NL8204049A - NEW ESTERS OF AROMATIC OR HETERO-AROMATIC ALKANOLS, METHOD AND INTERMEDIATES FOR THEIR PREPARATION, THEIR USE IN THE FIGHT AGAINST PARASITES AND COMPOSITIONS CONTAINING THESE ESTERS. - Google Patents

Description

323186 / ir / cd "- -1-

Short designation of new esters of aromatics or heteroaromatic alkanols, process and intermediates for preparation, use in the control of parasites and compositions containing these esters. The invention refers to new esters of aromatic sobs or better. aromatobe alkanols, a method and intermediates for their preparation, use in the combating of paraales and compositions containing these esters · 3 The invention refers to the compounds of formula 1 of foxmuleblad, vaaxin Aj. represents an optionally substituted aramic or better araronic group, Xj, Xg and X ^ are or are not yellow and represent a hydrogen atom or a balogen atom, wherein at least 44a of the groups X, Xg and Xj represents a balo-10 atom , and B either a) an alkyl group of 1-18 carbon atoms, or b) a group of formula 8 of the foxmuleblad, in which: - Z1 and% 2 * η represent aetbyl group, or - Z1 represents a hydrogen atom and Z2 represents a group with formula 9 of 15 the foxmuleblad, in which represents a hydrogen or balogen atom and and Eg are the same or different and represent a halogen atom or an alkyl group with 1-8 carbon atoms or and Eg together form a cycloalkyl group with 3-6 carbon atoms or a group with foxmule 10 of the foxmuleblad voxmen, in which the keto group zicb is in position a at 20 ° of the double bond and in which X represents an oxygen or sulfur atom or a group NH, or Z2 represents a group with foxmule 11 of the foxmuleblad, in which E ^ , Ry Eg and Sy are the same or different and each represent a balogen atom, or Z2 sen group with foxmule 12 of the foxmuleblad with E or Z-geome-23 trie, in which Eg represents a hydrogen or a chlorine, fluorine or bromine atom and E represents a straight, branched or cyclic, saturated or unsaturated alkyl group having 1-O carbon atoms, which is optionally substituted by 44a or more equal or different functional groups, an axyl group having 6-14 carbon atoms, which are also is optionally substituted by 44a or more equal or different functional groups, or a better cyclic 8204049 optionally substituted by 44a or more equal or different functional groups

} I

-2- group represents, or ο) B represents a group with the foxmule 13 yam Bet foxmuleblad, in which X in a villous position on the benzene core represents a halogen atom, an alkyl group with 1-8 carbon atoms or an alkoxy group with 5 1-8 carbon atoms where m represents the number 0, 1 or 2, in all the possible isomers voxms and mixtures of the isomers, with the exception of y and the y bonds with foxmole 1, in which £ ,, Xg and at the same time represent a fluorine atom and with the exception of 2- chlorine 1- (3-phenoxyphenyl) ethyl 3 ~ (2-methyl 1-propenyl) 2,2-dimethyl 1-10 cyclopropane-1-oarboxylate.

When Ar represents a sobstition oxide or hetero-aromatics group, it is preferably an aromatics or hetero-aromatics group, which is substituted by 6An or more hydroxyl groups, 44a or more alkyl groups with 1-4 carbon atoms, 44a or 15 more alkoxy groups of 1-4 carbon atoms, an aryloxy, arylcarbonyl », arylmethyl, aryltbio», arylsulfenyl or arylsulfonyl group, 86n or more balogen atoms, a trifluoromethyl group or a combination of these different sobstituents, and eyenes substituted aiders aromatisobe or hetero-aromatisohe group, 20 which may itself be substituted by 44a or more of the previously mentioned groups ·

The phenyl group is preferably the aromatobic group of yerstate.

Substituted aromatisobe group yerst preferably represents the groups with foxmule 14 of the foxmuleblad, wherein y, and at any position on the benzene nucleus represent a hydrogen atom, a halogen atom or a methyl group, n and n 'the numbers 0, 1 or 2 y and A represents an oxygen atom, a methylene group, a carbonyl group, a sulfur atom, a sulfoxide group or a sulfone group.

For example, as substituted aromatobic groups which are preferred, the groups of formulas 15 and 16 of the foxmuleblad may be mentioned.

Preferred heteroaromatic groups are the groups derived from pyridine, thiophene, furan or pyrimidine. Of these hetero-aromatics groups, the substituted hetero-aromatics groups, for example, the group with fozmule 17 or the group with foxmule 18 of the foxmuleblad called woxden.

When X, Xg and Xj represent a halogen atom, it is preferably fluorine, chlorine or bromine.

8204049 * <

When B represents an alkyl group, it is "preferably a straight chain, branched or cyclic alkyl group having 1-18 carbon atoms, such as for the Id, the methyl, ethyl, η-propyl, isopropyl, cyclopropyl, butyl -, tort.butyl, cyclobutyl or n-pentyl group * 5 When JLj, fig. η ^ represent a halogen atom, this is preferably a fluorine, chlorine or bromo atom.

When and fig represent an alkyl group, this hid Yoozkeor is the methyl group *

When and fig together represent an oyoloalkyl group, this is preferably the cyolopropyl group.

fi ^, fi5, fig and 2γ preferably represent fluorine, chlorine or broonone tones.

fi preferably represents a methyl, ethyl, n-propyl, isopropyl, tert-butyl, phenyl, bensyl, thienyl or furyl group.

Preferably, a halogen atom, for example a chlorine at 00 m, is substituted for the para-position of the benzene core.

m is preferable to 1.

The invention relates more particularly to the compounds of formula 1, where B represents a group of formula 8 of the formula sheet, where Z1 represents a hydrogen atom and Z2 represents a group of formula 9 of the formula sheet, see FIG. have the aforementioned meanings and, in particular, the compounds, which are shown in FIGS. and FIG. 1, represent the same halogen atoms and are a hydrogen atom.

The preferred compounds of the invention may be referred to as the compounds of formula I, hereinafter A 1. a group with formula H Ten represents the formula sheet, where y ^ and y2 represent a hydrogen atom, a halogen atom or a methyl group in a specific place of the benzene core, n and n * are equal to 30 1 or 2 and A is an oxygen atom, a methylene group , a carbonyl group, a sulfate group, a sulfoocyte group or a sulfone group, especially the compounds, in which A represents an oxygen atom and the compounds, in which Y and Yg each represent a hydrogen atom. The preferred compounds according to the invention can be very in particular, the compounds mentioned, wherein and Xg represent a hydrogen atom and Xj represents a halogen atom, especially the one where X3 is a chlorine atom.

The invention also relates to an alternative for the preparation of the varbindingan with foxmole 1, which is characterized in that one has a soar with foxmole 2. or a functional derivative of Tan this acid, subjected to the invexing of an alkanol with foxmole 5 3 Tan of the foxmule sheet, in which X ^, Xg · η They have the meanings mentioned, or a functional derivative of Tan such an alkanol, for the purpose of obtaining Tan de o Unified Tarbinding with foxmole 1 «

The functional acid derivate used at Tooxkeur is a 10 halogen, for example a chloride ·

Tolgena a preferred embodiment The invention of the invention is allowed to x-react the zuux and the alcohol in the presence of Tan dicyclohexylcarbodiimide or diisopropylcarbodiimide *

Bet speaks for himself that the Tereaterngax reaction can be output 13 according to other conventional Tereatera methods.

The invention relates more particularly to a method for the preparation of Tan de Terbindings with foxmole 1, which is characterized in that an acid is used with the foxmole BCOgH or a functional derivative of this acid, according to the above 20 meanings. has an alkanol with the foxmule 3A Tan, the foxmule sheet, subject to the invexking Tan, having T2> n, nf, A, Xf, X2 and X ^ possess the aforementioned meanings, or a phonetic derivative thereof, to obtain Tan de Eereenkometige Ter bond with foxmule 1A Tan the foxmuleblad · 23 Be alkanols with foxmule 3 Tan the foxmuleblad, in which X ^, Xg and Χ ^ have the aforementioned meanings, where X ^, Xg and X ^ cannot simultaneously have a fluorine atom, and the funotional DexiTaten thereto, are new products · The invention therefore relates to these products as new products.

The invention particularly relates to the alkanols with foxmole 3A as the foxmule sheet, which has the meanings mentioned above, and the funotional derivatives thereof, as described in FIG. 7, y2, η, η ', A, X ^, Xg on X ^. alkanols, all new products. 33 Tan the latter Terbindings with foxmole 3A, in particular the Terbindings with foxmole 3 * A Tan the foxmuleblad, y.j, y2, η, η ', X ^, Xg and X ^ may have the aforementioned meanings ·

The invention particularly relates to the 40 Terbindings with foxmule 3 "A Tan foxmuleblad, 8204049

p P

-5-

The compounds of the formulas 3 * 3A, 3'A and 3nA are, in particular, of interest without intermediate products for the preparation of the compounds of formula 1. The invention is therefore particularly concerned with the compounds having formula 3 »3 3A, 3 * A and 3nA ala necessary products for the execution of the Eezder described method ·

The compounds of fozmole 3 can be prepared by reacting a compound of formula 4 of the formula sheet, in which the exex has the meanings mentioned, with a compound of formula 4 'of the formula sheet, wherein X, Xg, the previously said meaning and to form the corresponding compound of the formula

Yolgena is a preferred embodiment at low temperatures of -30 ° G and -100 ° Cy in the presence of an alkali metal-13 alkanolate, potassium tert-butylate or also in the presence of any other base which is in anate around an anion to form with the compound of formula 4 *

When preparing compounds of formula 3, in which X1, Xg and X3 are chlorine or bromine atoms, one can react a compound of formula 3 of the foxmule leaf, which contains the aforementioned meanings, with a halogen * to form of the corresponding formula 6 compound of formula sheet, wherein nH equals 1, 2 or 3, which is subjected to the incorporation of a reducing agent to form the corresponding compound of formula 7 of the formula sheet.

As a reducing agent, use can be made of an alkali language borohydride such as, for example, HaBH4.

The compounds of formula 6 obtained as intermediates are new compounds and themselves constitute the invention.

When compounds of formula 7 containing two differing balogen atoms are wished to be obtained, ac- terally one of the two balogens is reacted and then the other halo is reacted with the compound of formula 3

Depending on the fiber constituents used, 33 compounds of formula 7 are obtained which contain 1, 2 or 3 balogen atoms

It is also possible to subject £ 4n of the resulting compounds of formula 7 to the softening of a reducing agent to replace the labile balogen atom with a hydrogen atom.

8204049 -6-

As a means of reduction. use (Bu) ^ SnH or any other di- or tri-alkyl tin hydroxide.

The compounds of the female 1 possess interesting properties which make it possible to use them in the control of parasites, for example paxaeites intended for intestinal-blooded animals and parasites that develop in rain. For example, the products according to the invention can be used for the control of insects, nematodes and on plants and venomous animal parasites at the end of mites. The invention relates to the use of the compounds of foxmule 1 in the control of parasites of pangled animals, plants and raids ·

The compound of Example II has given very remarkable results. The invention also relates to eamen counts, which are suitable for combating paraites from blood-fed animals, plants and rams, and are characterized as being a rare substance at least 44a. contain compound of formula 1

The compounds of Foxmule 1 can, in particular, be used to combat inland agriculture, for example flies, doob also aphids, larvae of lepidoptera and ooleoptera. They are used in doses of bags 10 and 300 g of active material. per ha

The compounds of foxmule 1 can also be used to combat insseating in reams, in particular flies, maskites and poop claws.

The invention is particularly troubling with regard to insecticidal compositions containing all the active ingredient at least 44a compound with foxmule 1. The compound with foxmule 1 may also be used to control plant-parasitic mites and nematodes ·

The compounds of formula 1 can also be used for the control of mite-like species that paraize on animals, for example tasks and in particular tasks of the species

Boophilua. Byalomnia, Amblyomnia and Bhipicephalus, or to combat all kinds of schuxft, in particular sarcoptic, psoroptic and chorioptic schuxft.

The invention also relates to assemblies for the beat-fighting of animal-paratizing nematodes and to pangled-blooded animals, in mines and on plan-parasitic mite-like species, which are characterized in that they terminate 44n. of the aforementioned compounds.

The invention particularly pertains to acaroidide counts, which contain only beneficial parts of the tenmiasta 44a of the aforementioned compounds.

In the fight against animal parasitic animals, the compounds according to the invention are often included in food supplements in combination with a food mixture for animal feed. The food mixture can vary depending on the animal type and can contain cereals, crops and seeds. , cooks of aoy beans, aazdnuts and sunflower seeds, flour of animal ear aprong, for example flour meal, amino acids for building, inorganic acids, vitamins and anti-oxidants.

The invention therefore also relates to such nutritional assessments.

The compositions according to the invention are prepared according to the usual methods of the land cultivation industry, the veterinary industry or the industry for the preparation of animal food products.

In the surveys for land use and use in gravel, 44n or more other peaticides may be added to the active parts of the crop. These compositions can be in the form of powders, grains, suspensions, emulsions, flours, aerosol flours, flammable strips, locks or other formulations commonly used for the use of this type of compound.

In addition to the active beat portion, these amounts generally contain a carrier an / or a nonionic surfactant which additionally imparts a uniform distribution of the aggregate beat portions of the mixture. The carrier may be a liquid, such as water, alcohol, hydrocarbons or other organo-solvents, an inorganiac, animal or vegetable oil, a powder, tallow, clays, silicates, kieselguhr or a flammable substance, such as taboo powder or pyre-tbrum - deductible.

The ineoticide aggregates according to the invention preferably contain 0.003 to 10 wt. Active substance.

8204049-8-Acadeide and nematicide compositions may be more particularly in the form of Tea, a powder, granules, suspensions, emulsions, solutions.

For the use of the aerosolicide, it is preferred to use 5 wettable powders for dusting, which contain 1 to 80 active substances, or liquids to leaf, which contain 1 to 500 g / l of active substance. It is also possible to use powders for powder bouncing of leaves containing 0.05-3 active agents. · 10 For the use of all nematioid use and preferably liquids for the coating of the soil containing 500-500 g / l of active bavate dust.

The acaricidal and neaatioid compositions according to the invention are preferably used in doses of tosses 1 and 100 g of active material per ha *

To enhance the biological dissemination of the compounds of the invention, conventional synergists, such as 1- (2,5 * 0-trioadodeoyl) 2-propyl 4> 5-ethylenedioxybenzene (or piperonyl-2-butoxide) or] f- (2-ethylheptyl) bicyolo. 2,2-2-1-5-benzene-2,3-dicarbo-xiaide, or piperonyl-bis-2- (2'-n-butoxy- ethoxy) ethyl acetal (or tropital) compound of formula 1 have excellent general tolerability and the invention also relates to the compounds of formula 1 as medicaments, in particular for the control of conditions caused by tasks and minutes.

The medicaments according to the invention can be used as much in human medicine as in veterinary medicine.

The medicaments of the invention are used particularly in human medicine for the preventive or curative control of lice and for the control of scburft.

the medicaments of the invention may be applied externally by spraying, bathing or smearing.

The medicaments of the invention for use in veterinary medicine may also be administered by applying the spinal cord in accordance with the so-called tppour-on "vmetbode. They may also be administered orally or parenterally.

8204049 -9-

The invention therefore relates to pharmaceutical compositions containing active ingredient terminate S6n of the aforementioned goose agents.

Toorta notes that the compounds of the invention can be used as biocides or growth regulators.

The invention also relates to combinations having an insecticidal, aicaricidal, fungicidal or neaatocidal activity, which are characterized in that they act as active ingredients on the one hand terminate 44a of the compounds of the general formula 1 and on the other hand. minate 44a of the pyretbrinol esters selected from the group of allet brolones eatera, 3,4,5,6-tetrahydrophthalimidomethanol, 5-benzyl-3-furylmethanol, 3-phenoxybenzyl alcohol and α-cyano-3-eno-xybenzylalkdols of ohryane hemic acids ; the 5-benzyl-3-furyline thy 1-eaters of 2,2-dimethyl 5- (2-oxo-5-tetrahydrothiophenylidenemethyl) cyclopropane-1-carboxylic acids; the 3-phenoxybenzyl esters and α-cyano 3-phenoxybenzylaters of 2,2-dimethyl-3- (2,2-dichloro-vinyl) cyclopropane-1-carboxylic acids; the α-eyane-3-phenoxybenzylater8 of 2,2-dimethyl 3- (2,2-dibromovinyl) cyclopropane-1-carboxylic acids; the 3-phenoxybenzyl esters of 2-parachlorophenyl 2-isopropyl acetic acids, the esters of all-20 tbrolones, 3,4,5 »6-tetrabydrophthalimidometbwanol, 5-benzyl 3-fury1-metbanol, 3-phenozybenzylalkobol and α-cyano 3- phenozybenzyl alcohols of 2,2-dimetbyl 3- (1,2,2,2-tetrahaloetbyl) cyclopropane-1-carboxylic acids, wherein "halo" represents a fluorine, chlorine or bromine atom, the compounds of formula 1 as well as the acid and alkobol portions of the above-mentioned pyrethroofdeeaters may have all possible atereoisomeric forms

The invention is illustrated by the following unspecified examples.

Example I: RS [2-Chloro 1- (3-phenoxyphenyl)] ethyl 1Ral3 (2,2-difluorovinyl) 2,2-dimethylcyclopropahcarboxylate.

30

A solution of 1.6 g of 1-fis-3- (2,2-difluorovinyl) 2,2-dimetbyloyclopropanecarboxylic acid in 20 ml of methylene chloride is cooled to 0 ° G. Subsequently 1.6 g of dicyclobezylcarbodiimide and 15 mg of N, 17-dime thylaminopyridine are added in 66 times. The mixture is stirred for 20 min.

35 and add 1.5 g of 1 & S 2-chloro 1- (3-phenoxyphenyl) -1-ethanol and 20 ml of methylene chloride. The resulting solution is stirred for 5 hours, where the temperature is allowed to rise gradually to room temperature. Filter, solid filtrate with water, dry and evaporate to dryness. 3.1 [beta] product is obtained, which is subjected to chromium 6204049-10 graphite, eluting with a mixture of hexane and ethyl acetate (95-5). 1.8 g of the desired product are obtained. MB CDCl 3 ppm - 1.18-1.22 3 * 8 of the CH 2 groups 5-1.85 3's of the oyolopropyl group on plate 1 and 3 - 3.67 - 5 * 77 B »s of CHgCl

4.3 * 4.7 3 of CH

nF

s

5.8-5.9-6 l of COgCH

10-6.9-7.6 aromatohe 3'a.

Image II. HS [2-fluoro 1- (3-phenoxyphenyl) J ethyl 13 cia 3 (2,2-difluorovinyl) 2,2-dimethylcyclopropanoarboxylate.

In the manner of example 1, 1.8 g of 13 ois 3 (2,2-difluorovinyl) 2,2-dimethyloyolopropanecarboxylic acid 15 and 1.5 g of 13S 2-fluoro 1- (3-phenoxyphenyl) -1-ethanol are obtained starting from 2.2 g of the desired product · BUR GDCl / ppm.

- 1.12 and 1.23 Hfs of the methyl groups on plants 2 - 1.8-2.08 3fs on positions 1 and 3 of the oyolopropyl group

20 - 4.15-4.25) Hb of CBUP

- 4 95-5 'S

- 4, 17 -5 H of CH -

-5.8-5.9-6 1-3 of COg-CH

-6 -6.1-6.2 y - 6.9-7.6 aromatics B * a 25 Example III. HS [2-bromo-1 (3-phenoxyphenyl) methyl 13 ois 3- (2,2-difluorovinyl) 2,2-dimethyloyolopropanecarboxylate.

In the manner of Example 1, starting from 0.88 g of 13 cia 3- (2,2-difluorovinyl) 2,2-dimethylcyclopropanoarbomour and 1 g of 1HS 2-bromo 1- (3-phenoxyphenyl) -1-ethanol are obtained 1.33 β of the 30th product.

ME CDCl ^ ppm - 1.1-1.22-1.25 3 * a of the methyl groups on plants 2 - 1.75-1 »92 3 of the oyolopropyl group - 3.5-3.6 H of CH-Br

* * IP

35 - 4.25-5 3 of CB «C ^ ✓

5.8-5.9-6 H of COgCH

- 7 - 7.6 aromatisohe 3 * 8

Example 17. HS [2-fluoro-1- (3-phenoxyphenyl) methyl 13 trans 3- (2,2-8204049-11-difluorovinyl) 2,2-dimethylcyclopropanecarboxylate.

On da. the manner of pre-lane I is obtained, starting from 1.8 g of 1-trane 3- (2,2-difluorovinyl) 2,2-dimethylcyclopropane carbonate and 1.3 g of 1HS 2-fluoro 1- (3-phenoxyphenyl) -1-e thaaol 1.6 g of the 3 gawanata product.

HMB CDCl ^ ppm.

- 1.13-1.23 H'e of daethyl groups on plate 2 of da cyclopropane ring ** 1.32 * 1.6 H on platea of COg 10 -3.75-3.88} - 4.2- 4.3 IH τιη «« Ν »- 4.12-4.2) - 4.9-5 (HT“ ^ - 5.7-6.25 a tu oo2qs 13 - 6.8 - 7.3 aromatiaeha H's

Pre-punched Vi BS [2-bromo 1- (3-fanoxyfanyl) Jathyl 1-trana-3- (2,2-di-fluorovinyl) 2,2-dimethylcyclopropanoarboxylate ·

On the basis of prepunched I vax, man is given 0.88 g of 1B trane 3- (2,2-difluorovinyl) 2,2-dimethycyclopropane carbon-20 aure and 1BS 2-bromo 1- (3-f anoxypheny1) -1- athanol 1.38 g of the ga-vanata product · SMB GDGl ^ ppm - 1.13-1.2 * 1.27 H'e of da mathylgroapan on plate 2, - 1.5-1.6 Hop platea of CO2 23 - 1.88 * 2.2 da Hare of da cyclopropyl group - 3.55-3.65 3 of CH ^ - 3.8-3.9 H of CH - - 4.2-4.3} v

coca /: I a from C0oGH

- 5.8-5.9-6 \ 2 \ 30 Pre-billed Yl: BS [2-chloro 1 (3-phenoxyphenyl) J ethyl 1B trane 3- (2,2-difluorrinyl) 2,2-dimathylcyclopropane carbozylate ·

The ala in Example 1 is obtained starting from 1.6 g of 1B trans 3- (2,2-difluorovinyl) 2,2-dimethylcyclopropane-carboxylic acid and 1.5 g of 1BS 2-chloro 1- (3-fanoxyfanyl) - 1-ethanol 1.7 35 g of the desired product · BUB CDCl 3 ppm · - 1.15-1.18-1.21 H of th CH groups - 1.53-1 »62 H on plate 1 of the oyclopropyl group - 1.88-2.13 a on plate 3 of the cyclopropyl group 8204049 -12- - 3.72-3.8 H of CHgCl - 3.42-4.36 H of CH - <£ *

5.9-6-6.1 H of COg-CH

- 6.9-7.6 aromatiaohe H * a 5 Pre-prepared VII »BS [2,2-dichloro-2-fluoro-1- (3-phenoxyfanyl) methyl 1R trans 3 (2,2-difluorovinyl) 2,2-dimathylcyclopropanoarboxylate ·

In the same way as in example 1 verier! 2.2 g of 1E trans 3- (2,2-difluorovinyl) 2,2-dimethylcyclopropanecarbonzunr an 3.8 g of 1BS 2,2-dichloro 2-fluoro 1 (3-fanoxyphenyl) -1-ethanol are used 10 4 g of hat Gewenata product · HMR GDGlj ppm - 1.15-1.18-1.21 Η * β of da methyl groupan on plate 2 - 1 92 - 2 13 1 '1 H'a of doolopropane ring - 1, 55-1.64) 15 - 3.8-3.9} ^ -4.2-4.3 y Hiaig. C, - 6.18—6.33 Ji

- 6.38} H T “®2BH

20 - 6.9 - 7.6 arcmatic H's

Example Till, HS 2-fluoro-2-chloro 1 (3-phenoxyphenyl) J ethyl (1R cia) 3- (2,2-difluorovinyl) 2,2-dimethylcyclopropanoaroxylate.

In the same manner as in Example 1, man obtains, based on 0.86 g (1R cia) 3- (2,2-difluorovinyl) 2,2-dime thyloyclopropane-25 carboxylic acid, and 1 g 2-fluoro 2-chloro 1- (3 -fanoxyfanyl) -1-ethanol 1.4 g of the sweetened product.

ME GDCl 3 ppm - 1.15-1.25-1.26 H'a of da methyl groups on plate 2 - 1.75-2 H'a of daolopropane ring 30 - 4.17-4.9 H of - 5, 75-6.2 H of CO, m - 6.6-6.7 2 \

H from -CH

> '

Cl - 6.9-7.5 aromatic Aroma H'a 35 7 Figure IX. HS [2,2-dichloro-2-fluoro 1 (3-fanoxyfanyl) J ethyl 1E ois 3 (2,2-dibromovinyl) 2,2-dimathylcyolopropane carboxylate ·

Man chooses a solution of 1.2 g of 1RS 2,2-dioHor 2-fluoro 1- (3-phenoxyphenyl) -1-ethanol, 40 cm -1 of benzene and 1.8 g of 1B cia 3- (2,2-8204049 -13- dibrocmvinyl) 2,2-dimethyloyolopropanecarboxylic acid chloride at 0-5 ° C *

Them adds 0.7 cm 3 of pyridine. The temperature is allowed to rise until # room temperature is stirred for 17 hours. and evaporates under dry pressure to dryness. 2.9 g of product are obtained, which is exploded by chromatography on silica, eluting with a mixture of hexane and ethyl acetate (8-2). 1.9 g of the given product · BMR CDCl 3 PP · 10 - 1.18 - 1.26 - 1.34 H's are obtained in the methyl groups in position 2 - 2 - 2.03 H's of doopropane.

- 6-6.2) H of <2 CH

-6.3) - 6.6-6.8. ethylenisohe H'e 15-6.9-7.3 aromatic H's

Example X »BS [2-fluoro 1 (3-phenoxyphenyl) J ethyl 1R cis 3- (2,2-dibromovinyl) 2,2-dimethylcyclopropane carbozylate.

In the same manner, ale in Example IX is added starting from 1.2 g of 1 BS 2-fluoro 1- (3-phenazyphenyl) -1-ethanol and 2.5 g of 1B cis 20 3- (2,2-dibromo vinyl) 2 , 2-dimethylcyclopropanecarboxylic acid chloride 1.7 g of hot desirable product · HMB GDCl ^ ppm - 1.15 and 1.27 B's of the methyl groups in position 2 - 1.83-2.08 H's of the cyclopropyl group 25 - 4.13 -4.22) - 4.9-5 IH Van

- 5.7-6.25 H of COgCH

- 6.6-6.9 H of CH-C 3 × 3 30 - 6.8-7.5 aromatics

Example XIBS [2-chloro 1- (3-pheno-yphenyl) methyl 1B cis 3-L-dihydro 2-oxo 3- (21-thienylidenemethyl] 2,2-dimethylcyclopropanecarboxylate.

Preparation of Acid Chloride:

A mixture of 5 g of 1fl cis 3-L-dihydro 2-oxo 3-35 (2H-thienylidene) methyl] cyclopropane-1-carboxylic acid, 50 ml of petroleum ether and 10 ml of thionyl chloride is refluxed for 4 hours. It is evaporated to dryness, it is taken up in benzene and it is again evaporated to dryness

50 ml of benzene are added to the acid chloride thus obtained, cooling to + 5 ° C and 6.5 g of 1RS 2-chloro 1- (3-phenoxyphenyl) -1-ethanol in 60 are added. go? benzene. Stir them and add 7.3 cm at + 5 ° C in 30 min. pyridine in 20 ml of benzene. The mixture is stirred at 20 ° C for 16 hours, poured into water, decanted, the organiaohe fees are watered with 5 0.12Γ hydrochloric acid and then with water, dried and evaporated to dryness.

The residue is chromatographed on silica, eluting with a mixture of cyclohexane and ethyl acetate (75-25) to give 9.3 g of the wenated product roof.

n £ °. 1,583. 0¾ - + 25.5 ° + 1 ° (° -1 * CBOlj).

10 7 Example XII. R, S and S [2-chloro 1- (3-phenoxyphenyl) J ethyl 1fia 3- (2,2-dibromoethenyl) 2,2-dimethylnyclopropanecarboxylate.

Mien similarly describes in example UL starting from 5.05 g of 1fia 3- (2,2 »d ± bromoethenyl) 2,2-dimethylcyclopropanecarboxylic acid and 4» 2 g of 1BS 2-chloro 1- (3- phenoxyphenyl) -1-ethanol. After chromatography on aluminum dioxide, eluting with a mixture of petroleum ether and isopropyl ether (9-1), 6.1 g of product are obtained, which is crystallized in petroleum ether.

1.9 g of the S * isomer with a melting point of 76 ° C + 67 ° + 1.5 ° (c - 1% CHCl) are obtained. The mother liquors evaporated to dryness provide 3.6 g of the (SS) -is <aner. «D =» 26 + 1.5 ° (C = 1% CDCl3)

Yoorbeeld HU. BS [2-chloro 1- (3-phenozyphenyl) J ethyl 1R cia Az) 2,2-dimethyl 3- (2-methoxycarbonylethenyl) cyclopropanecarboxylate.

It is likewise described in Example 1 starting from 1.8 g of (1R ciaA2) 2,2-dimethyl 3- (2-methoxycarbonyls thenyl) cyclopropanecarboxylic acid and 1.5 g of alkanol. 1.8 g of the wenate ester are obtained.

Analysis: G ^^ GIQ ^ (428,912).

Calculated: G% 67.2 5.9 01% 8.3

Found 67.0 5.9 8.8 30 Example XIV. BS [2-fluoro 1- (3-phenoxyphenyl) methyl 1R cisAZ) 2,2-dimethyl 3- (2-methoxycarbonylethenyl) cyclopropanecarbylate ·

The procedure is similar in that of Example 2, starting from 1.98 g (1-ficyl) 2,2-dimethyl 3- (2-matho-xy carbonyls thenyl) cyclopropanecarboxylic acid and 1.5 g alkanol. 2.5 g of the wenate ester are obtained.

Analysis: (412,457)

Calculated: G% 70.0 E% 6.1 B% 4.6 Found: 69.7 6.1 4.8

Figure XV. B and s [2-Bromo-1- (3-phenoxyphenyl) methyl (1-cis) 3- (2,2-8204049 -15-dibromoethenyl) 2,2-dimethylcyclopropane carboxylate.

A similar product to the one used in Example 3 is described as starting from 6.3 g (1R cis) 3- (2,2-dibromoethenyl) 2,2-dimethylcyopropano-carboxylic acid chloride and 5-86 g alkanol, being prepared in the presence of yen pyridine. in benzene · After crystallization in petroleum ether, 1.9 g of the S-isomer of the alkanol with a melting point of 76 [deg.] C. - + 66.5 [deg.] ± 1.5 [deg. 5 & 8 of the R isomer [α] - -18 + + 1 ((- 1.5 CH CHCl)).

10 n ^ 1 - 1,593 · (evaporate to dry from the Mudesi eyes) ·

Example XVI. (SS) [2-broam-1- (3-isnoxyphenyl) methyl (1R cis) 3 - [<1-hydro 2-oxo 3- (2H) -thienylidenemethyl] 2,2-dimethylcyclopropanecarboxylate.

Similarly, it is described in Example XI starting from 5 of the acid and 7.6 g of 1HS 2-bromo 1-15 (3-phenoxyphenyl) -1-ethanol. The yield product is purified by chromatography on silica, eluting with a mixture of benzene and ethyl acetate (8-2).

(¾ - + 24.5 ° ± 1.5 ° (0 - 0.8jt OBOlj)

Example XVII. (SS) [2-Bromo 1- (3-phenoxyphenyl] ethyl 1R trans 3-20 (2,2-dimethylethenyl) 2,2-dimathyl cyclopropanecarboxylate.

A process similar to that described in Example 3 is used starting from 5.6 g of 12 trans 3- (2,2-dimethylethenyl) 2,2-dimethylcyclopropano carboxylic acid chloride and 8.8 g of alkanol, with operation in benzene in the presence of pyridine. 6.15 g of the give product are obtained.

43.1,554.

Analyzes Cg ^ HgyBrOj (443 »38)

Calculated: C $ 65.0 Br 6.13 Br $ 18.02

Found 64.9 6.2 17.8 Example XVIII. (RS) [2-Bromo 1- (3-phenoryphenyl)] ethyl (1R cis, A Z) 2,2-dimethyl 3- (2-methoxyoarbonylethenyl) cyclopropanecarboxylate.

Similarly, described in Example 3, starting from 0.99 g (1R cis, Δζ) 2,2-dimethyl 3- (2-methoxycarbonylethenyl) cyclopropanoic carboxylic acid and 1 g alkanol.

1.33 g of the Getenete ester are obtained.

Analyzes Cg ^ Hg ^ BrO ^ (473 »368)

Calculated C $ 61.15 5.3 Br $ 16.95

Found 60.8 5 »4 17» 0

Example XIX. (HS) [2-fluoro 2-chloro 1- (3-phenoxyphenyl) methyl 1R 40 trans 2,2-dimethyl 3- (2,2-difluoroethenyloydopropanecarboxylate).

8204049 -16-

A similar procedure as in example TUI is started, starting from 0.86 g of 1R trans 2,2-dimethyl 3- (2,2-difluoroethenyl) cycl opropanoic carboxylic acid and 1 g of alkanol. 1.5 8 of the denate ester · 5. Analysis: C ^ H ^ Cl? ^ (424,846).

Calculated: C $ 6 62.2 B # 4.75 01 # 8.3 I # 13.4

Found: 62.5 4.8 8.3 13.6

Example XX. (as) [2,2,2-trichloro-1- (3-enoxyphenyl) ethyl 1E o 2,2-dimethyl 3- (2,2-dibromoethenyl) oyolopropanecarboxylate.

10 Them is described in a similar way in Example XV

starting from 10 g of the salt, which is consumed in the acid chloride, and 3.8 g of 1RS [2,2,2-trichloro-1- (3-phenoxyphenyl) J-1-ethanol, 5 are obtained, 97 g of the wished eater

Analysis: C22Sl9Br2G13 ° 3 (597.571) 15 Calculated: C # 44.2 H # 3.2 Br # 26.7 Cl # 17.8

Found: 44.4 3.3 26.3. 17.4

Example XXI. (as) [2,2,2-trichloro-1- (3-pheno * yphenyl) J ethyl 1E trans 2,2-dimethyl 3-cyolopentylidene methyl cyolopropane carbozylate ·

21.6 g of sodium 1S-trans 2,2-dimethyl-3-cyclo-3-3-pentylidene-methylcyclopropanoarboxylate are suspended in 75 benz benzene and 60.5 car 0 3 pyridine. They are slowly added at a temperature of 12 C 32.5 β ». oxalyl chloride, hold at +5, + 10 ° C for 15 min, add 30 c® benaene and hold at 20 ° C for 3 h. Filter them, evaporate the filtrate to dryness, add 30 ml of benzene the residue increases and concentrates at-25 new.

Solidification:

They proceed as in Example 11, starting from 3.96 g of alkanol. After chromatography on silica, eluting with a mixture of cyclohexane and ethyl acetate (9-1) on 30 with a mixture of petroleum ether and ethyl ether (95-5), the resulting ester is obtained.

Analysis: G26% 7013 ° 3 (493.862). '

Calculated: C # 63.2 H # 5.5 01 # 21.5

Found: 63.5 5.5 21.6 Example XXII · (fiS) [2,2,2-tribromo-1- (3-enoxyphenyl) methyl 1R trans 2,2-dimethyl 3-cyclopentylidene methylloyolopropane carboxylate.

They proceed in a similar manner to that in Example XXI starting from 9.115 8 1HS 2,2,2-tribromo 1- (3-phenoxy-phenyl) -1-ethanol. 3.76 g of the first eater, 8204049 -n-, are obtained.

Analyzes ¢ 26 ^ 27 ^ 3 ^ 3 (^ 27 »25)

Calculated C * 49.8 H £ 4. Br £ 38.2

After 30.2 4.6 38.4

Yoorbeeld Hill. (IS) [2,2,2-tibibroco-1- (3-phenoxyphenyX)] etbyX H 5 o 2,2-dimethyX 3- (2,2-cibromoethenyX) cyoXopropanoarboxyXate.

goes on similarly as described in pre-XYX starting from 10 g of bat acid, which converts man into acid-cbloxid # an 4.51 g 1BS 2,2,2-trlbrooa 1 - (3-f "enaxyphenyl -1-ethanol.

Han vex receives 4.71 g of da gawanata aster * 10 a pec trust GDCl ^ ppm - 1.21-1.28-1.31 H'e ran da stethylgroapen op pXaats 2 - 2.0έ S ran da oyclopropane ring - 6, 4 an 6.43 H on pXaats an da -000-group - 6.72-6.88 H of -CH-C% "15 - 7 -7.67 aromatiacbe H'e

YoorbaaXd ΧΧΓ7. (IS) [2,2-dichloro-1- (3-fanoxyfanyX) J athyX 11 cis, A Z) 2,2-diaathyX 3- (2-methozycarbonylethenyl) eye propanecarboxy-Xate.

Han goes in accordance with tavaxk aXa in yoorbaaXd XXII 20 starting from 1 g of bat snur an 0.89 g 1fiS 2,2-diobXoor 1- (3-fano-xyphenyI) -1-etbanoI. 1 g of da gawanata eater is obtained.

HME apeotrusts CDCX ^ ppm - 1.22-1.28-1.32 H'e of da CHj group on plants 2 - 2-2.14 H on plants (¾of the -COO group 23 - 3.13- 3.43 H of daolopropane ring - 2.7-2.27 H of -COOCH ^ - 5.73-6.08 atbyXaniacbe H on pXaatSran -COO-CHj an H of -CHCX2 - 6.33-8.72 Ξ on plants of -COOCH 30 - 6.92 - 7.5 aromatiaoba Ha

YorbeeXd XXY * (IS) [2,2-dicboro 1- (3-phenoxyphenyl) ethyl 11 cis 3- dihydro 2-ozo 3- (2H-tridaylidenemathyX] 2,2-dimethylcyclopropane carboxylate.

Man similarly goes tawezk aXa described in 33 yoorbaaXd XI starting from 5 g of the acid and 7 »3 β 1lS 2,2-di-cbXoor 1- (3- £ anoxyfany]) - 1-atbanoX · 10 g are obtained of the desired aster * ojj - +27.50 + 1.5 ° (c - 1 # CHCXj)

Analyzes C25¾4C1204S ^ »422) 8204049 -18-

Calculated: C # 61.09 3 # 4.92 Cl # Η, 42 S # 6.52

Found: 61.2 5.0 14.4 6.4

Yoorbeeld mi. (2S) [2,2-dichloro-1- (3-phenoxyphenyl) J ethyl 1H requirement 2,2-dimethyl 3- (2,2-dibroamethenyl) cyclopropanecarboxylate. 5 Similarly described in

Example IX starting from 6.3 g of the acid chloride and 6.52 g of 1HS

2.2-dichloox 1- (3-phenoxyphenyl) -1-ethanol. 9 g of the desired product are obtained.

a ^ 8.6 ° - 1.5915.¾ - + 11.5 ° ± 1 ° (c - 0.5 # CHCl3).

10 Analysis: C22B20Br2G12 ° 3 (563.13)

Calculated: C # 46.92 B # 3.57 Br # 28.38 Cl # 12.59

Found: 47.0 3.6 28.2 13.0

Example XXVII. (BS) [2,2-dichloro-1- (3-phenoxyphenyl) methyl 1R trans 2,2-dimethyl 3- (2-methyl-1-propenyl) oyclopropanecarboxylate. 15 Proceed in a similar manner as described in Figure XXYI. starting from 4.04 8 12 trans 2,2-dimethyl 3- (2-methyl 1-propenyl) cyclopropanecarboxylic acid chloride and 6.32 g alkanol. 6.25 g of the desired eater, n 18.6-1.556, are obtained. (¾ - + 1 ° + "1 ° (c. 0.9 # CHGlj).

20 Analysis: C2 ^ 6C12 ° 3 (433.36)

Calculated: C # 66.31 H # 6.04 Cl # 16.36

Found: 66.2 6.1 16.3

Preparation 1: 1BS 2-chloro 1- (3-phenoxyphenyl) -1-ethanol Step A: 3-phenoxy * Achloroacetophenone.

23 A solution of 3.6 g of chlorine in 50 ml of acetic acid in a solution of 10.5 g of 3-enoxy-3-acetophenone in 50 cm of acetic acid is introduced at 21 ° C over 30 min. It is left to stand for 30 min at room temperature and then evaporated to dryness under reduced pressure. It is taken up in ether, solid with a saturated solution of sodium bicarbonate, the organic phases are dried and evaporated to dryness. 11.5% of the product is obtained, which is subjected to chromatography on silica, eluting with a mixture of benzene and petroleum ether (boiling range 60-80 ° C). 8.1 g of the desired product are thus obtained.

Step B: 1SS 2-chloro 1 (3-phenoxyphenyl) -1-ethanol.

3.7 sodium borohydride is added at 10 [deg.] C. in 30 min. To a solution of 11.8 g of the product prepared in step A in 3 o 3 in 70 ml of methanol. The mixture is stirred at 10 DEG C. for 30 minutes and 4.5 omacetic acid is added. It is evaporated to dryness, taken to dryness in 8204049-19 in methylene chloride, washed with water, extracted again with methylene chloride, dried and evaporated to dryness under reduced pressure.

They obtain 8.3 g of the desired product. n2 - 1.5855.

Preparation 2s 1BS 2-bromo 1- (3-phenoxyphenyl) -1-ethanol;

Step 1: 3-phenoxybromoacetophenone.

16 g of bromine are added dropwise to a solution of 21.2 g of 3-phenoxyacetophenone, 120 ml of diozan and 60 ml of ethylather.

The mixture is stirred for 40 minutes. The mixture is concentrated to dryness, the mixture is taken up in 200 ml of ethyl acetate, the mixture is watered with water, dried and the mixture is concentrated to dryness at 50 ° C under reduced pressure. 29 g of a product are obtained, which is subjected to chromatography on silicon dioxide, eluting with a mixture of benzene and petroleum ether (boiling point 60 DEG-70 DEG C.) (8-1). 21.5 g of the desired product are obtained. n p = 1.613 15 Step B: 1BS 2-bromo 1- (3-phenoxyphenyl) 1-ethanol:

6 g of the product prepared in step A are added to 60 ml of methanol under stirring at 20 ° G in 30 min. 3.8 g of sodium borohydride are then added, the mixture is kept at 20 [deg.] C. for 30 minutes, the pH is adjusted to 2 by adding acetic acid and poured into 400 ml of water. The extract is extracted with ethyl ether, the organic phase is dried, dips to dryness at 50 ° G under reduced pressure to obtain 11 g of the desired product. n £ 5 - 1,605.

Preparation 3s 1HS 2,2-dichloro-2-fluoro 1- (3-phenoxyphenyl) -1-ethanol.

25 A. Condensation.

30 cm @ 2 at -40 [deg.] C. under nitrogen nitrogen condensed 3 2,2-dichloro-2-fluoromethane, 40 g of 3-alpha-enozybenzaldehyde and 250 carboxylic ethyl ether to -60 ° C. 43 g of potassium tert are then added.

z 3 butylate dissolved in 200 cm3 of tetrahydrofuran and 150 cm3 of tert. butyl-30 alcohol. The mixture is stirred at -40 [deg.] C. for 17 µl and poured onto monosodium phosphate, extracted with methylene chloride, west with water, dried and evaporated to dryness. 59% of the crude desired product is obtained.

B. Blockage with dihydropyran.

34 g of the product prepared in step A, 300 ml of benzene, 18 ml of dihydropyran and 100 mg of paratoluenesulfonic acid are stirred at room temperature for 45 minutes. The mixture is concentrated to dryness under reduced pressure. 50 g of a product are obtained, which is subjected to chromatography on silica, eluting with a mixture of benzene. 8204049

• I

-20- and ethyl acetate (95-5). Aldua obtains 16.4 g of the gaveate blocked product.

G · Unblocking.

16 g of the finished product in step B are added in 200 ml of methanol and 100 mg of paxatolueansulfonzuux. Ken roext at room temperature-tuux and then heats 2 uux at 40 ° C. Know the density with water, extahext with methylene chloride, solid organic phase with water, dry and evaporate to dryness under reduced pressure. The residue is subjected to chromatography on silica with alluation with a manganese of hexane and ethyl acetate (8-2). Aldua obtain 11.4 g of 1 & S 2,2-dichloro-2-fluoro 1- (3-phenoxyphenyl) -1-ethanol.

HMR GDG1 ^ ppm

- 2.95-3 mobile E of OH

-5 - 5 * 13 H of CH OH

15 - 6.9 - 7 »6 aromatic H'e.

Preparation 4s 133 2ES 2-fluoro 2-chloox 1- (3-phenoxyphenyl) -1-ethanol.

A mulch of 4 µg of 1HS 2,2-dichloro-2-fluoro 1- (3-phenoxyphenyl) -1-ethanol such as in preparation 3, 10.2 g of 3 tributyltin hydride and 50 ml of benzene is refluxed for 10 hours. 20 Allow to cool. 100 ml of ethyl ether are added and the mixture is stirred vigorously with an aqueous solution of 100 g of potassium fluoride per liter. Ken filters, decant the aqueous faee and wait the organic faee several times with water. It is dried and evaporated to dryness under reduced pressure. The residue is subjected to silica gel chromatography, eluting with a mixture of hexane and ethyl acetate (8-2). 2.4 g of the desired product are obtained. HMR GDCl / ppm - 5.7-5.75) -6.3-6.6) HV "° Sx01

30-4.7-5 H niHOH

- 2.65-2.7-2.8-2.9 E of OH

- 6.8-7.3 aromatic H'a

Preparation 5s 1BS 2-Fluoro 1- (3-phenoxypheny1) -1-ethano1.

10.5 µl of 2,2-dichloro-2-fluoro-1- (3-phenoxyphenyl) 3 -1-35-ethanol as obtained in preparation 3, 200 cm xylene and 318 tributyltin hydride are refluxed for 34 hours. The xylene is evaporated. It is taken up in ethyl ether and stirred with an aqueous solution of 100 g of potassium fluoride per liter. It is filtered, the filtrate solid with water, dried and evaporated under reduced pressure to 8204049-21. The product obtained is subjected to chromatography on silica, eluting with a mixture of Tan hexane and ethyl acetate (8-2). 7.4 g of the desired product are obtained.

HMR GDCl ^ PI®5 - 2.5 - 2.55 I Tan 01

- 5.9 - 4.2 a Tan CH OH

- 4.7 - 5.25 H of <2y - 6.8 - 7.5 arcmatic H's

Preparation 6 1BS 2,2,2-triobloro 17 (3-phenoxyphenyl) -1-ethanol.

4.95 g of m-phenoxybenzaldehyde are dissolved in a 40 ml dimethoxy ether pathway, 4 ml chloroform is added, cooled to -35 ° C and a solution of 3.36 g potassium tert-butylate is dissolved in 3 min. 15 cm tert.

5 butanol and 15 cm of dimethozyethane. The mixture is stirred for 55 minutes and poured into ice-cold water, which is 35 mmole of hydrochloric acid. The mixture is stirred, extracted with ether, the ether phase is watered with water, dried and the solvent is evaporated off. The residue is subjected to chromatography on silica, eluting with a mixture of cyclohexane and ethyl acetate (8-2), and 7.5 g of the desired product are obtained.

Analysis C ^ H ^ CljOg (317,602) 20 Calculated * OffL 52.9 Φ 3.5 Cl £ 33.5 Found »52.9 3.6 33.5

Preparation 72 1fiS 2,2,2-tribromo 1- (3-phenoxyphenyl) -1-ethanol.

The procedure is similar to that described in the preparation 6 starting from Tan 9.9 g m-phenoxybenaldehyde and 8.7 curb bromoform. After purification by chromatography on silica, eluting with a mixture of cyclohexane and ethyl acetate (85-15), 24.25 g of the desired product are obtained, which is recrystallized in a mixture of petroleum ether and isopropyl ether. 19.4 g of the desired product are obtained, with a melting point of 70 [deg.] C.

30 Analysis * (450.96)

Calculated * <& 37.3 2.4 Br # 53.1

Found * 37.2 2.7 52.8

Preparation 82 1BS 2,2-dichloro 1- (3-phenoxyphenyl) -1-ethanol.

Step A * 2,2-dichloro 1- (3-phenoxyphenyl) -1-ethanone.

3 21.2 g of methylene chloride, 200 ml of tetrahydrofuran and 100 ml of ethyl ether are mixed, and 123 ml of a solution with 15 g / 100 g of butyl lithium in hexane are added at -100 [deg.] C. with stirring. The mixture is stirred for 30 minutes and then 24.2 g of ethyl 3-3-phenoxybenzoate in 100 cm of vessel-free ether are added. It is stirred for 3 hours at 8204049 -22- -100 ° C, and then 150 ml of hydrochloric acid are added at -60 ° Q. The temperature is allowed to rise to 0 ° C, decanting, extracting with ethyl ether, drying and evaporating the solvent. The residue is re-heated (boiling point 0.1 - 142-144 ° C) and 18 g of the desired product are obtained. N2 ^ 1.610. Erap B: 1ES 2,2-dichloro 1- (3-fendxypheny 1) 1-ethanol.

3

18 g of 3-phenoxyipr-diochloroacetophenone and 73 ml of ethanol are mixed, then 7 g of sodium borohydride are added at 20 ° C and the mixture is stirred for 1 hour at 20 ° C. with ether, the organic phase is watered with water, dried, the solvent evaporated, taken up in ether, treated with activated carbon, filtered, the solvent evaporated and dried. 13 g of the desired product are obtained.

15 n £ 4 - 1.5950.

Analysis C ^ H ^ Cl ^ (283.15)

Calculated <# 59.38 Έ & 4.27 Cl # 25.04

Found 59.4 4.5 24.9

Yoorbeeld XX.Vill. Preparation of a soluble concentrate: 20 A homogeneous mixture of - Product of example 1 0.25 g - Piperonyl butoxide 1 g - Tween 80 0.25 g - Topanol A 0.1 g 25 - Water 98.4 g is prepared

Example XXIX: Preparation of an emulsifiable concentrate. An intimate mixture of - Product of Example 1 Q, 0.15 g - Piperonyl butoxide 0.5 g 30 - Topanol A 0.1 g - Aylean 99.365g is prepared

Yoorbeeld XXX. Preparation of an emulsifiable concentrate.

A homogeneous mixture of: - Product of Example X 1.5 g 35 - Tween 80 20 g - Topanol A 0.1 g - Xylene 78.4 g is prepared

Yoorample XXXI. Preparation of a smoke-developing composition.

A homogeneous mixture is prepared of: 40 - Product of Example I 0.25 g 8204049 -23- - Tabu powder 25 g - Cedar leaf powder 40 g - Coniferous wood powder 53.758 - Brilliant green 0.5 g 5 - p-nitrophenol 0.5 g

Investigation of the efficacy of da compounds according to the invention began paraaletan

Investigation of the ability of the compound of Example IX by topical application to houseflies (Musca domestica).

10 Toapaeta insactan are female 4 to 5 dagan domestic flies, and 1 mioroliter of a solution of the compound in acetone is applied locally to the dorsal thorax of the insects with the bahump of an Arnold micromanipulator, examining 50 individuals in par doaia.

The mortality determinations are made 24 hours after treatment. Experimental results expressed in LD ^ show that a 66.46 nanogram sample per individual is necessary to kill 50% of the flies.

Consequence s The compound of Example II has an interesting insecticidal activity against houseflies.

Investigation of the lethal potency of the compound of Example II by eontaot through the legs of aphids (Blattella gexmani-ca) · 25 male aphids stay for 1 hour on the glass bottom of a Fetri dish pre-treated with a dissolution of the test compound in acetone. The mortality determinations are made 1 hour, 24 hours and 3 days after the start of proof, with insects being transferred into normal breeding conditions upon contact with the poison. The experimental results expressed in LB 1 show that a concentration of 2.09 mg / m 2 is necessary to kill 50% of the insects by contact with the legs.

Consequence drawing The compound of Example II has an interesting inactivity against aphids *

Investigation of the knock-down activity of the compound of Example II by spraying on houseflies:

Insects used are female flies, 4 days 40 years old. Hen beckons by direct atomization into a room of Kears and 8204049 -24-

March with a solution of the compound to be tested in a mixture of equal parts by volume of acetone and petroleum solvent (isopar L) *

50 insects per day are used and the assays of 5 knockdown alia ainutes for up to 15 minutes are carried out, after which the KT 50 or the time required for anesthetizing 50/6 of the insects is determined by conventional methods.

For the connection of Example U, the reactants show a ΚΪ 50 of 9 »86 min · 10 Conclusion:

The compound of Example IX has a good knock-down ability on temper flies.

Investigation of the acaricidal activity of the compound of Example II against mites of the tetranyobua urticae species.

15 Planting beans with two leaves from the cotyledons are treated with discarded doeea. After pigeons and drying, 50 female mites per doaia are applied to the leaves. The measurements of the attenuation are carried out after 24 hours and the results obtained make it possible to calculate the LD 50.

In the compound of Example II, the ID 50 is 1732.7 mg / bl.

Inference:

The compound of Example II has good acaricidal activity against fetranycbua urticae.

-Goncluaiee- 8204049

Claims (11)

1 · The compounds of formula 1 of the formula sheet, in which A represents an optionally substituted aromatisohe or hetero-aromatics group, Xj, Zg an Z ^ are the same or different from a vatar-substance atom or halogen atom atoms, wherein at least 44a 5 of da groups, Xg an Z ^ on halogen atom, an B a) an alkyl group mat 1-18 carbon atom or b) on group oat formula 8 of the foxmuleblad, in which - orwal an 2g each of methyl group foratallan, - ofwal 2 ^ to hydrogen atom an 2g to group mat formula 9 of hat 10 foxmuleblad, in which B ^ is hydrogen atom or halogen atom, B ^ an Bg may or may not be equal to halogen atom or to alkyl group mat 1-8 carbon atom representation of a fig together on oyoloalkyl group mat 3-6 carbon atom or on group mat formula 10 of the foxmule leaf forms, in which da 15 keto group contains ssioh on plants a relative to the dubbala bond in which Z is attached to oxygen or sulfur atom or a NH group, or wal Z2 on groap mat formula 11, in which B ^, Hg and may or may not be equal to any halogen atom, 20. orwal Zg on groap mat formula 12 mat B or Z-gaometria, in which fig. to hydrogen-) fluorine * * chlorine or broam atom an B to rachta, vartakte or oyoliaoha, varsadigda or unsaturated alkyl group mat 1-13kooletofatoman, optionally gas substitute by 44a or maer dazelfda or different functional group, or to aryl group mat 6 -14 carbon atom, which is avantuael gas substituent by 44n or maer dazelfda or different functional groups, or to heterocyclic group, which is avantuael gas substituueard by 44a or maer represents the same or different functional groups, or 30 c) B to group mat formula 15 of the formula sheet, in which Y represents at any position on the banana comb on the halogen atom, on the alkyl group mat 1-8 carbon atom or an alkoxy group mat 1-8 carbon atom, wherein m is a an 0, 1 or 2, in all their possible isomers, are formed in the form of 35 mangals of isomers, with the exception of the compounds of formula 1, in which Z 2, Zg and Z 2 simultaneously represent a fluorine atom with the exception of 2 chlorine 1- (3-phenoxyphenyl) ethyl 8204049 * • 26 · 3- (2-methyl 1-propenyl) 2,2-dimethylcyclopropane 1-car boxy late. 2 · The compounds of formula 1 according to claim 1, in which B represents a group with foxmule 8 of the foxmulehlad, in which Zj represents a water atom or atom and a group with foxmule 9 of the formula-muleblad, in which Bj, Bg and The meaning mentioned in claim 1 is correct. 3. Compounds with foxmule 1 follow claim 2, in which B.j and Bg represent the same halogen atoms and Bj is a water atom. Claims with foxmule 1 according to 44a of claims 1-3, in which A represents a group with foxmule H of the foxmulehlad for Jk, in which and Yg in a random position on the henzeenkexn represents a hydrogen or halogen atom or a methyl group a and n * are equal to 1 or 2 and A represents an acid atomic atom, a methyl-13-boron group, a carbonyl group, a sulfur atom, a sulfoxide group or a sulfone group. 3 · The compounds with foxmule 1 to 44a of claims 1-4, in which X1 and Xg θβη hydrogen represent an atom and X ^ represent a halogen atom. 6. Method for the preparation of the compounds of formula 1 according to 46a of claims 1-3, characterized in that an acid with formula 2 of the formula sheet is used, in which B is the meaning of the meaning mentioned in claim 1, or a functional Dexifers of such an acid are subjected to the action of an alkanol with foxmule 3 of the foxmule shell, which contains A, X, Xg and the meaning mentioned in claim 1, or a functional derivative of such an alkanol. formation of the corresponding compound with foxmule 1. Method for the preparation of the compounds of formula 1 according to claim 4, characterized in that an acid with foxmule 2 or a functional derivative thereof, in which B contains the hetekeniases mentioned in claim 1, is subjected to the action of an alkanol of formula 3A of the formula sheet, wherein Y 1, Y 2, n, n 'and A are the meaning of the meaning as claimed in claim 4 and 33, X 2, X 2 and X 2 are the meaning of the meaning as defined in claim 1, or a functional derivative thereof to form the corresponding compound with foxmule 1A. 8204049 -27- 8 · As new industry products, the alkanols of the formula III, which are in Xj, Xg and X3 in claim 1, have the meanings mentioned, but cannot simultaneously represent a fluorine atom, and funotional derivatives of these alkanols · 5 9 · - All new industrial products as defined in claim 8, the alkanols of formula 3A, wherein Yj, Y2, n, nf, and A have the meanings mentioned in condusion 4 and, and have the meanings listed in conolue 8, and funotional derivatives of these alkanols · Use of the compounds of formula 1 as defined in 44n of claims 1-3 in the control of parasites of intestinal blood animals, plants and in spaces · Compositions for the control of parasites of wax-blooded animals, plants and in spaces, characterized in that they contain at least 44n product as defined in 44n of claims 1-3 as a rare ingredient. 11. Insecticidal compositions, characterized in that they contain at least 44n of the product as defined component as defined in 44n of claims 1-3 1-3 Acaricidal compositions, characterized in that they contain at least 44n product as defined in 44n of claims 1-3. * Compositions for the feeding of animals, characterized in that they contain at least 44n 23 of the product as defined in 44n of claims 1-3 as a constituent ingredient. H · As medicaments, the compounds as defined in 44n of claims 1-3 · Pharmaceutical compositions, characterized in that they contain at least έέη of the medicaments according to claim 14 as a rare ingredient. 16 · Combinations with an insecticidal, acaricidal, fungicidal or nematocidal action, characterized in that they are selected as the active ingredient on the one hand at least 44n of the compounds of the general formula 1 according to claim 1 and on the other hand at least 33 44n of the pyrethrinol esters from the group of the esters of allethrolones, 3,4,3,6-tetrahydrophthalimidomethanol, 3-benzyl 8204049 -28-3-furyl-methanol, J-phenoxybenzyldkohol and α-cyaaa 3-phenoxybenzyl alcohols of chrysanthemum acids, the 3- benzyl 3-furyl-phenyl esters of 2,2-dimethyl 3- (2-oxo-3-tetrahydrothiophenylidenemethyl) cyolopropane-1-carboxylic acids, the 3-phenoxybenzyl ether and α-cyano-3-phenoxybenzyl-5-esters of 2,2-dimethyl-3- (2,2-dichlorovinyl) cyclopropane-1-carboxylic acids, the α-cyano 3-phenoxybenzyl ester of 2,2-dimethyl 3- (2,2-di-bromovinyl) cyclopropane-1-carboxylic acids, the 3-phenoxybenzyl esters of 2- parachlorophenyl 2-isopropylacetic acids, the esters of allethrolones, 3,4,3,6-tetrahydrophthalimidamethanol, 3-benzyl 3-furylmeth anol, 10 3-phenoxybenzyl alcohol enoeoyane 3-phenoxybenzyl alcohols of 2,2-dimethyl 3- (1,2,2,2-tetrahaloethyl) cyolopropane 1-carboxylic acids, vaaxin "halos" represents fluorine, chlorine or bromine atom, wherein both the compounds of formulas I & Is may be present in the acid and alkanol portions of said pyrethrin orde tera in all their stereoisomeric forms. 8204049