is hydrogen in the presence of a catalyst such as palladium in the presence of traces of quinoline.

The o "a" method contains an evident variant according to which the stages of hydrogenation and esterification are reversed.

The invention also relates to a process as defined above, characterized in that a compound of the formula (XV)

in which A * is defined above, undergoes the action of an esterification agent to obtain the compound of formula (X)

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11/12/1981

AP C 07 C / 231 372/5 59 416/11

RO C-CHC / \ COA ¹ (X) ₁

in which R and A * are as previously defined, which are subjected to the action of a hydrogenation agent to obtain the compound of formula (I *).

The preferential conditions of execution of the o »a, procedure are identical to those previously defined for analogous procedures«

In the event that it is desired to prepare a compound of formula (I ") in which R represents an alkyl radical substituted by one or more hydroxy radicals, one first calculates a compound of formula (I) according to any o _# a _# method ¹ ), in which R represents an alkyl radical substituted by one or more protected hydroxy radicals, for example by a dioxolanyl or tetrahydropyranyl group, then said compound is hydrolyzed by means of an acid hydrolysis reagent.

The method used in Säurehydrolyseagens can z «B _# be hydrochloric acid or paratoluene sulphonic acid,

The majority of the methods just described above result in compounds in which the double bond has the geometry 2. These are of course methods which are best adapted for the preparation of the compounds of formula (I ') in which the double bond is the geometry Z has »

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31372 5 ^{36-59 416/11}

Excellent yield is obtained, as clearly shown by the experimental part below.

The compounds (II), (VI) and (VII) and the compounds (IX) and (X) which can be prepared according to the invention are novel chemical products. The invention thus likewise relates to these products in the sense of new chemical products *

Ausführuncjsbeispiel

The following examples illustrate the invention without limiting it.

Example 1: (1R-cis) -2,2-dimethyl-3 - / (Z) -3- (2,2,2-trifluoroethoxy) -3-oxo-1-propenyl / cyclopropane carboxylate of (S) aC-cyan-S-phenoxy-benzyl

1.3 g of the acid (1R-cis) -2,2-dimethyl-3 - / (Z) -3-oxo-3- (2,2- _f 2-trifluoroethoxy) -l-propenyl are mixed with agitation. Cyclopropane-carboxyl, 0.1 cm of pyridine and 15 cm of chloride of methanol, then 1.05 g of dicyclohexylcarbodiimides are added. Then, 1 to 35 g of (S) -cyclo-3-phenoxy-benzene-acetonitrile are added in solution in 5 cm. of methanol chloride. It is stirred at ambient temperature for 5 hours, filtered insoluble, and rinsed in methanol chloride. The filtrate hydrochloric acid 2N is added. The mixture is poured off, washed with water, dried and brought to dryness Oil by chromatography with silica

(Eluent: cyclohexane - ethyl acetate (95 - 5)) »This gives 1.33 g of the sought after product, = + 42 ° + 2 ° (c = 0.7 % benzene)

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RMN . CDCl ₃ : ppm

1.26 and 1.28 H of methyl in 2

1.97-2.11H of carbon in 1 of cyclo-

propane 3.1 to 3.4 H of carbon in 3 of cyclopropane

propane 6.5 to 6.9 H of carbon in 1 propenyl

Radical 5.9-5.93 H of carbon in 2 propenyl

carrying radically 6.3 H of carbon

Group CN 4.3 to 4.7 H of trifluoroethoxy radical

In Example 1, the acid used is prepared as follows:

Preparation I: Acid (1R-cis) * - 2,2 ~ Dimethyl-3 - / (Z) - '3- (2,2,2-trifluoroethoxy) -3-qxo-1-propenyl / cyclopropane-carboxyl A: (1R-cis) -2,2-dimethyl-3 ~ (3 ~ hydroxy-3-oxo-l ~

^ § thvl

26 g of (1R-cis) -2,2-dimethyl-3- (2,2-ibromo-vinyl) -cyclopropane carboxylate of 1-dimethylethyl in 175 cm of tetrahydrofuran is anhydrified. 65 C 60 cm of a solution of butyllithium to 20 % in cyclohexane at. It is stirred for one hour at -60 ⁰ C, then allowed to flow through a stream of carbon dioxide for 1 and Y2 hour, poured the reaction mixture into ice water, the soda N is added. It is washed in ether. The aqueous basic phase is acidified to pH 4 and extracted in ether. The organic phases are dried, and the product is dried to a reduced pressure.

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AP C 07 C / 231 372/5 313 7 2 5 - ³⁸ - ^{59 415 /} "

This gives a product which is recrystallized in petroleum ether (Eb 60 to 80 ⁰ C) ^ boiling temperature). This gives 8.3 g of the desired product, melting at 144 C, RMN, CDCl; ppm

1.22 and 1.37: protons of the methyl in 2 of cyclopropane 1.78: proton in 1 and 3 of cyclopropane 1.47: protons of tert -butyl 8.25 Γ proton of the group -C-OH

Il

Äthvl

4 g of the product prepared in stage A, 3.5 g of dicyclohexylcarbodiimide are introduced into a solution containing 20 cm of methanol chloride and 1 cm of pyridine. The reaction mixture is stirred for one hour while stirring. 2.15 g of trifluoroethanol and 5 cm of methanol chloride are then added added. The mixture is stirred at 20.degree. C. for 16 hours. It is filtered and rinsed in methanol chloride. The filtrate is brought to dryness. The residue is again taken up in sulfuric ether, washed with hydrochloric acid, then with water, and dried Product subjected to silica chromatography (eluent: benzene-ethyl acetate (95-5))> This gives 3.5 g of the product sought * RMN ^ CDCl ₃ S ppm

1.2 and 1.37 H of the methyls in 2

1.77 H of the carbons in 1 and 3 of cyclo

propane

1.43 H of the methyls of radical 1,1-dimethyl

ethyl

4.3 to 4.7 H of the trifluoroethoxy radical

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231372

Stage ^ C: flR-ice) -2 _ί 2-0ΐπιβΐΗγ1-3- / 3-0xo-3 ~ £ 2,2,2-tri-

The mixture is brought into the reflux mixture with 3.3 g of the product prepared in the previous stage, 30 cm of toluene and 100 mg of para-toluene sulfonic acid, keeping the reflux until the end of gas evolution * It is cooled, washed in water, dried and brought it is dry * So you get 2.6 g of the product you are looking for, which you use as in the following stage »

Stadium.D: acid

Add 500 mg of palladium hydroxide to 10 % with barium sulfate and 5 cm of ethyl acetate in a flask connected to a hydrogenator. Add 2 g of the product prepared in the previous stage, 45 cm of ethyl acetate and 0.5 cm of quinoline End of absorption "Filter the product obtained." Wash the filtrate with hydrochloric acid N then in water and bring to a dry state. 2 g of a product are obtained which is subjected to silica chromatography (eluent: cyclohexane-ethyl acetate-acetic acid (70 - 30 - I)). This gives 1.3 g of the desired product.

Spectrum RMN. CDC I, ppm

H of methyl in 2

H of carbon in 1 of cyclopropane H of carbon in 3 of cyclopropane H of carbon in 1 of propenyl radical

1 * 3 and 1.32 1, 92 - 2.06 3.07 to 3.38 6.6 to 6.9

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5.9-6.0 H of carbon in 2 of propenyl

radically 4.3 to 4.7 H of trifluoroethoxy radical

Example 2: (1R-cis) -2,2-dimethyl-3 / fZ) 3-oxo-3- (2,2,2-trifluoroethoxy) -1-propenyl / cyclopropane carboxylate of (IS) -2-0imethyl ~ 4-0xo-3 ~ (2-propenyl) -2-cyclopentene-l-yle

1.9 g of the acid (1R-cis) -2,2-dimethyl-3 - / (Z) -3-oxo-3 - (2,2,2-trifluoroethoxy) -1-propenyl / cyclopropane are mixed Carboxyl, 12 cm of methanol chloride and 100 mg of dimethylamino-pyridine. »1.4 g of dicyclohexylcarbodiimide are then introduced, followed by 1.1 g of (S) -3- (2-propenyl) -1-hydroxy-2-methyl-4-one Oxo ~ cyclopentene «-2 and 5 cm of methanol chloride» Maintained with stirring at ambient temperature for 2 hours. * The insoluble material is eliminated by filtration. The filtrate is washed in hydrochloric acid O,: 5 N, then in water, dried and brought into water dry state »This gives 3 g of a product, which is subjected to silica chromatography (eluent: benzene-ethyl acetate (95-5)). This gives 2.2 g of the desired product» ^ ₀ = +38 ° + 2 , 5 ° (c = 0.5 % benzene)

Spectrum RMN; ^CDC 1 ₃ »

1 _# 29 and 1.32 H of methyl in 2 of cyclopropane

1.97-2.11 H in 1 of cyclopropane

3.05-3.37 H in 3 of cyclopropane

6.7 to 7 H of carbon in 1 of propenyl

radical

* H of carbon in 2 of propenyl

⁶ '- * ¹ radical

4.3 to 4.75 H of trifluoroethoxy radical

5.7 H of cyclopentene in pC of CO ₂

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313 7 2 5 - ⁴¹ - ^{59 4i5 / i1}

2 H of methyl, carried by cyclopentene

4.8 to 5.25 H in 3 of propenyl supported by cyclopenes

Example 3: (1R-cis) -2 _t 2-Dimethyl-3-il / (Z) -3-oxo-3- (phenylmethoxy) -l-propenyl Z-cyclopropane carboxylate of (IS) -X-cyan-3-yl phenoxybenzyl

A mixture is stirred for 5 hours under nitrogen stream with 1.5 g of the acid (1R-cis) -2,2-dimethyl-3 - / (Z) -3-oxo-3- (phenylmethoxy) -1-propenyl / cyclopropane -Carboxyl> 10 cm of isoprene and 1 cm of thionyl chloride, concentrated to give 2 g of a product, which is used as in the following stage,

Stradium Bi _- (IR-CiSi-S ^ -dimethyl-3 - / £ Z) -320xo-3 ^ (Phenyl-2Si-222SY2ziz- ££ E £ HXk Zz ^z Y-i2E £ 2EaezS ^a £ ^ 22 ^ I ^ J22Ü-§ 2zS ^ Oz ^ z phenoxy-benzene / l

Is carried out 1 g of the prepared in stage a product into a solution containing 700 mg of (S) * ·-hydroxy-3-phenoxy-benzene-Azetonitriljt 20 cm of benzene, and 0/5 cm pyridine, the one Reaktionsgemiech maintains during movement during 16 hours at ambient temperature, pour into a mixture of ice-water and hydrochloric acid N, agitate the resulting slurry and extract in benzene. * Wash the benzene extracts in water, dry, filter and bring to dryness. 1.5 g of a product which is subjected to silica chromatography (eluent: cyclohexane-ethyl acetate (8-2 )) _Φ

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Han receives so 851mg of the product sought, melting at 83 ⁰ C,

^ D ^{= +69} ° t ⁵ ° i ^{c =} ° ' ^{2% Ben201} ) Spectrum RMN, CDCl ^: ppm

1.25 H of methyl in 2 of cyclopropane

6.33 H of carbon bearing the group CN »

Production II; Acid (lR-cis) -2 _i 2-dimethyl-3 ~ / (Z) -3-oxo ~ 3 (Phenylmetnoxy) -l ~ propenyl / ~ cyclopropane-carboxy l

Z ^ ^ klogropan carboxylate

Hydrogenated 2 g of (1R-cis) -2,2-dimethyl-3 '- / 2-carboxy-ethynyl / -cyclopropane carboxylate of Ijl-dimethylethyl in 40 cm Äthylazetat in the presence of 0.38 g of palladium

3 *

The filtrate is washed in hydrochloric acid 0.5 W, then in water to neutrality, dried / concentrated to dryness under reduced pressure and receives 2 g of the desired product, 10 % with barium sulfate and 0.4 cm of quinoline, filtered melting at 94 ^° C.

ethyl

Add 2.4 g of the product prepared in stage A in 20 cm of ethyl acetate. Then 2.34 g of O-benzyl-N, N-diisopropyl isouric acid are added. (described by E. Schmidt and Liebigs Ann, 'Chem. 1965 * 685 , 161), stirred for 16 hours at ambient temperature, filtered and condensed.

11.12,1981 AP C 07 C / 231 372/5 231 372 5 ⁴³ ~ ⁵⁹ 416/11

the filtrate is concentrated under reduced pressure, 4 _r 3 g of a yellow oil, which is subjected to silica chromatography (eluent: benzene - cyclohexane (7 - 3)) to give 2 g of the desired product »

Spectrum RMN, CDCl: ppm

1,22 and 1,28 H of the methyls in 2 of cyclopropane

1.77-1.91 H of carbon in 1 of cyclopropane

2.98 to 3.3 H of carbon in 3 of cyclopropane

6.5 to 6.8 H of carbon in 1 of propenyl

radical

5.8-6 H of carbon in 2 of propenyl

radical

1.43 H of the methyls of diraethylethyl radical

5.1 H of methoxy of phenylmethoxy radical

Stage C: Acid (lR ~ cis) ~ 2,2-Dimethyl-3 - / (Z) ~ 3-Oxo ~ 3-l-Ph-en-1-hox ^ 2 ~ i ~ P

Is brought to 90 ⁰ C a mixture of 2 g of the product prepared in the preceding stage, 30 cm Toluoly 100 mg paratoluene sulfonic acid * one maintains under agitation for 2 hours approximately. The mixture is dried and 2 g of a product are obtained, which is subjected to silica chromatography (eluent: cyclohexane-ethyl acetate-acetic acid (60-40-I)). This gives 1 * 4 g of the product you are looking for «

Spectrum RMNy CDCl ₃ : ppm

1.25 and 1.3 H of the in2 methylcyclopropane 1.84 - 1 * 98 H of carbon in 1 of cyclopropane

3.14 to 3.43 H of carbon in 3 of cyclopropane

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\ λ I / * S-44-59 416/11

1 w / <fc «w

6.4 to 6.77 H of carbon in 1 of propenyl

Radical 5.98 H of carbon in 2 of propenyl

radical

Example 4; (lR-cis) -2, Σ-Ρΐιηθΐη ^, Ι - ^ - ΛΖ ^ -Οχο-ο-ΡηθηνΙ-πίΒΐηοχν) -l-propenyl / - »cyclopropane - carboxylate of (IS) -2-methyl-4- pxp- _i 3 "(2-» Propenyl) "2-" Cyclops _i n ~ l-yle -

1 g of the chloride of the acid (1R.cis) -2,2-dimethyl-3 - / (Z) -3-oxo-3- (phenylmethoxy) -l-propenyl / -cyclopropane-carboxyl is introduced into a mixture of 450 mg of (S) -3- (2-propenyl) -1-hydroxy-2-methyl-4-oxo-cyclopent-2-enyl,

3 3

20 cm of benzene and 0.6 cm of pyridine. It is maintained under agitation for 16 hours and the reaction mixture is poured onto a mixture of ice-water and hydrochloric acid N, extracted into benzene, the benzene phases are reunited, washed in water, dried and brought to dryness, giving 1.5 g a product which is subjected to a silica Chrontatographie (eluent: cyclohexane ethyl acetate ~ (8 - 2)) "

This gives 500 mg of the product sought. ^ ₀ = + 37 ° + 2.5 ° (c = 0.5 % benzene)

Spectrum RMN, CDCl ₃ ): ppm

1.27 and 1.31 H of the methyls in 2 of cyclopropane

1.87-2 H of carbon in 1 of cyclopropane

3.12 to 3.45 H of carbon in 3 of cyclopropane

5.8 to 6.8 H in 1 and 2 of the propenyl radical

5.2 H of methoxy of phenylmethoxy radical

5.6 to 5.7 H of cyclopentene in oi of CO ₂

11.12.1981 AP C 07 C / 231 372/5 - 45 - 59 416/11

2 H of methyl, carried by cyclopentene

4.8 to 5.2 H of propenyl, carried by cyclo

pentene »

Example 5; flRcis) -2,2-dimethyl-3 - / (Z) -3-oxo-3-phenoxyl-Probenyl / cyclopropane carboxylate of (S) g4-cyano-3-phenoxybenzyl

The procedure is as in Example 1, starting from 1.5 g of the acid (1R-cis) -2,2-dinethyl-3 - / (2) -3-oxo-3-phenoxy-l-propenyl / -cyclopropane-carboxyl and 1.45 g of (S) C-hydroxy-3-phenoxy-benzene-acetonitrile to give 1.8 g of the desired product

^ _Q = +54 ^G + 2.5 ° (c = 0.5 % in benzene)

Spectrum RMNy CDCl ₃ : ppm

H in 2 of cyclopropane H in 1 of cyclopropane H in 3 of cyclopropane H in 1 of the propenyl radical H in 2 of propenyl radical H aromatic of the radical 3-phenoxy-phenyl.

Preparation III: Acid (1R-cis) ~2,2-dimethyl-3 ~ / (Z) -3-oxo

3-phenoxy »l-propenyl / -Zyklopropan carboxyl

Stage A:

1.25 to 2.12 1.97 to 3.6 3.25 - 7 6.6 to 6.3 6.1 7.7 6.9

Dissolve 25 g of (1R-cis) -2,2-dichloro-3- (2 *, 2'-oibromovinyl) -cyclopropane carboxylate of 1,1-ethylethyl

11.12.1981. "AP C 07 C / 231 372/5

2313725 " ⁴⁶ " ⁵⁹

250 cc of tetrahydrofuran. Then one introduces under agitation at -65 ⁰ C 48 cm of a solution of 20% butyllithium in cyclohexane "One entertaining, the movement for one hour at -65 C and introduces a 9.6 cm of chloroform phenyl. Keep up to date with stirring at -65 C for an hour and return to ambient paper while entertaining the movement. It is poured onto an aqueous saturated solution of monosodium phosphate, extracted with ether, washed with water, dried to give 24.6 g of an oil, which is purified by silica chromatography (eluent: cyclohexane-ethyl acetate (9-1)}. 14.4 g of the desired product are isolated

Spectrum RMN ₁ CDC l ₃ : ρρφ

1.23 and 1.42 H of the methyls in 2 of cyclopropane 1.82 H in 1 and 3 of cyclopropane

1.5 H of the radical dimethylethyl

7 to 7.6 H aromatic.

In the presence of 800 mg of palladium hydroxide on barium sulfate _f 0.8 cm of quinoline and 20 cm of ethyl acetate is hydrogenated 4 g of the product prepared in stage A in solution in 60 cm of ethyl acetate, filtered and added 200 cm of a solution of hydrochloric acid 2N. It is poured off, washed with water and dried. 4.1 g of an oil are obtained, which is purified with silica (eluent: cyclohexane-ethyl acetate (95-5)). 3.35 g of the desired product are obtained.

72 and 5 • 47 1 2 11/12/1981 Spectrum RMN, - CDCl, H ppn 1 AP C 07 C / 231 372/5 113 1.23 to 1.3 H in 3 59 416/11 1.83 1.97 H in 1 f 3 to 3.33 H in 1 from cyclopropane 1.44 to H in front 2 from cyclopropane 6.7 to 7 H in aromc from cyclopropane 6.03 1 C: saw 6.21 H in Radical methyl ethyl 7 7.5 of propenyl radical Stadiun of propenyl radical 3tisch. acid (IR-cis) -2,2 ^ -methyl-3 - / (Z) -3-0x0 ^ -3- Phenoxy_-l-Progeny _> l / ~ Zy _> kloD _< rojDan-carboxy _i l.

A mixture of 3.3 g of the product prepared in the preceding stage, 35 cm of toluene and 100 mg of paratoluene-sulphonic acid, monohydrated, is introduced into a reflux. The reflux is stopped at the end of gas evolution. The mixture is brought to dryness under reduced pressure to give 3.4 g of a product which is subjected to silica chromatography (eluant: cyclohexane-ethyl acetate-acetic acid (70-30 I)) to give 2.4 g of the desired product , melting at 57 ⁰ C.

Spectrum RMN, CDCl ₃ 1 ppm

1.25 to 1.33 H of the methyls in 2 of cyclopropane

1.9 ~. 2.04 H in 1 of cyclopropane

3.2 to 3.5 H in 3 of cyclopropane

6.6 to 6.9 H in 1 of propenyl

6.0-6.2 H in 2 of propenyl

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AP C 07 C / 231 372/5

5- 231372 ^48-59416 Z ¹¹

Example 6: (lR ~ cis) -2,2-dimethyl-3 ~ / (Z) -3-oxo-3-phenoxy-l-propenyl / - »cyclopropane carboxylate of (IS) ~ 2 ~ Methyl 4-oxo-3- (2-propenyl) -2-cyclopentene-1-yl ......

The procedure is as in Example 2, starting from 1.5 g of the acid (lR-cis) -2,2-diraethyl-3 - / (Z) -3-0xo-3-phenoxy-l-propenyl / -cyclopropane-carboxyl and 1 g of (S) -3- (2-propenyl) -1-hydroxy-2-methyl-4-oxo-cyclopent-2-en-1-yl, giving 1.6 g of the desired product. * L _Q = + 66 ° + 2.5 ° (c = 0.5 % benzene)

Spectrum RMN, COC l ₃ ppm

H in 2 of cyclopropane H in 1 of cyclopropane H of cyclopentene in a ^ of COp H in 3 of propenyl supported by cyclopentene

H of methyl, supported by cyclopentene H of propenyl, supported by cyclopropane, H aromatic

Example 7: (lR-cis) _-2-r -2 Dimet'hyl-3 ~ / (Z) -3-methoxy-3 ~ 0XO-> Metnoxv-l-PropenvlZ-cyclopropane-carboxylate of (RS) oC -ZY an-3 "" phenoxy - benzyl stage A: (lR-cis) ~ 2,2-dimethyl-3 ~ (3-oxo-3-methoxy-methoxy) -

1.26 and 1.33 1.95 - 2.09 5.7 4.8 to 5; 2 2 6.1 to 6.7 7 to 7.7

Phenoxy-benzyl *

It is cooled at +10 C, a solution of 3 g of (lR-cis) 2 _t 2-dimethyl-3- (3-hydroxy-3-oxo-l-propynyl) -cyclopropane

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AP C 07 C / 231 372/5

231372 5 ~ ⁴⁹ ~ ⁵⁹⁴¹⁶ Z ¹¹

Carboxylate of (RS) "* -Zyan-3-phenoxy-benzyl in 30 cm dimethylformamide ⁰ anhydride, added through fraction added 300 mg of sodium hydride 61% in oil, then 2.5 cm of the solution of Chloromethyläther produced in 15 minutes, as below. The mixture is stirred for 2 hours, poured onto an aqueous solution of monosodium phosphate and extracted into ethyl acetate, washed with water, dried and concentrated to dryness. Silica chromatography of the residue is carried out, eluted with a mixture: cyclohexane, ethyl acetate (75-25). and receives 2 g of the expected product, RMN, CDCl ₃ : ppm

1.23-1.27 and 1.35-1.45 protons of the methyls

in 2 of cyclopropane

1.95 protons in 1 and 3 of cyclopropane

5.28 proton of methanol from methoxy

Methoxyl 3,5 proton of methyl from methoxy

Methoxyl 6,42 and 6,47 protons carried by the same

Carbon like CN 6.92 to 7.58 protons aromatic

Preparation of chloromethyl ether solution

Mix 4.5 cm of methylal and 0.52 cm of methanol, then slowly add 3.53 cm of acetyl chloride. * Move for 36 hours at ambient temperature to obtain the expected solution. *

11.12,1981

AP C 07 C / 231 372/5

2 ^ 1 ^ 79 K - 50 - 58 416/11

Stage B: (lR ~ cis) -2,2 ~ dimethyl-3 - / (Z) -3-oxo-3 ~ methoxy-3-phenoxy-8-benzyl

Hydrogenating 2.2 g of the product obtained as o, a < in 50 cm of ethyl acetate in the presence of 450 mg of palladium hydroxide to 10 % on barium sulfate in 30 cm " ³ ethyl acetate and 0.5 cm of quinoline. The filtrate is washed in hydrochloric acid N, in water, dried and brought to dryness * Recrystallize by silica chromatography, elute with a mixture: cyclohexane-ethyl acetate (8 - 2) to obtain 1.2 g of the expected product

i * _D = + 41 ° + 3 ° (c = 0.3 % CHCl ₃ )

RMN, CDCl ₃ : ppm

1.27-1.28 and 1.33-1.35 protons

Methyls in 2 of cyclopropane

1.93 - 2.1 proton in 1 of cyclopropane

3.17 to 3.5 proton in 3 of cyclopropane. 6.47-6.82 proton ethylene in 1.55-6.0 and 5.88-6.1 proton ethylene in 5.27 and 5.3 protons of "CH" methoxy 3.47 and 3.5 Protons of methyl from methoxy

6.4 proton, carried by the same

Carbon like CN

6.92-7.67 protons aromatic

(lR-cis) -2 _J 2-dimethyl-3 '- / 3-hydroxy ~ 3 * -oxo - l-propynyl / ~ cyclopropane carboxylate of (RS) d ~ 3 ~ cyan-phenoxy-benzyl

231372 5 - «-

11.12 * 1981

AP C 07 C / 231 372/5 59 416/11

used at the beginning of the example in an analogous manner to that of ester (S) described later using the corresponding alcohol (RS),

Example 8: (1R-cis) -2j2-dimethyl-3 - »/ (Z) -3-oxo-3-cyano-hethoxy-1-propenylZ-cyclopropane carboxylate of (S) -» 3-phenoxybenzyl .......

Progy _< ny _i l / ~ ZyJ <lo |> rogan-capbpxyJLat

The procedure is as in Example 7 using 2 cm chloro-acetonitrile; after extraction with ether and elution with a mixture: cyclohexane - ethyl acetate (9-1) gives 2, .69 g of the expected product,

3-phenoxy-benzyl

The procedure is as in Example 7, starting from 2.69 g of the product obtained beforehand, giving 2.02 g of the expected product after elution with a mixture: cyclohexane - ethyl acetate (9 - 1) »

^from

Chromatography on silica of 1.4 g of the o, a »product elutes in methanol chloride and gives 0.41 g of the expected product, Qi ₀ = + 55 ° + 1.5 ° (c = 1% CH 2 Cl 2 ₃ )

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231372 5 - ⁵² - ^{59 415} Z ¹¹

Example 9: (1R-cis) -2,2'-dimethyl-3 - / (Z) -3-oxo-3-ethoxy-ethoxy-1-propenyl / ~ cyclopropane carboxylate of (S) <s < -cyan 3 Phenoxy-benzyl ........

Phenoxy-benzene

2 g of (1R-cis) -2,2-dimethyl-3- / 3-hydroxy-3-oxo-1-propynyl) -cyclopropane carboxylate of (S) · £ are cooled at 0 to + 5 ° C -Cyan-3-phenoxy-benzyl, 20 cm of methanol chloride and 0.7 g of ethoxyethanol. 1.1 g of dicyclohexylcarbodiimide, 5 cm of methanol chloride and 15 mg of dimethylaminopyridine are added. The mixture is stirred for 1 hour at + 5 ° C. and 2 hours At ambient temperature »filter, concentrate to dryness the filtrate and chromatograph the residue, eluting with a mixture: cyclohexane-ethyl acetate (75-25) and obtain 1 * 3 g of the expected product»

Protons of the methyls in 2 of cyclopropane

Protons in 1 and 3 of cyclopropane protons in 1 of COO-CH ₂ -CH ₂ -O protons in 2 of COO-CH ₂ -CH ₂ -O protons, supported by the same carbon as CN protons aromatic

1,3 and 1,52 (q) protons from

ethyl

RMN, CDCl., : · Ppm 32 1.22 1, 1.93 38 4.17 to 4, 73 3.55 to 3V 6.57 67 7 to 7, 2 1, 08 1,

11,12.1981

OO t O * 7 OC ^{AP C} ° ^{7 C / 231 372/5}

£ J! Z I ZD - 53 - 59 416/11

ethoxv-1-propenylZ-cyclopropane carboxylate of (S) o -cyan

The procedure is as in Example 7, Stage B, starting from 1.3 g of the product obtained as a »a«, giving 1.0 g of the expected product

oL _D = + 37.5 ° + 2.5 ° (c = 0.5 % CHCl ₃ )

Example 10: (1R-cis) -2,2-dimethyl-3 - / (Z) -3-oxo-3 - ((RS) -1,1,1-trifluoromethylethoxy) -1-propenyl / cyclopanopane -Carboxylate of (S) 'o <r-cyan-3-pherioxy-benzyl

The procedure is as in Stage B of Example 7 using 2.6 g of (Ir-cis) -2 _a 2-dimethyl-3- / 3-0xo -3 ((RS) -I ₁ I, 1-trifluoromethylethoxy) -Propynyl / cyclopropane carboylate of (S) o-cyano-S'-phenoxy-benzyl. Mach elution by a mixture cyclohexane <- ethyl acetate (9 - 1) are obtained 2 _f lg of the expected product

O ^ = + 44 ° + 2 ° (c = 0.4 % benzene)

Preparation of (IR ~ cis) ~ 2,2-dimethyl-3 ~ / 3-oxo-3- ((RS) -1 ,1 , 1-trifluoromethylethoxy) -propynyl / -cyclopropane carboxylate of (S) pi -Zyan-3-phenoxy-benzyl

The procedure is as in Stage A of Example 9 using 4.6 g of 1, 1, 1-trifluoromethylethanol and 3.8 g of (1R-cis) -2,2-dimethyl-3/3-oxo 3 ~ hydroxypropynyl / ~ cyclopropane carboxylate of (S) c ^ -cyano-3-phenoxybenzyl to give, after elution with a mixture of cyclohexane-ethyl acetate (8-2), 2.6 g of the expected product .

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3 13 7 2 5 - ⁵⁴ - ^{'59 416/11}

Example 11; (lR-cis) ~ 2 _f 2 -imethyl-3 - * / (Z) - 3-oxo-3- (2 ₁ 2 -difluoroethoxy) propenyl / cyclopropane carboxylate of (S) cyan-5-phenoxy benzyl

The procedure is as in Stage A of Example 9, starting from 5 g of (1R-cis) -2 _t 2-dimethyl-3- / 3-hydroxy-3-oxo-1-propynyl-cyclopropane carboxylate tert-butyl, and eluting with a mixture of n-hexane - isopropyl ether (7 - 3) gives 5 * 25 g of the expected product * IR, CHCl ₃

-C ^ = O conj 2232 cm ** ¹

      , '-i

C = O ester 1725 cm

~ 1 asymmetric 1710 cm

- I gem dimethyl C 1393 cm

I 1380 cm ^-1 "tert -Butyl 1372 cm" *

Stage B: acid £ lR-cis) -2,2-Dimeth ^ l-3- / 3-oxo-3 ~ (2 _/ 2-

5 * 2 g of the product obtained as above, 500 mg of para-toluene-sulphonic acid in 40 cm of toluene are heated for 25 minutes. After cooling, 400 cm of ether are added, the product is washed in water, the organic phase is dried and concentrated in a dry state To obtain 4.1 g of the expected product »

3-benzyl Phenox ^

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231372 5 - ⁵⁵ - ^{S9416 /} "

The procedure is as in Stage A of Example 9, starting from 4.1 g of the acid obtained as above and 4.5 g of alcohol (S) o ~ cyanyl-3-phenoxy-8enzyl, obtained after elution with a mixture of petroleum ether ( eb 40 to 70 C) - isopropyl ether (6-4) 4.7 g of the expected product.

IR, CHCl ₃

^^ b ^^ k ι ^^mim in the A r Λ^^ a ^ n.^ ß ^ mimy

cm

OH 3580 cm " ¹ gem di Me (1392

-CS == C- con j 2235 cm

C = O Ester 1755 cm ^-1

-1 ester conj 1725. cm

aromatic fl588 cm "

1 1488 cm "" ¹

I ^ au cm -1

(1380 cm

Z ^ aη-3 ^ phenoxy-benzene

4.7 g of the product obtained above are hydrogenated in the same manner as in stage B of Example 7. After elution with a mixture of n-hexane-isopropyl ether (7 - 3), 3.2 g of the expected product are obtained (X. _{0 s} +44 ° t 2,: 5 ° (c = 0.5 % CHCl ₃ )

Example 12: f lR-cis) - "2 _t 2-dimethy-.3" - / (Z) -5- (2 ₁ 2-dichloroethpoxy) -. L-Prppenyl / -cycloprop _i An-carboxylate of (S) o -cyan-3-phenoxy-benzyl

The procedure is as in Example 9 _f Stage A _1, starting from 4.8 g (lR-cis) -2,2-dimethyl-3 - / (Z) -3-hydroxy-3-oxo-1-propenyl / ^ cyclopropane -Carboxylate of tert-butyl and 2 cm

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AP C 07 C / 231 372/5

3 13 7 2 5 - ^5δ - ^{59 4i6 / i1}

2 ₄ 2-dichloroethanol »After elution with a mixture of cyclohexane <- ethyl acetate (9 - 1), 5.6 g of the expected product are obtained,

Stage B: acid ^(R l - £ is2-2,2-dimethyl-3- / £ Z) -3- £ 2,2-dichloro-

The procedure is as in Stage B of Example 11, starting from 5.6 g of the product obtained above, to give 4.5 g of the expected product.

Stage ^ C: (lR-cis) -2,2-dimethyl ~ .3 ~ / £ Z) -3- (2 _i ~ 2 ~ et dichloro hoxy2-l - P rogenyJ ^ - Zy klog Rogan-Ca.

The procedure is as in Stage A of Example 9, starting from 3 g of the product obtained in B and 2.25 g of alcohol of (S) o-cyano-3-phenoxy-benzyl. After elution with the mixtures cyclohexane - ethyl acetate (8 - 3) then (9 - 1) one obtains 1.6 g of the expected product »t 2 ° (c = 1 % in benzene)

The following examples are prepared in a manner analogous to that described in Stage A of Example 9, starting from:

1 °) of the acid (1R-cis) -2,2 ~ dimethyl ~ 3 ~ / (Z) -3 ~ oxo-3- (2 _# 2-difluoroethoxy) -1-propenyl / -cyclopropane-carboxyl and alcohol, respectively

Example 13: (1R-cis) * - 2 ^ 2-.Dimethyl.-3 ~ / (Z) -. 3'-0xo'-3> - (2 , 2 ~ Dif luore.thpxy) ~ "Propenvl /> - Zvklopropan- "Garboxylat of (RS) oC-cyan"6-oxy'Phen _i ~ 2 ~ In Pyridy ethyl ^ ₀ = +50.5 ° + 2 ° (c = 0.8% CHCl ₃₎

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AP C 07 C / 231 372/5

3 13 7 2 5 - ⁵⁷ - ⁵⁹

Example 14: (lR-cis) -2,2-dimethyl-3 - / (Z) -3--0xo-3- (2 _J 2-difluoroethoxy) -1-propenyl / -Zyklopropan-carboxylate of (R) ^ "Cyan-3-phenoxy-benzyl

ot _D = +117.5 ° + 3 ° (c = 0.6 % CHCl ₃ )

Example 15: (1R-cis) -2,2-dimethyl-3 ~ / fZ) -3-oxo-3- (2,2-difluoroethoxy) -1-propenyl / cyclopropane carboxylate of (3-proparqyl-2 , 5-dioxoimidazolidinyl) -methyl .

Sl ₀ = + 18 ° + 2 ° (c = 1 % CHCl ₃ )

Example 16: (1R-cis) -2,2-dimethyl-3 - / (Z) -3-oxo-3- (2,2-difluoroethoxy) -1-propenyl / cyclopropane carboxylate of (R) oC- Ethynyl-3-phenoxy-benzyl

^ ₀ = + 47 ° + 1.5 ° (c = 1 % CHCl ₃ )

The acid {lR-cis) -2,2-dimethyl-3 - / (Z) -3-oxo-3- (2,2-difluoroethoxy) -l-propenyl / -cyclopropane-carboxyl was prepared in an analogous manner to in of preparation 6, starting from 2,2-difluprethanol »2 °) of the acid (1R-cis) -2,2-direthyl-3 - / (Z) -3-oxo-3- (2-fluoroethoxy) -1 Propenyl / cyclopropane carboxyl and corresponding alcohol »

Example 17: (1R-cis) -2,1-Dimethyl-3 - / (Z) -3-oxo-3- (2-fluoroethoxy) -1-propenyl / ~ cyclopropane carboxylate of (3-propargyl) 2, S-Dioxoiroidazolidinyl) -methyl

^ _n = +18 ° + 2 ° (c = l% CHCl-)

2 313 7 2 5 - ⁵⁸ -

11.12,19Sl

AP G 07 C / 231 372/5

Example 18: (1R-cis) -2,2-Diniethyl "-3- / fZ) -3-0xo-3" - (2-fluoro-thio) -l-propenyl-cyl-1-propanol ~ Ca _i rboxylate of _r (RS) oC-cyano-C6-phenoxv-2-pyridyl) ^ methyl

= +49.5 ° + 2.5. ° (c = · 0.5 % CHCl ₃ )

Example 19: ( 1R-cis) -2: 2-dimethoxy "3" / f Z) -3-Qxo-3- (2-fluoroethoxy) -1-propenyl / cyclopropane carboxylate of (R ) o £ -Methyl-3-phenoxy-benzyl ....

_D = + 123 ° + 1.5 ° (c »1 % CHCl ₃ )

Example 20: flR-cie) -2,2-dimethyl-3 - / (Z) -3-oxo-3-f2-fluoroethoxy) -1-propenyl / cyclopropane-Ca _i rboxylate of <> i-Athynyl-3-phenxy-benzyl

<£ = +47 ° + 1.5 ° (c = 1 % CHCl)

The acid (1R-cis) -2,2-di-ethyl-3 - / (Z) -3-oxo-3- (2-fluoroethoxy) -l-propenyl / -cyclopropane-carboxyl was prepared in a manner analogous to that of US Pat in Preparation VI, starting from 2-fluoroethanol,

3 °) of the acid (1R-cis) -2 _{l of} 2-dimethyl-3 - / (Z) -3-oxo-3- (2- (1,1,1,3,3,3-hexafluoro) -propoxy ) -1-propenyl / -cyclopropane-carboxyl (Preparation VI) and the corresponding alcohol.

Example 21: (lR ~ cis) -2 _t 2-dimethl * -3 - / (Z) -3-oxo-3- (2-

) -Propoxy) -l- propenyl / -cyclopropane

Carbpxylat of (R) g <-ethynyl-S-phenoxy-benzyl ^ ₀ = +31.5 ° + 1.5 ° (c = 1% CHCl)

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313 7 2 5 - ⁵⁹ - ^{59 416/11}

Example 22: (1R-cis) -2,2-dimethyl-5 / fZ) -3-0xo-3- (2- (1,1,1,3,3,3,3-hexafluoro) -propoxy) -l ~ propenyl / -cyclopropane carboxylate (R) & £, Hethyl ~ ~ 5 ~ phenoxy-benzyl

O ^ = + 97 ° + 2 ° (c = 1 % CHCl ₃ ) Example 23: (lRr-cis) -2, Σ-

-Per

Carboxylate of C ₁ S) <><- Cyan-3-phenoxy-benzyl . & _D = + 23.5 ° + 2 ° (c = 0.5 % benzene)

Example 24: { lR-cis) -2,2-diiriethyl ~ 3 - / f Z) -3 "0xo-3 ~ (2- (1 _t l pl ^ fS / S-hexafluoro) ~ propoxy) -l-propenyl / -cyclopropane carboxylate of S ^ tSve

** _Q = -30 ° + 1 ° (c = 1 % CHCl ₃ )

Example 2.5: (lR> -cis) -2 / 2-dimethyl-5- / fZ) -3-0xo * -3- (2 ~ (l, l _r l _r 3, Z \ 3 ~ Hexaf luor) -propoxy) -l-propenyl / ~ cyclopropane carboxylate of (RS) pi -Zyan-S-phenoxy - ^ - pyridyl-methyl

^ ₀ = + 33.5 ° + 2.5 ° (c = 0.2 % CHCl ₃ )

4 °) of the acid (1R-cis) -2 _/ 2-dimethyl-3 - / (2) -3-oxo-3- (2,2- _i- 2-trifluoroethoxy) -1-propenyl / -cyclopropane-carboxyl (Preparation I) and corresponding alcohol,

Example 26: (1R-cis) -2, 2 ~ dimethyl ~ 3 ~ / fZ) -3-0xo- »3 ~ (2, 2 _} 2 ~ Trifluoroethoxy) -1-propenyl / cyclopropane carboxylate of (3-proparqyl-2 _> 5-dioxoimidazolidinyl) -metfiyl ·

OC ₀ = -4 ° + 1 ° (c = 1 % benzene)

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AP C 07 C / 231 372/5

5- 231372 ^50-59

Example 27; (IR ci3) -2 ₁ 2-dimethyl-3 - / (Z) -3-0xo-3 _"(2> 2 _t 2 Trifluoret _i hoxy) ~ l ~ P ro propenyl / -Zykloprop3n - carboxylate of ( R) et-methyl-3-phenoxy-benzyl ..

^ ₀ = +108.5 ° + 2 ° (c = 1% CHCl ₃₎

Example 28; f lR-cis) -2,2-dimethyl-5 -> / (Z) -3-oxo-3-bis (2,2,2-trifluoroethoxy) -1-propenyl - '' - cyclopropane carfaoxylate of 5 , 4,5,6-tetrahydrophthalimide-methyl

<^ _D = + 2.5 ° * + 2 ° (c = O ₁ 5 % CHCl ₃ )

Example 29; ( 1R-cis) -2,2-dimethyl-> 3- / CZ) -3-oxo-3- (2 ₁ 2, 2-Trif 1-uphoxy) -1-propenyl / -cyclopropane * Ca rboxyla t of (R) t <~ ethynyl-3 ~ phenoxy-8-benzyl

O ^ = + 42 ° + 1.5 ° (c = 1% CHCl ₃ )

Example 30: f lR- »cis) -2, 2 ~ dimethyl-3- / CZ) -3 ~ 0xo - 3 '- (2 2 , 2-trifluoroethoxy) -1-propenyl / ~ cyclopropane carboxylate of (RS) _< g6 ~ cyanogen _i 6 ~ phenoxy-2 ~ pyridyl-methyl

oL _Q = + 46.5 ° + 2 ° (c = 0.7 % CHCl ₃ )

5 °) (1R-cis) -2, 2-Diniethyl-3 - / (Z) -3-hydroxy-3-oxo-1-propenyl Z-cyclopropane carboxylate of (S) 45i-cyano-3-phenoxy -Benzyl (Preparation VII) and corresponding alcohol.

Example 31; (lR "cis) -2.- _< i2-O-niethyl-3>" / (Z) -3-oxo-3- (2-trichloroethoxy) -l-propenyl / -cyclopropane-carboxylate of (S)

- Benzyl ..........

= + 42.5 ° + 2 ° (c = 0.5 % benzene)

2 313 7 2 5 - ⁶ⁱ -

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Example 32; (lR-cis) -2,2 diirethyl "3- / f Z) -3 ~ 0xo ~ 3- (

ethoxy) -l-propenyl / -cyclopropane carboxylate of (S) s4-cyano-3-phenxy-benzyl - ..., -.

^ ₀ = + 39 ° + 4 ° (C = 0.25% benzene)

Example 33: (1R-cis) -2 _t 2-dimethyl-3 - / (Z) -3-oxo-3-f2-methoxyethoxy) -l-propenyl / ~ cyclic propane carboxylate of ( S) ΰ- cyano ~ 3-phenoxybenzyl . ... ,

<^ _D = + 37.5 ° + 2 ° (c = 1% CHCl ₃ )

Example 34; (1R-cis) -2,2-dimethyl-3 - / (Z) -3-oxo-3- (RS) -1-cyanethoxy) -1-propenyl / -cyclopropane -carboxylate from (S) o & .-cyan 3-phenoxy-3enzyl

<* = + 64.5 ° + 3 ° (c = 0.3 % CHCl,)

Example 35: (1R-cis) -2 ₁ 2-0-methyl-3 - »/ (Z) - 3-oxo -3- (2-fluoroethoxy) -1-propenyl / -cyclopropane carboxylate from CS) o ^ -cyan ~ 3-phenoxy-benzyl

⁰ ^ ₀ = + 48 ° (c = 0.25 % benzene)

Example 36: "flRcis" -2-Y 2 -dimethyl-3 ~ / (Z) -3 ~ oxo-3-phenethoxy-1-propenylZ-cyclopropane ^ carboxylate of (S) <? 4-2 3-phenoxybenzyl ..

= + 46 ° + 2.5 ° (c = 0.5 % benzene)

Example 37; (lR-ci3) -2 ₁ 2-Dimethvl »3 ~ / (Z)» 3 ' _! -OxO "3 -" (2 ₁ 2 ~ pimethyldioxplanyl _i - 4 ~ (RS) -methoxy) "1-propenyl /" cyclopropane carboxylate of (S) p £ -cyan-3-phenoxy- "benzyl .

o6 _Q - ₊ 4 ₆ ° + 2 ° (c = 0.75 % benzene)

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δ °) (1R-cis) -2,2-dimethyl-3 - / (2) -3-hydroxy-3-oxo-1-propenyl / cyclopropane carboxylate of (RS) s <-cyan-3-phenoxy -Benzyl and appropriate alcohol.

Example 38: (1R-cis) -2,2-dimethyl-3 - / (Z) -3-oxo-3- (2-dimethylaminoethoxy) -l-propenyl / -cyclopropane carboxylate of (RS) c 1- cyano -3-benzyl-P'nenoxy

oL _Q = + 23 ° + 3 ° (c = 0.25 % CHCl ₃ )

(lR-cis) ~ 2,2-dimethyl-3 - / (Z) -3-hydroxy-3-oxo-1-propenyl / cyclopropane carboxylate of (RS) £ <-cyan-3-phenoxybenzyl, used at the beginning of the preceding Example 1 was prepared in an analogous manner to that of ester (S) 1-cyano-3-phenoxy-benzyl of Preparations IV and VII.

7 °) (1R-cis) -2,2-dimethyl-3 - / (Z) -3-hydroxy-3-oxo-1-propenylZ-cyclopropane carboxylate of (R) oC-methyl-3-phenoxybenzyl (Preparation VIII) and corresponding alcohol.

Example 39: { 1R-cis) -2,2-dimethyl-3 / fZ) -3-oxo-3- (2-methoxyethoxy) -1- »

(R) y: -methyl-3-phenoxy-benzyl

RMN, CDCl ₃ : ppm

1.22 - 1.25 protons of the methyls in 2 of cyclo-

propane 1.45. - 1 * 55 protons of methyl esters in 1 of

Cyclops ropan *

5.7 to 5.0 benzylpotonone 3.42 methoxyl protons

From 4.22 to 4.38 protons in 1 of ester in 3 of

cyclopropane

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3.55 to 3.72 protons in 2 of ester in 3 of cyclo-

propane 5,85 - 6,05 and 6,32 to S, 8 ethylene protons

Example 40; (1R-cis) -2,2-dimethyl-3 - / (Z) -3-oxo-3- (1-methoxy-1-trifluoromethylethoxy) -1-propenyl / ~ cyclopropane carboxylate of (S) aC -Zyan-3-phenoxy-benzyl

In an inert atmosphere, 1.02 g of (IR-cis) -2,2-dimethy1-3- / (2) -3-chloro-3-oxo-1-propenyl! -Cyclopropane carboxylate from (S) are agitated. Add 4-cyano-3-phenoxybenzyl and 9 cm of methanol chloride. Add 1.12 g of 1-methyl-1-trifluoromethylethanol and maintain the motion for 48 hours! Ambient temperature. It is concentrated in a dry state under reduced pressure. "Silica chromatography of the residue is carried out, eluting with a mixture: hexane-ethyl ether (8-2), giving 250 mg of the expected product. F ~ 59 ⁰ C *

^ D = + 57 ° + 2 ° (c = 0> 4 % benzene)

(lR-cis) -2 _i 2-dimethyl-3 - / (Z) -3 ~ chloro ~ 3 ~ l ~ 0XO-propenyl / -Zyklopropan-carboxylate of (SJ ^ -Zyan-S-phenoxy-benzyl, used on Exit of Example 40 was prepared by the action of thionyl chloride on (1R-cis) -2,2-dimethyl-3 - / (Z) -3-hydroxy-3-oxo-1-propenyl / cyclopropane carboxylate of (S. ) oC-Cyan-3-phenoxybenzyl, Preparation VII,

Example 41: (1R-cis) -2,2-dimethyl-3 - / (Z) -3-qxo-3- (1-trifluoromethyl-1-methylpropylpoxy) -1-propenyl / cyclopropane carboxylate of ( S) gC-cyan-3-phenoxy-benzyl

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3 1 O / ZD - ⁶⁴ - "59 416/11

Dissolve 900 mg of (1R-cis) -2,2-dimathyl-3 - / (Z) -3-chloro-3-oxo-1-propenyl / -cyclopropane carboxylate of ( S) oi -cyan-3- Phenoxy-benzyl in 3 cm of methanol chloride, add 1 cm of 1-trifluoromethyl-l-methyl-propanol and stirred for 16 hours at ambient temperature under inert atmosphere and protected against moisture »After 3 days at ambient temperature, the reaction mixture is washed with an aqueous saturated solution of sodium bicarbonate, then in water, dried and concentrated in the dry state. »Silica chromatography of the residue is carried out» eluted through a mixture of hexane-ethyl ether (3-2) to obtain 570 mg of the expected product.

Example 42; (1R-cis) -2,2-dimethyl-3 / fZ) -3-0xo-3- (2,3-dihydroxypropyloxy) -1-propenylZ cyclopropane caroxylate yon (S) o £ -Zyan-3-phenoxy-Senzyl

4.65 g of (1R-cis) -2,2-dimethyl are heated in the reflux. 3 - / (Z) -3-Oxy-3- (2 _J 2-dimethyl-dioxolanyl-4- (RS) -methoxy) -1-propenyl Z-cyclopropane carboxylate of (S) oxy-cyano-3-phenoxy Benzyl (Example 37), 46 cm dioxane, 9 cm water and 0 5 g paratoluene sulfonic acid during 45 minutes. The majority of dioxane is eliminated by distillation at 40 ° C. under reduced pressure, the residue is taken up again through 150 cm 25 cm of water. The mixture is stirred and poured, the organic phase is washed with water, dried and concentrated under reduced pressure under reduced pressure. Silica chromatography of the residue is carried out, eluting with a mixture of cyclohexane and ethyl acetate (3 - 7) , 85 g of the expected product.

'egg -

_D = +53 + 2.5 (C = 0.5% CHCl ₃₎

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Example 43; ClR ~ cis) ~ 2, 2-dimethyl-3 ~ / (Z) -3-oxo-3- (2-tetrahydropyranyloxyethoxy) -l-propenyl / -cyclopaedic carboxylate of (RS) ql-cyano 3-phenoxy-benzyl

The procedure is analogous, as described in Stage A of Example 7, starting from 2.3 g of (IR-cis) -2,2-dimethyl-3 - / (Z) -3-hydroxy-3-0xo- l-Propynyl / ~ cyclopropane carboxylate of (RS) * £ -cyan ~ 3 ~ phenoxy ~ benzyl and 7.5 · g l-bromo-2- (2 ~ tetrahydropyranyl) ~ 0xy-ethane. This gives I _x S g of the expected product after silica chromatography in the mixture cyclohexane - ethyl acetate (75 - 25) · »

The procedure is the same as described in Stage B of Example 7, starting from the product obtained in Stage A above. "After purification by chromatography in the mixture cyclohexane-ethyl- is obtained. Acetate (80 - 20) 1.3 g of the expected product «

<* _D = +33 ° ± 1 ° (c = 1% CHCl ₃₎

- (1R-cis) -2,2-dimethyl-3 - / (Z) -3-hydroxy-3-oxo-1-propynyl / cyclopropane carboxylate of (RS) oxy-cyano-3-phenoxy-benzyl at the beginning of the previous example was prepared in the same manner as that of ester (S) pC-cyan-3-phenoxybenzyl of Preparation IV.

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Example 44; (1R-cis) -2,2-dimethyl-3 - / (Z) -3-oxo-3- (2- (hydroxyethoxy) -l-propenyl) cyclopropane carboxylate of (RS) g <-cyan-5 ~ phenoxy 8enzyl

0.85 g of the product obtained in Example 43 is mixed,

3 3 3 3

17 cm of ethanol, 5 cm of dioxane, 1 cm of water and 4 cm of hydrochloric acid 2N, then moves at 20 C for 3 hours. It then moves 1 cm of triethylamine, evaporated to dryness, takes up again through a Wasaer ice mixture, extracted in methanol chloride, the extract is washed with water, dried and the solvent is evaporated * It is Siliziuradioxid-chromatography of the residue, eluted with a mixture of cyclohexane-ethyl acetate (65-35) and receives 0.65 g of the expected product *

^ ₀ = + 42.5 ° + 2.5 ° (c = 0.5 % CHCl ₃ )

The following compounds can also be obtained according to methods of the invention, starting from acids and alcohols of the corresponding type:

- (IR-cis) -2,2-dimethyl-3 - / (2) -3-oxo-3- (I ₁ I, 1,3,3,3-hexafluoropropoxy) propenyl / cyclopropane carboxylate from 3 phenoxy-benzyl

^ ₀ = + 26.5 ° + 2.5 ° (c = 0.5 % CHCl ₃ )

- (lR ~ cis) ~ 2,2-dimethyl-3 - / (Z) ~ 3 ~ 0xo ~ 3 ~ (1,1,1,3,3,3-hexafluoropropoxy) -propenyl / -cyclopropane carboxylate of ( S) o-cyano-3-phenoxy-4-fluoro-benzyl

= + 27 ° + 2 ° (c = 0.8% benzene)

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Preparation IV: (1R-cis) -2,2-dimethyl-3 - (5-oxo-5-hydroxy-1-propynyl) -cylopropanol carboxylate of ( S) ga -Zyan-3-phenoxy-benzyl

propane carboxylate of tert -butyl

Is introduced 26 g of (lR-cis) _-2-i 2 Diraethyl-3- (2 _J! 2-Oibromvinyl) -Zyklopropan-carboxylate from tert-butyl in 175 cm of anhydrous tetrahydrofuran. It is then added at -65 C 60 cm of a solution of butyllithium to 20 % in cyclohexane * It is stirred for 1 hour at -60 ⁰ C, then allowed to flow through a stream of carbon dioxide for 1 and / 2 hours, pour the reaction mixture into ice water, the Soda N is added, the product is washed with ether. The aqueous basic phase is acidified to pH 4 and extracted with ether, the organic phases are dried, brought to dryness under reduced pressure. This gives a product which is recrystallized in petroleum ether (Eb: 60 to 80 ° C). This gives 8 * 3 g of the desired product »melting

ppm

144 ° C. RMN, CDCl, 1, and 1. 1; 8th; , 22 , 78 , 47 25

1.37 protons of the methyls in 2 of cyclopropane

Proton in 1 and 3 of cyclopropane terbutyl proton proton of the group -C-OH

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5.2 g of dicyclohexylcarbcdiimide are introduced into a solution containing 7.15 g of (1R-cis) -2 _# 2-dimethyl-3- (2-carboxyethynyl) cyclopropane carboxylate of tartaric butyl and 80 mg of dimethylaminopyridine in 35.degree cm ^"5 methanol chloride. it moves the reaction mixture for 10 minutes and added 4.5 g of 2,2,2-trichloroethanol added" one dependent under agitation for one hour and eliminated by filtering the precipitate formed, washing the hydrochloric acid in FiItrat N It is then dried in water to neutrality, dried and brought to dryness. 14 g of an OTsy subjected to silica dioxide chromatography are eluted through the mixture of benzene-ethyl acetate (97-3) to give 9 g of the desired product, melting at 70 to 71 C,

Stedium ^ Ch Acid ^ lR-cisJ ^ S ^ -Dimeth) / 1 ^ 3- {2

The mixture is refluxed for one hour with 11.4 g of the product prepared according to stage B, 120 e of toluene and 300 mg of para-toluene-sulphonic acid. It is allowed to return to ambient temperature, the reaction mixture is washed in water, dried and brought to a dry state, to obtain 9.5 g of the sought product, which is used as for the following stage.

Karhonyl-Äthynvl) ~ cyclopropane ~ carboxylate of (S) oi-cyan-3-phenoxy-benzene

Add 6.2 g of dicyclohexylcarbodiimide to a solution containing 9.5 g of the product prepared in stage C, 30 cm

231372

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Methanol chloride and 3 cm pyridir ... The reaction mixture is stirred for half an hour and 6.3 g of alcohol (S) ^ t-cyan-3-phenoxy-benzyl is added. It is maintained under agitation for 1 and '/ 2 hour , The filtrate is eliminated by filtration in hydrochloric acid N _# then in water until neutrality. * It is dried, filtered and brought to dryness. This gives 16.3 g of an oil, which is subjected to a silica chromatography, eluted by the mixture of benzene - ethyl acetate (97 - 3) * Thus 12 g of the desired product is isolated, melting at 101 C.

Stage E ^ benzyl

5.9 g of zinc powder are introduced into a solution containing 6.5 g of the product prepared in stage D, 23.4 cm of acetic acid and 2.5 cm of water. The mixture is kept in motion for one hour. Filter and pour off the filtrate * Wash the organic phase in water and extract the aqueous phase in methanol chloride, combine the chloromethane solutions, dry, filter and bring to dryness. This gives 4.7 g of the crude product »

Production V; (1R-cis) -2,2-dimethyl-3 - / (Z) - (3-hydroxy-3- oxo-1-propenyl / cyclopropane carboxylate of tert-butyl

Hydrogenated 2 g of (1R.cis) -2,2-dimethyl-3/2-carboxy-ethynyl / cyclopropane carboxylate of tert-butyl prepared in Stage A of Preparation IV in 40 cm of ethyl acetate

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Preparation of O, .38 g of palladium hydroxide to 10 % on barium sulfate and 0.4 cm of quinoline. Filter, wash the filtrate in hydrochloric acid 0.5 N ₁ then in water until neutrality _t , concentrate in drying under pressure, reduce and receives 2 g of the desired product, melting at 94 C,

Preparation VI; Acid (lR-cis) -2 _'f 2-0imethyl- "3 - / (Z) -3-0xo 3 ~ (2 ~ (1,1,1,3.3,3-hexafluoro) propoxy) -l-propenyl / -Cyclopa nope ~ Ca rboxyl

Carboxylate of tert-butyl ^

The procedure is as in Stage A of Example 9, using 3.6 g (lR ~ cis) ~2.2 ~ dimethyl ~ 3 - / (Z) ~ 3-hydroxy-3 ~ 0xol propenyl / cyclopropanecarboxylate of tert -butyl (Preparation V) and 3 g of hexafluoroisopropanol. After elution by a mixture of benzene - cyclohexane (4 - 6), one obtains 4.9 g of the expected product, m.p. = 92 ⁰ C.

carboxyl

The procedure is as in Example 11, Stage B, starting from 4.9 g of the product obtained above and receiving 4.2 g of the expected product. "

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231372 5

IR CHCl ₃

OH acid mono 3500 cm ""

+ dimer

-1 C ester coni 1755 cm batch

H-1

O. 1744 cm maxi

-1 acid 1695 cm

-1 c = C con,] 1627 cm

•••1

gem, dimethyl 1380 cm approach

Preparation VII: (1R-cis) -2,2-dimethyl-3-OZ) -3-hydroxy-3-Qxp-1-propenyl / cyclopropane carboxylate of (S) s-cyan-3-phenoxy -Benzyl _:. , ...

Hydrogenating 4.7 g of (1R-cis) -2,2-dimethyl-3 ~ (2-carboxy-ethynyl) -cyclopropane carboxylate of (S) <-> cyan-3-phenoxybenzyl (Preparation IV) In 45 cm of ethyl acetate in the presence of 500 mg of palladium hydroxide to 10 % on barium sulfate and 6.5 cm of quinoline, one filters, the filtrate is washed in hydrochloric acid N, then in water until neutral, dried and bring it to a dry state »5 is obtained , 1 g of an oil which is subjected to a silica gel chromatography, eluted by the Mischung'Hexan - ethyl acetate acetic acid (70-30 - 1) _# is thus obtained 3.8 g of the desired product ·

Preparation VIII: (1R-cis) -2,2-dimethyl-3 ~ / (Z) -3-> hydroxypropyl-3-oxo-1-propenyl / ~ cyclopropane carboxylate of (R) -fli-methyl-

3-phenoxy-benzyl - - -.

Stage ^ A: ^ lR-cisj-gjg-dimethYl-S - ^ / S-oxo-S ^ e-hoxy) -propynyl / -Z ^ klogropane-carboxy / lat

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The procedure described in Stage D of Preparation IV, with the use of 6 g of the acid (I R-cis) ~ 2,2-dimethyl-3 ~ / 3--0xo> 3- (2 ₄ 2,2-trichloroethoxy) -Propynyl / -Cyclopropane - carboxyl and 4.1 g of 1- (R) - (3-phenoxy-phenyl) -ethanol. Chromatography in a mixture of cyclohexane-ethyl acetate (8-2) gives 4.38 g of the expected product ,

Stage B:

£ ^r 22Y ⁿ yiZr

Phenoxy-benzyl

To 4.16 g of the like o. A. obtained product dissolved in

3 3

4 cm of methanol chloride, add 45 cm of acetic acid to 10 % water and 0.53 g of zinc powder and agitate for 30 minutes at ambient temperature, add again 0.53 g of zinc powder until the end of the reaction (4 times), after 3 hours of contact filtering and extracted in methanol chloride. The organic phase is washed in water, dried, concentrated by drying through azeotropic stripping with toluene and gives 3.05 g of the expected product.

ίΐ2ΕΓ2Ε20! Ζ £ Γ-22Υ]: 2ί ^V 2 ⁿ Phenoxybenzene

The procedure is as in stage 8 of example 7, starting from the product obtained at stage B o »a ,, and obtaining 2.9 g of the expected crude product»

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Examples of the compositions

Example A: Preparation of a Soluble concentrate 0.25 g. It leads from a homogeneous mixture of 25 g Product of Example 1 0.25 g 40 g Butoxide of piperonyl 1 g 33.75 g Tween 80 0.25 g 0.5 g Topanol A 0.1 g 0.5 g water 98.4 g Example B: Preparation of an emulqierba concentrate One mixes closely: Product of Example 1 0.015 g Butoxide of piperonyl 0.5 g Topanol A 0.1 g Tween 80 3.5 g xylene 95.885 g Example C: Preparation of an emulqierba concentrate It leads from a homogeneous mixture of _:; , Product of Example 1 1.5 g Tween 80 20 g Topanol A o, l g xylene 78.4 g Example D: Preparation of a fogging composition      , -. # ....... ......... Mixing in a homogeneous way: Product of Example 1 Tabu powder Powder of cedar leaves Powder of pine wood brilliant green p-Nltrophenol

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Study of the activity of the compounds according to the invention on the parasites

The test insects are 4/5 day old female house flies. * Local application of 1 liter of the acetone solution of the product on the dorsal chestpiece of the insect using the Arnold micromanipulator. One uses 50 individuals per dose and per treatment. One controls mortality 24 hours after treatment.

The result obtained in terms of DL 50 or dose (in nanograms) required to kill 50 % of the insects is the following:

Product of the DL 50

Example (ng per individual)

1 1,115

23 0.952

29 0.825

Schlußfolqerunq: When the used test the products show are examples 1, 23 and 29, a remarkable activity,

2 Ji "Studie_dej3_Ef f ekt s.an ^ larvae ^ of ^ Spodog ^ era ^ littorali

The experiments are carried out by applying locally an acetone solution of the product to be tested by means of the

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Arnold micromanipulator on the dorsal chestpiece of the larvae. Take 15 larvae per dose of the product to be tested. The larvae used are larvae of the fourth instar, about 10 days old when grown at 24 ° C * and 65 % relative humidity. After treatment, the individuals are placed on an artificial nutrient medium (bottom of Poitout).

The mortality check is carried out 48 hours after treatment «

The experimental result obtained is as follows:

Connection of the DL

Example (ng per individual)

1 '4,699 35 0,544

CONCLUSION: In the test, the products of Examples 1 and 35 show good activity »

ying

The test insects are 4/5 day old female house flies, one proceeds by pulverization of direct kind in the Kearns and March chamber, using as solvent a mixture in equal volume of acetone and isopar L (quantity of the used solution 2 χ 0.2 cm), One takes about 50 insects per dose of the treatment. One leads the

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Check every minute up to 10 minutes, then 15 minutes and determine the KT 50 by the usual methods *

The results obtained are the following:

Product of the example KT 50 in mn Concentration g / i 1 3, .534 1 2 3,608 0.25 26 1,550 0.25 30 · 3,498 1 35 2,894 1 Conclusion: At the test show the products of

Examples 1 ,. 2, 25, 30 and 35 is a good activity.

The insects tested are males of the Germanic cockroach (Blatella qsrmanica). "The procedure is by depositing an acetone solution of the specified concentration on the bottom of a box of 20 cm diameter Petri." After drying, 20 cockroach males are allowed to stand by concentration for 1 hour, then transferred the insects in a healthy environment and controls their mortality 24 hours »48 hours, 3 and 5 days,

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The result, expressed in lethal concentration (CL 50),

2 gives for the considered product 0.216 mg / m.

Conclusion; After the test, this product shows a very good activity.

5 ^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^

1) adultizider attempt

Two seedleaf bean plants are used. These plants are treated with the Fisher gun with an acetone solution of the product. After drying, 25 females of the mite Tetranychus urticae are brought to the leaves, 50 individuals per experiment dose per leaf »The effectiveness checks are carried out after 1, 24, 48 and 72 hours of contact,

At the 2.8 mg / 1 dose, the product shows very good activity.

Claims (4)

3 1 3 7 2 5 -ν- 3 * 8.1981 59 416/11/39 Appealed to Wags 1. Process for the preparation of the compounds of the formula (P) in all possible isomeric forms or in the form of mixtures: EO ₂ CCH = in the A 'represents either an alkyl radical having 1 to 18 carbon atoms, or a benzyl radical, possibly by one or more radicals from the group consisting of the alkyl radicals having 1 to 4 carbon atoms, the alkenyl radicals having 2 to 6 carbon atoms, the alkenyloxy radicals having 2 to 6 carbon atoms, the alkadienyl radicals having 4 to 8 carbon atoms, the methylenedioxy radical and the halogen atoms, substituted, - or a group in which the substituent E ^ is a hydrogen atom or methyl radical and the substituent E _{2 is} a monocyclic aryl or a -CH ₂ -C = CH group and .insbesondere 313 7 2 5 -? - 3.8.1981 59 416/11/39 a 5-Ben.zy 1-3-fuiy 1-me t hylgruppe, - or a Grappe in which a represents a hydrogen atom or a methyl radical, and E ~ an aliphatic organic radical having 2 to 6 carbon atoms and one or more unsaturated carbon-carbon radicals and in particular the -CH ₂ -CE = CH ₂ -, -CH ₂ - CH = TCH-CH ₃ -, -CH ₂ -CH = CH-CH = CH ₂ -, -CH ₂ -CH = CH-CH ₂ -CHO-eadical, - or a group wherein a represents a hydrogen atom or a methyl radical, Ε- maintains the same meaning as above, E 'and E' _{2 are the} same or different from each other, a hydrogen atom, a halogen atom, an alkyne radical 1 to 6 carbon atoms, an aryl radical having 6 to 10 carbon atoms, an alkyloxycarbonyl group with Represent 2 to 5 carbon atoms or a cyano group - or a group 2 313 7 2 5 3.8.1981 59 416/11/39 in the B, an oxygen atom or sulfur atom or a 0 ti C represents - or -CHp group, and IL represents a hydrogen atom, a -CsN radical, a methyl radical, a -CONH ₂ radical, a CSNE ₂ radical or a -CSCH radical, Ec is a halogen atom or a Methyl radical, and η is a number equal to O, 1 or 2, and more particularly the 3-phenoxybenzyl, cC-cyano-3-phenoxybenzyl, cc-ethynyl-3-phenoxybenzyl, 3-benzoylbenzyl , 1- (3-phenoxy-phenyl) -ethyl or QC-2hioamido-3-phenoxybenzy!
- or a G-group 231 372 5 3.8,1981 59 416/11/39 - or a group in which the substituents Bg, R- ,, Eg, Eq represent a hydrogen atom, a chlorine atom, or a methyl radical, and in which S / I symbolizes an aromatic ring or an analogous dihydro- or tetrahydro ring, - or a group -CH ₂ -N - CH ₂ - C 5 CH - or a group - CH - -O wherein R _{10 represents} a hydrogen atom or a, CN radical, R _{12 represents} a -CH ₂ radical or an oxygen atom 2 313 7 2 5 - * 59 416/11/39 H, represents a thiazolyl or thiadiazolyl radical; its binding with -CH- is in any available position can be located at R ^ at IL. is bound by the carbon atom between the sulfur atom and a nitrogen atom,
- or a group - or a group in which E ₁ O sin represents a hydrogen atom or a CIT-Badikal,
- or a group 23U72 5 3-8.1981 59 416/11/39 in which ILo is as defined above and the benzoyl radical is in position 3 or 4, - or a group in which IL 1 represents a hydrogen atom, a methyl, ethynyl or cyanoradical, and R -, - and B ^ g »each other represent a hydrogen, fluorine or bromine atom,
- or a group --Es-- f wherein E 1 is as defined above, each of IL ₁ - independently represents an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an alkylthio group having 1 to 4 carbon atoms, an alkylsulfonyl group having 1 to 4 carbon atoms, trifluoromethyl , 3 'is 4-methylenedioxy, chlorine, fluorine or bromine, ρ is a number equal to O, 1 or 2, and B * is an oxygen or sulfur atom, and E is an alkyl radical having 1 to 18 carbon atoms. oil 2q 1 * 3 7 Ο S "^ ~ 3.8.1981 represents, substituted by one or more identical or different functional group, or an aryl group having 6 to 14 carbon atoms, possibly substituted by one or more same or different functional group, or a heterocyclic radical optionally substituted by one or more identical or different functional groups represents compounds in which the double bond has Z or! geometry, characterized in that an acid of the formula (II): EO ₂ C - CH s CH._ / \ CO ₉ H (II), E in the same meaning as above, or a functional derivative of this acid with an alcohol of the formula (III) A * - OH (III), in the A ^! has the same meaning as above, to obtain the corresponding compound of the formula (I ¹ ). 313 7 2 5 -w- 3-8.1981 59 416/11/39 a, process according to item 1, characterized in that initially a compound of the formula II is used in which the double bond has Z geometry, Method according to one of the items 1 ', characterized in that compounds are used at the beginning in which the coupling component cyclopropanoic acid 1E has an egg or 1E trans structure. if. Process according to one of the items 1 to 3, characterized in that initially compounds of the formula III, XI or XV are used in which A * is a ς-cyano-3-pheno-3-cybenzyl group in S-, E- or ES- Form or a 2-methyl-4-oxo-3- (2-propenyl) -2-cyclopentenyl-d) group in S, E or ES form.  Method according to one of the items 1 to Ί-, characterized in that initially compounds of the formula II, B2, VI or esterifying agents are used which contain a Ε group which is an alkyl eadical having 1 to 18 carbon atoms which is substituted by one or more functional groups, G, method according to item 5 *, characterized in that E represents an alkyl radical which is represented by an or 2 313 7 2 5 - »- a plurality of halogen atoms is substituted. 11/12/1981 AP G 07 C / 231 372/5 Method according to item £ , characterized in that R is substituted by one or more fluorine atoms » Method according to item ^ _1, characterized in that R represents a -CHp-CF group, Method according to one of the items 1 to 3 and 14 to 16, characterized in that one of the compounds of the formula (I ¹ ) is prepared, the names of which are listed below: - (S) o-cyano-3-phenoxybenzyl (lxR-cis) -2j, 2-dimethyl-3 - / {Z) -3- (2,2- _J- 2-trifluoroethoxy) -1-oxo l'-propenyl7- cyclopropane-carboxylate, - (S) # i-cyano-3-phenoxy * -benzyl- (lR-cis) -2,2-dimethyl-3 - / (2) -3-oxo-3- (2- (l _i l ₁ l _{t J} 3.3 3-hexafluoro) propoxy) -l- propenylZ-cyclopropane-carboxylate, - (R) E-SORT + ethynyl-3-phenoxy-benzyl- (IR cisJ-S ^ -dimethyl-3- ^ f (Z) -3-oxo-3- (2,2,2-t-rifluoroethoxy) -l-propenyl7- cyclopropane carboxylate , - (RS) -cyano-6-phenoxy-2-pyridyl-methyl- (IR-cis) _-2-t 2- dimethyl 3i - / (Z) -3-oxo-3- (2,2 _I 2-trifluoroethoxy } ~ ipt? openyl7-cyclopropane-carboxylate _t - (lR-cis) ^-2:, 2-dimethyl-3 '- / t ^z) -3-oxo-3- (2-fluoroäthoxy) -l-propenyl ^ -cyclopropane-carboxylate of (S) ^ C-Cyano -3-phenoxybenzyls, (lR-cis) -2,2-dimethyl-3. ~ / T [Z) -3-oxo- (2 ₁ 2 _J 2-trifluoro-ethoxy] -1-propenyl-cyclopropane-1-carboxylate of (3 propargyl-2,5-dioxoimidazolidinyl) -methyls, (IR-cis) -2 _f 2-dimethyl-3- (XZ) -3-oxo-3- (2,2,2-trifluoroethoxy) -3'-2-propenyl-7-cyclopropane-carboxylate of (IS) - 2-methyl-4 ~ oxo-3- (2-propenyl) -2-cyclopenten ~ l ~ YLS.