CA1254227A - Substituted phenoxybenzyloxycarbonyl derivatives and their use as insecticides and acaricides - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE

The present invention provides, as new compounds, the substituted phenoxybenzyloxycarbonyl derivatives of the general formula

Description

~2542~Z7 This application is a division of Canadian Application Serial No. 306,758, filed July 4, 1978.
T}~e present invention relates to certain new su~-stituted phenoxyben~.yloxyc~rbonyl derivatives, to a pro-ces~ for theiI~ preparation, and to their use as insecticides an~ acaricides.
It is already known that certain phenoxybenzyl acetates or carboxylates, for example 3'-phenoxybenzyl ~-isopropyl-(3,4-dimethoxy-phenyl)-acetate, ~-chloro-~iperonyl 2,2-dimethyl-3-(2,2-dimethyl-vinyl)-cyclopropanecarboxylate and 3'-phenoxybenzyl 2l2-dimethyl-3-indenyl-cyclopropane-carboxylate, possess insecticidal and acaricidal properties ~see Cerman Offenlegungsschriften (German Published Specifications) 2,335,347 and 2,605,828 and U.S. Patent

2,857,3Q9)-Ihe invention of the above parent application originally provided, as new compounds, the substituted phenoxybenzyloxy-carbonyl derivatives of the general formula ~ ~ CH-0-C ~ CH=C (I) in which R, Rl and R2, which need not be identical, each re-present hydroEen or halo~en, R3 represents phenyl or phenylthio, and in either case the phenyl ring may optionally carry one or more substituents selected independently from alkyl %5 ~roups and halogen atoms, Y represents hydrogen or nitrile, n represents l, 2, 3, 4 or 5 and m represents l, 2, 3 or 4.

~Z542:~7 These new compounds sre distinguished by powerful insecticidal and acaricidal properties.
Preferably,R and Rl each represent hydrogen or fluorine, n2 represents hydrogen, chlorine or bromine, R3 represents phenyl, phenylthio, halogenophenyl (pre-ferred halogens bein~ chlorine or rluorine) or alkylphenyl, the alkyl radical Or which has 1 to 6 (especially 1 to 4) carbon atoms and Y represents hydrogen or nitrile.
The general formula (I) here encompasses the various possible stereoisomers, the optical isomers and mixtures Or these components.
The parent invention also oriF~inally provided a process for the preparation Or a substituted phenoxybenzyloxycarbonyl derivative (I~,in which (a) a phenoxybenzyl alcohol Or the Eeneral formula ~ ~ CH (II), in which R, Rl, Y, n and m have the above-mentioned meanings, 2C is reacted with a cyclopropanecarboxylic acid derivative Or the general ~ormula R ~ ~ CH=c\
R (III), H3C ~CH

-- ~254227 in which R2 and R3 have the above-mentioned meanings and R4 represents halogen, pre:~erably chlorine, or Cl_ alkoxy, preferably methoxy or ethoxy, ir appropriate in the presence of an acid acceptor and, i~
appropriate, in the presence of a diluent, or (b) a phenoxybenzyl halide of the general rormula CH-Hal (IV), Rn 1m in which R, Rl, Y, n and m have the above-mentioned meanings and Hal represents halogen, preferably chlorine or bromine, is reacted, if appropriate in the presence of a diluent, 15 with acyclopropanecarboxylic acid derivative of the formula H0-OC ~ CH=C/ 3 (V), in which R2 and R3 have the above-mentioned meanings, the latter being en.ployed either in the form of an alkali metal salt, alkaline earth metal salt or ammonium salt or as such in the presence o~ an acid acceptor.
Surprisingly, the substituted phenoxybenzyloxy-~2542267 carbonyl derivatives according to the parent invention exhibit a better insecticidal and acaricidal action than the corres-ponding previously known products of analogous structure and of the same type of action. The products according to the parent invention thus represent a ~enuine enrichment of the art.
If, for example, 3-(4-fluorophenoxy)-benzyl alcohol and 2,2-dimethyl-3-(2-phenylvinyl)-cyclopropanecarboxylic acid chloride are used as starting materials in process variant (a) and the sodium salt of 2,2-dimethyl-3-(2-phenylthiovinyl)-cyclopropanecarboxylic acid and 3-phenoxy-~-cyano-benzyl bromide are used as starting materials in process variant (b), the course of the reactions can be represented by the following equations:
+ acid a) ~ ~_~ acceptor F ~ ~ CH2-OH ~ Cl-OC ~ H~CH ~ ~_ ~ ~ CH2-O-C ~ CH~CH

(b) CN
CH-~r + MaO-C ~ CH=CH-S ~ - NaBr CN
CH-O-C ~ H=CH-S

~254~Z~

The phenoxybenzyl alcohols (II) to be used as starting compounds are known in the majority of cases; they can all be prepared in accordance with generally customary processe~
described in the literature (see German Offenlegungsschrift (German Published Specification) 2,547,534).
The following are specific examples: 3-phenoxy-benzyl alcohol, 3-(4-fluorophenoxy)-benzyl alcohol, 3-(3-fluoro-phenoxy)-benzyl alcohol, 3-(2-fluorophenoxy)-benzyl alcohol, 3-phenoxy-4-f`luoro-benzyl alcohol, 3-(4-fluoro-phenoxy)-4-fluoro-ben7yl alcohol, 3-(3-fluorophenoxy)-4-fluoro-benzyl alcohol, 3-(2-fluorophenoxy)-4-fluoro-benzyl alcohol, 3-phenoxy-~-cyano-benzyl alcohol, 3-(4-fluoro-phenoxy)-~-cyano-benzyl alcohol, 3-(3-fluorophenoxy)-~-cyano-benzyl alcohol, 3-(2-rluorophenoxy)-a-cyanobenzyl alcohol, 3-phenoxy-4-~luoro--cyano-benzyl alcohol, 3-(4-fluorophenoxy)-4-fluoro-~-cyano-benzyl alcohol, 3-(3-fluoro-phenoxy)-4-fluoro-a-cyano -benzyl alcohol, 3-(2-(fluoro-phenoxy)-4-fluoro-~-cyano-benzyl alcohol, 3-phenoxy-6-fluoro-~-cyano-benzylalcohol, 3-(4-fluorophenoxy)-6-fluoro ~-cyano-benzyl alcohol, 3-(3-fluorophenoxy)-6-fluoro-~-cyano-benzyl alcohol and 3-(2-~luorophenoxy)-6-fluoro-~-cyano-benzyl alcohol.
The cyclopropanecarboxylic acid derivatives (V) also to be used as starting compounds can be prepared from the cyclopropane-carboxylic acid ethyl esters, some of which are known (see Tetrahedron Letters 1976, 48, pages 4,359-4,362), by acid or alkaline saponification. The free acids are converted in accordance with known processes into the corresponding salts or acid halides (III) and (V). The ethyl esters, some Or which are known, can in turn be prepared - ~ 254Z27 in accordance with processes known from the literature, for exa~.ple rrom 2,2-dimethyl-3-formylcyclopropanecarboxylic acid ethyl ester and O,O-diethylmethanephosphonic acid diester derivatives in accordance with the following equation:

N C~

~ ~

O

O =P~ O =~

N N

-o N

-~:ZS42~

The followin~ may be mentioned as specific examples of the cyclopropanecarboxylic acid derivatives (I~)and (V): 3-[2-phenyl-vinyl]-, 3-[2-(2-chlorophenyl)-vinyl]-,

3-[2-(4-chlorophenyl)-vinyl]-, 3-~2-(3,4-dichlorophenyl)-vinyl]-, 3-[2-(4-fluorophenyl)-vinyl]-, 3-[2-pentachloro-phenyl-vinyl]-, 3-~2-pentafluorophenyl-vinyl]-, 3-[2-phenylthio-vinyl]-, 3-[2-(2-chlorophenylthio)-vinyl]-, 3-[2-(4-chlorophenylthio)-vinyl]-, 3-[2-(3,4-dichlorophenyl-thio)-vinyl]-, 3-[2-(4-fluorophbnylthio)-vinyl]-, 3-[2-pentachlorophenylthio-vinyl]-, 3-t2-pentaf`luorophenylthio-vinyl]- and 3-[2-(4-tert.-butylphenyl)-vinyl]-2,2-dimethyl-cyclopropanecarboxylic acid and -2,2-dimethylcyclopro-panecarboxylic acid chloride, as well as 3-[2-phenyl-2-chlorovinyl]-,3-[2-(2-chlorophenyl)-2-chloro-vinyl]-, 15 3-[2-(4-chlorophenyl)-2-chloro-vinyl]-, 3-[2-(3,4-dichloro-phenyl)-2-chlorovinyl]-, 3-[2-(4-fluorophenyl)-2-chloro-vinyl]-, 3-[2-pentachlorophenyl)-2-chloro-vinyl]-, 3-(2-pentafluorophenyl-2-chlorovinyl)-, 3-[2-phenylthio-2-chloro-vinyl]-, 3-[2-(2-chlorophenylthio)-2-chloro-vinyl]-, 20 3-[2-(4-chlorophenylthio)-2-chlorovinyl]-, 3-[2-(3,4-dichlorophenylthio)-2-chloro-vinyl]-, 3-[2-(4-fluorophenyl-thio)-2-chloro-vinyl]-, 3-[2-pentachlorophenylthio-2-chloro-vinyl]-, 3-[2-pentaf`luorophenylthio-2-chloro-vinyl]- and 3-[2-(4-tert.-butylphenyl)-2-chlo~-vinyl]-2,2-dimethyl-cyclopropanecarboxylic acid and -2,2-dimethylcyclopropane-carboxylic acid chloride, and also 3-[2-phenyl-2-bromo-vinyl~-, 3-[2-(2-chlorophenyl)-2-bromo-vinyl]-, 3-[2-(4-chlorophenyl)-2-bromovinyl]-, 3-[2-(3,4-dichlorophenyl)-2-bromo-vinyl]-, 3-[2-(4-fluorophenyl)-2-bromo-vinyl]-, 3-[2-pentachlorophenyl-2-bromovinyl]-, 3-(2-pentafluoro-phenyl-2-bromo vinyl~-, 3-[2-phenylthio-2-bromo-vinyl]-, ~2542;2~

3-[2-(2-chlorophenylthio)-2-bromo-vinyl]-, 3-[2 (4-chloro-phenylthio)-2-bromo-vinyl]^, 3-[2-(3,4-dichlorophenylthio)-2-bromo-vinyl]-, 3-[2-(4-fluorophenylthio)-2-bromovinyl]-, 3-[2-pentachlorophenylthio-2-bromo-vinyl]-, 3-[2-penta-fluorophenylthio-2-bromo-vinyl]- and 3-~2-(4-tert.-butyl-phenyl)-2-bromo-vinyl]-2,2-dimethylcyclopropanecarboxylic acid and -2,2-dimethylcyclopropanecarboxylic acid chloride.
In addition, the phenoxybenzyl halides (IV), which can also be prepared in accordance with processes known from the literature, are used as starting compounds. The following may be mentioned as specific examples of these: 3-phenoxy-benzyl chloride and -benzyl bromide, 3-(4-fluorophenoxy)-benzyl chloride and -benzyl bromide3 3-(3-fluorophenoxy)-benzyl chloride and -benzyl bromide, 3-(2-fluorophenoxy)-benzyl chloride and -benzyl bromide, 3-phenoxy-4-fluoro-benzyl chloride and -benzyl bromide, 3-(4-fluorophenoxy)-

4-fluoro-benzyl chloride and -benzyl bromide, 3-(3-fluoro-phenoxy)-4-fluoro-benzyl chloride and -benzyl bromide, 3-(2-fluorophenoxy)-4-fluoro-benzyl chloride and -benzyl bromide, 3-phenoxy-~-cyano-benzyl chloride and -benzyl bromide, 3-(4-fluorophenoxy)-~-cyano-benzyl chloride and -benzyl bromide, 3-(3-fluorophenoxy)-~-cyano-benzyl chloride and -benzyl bromide, 3-(2-fluorophenoxy)--cyano-benzyl chloride and -benzyl bromide, 3-phenoxy-4-fluoro-Q-cyano-benzyl chlorlde and -benzyl bromide, 3-(4-fluorophenoxy)-4-fluoro-~-cyano-benzyl chloride and -benzyl bromide, 3-(3-fluorophenoxy)-4-rluoro-~-cyano-benzyl chloride and -benzyl brom:ide, 3-(2-fluorophenoxy)-4-fluoro-~-cyano-benzyl chlor:ide and -benzyl bromide, 3-phenoxy-6-fluoro-~-cyano-benzyl chloride and -benzyl bromide, 3-(4-fluoro-125~227 phenoxy)-~-fluoro--cyano-benzyl chloride and -benzyl bromide, 3 (3-fluorophenoxy)-6-fluoro-~-cyano-benzyl chloride and -benzyl bromide and 3-(2-fluorophenoxy)-6-fluoro--cyano-benzyl chloride and -benzyl bromide.

The present invention is conce~ned with compounds of the general formula (I) wherein R and R can each separately be hydrogen or halogen, but both cannot be hydrogen, as well as with methods for the~r preparation.
The parent application is now directe~ to those compounds of the general formula (I) wherein R and R are each hydrogen only.
All customary acid-binding agents can be used as acid acceptors. Alkali metal carbonates and alkali metal alcoholates, such as sodium carbonate, potassium carbonate, sodium methylate, sodium ethylate, potassium methylate and potassium ethylate have proved particularly suitable, as have aliphatic, aromatic or heterocyclic am.ines, for example trievhylamine, trimethylamine, dimethylaniline, dimethylbenzylamine and pyridine.
The reaction temperature can be varied within a sub-stantial range. In general, the reaction is carried out at between 0 and 150C, preferably at from 10 to 40C in process variant (a) and at from 100 to 130C in process variant (b).
The reaction is in general allowed to take place under normal pressure.
Process variants (a) and (b) for the preparation of the compounds according to the invention are preferably carried out in the presence Or a suitable diluent. Virtually all inert organic solvents can be used ror this purpose, especially aliphatic and aromatic, optionally chlorinated, hydrocarbons, such as benzene, toluene, xylene, benzine, methylene chloride, chloroform~ carbon tetrachloride and chlorobenzene; ethers, for example diethyl ether, dibutyl ~25~LZ~'7 ether and dioxan; ketones, Por example acetone, methyl ethyl ketone, methyl isopropyl ketone and methyl isobutyl ketone; nitriles, such as acetonitrile and propionitrile;
and formamides, for example dimethylformamide.
To carry out process variant (a), the starting materials are preferably employed in equin;olar amounts. An excess of one or other reactant produces no signiPicant advantages.
In most cases, the reactants are brought together in one Or the stated solvents and are stirred in the presence of an acid acceptor, in most cases at an elevated temperat~re, for one or more hours. The reaction mixture is then worked up by pouring it intc water, separating off the organic phase and then workin~ up the latter in the usual manner by washing, drying and distilling off the solvent.
In the case of the transesterification according to process variant (a), the procedure followed in the usual manner is to take the methyl ester or ethyl ester of the cyclopropanecarboxylic acid, if appropriate in a suitable solvent, together with 10-30% excess oP the alcohol of the formula (II), and heat the mixture with addition of alkali metal methylate or alkali n-.etal ethylate. The lower-boiling alcohol produced is at the same time distilled oPf continuously.
In carrying out process variant (b), the cyclopropane-carboxylic acid derivative is preferably employed in the ~orm of an alkali metal salt. This salt, in one of the stated solvents, is heated with the benzyl halide deriva-tive to 80-140C. An excess Or one or other reactant produces no aclvantages. APter completion of the reaction, the solvent is distilled orf, the residue is taken up in nethylene chloride and the organic phase is worked up as described above.

~2~;4~

The new compounds are obtained in the form of oils~
which in most cases cannot be distilled without decom-position but are freed rrom the last volatile constituentsby so-called "incipient distillation", that is to say by prolonged heating under reduced pressure to moderately elevated temperatures, and are purified in this manner.
They are characterised by the refractive index or the boiling point.
The substituted phenoxybenzyloxycarbonyl derivatives according to the invention are not only active against plant pests, pests harmful to health and pests of stored products, but also, i~ the veterinary medicine field, against animal parasites ~ectoparasites), such as para-sitic fly larvae and ticks.
15The active compounds are well tolerated by plants, have a favourable level of toxicity to warm-blooded animals, and can be used for combating arthropod pests, especially insects and acarids, which are encountered in agriculture, in forestry, in the protection of stored products and of materials, and in the hygiene field. They are active against normally sensitive and resistant species and against all or some stages of development. The above-mentioned pests include:
from the class of the Isopoda, for example Oniscus

5 asellus, Armadillidium vul~are and Porcellio scaber;
from the class of the Diplopoda, for example Blaniulus guttulatus;
from the class of the Chilopoda, for example Geophilus carpophaæus and Scutigera spec.;
30from the class of the Symphyla, for example Scuti-gerella immacula,ta;
from the order o~ the Thysanura, for example Lepisma 12~i422~

saccharina;
from the order Or the Co'llembola, for example Onychiurus armatus;
from the order of the Orthoptera, ~or example Blatta orientalis, PerIpl'a'n'eta americana, Le'ucoph'~ea maderae, Blattella germanica, Acheta domesticus, ~
talpa spp.~ Locusta mi~'rat'oria migratorioides, Me'l'an'oplus differentialis and Schi'stocerca gre~aria;
from the order of the Dermaptera, for example 10 Forficula auriculaFia;
. from the order of the Isoptera, for example Reticulitermes spp.;
from the order of the Anoplura, for example Phylloxera vastatrix, Pemphigus spp., Pediculus humanus corporis, Haematopinus spp. and Lino~nathus spp.;
_ . _ from the order Or the Mallophaga, for example Trichodectes spp. and Damalinea spp.;
rrom the order of the Thysanoptera, for example Hercinothrips femoralis and Thrips tabaci;

20from the order of the Heteroptera, ~or example Eury~aster spp., Dysdercus intermedius, Piesma quadrata, Cimex lectularius, Rhodnius prolixus and Triatoma spp.;
from the order of the Homoptera, for example Aleurodes brassicae, Bemisia tabaci, Trialeurodes vaporariorum, Aphis gossypii, Brevicoryne brassicae, Cryptomyzus ribis, Doralis ~abae, Doralis ~ , Eriosoma lani~erum, Hyalo~terus arundinis, Macrosiphum avenae, Myzus spp., Phorodon humuli, Rhopalosiphum padi, Empoasca spp., Euscelis bilobatus, Nephotettix cincticeps, Lecanium corni, Saissetia oleae, Laodelphax striatellus, .
Nilaparvata lugens, Aonidi'e'lla au'rantii, 'Aspidio't'us hederae, Pseudococcus spp. and PYY11a ~PP .;

~25422~

~ rom the order Or the Lepidoptera~ for example Pectinophora gossypiella~ Bupalus ~ , Cheimatobia brumata, Lithocolletis blancardella, Xyponomeuta padella, Plutella maculipennis, Malacosom neustria, Euproctis 5 chrysorrhoea, Lymantr:;a spp., Bucculatrix thurberiella, Phyllocnistis citrella, A~rotis spp., Euxoa spp., Feltia spp., Earias insulana~ Heliothis spp., Laphy~ma exigua, Mamestra brassicae, Ptmolis ~lammea, Prodenia litura, Spodoptera spp., Trichoplusia n:L, Carpocapsa pomonella, Pieris spp., Chilo spp., Pyrausta nubilalis, Ephestia kuehniella, Galleria mellonella, Cacoecia podana, Capua reticulana, Choristoneura fumi~erana, ~ ambiguella, Homona magnanima and Tortrix viridana;
from the order o~ the Coleoptera, for example Anobium punctatum, Rhizopertha dominica, Bruchidius obtectus, Acanthoscelides obtectus, Hylotrupes bajulus, Agelastica alni, Leptinotarsa decemlineata, Phaedon cochleariae, Diabrotica spp., Psylliodes chrysocephala, Epilachna varivestis, Atomaria spp., Oryzaephilus surinamensis, Anthonomus spp., Sitophilus spp., Otiorrhynchus sulcatus, Cosmopolites sordidus, Ceuthorr-hynchus assimilis, Hypera postica, Dermestes spp., Trogo-derma spp., Anthrenus spp., Attagenus spp., Lyctus spp., Meligethes aeneus, Ptinus spp., Niptus hololeucus, Gibbium psylloides, Tribolium spp., Tenebrio molitor, Agriotes spp., Conoderus spp., Melolontha melolontha, Amphimallon solstitiali_ and Costelytra zealandica;
from the order Or the Hymenoptera, ~or example Diprion spp.~ Hoploc~ampa spp., Lasius spp., Mon~omo~ium 0 pharaonis anct Ve's'pa spp.;
from the order Or the Diptera, ror example- Aedes spp., Anopheles spp., Culex spp., Drosophila me'l'an-ogaster, Musca ~254227 spp., Fannia spp., Calliphora erythroce~hala, Lucilia spp., Chrysomy~_ spp., Cuterebra spp., Gastrophilus spp., _ _ Hyppobosca spp., Stomoxys spp., Oestrus spp., Hypoderma spp., Tabanus spp., Tannia spp., Bibio hortulanus 3 Oscinella frit~ Phorbia spp., Pegom~ia hyoscyami, Ceratitis capitata, Dacus oleae and Tipula paludosa;
from the order of the Siphonaptera, ror example Xenopsylla cheopis and Ceratophyllus spp.;
from the class Or the Arachnida, for example Scorpio 0 maurus and Latrodectus mactans;
from the order Or the Acarina, ror example Acarus siro, Argas spp., Ornithodoros spp., Dermanyssus ~allinae, Eriophyes ribis, Phylloco~truta oleivora, ~ spp., Rhipicephalus spp., Amblyomma spp., Hyalomma spp., Ixodes spp., Psoroptes spp. J Chorioptes spp. 9 Sarco~tes spp., Tarsonemus spp., Bryobia praetiosa, Panonychus spp. and Tetranychus spp..
The active compounds can be converted into the customary formulations, such as solutions, emulsions, wettable powders, suspensions, powders, dusting agents, foams, pastes, soluble powders, granules, aerosols, suspension-emulsion concentrates, seed-treatment powders, natural and synthetic materials impregr.ated with active compound, very fine capsules in polymeric substances, coating compositions for use on seed, and formulations used with burning equipment, such as ~umigating cartridges, fumigating cans and fumigating coils, as well as ULV
cold mist and warm mist formulations.
These formulations may be produced in known manner, ror example by mixing the active compounds with extenders, that is to say liquid or liquefied gaseous or solid diluents or carriers, optionally with the use of surrace-~LZ542~7 active agents, that is to say emulsifying agents and/ordispersing agents and/or foam-rorming agents. In the case Or the use Or water as an extender, organic solvents can, rOr example, also be used as auxiliary solvents.
As liquid solvents diluents or carriers, especially solvents, there are suitable in the main, aromatic hydrocarbons, such as xylene, toluene or alkyl naphthalenes, chlorinated aromatic or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic or alicyclic hydrocarbons, such as cyclohexane or parafrins, for example mineral oil fractions, alcohols, such as butanol or glycol as well as their ethers and esters, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, or strongly polar solvents, such as dimethylformamide and dimethylsulphoxide, as well as water.
By liquefied gaseous diluents or carriers are meant liquids which would be gaseous at normal temperature and under norr;al pressure, ~or example aerosol propellants, such as halogenated hydrocarbons as well as butane, propane, nitrogen and carbon dioxide.
As solid carriers there may be used ground natural minerals, such as kaolins, claysJ talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and ground synthetic minerals, such as highly-dispersed silicic acid, alumina and silicates. As solid carriers for granules there may be used crushed and fractionated natural rocks such as calcite, marble, pumice, sepiolite and dolomite, as well aq synthetic granules of inorganic and organic meals, and granules Or organic material such aq sawdust, coconut shells, maize cobs and tobacco ~:254227 stalks.
As emulsifying and/or foam-forming agents there may be used non-ionic and anionic emulsiriers, such as polyoxyethylene-fat'y acid esters, polyoxyethylene-fatty alcohol ethers, ror example alkylaryl polyglycolethers, alkyl sulphonates, alkyl sulphates, aryl sulphonates as well as albumin hydrolysis products. Dispersing agents include, for example, lignin sulphite waste liquors and methylcellulose.

Adhesives such as carboxymethylcellulose and natural and synthetic polymers in the form Or powders, granules or latices, such as gum arabic, polyvinyl alcohol and polyvinyl acetate, can be used in the formula-tions.

It is possible to use colorants such as inorganic pigments, for example iron oxide, titanium oxide and Prussian Blue, and organic dyestuffs, such as alizarin dyestuffs, azo dyestuffs or metal phthalocyanine dyestuffs, and trace nutrients, such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.
The formulations in general contain from O.l to 95 per cent by weight Or active compound~ preferably from 0.5 to 9O per cent by weight.
The active compounds according to the invention may be used in the form of their formulations of the types that are commercially available or in the use forms prepared from these formulations ~ he active compound content of the use forms pre-pared from the formulations of the types that are commerciall~ available can vary within wide ranges.
The active compound concentration of the use forms can be from O.OOOOC)Ol to lOOg by weight of active compound, ~Z54ZZ7 preferably from C.01 to 10% by weight.
The compounds may be employed in a customary manner appropriate for the particular use forms.
When used against pests harmful to health and pests of stored products, the active compounds are distinguished by an excellent residual activity on wood and clay as well as a good stability to alkali on limed substrates.
In the veterinary field, the active compounds accord-ing to the invention may be used in a known manner, such as orally in the form of, for example, tablets, capsules, drenches and granules; dermally by means of, for example, dipping, spraying, pouring-on, spotting-on and powdering; and parenterally, for example by means of injections.

The present invention also provides an arthropodicidal composition containing 2S active ingredient a compound of the present invention in admixture with a solid or liquefied gaseous diluent or carrier or in admixture with a liquid diluent or carrier containing a surface-active agent.
The present invention also provides a method o~
combating arthropods (especially insects or acarids) which comprises applying to the arthropods , or to a habitat thereo~, a compound of the present invention alone or in the form of a composition containing as active ingredient a compound of the present inmention in admixture with a di.luent or carrier.

The present invention also provides a method of freeing or protecting domesticated animals from ecto-parasitical insects or acarids which comprises applyingto said animals a compound according to the present invention, in admixture with a diluent or carrier.

- ~.2S422~

The present invention further provides crops protected from damage by arthropods by being grown in areas in which immediately prior to and/or during the time of the growing a compound of the present invention was applied alone or in admixture wlth a diluent or carrier.
It ~ill be seen that the usual methods of providing a harvested crop may be improvecl by the present invention.
The present invention further provides domesticated animals whenever freed or protected from ectoparasitical insects or acarids by the application to said animals of a compound according to the present invention, in admixture with a diluent or carrier.
The insecticidal and acaricidal activity of the compounds of this invention is illustrated by the follow-ing biotest Examples.
In these Examples, the compounds according tothe present invention are each identified by the number (given in brackets) of the corresponding preparative Example, which will be found later in this specification.

The known comparison compounds are identified as follows:

(A) ( ~ 1 CH ~CH CH3 3 ~ C _ CH3 (B) - ~ ~ 0 ~ CH2-0-C0~ H ~ H3 (C) = ~ CO-O-CH2~ ~

~254Z27 Example A
Phaedon larvae test Solvent: 3 parts by weight Or dimethylformamide Emulsifier: 1 part by weight Or alkylaryl polyglycol ether To produce a suitable preparation of active compound, 1 part by weight cf the active compound was mixed h~ith the stated amour.t of solven~ containing the stated amount Or emulsifier and the concentrate was diluted with water to the desired concentration.
Cabbage leaves (Brassica oleracea) were sprayed wit~. the preparation Or the active compound until dripping wet and were then inrested with mustard beetle larvae (Phaedon-cochleariae).
After the specified periods Or time, the degree Or destruction was determined in %: 100% meant that all Or the beetle larvae had been killed whereas 0%
meant that none Or the beetle larvae had been killed.
The active compounds, the concentrations Or the active compounds, the evaluation times and the results can be seen from the following table:
T a b 1 e A
.
(insects ~hich damage plants) Phaedon larvae test Active Active compound Degree o~ de-compounds concentration in struction in % % after 3 days (A) 0.1 100 O.01 100 0.001 0 (~) 0.1 100 O . 01 90 0.001 0 (2) 0.1 100 0.01 100 O . 001100 ( 10 ) O . 1 100 0.01 100 O.001 100 ~0 (1) 0.1 100 O . 01 100 0.001 100 25422~7 Example B
Myzus test (contact action) Solvent: 3 parts by weight of dimethylformamide Emulsifier: 1 part by weight of alkylaryl polyglycol ether To produce a suitable preparation cf active compound, 1 part by weight of the active compound was mixed with the stated amount of solvent containing the stated amount Or emulsifier and the concentrate was diluted with water to the desired concentration.
Cabbage plants (Brassica oleracea) which had been heavily infested with peach aphids (Myzus persicae) were sprayed with the preparation of the active compound until dripping wet.
Arter the specified periods of time, the degree Or destruction was determined as a percentage: 100 meant that all Or the aphids were killed whereas 0 meant that none of the aphids were killed.
l`he active compounds, the concentrations of the active cGmpounds, the evaluation times and the results can be seen from the following table:
T a b 1 e B
(insects which da~a~e plants) ~ test Active Active compound Degree of de-compounds concentration in struction in % g after 1 day (C) 0.1 50 0.01 (2) 0.1 100 O . 01100 (7) 0.1 100 0.01 90 (10) 0.1 lOG
0.01 90 (11) 0.1 100 0.01 95 (1) O.1 100 O . 01100

(6) 0.1 100 O . 01100 ~" ~2542Z7 Exam~le C
Tetranychus test (resistant) Solvent: 3 parts by weight of dimethylformamide Emulsifier: 1 part by wei~ht Or alkylaryl polyglycol ether To produce a suitable preparation of active compound, 1 part by weight of the active compound was mixed with the stated amount of solvent and the stated amount of emulsifier and the concentrate was diluted with water to the desired concentration.
~ ean plants (Phaseolus vul~aris) which were heavily infested with the two-spotted spider mite ( ~
urticae) in all stages of development were sprayed with the preparation Or the active compound until dripping wet, After the specified periods Or time, the degree Or destruction was determined as a percentage: 100%
meant that all of the spider mites were killed whereas 0~ meant that none o~ the spider mites were killed.

The active compounds, the concentrations of the active compounds, the evaluation times and the results can be seen from the following table:
T a b 1 e C
(Mites which damage plants) Tetranychus test Active Active compound Degree of de-compound concentration struction in in % ~ after 2 davs ., (A) 0.1 0 tC) 0.1 0 (2) 0.1 90 - ~2 -~25~227 T a b 1 e C (continued) (mites which damage plants) Tetranychus test Active Active compound Degree of de-5compound concentration struction in in g % after 2 d~s

(7) 0.1 98 t4) 0.1 9B
(11) 0.1 90 (1) 0.1 98 (6) 0.1 100 Example D
Test with parasitic adult cattle ticks Solvent: alkylaryl polyglycol ether To produce a suitable preparation of an active compound, that compound was mixed with the stated solvent in the ratio of 1:2 and the concentrate thus obtained was diluted with water to the desired concentration.
10 adult cattle ticks (~oophilus microplus res.) were dipped for 1 minute in the preparation of active compound to be tested. After transrerring the ticks into a plastic beaker and keeping them in a climatically controlled chamber, the degree o~ destruction in per cent was de-termined, with 100~ denoting that all of the ticks had been killed and 0% denoting that no ticks had been killed.
The results are shown in the following table.
T a b 1 e D

Active Active compound Degree of de-compound concentration struction in in ppm __ %
(7) 10,000 100 Example E
Test with parasitic fly larvae Emulsirier: 80 parts by weight of alkylaryl glycol ether To produce a suitable preparation of active compound, :L2542~2,7 20 parts by weight of the active compound in question were mixed with the stated amount of the emulsifier and the mixture thus obtained was diluted with water to the desired concentration.
About 20 fly larvae (Lucilia cuprina) were introduced into a test tube which contained about 3 ml of a 20%
strength suspension o~ eg~ yolk powder in water, and which was fitted with a cottonwool plug of appropriate size. 0.5 ml of the active compound preparation was placed on this egg yolk powder suspension. After 24 hours, the degree Or destruction in % was determined.
lC0% meant that all of the larvae had been killed and 0% meant that none of the larvae had been killed.
The active compound, amounts used and results can be seen from the table which follows:

T a b 1 e E
Active Active compound Destructive compound concentration action in in ~Dm %

(2) 1,000 100 ( 10 ) 1, 000 100 Preparative Examples Example 1:

CN

~ H3C ~C~3 7.3 ~ (0.03 mol) of 3~(4-fluorophenoxy)-~-cyanobenzyl alcohol and 8.1 g (0.03 mol) of 2,2-dimethyl-3-(2-phenyl-2-chlorovinyl)-cyclopropanecarboxylic acid chloride were -" ~Z5422~7 dissolved in 150 ml of anhydrous toluene and 2.4 g ~0.03 mol) Or pyri~ine, dissolved in 50 ml of toluene, were added dropwise at 25-30C, whilst stirring. Thereafter, stirring was continued for 3 hours at 25C. The reaction mixture was poured into 150 ml of water and the organic phase WâS separated off and again washed, with 100 ml of water.
The toluene phase was then dried over sodium sulphate and the solvent was distilled off uncler a water-pump vacuum.
The last remnants Or solvent were removed by brief incipient distillation under 1 mm ~g at 60C bath temperature. 12.0 g (~4% of theory) of 3'-(4-fluorophenoxy)-~-cyanobenzyl 2,2-dimethyl-3-(2-phenyl)-2-chlorovinyl)-cyclopropane carboxy-late were obtained asayellow oil having a refractive index n24 of 1.5670.
~xample_2:

0 ~ CH2-0-C0 ~ CH-C ~ (2) 24.3 g (0.05 mol) Or the sodium salt of 2,2-dimethyl-3-(2-phenylthio-2-chlorovinyl)-cyclopropaneCarboxyliC acid were dissolved in 150 ml of dimethylformamide and heated to 120C, together with 15.8 g (o.o6 mol) Or 3-phenoxy~
benzyl bromide for 4 hours. After completion of the reaction, the dimethylformamide was distilled off in vacuo and the residue was taken up in 200 ml o~ methylene chloride. It was then extracted by shaking with twice 150 ml of water, the organic phase was dried over sodium sulphate and t;he solvent was stripped O~r in vacuo. The last remnants Or solvent were removed by brief incipient distillation under 1 mm Hg at 60C bath temperature.

~L254227 15 g (53.8% o~` theory) of 3'-phenoxy-benzyl 2,2-dimethyl-3-(2-phenylthio-2-chlorovinyl)-cyclopropane carboxylate were obtained as a yellow oil having a re~ractive index n23 of 1.5948~
The following compounds could be prepared analogously:

:ILZ5422~7 c ~o ~ ~a~ ~'~

--~ O 0 ~
~ s ~ t_ t~
Q~
.,, c~
o c~

a c~
z,:~:
o~ ~ o~ ~

r~ Z

~X o ~ ~ o _ ~ N~ N~q N~
~ O
~ 0' U~ , ~ ~ ~ ~

~ .
L~ ~ ~ ~ O

~.2S4~ ~

a~
~ ~o ~ o c~ ......... a~
X U~
~a ~ ~ .
a ~ a o Q) ~ S O~
~rl ~ ~1 ~ ~D
o U~

3 ~

E o Z

.` 2 -~ :iL254227 Q) r-v u~ 8 c~ N~a ~ a ~ a o a~
~, ~ ~ ~ o . c~

,~
~ z u~

~25~L2Z7 ~ X
h ~ ~ Q

~S Cl~
:~0 ~ < m~

~ o~ U ~ ~ o, N Z ~ ~N

o~

~:z a~

1 2~;i 42d~7 a~
.~
X

~: , ~o o ~ Q~
.,~

V

b X N t~J N
k~

~S~227 a~

.,, ..
h ~ O
~I;

O
~ .C ~
~ O

~3 U U~a m o o o ~ ~ 0~

O N ~ O

~LZ54ZZ7 a:~
Q~ ~D
C~ . . .`
to X
F~ ~ ..
U~
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~O ~ r~ ~
a) ~ _ ~-1 ~ co J
o a~

rl ~) r~
U I ~

o ~ n U
a~ æ~

r -~ ~4 r~ ) J
x~.

1254~

t`
a~
.,,U~
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a~
..
o ~h ~ O
~a~ 0 ~ ~
~ _ _ ~
a~ ~ ~D
~1 ~HL~
:~ O

E
O ~
1::, 11 11 ~ X~

O
~ C z C~ - O C~- -O ~)- -O
0~

~1 ~0 XZ ~ r~

-~542:Z7 The cyclopropanecarboxylic acids (V), or their salts and acid chlorides (III)required as starting compounds, could be prepared as described below:

/Cl (a) C2~l5o-c ~ CH~C ~
H3C CH3 Cl 2~.3 g (0.1 mol) of 4-chlorobenzyl-phosphonic acid diethyl ester were dissolved in 400 ml of absolute tetra-hydrofuran and the solution was cooled to -70C. 0.11 nmol of n-butyl-lithiun (as a 15~ strength solution in hexane) were added drcpwise under a counter-current of nitrogen and whilst stirring well, and the reaction mix-ture was then stirred ror a further 15 minutes at -70C.
Thereafter, 15.4 g (C.l mol) of carbon tetrachloride were added dropwise at -70C, still under nitrogen; in the course thereof, the reaction mixture assumed a red-brown colour. After stirring for a ~urther 15 minutes, 18.6 g (0.1 nmol) of 2,2-dimethyl-3-formyl-cyclopropanecarboxylic acid etnyl ester were added at -65C. The reaction mix-ture was then allowed to come to room temperature and was stirred for a further 3 hours at 25C. The reaction batch was then poured into 2 litres of water and extracted with 600 n;l of ether. The ether phase was dried over sodium sulphate, the solvent was stripped off in ~acuo and the oily residue was distilled at 150-155C/2 mm Hg. 2,2-Dimethyl-3-~2-chloro-2-p-chlorophenyl-vinyl)-cyclopropane-carboxylic acid ethyl ester was obtained in 54.3% yield.

The follow:ing could be prepared analogously:

~2542Z7 Yield Physical (% of data (re-Formula theory) fractive index;
boiling goint ~
C/mm Hg) , _ _ Cl C2 5 ~ ~ C/ nD3:1,5222 ~2H5-C ~ CH~C ~ Cl 45~4 n25:1,5621 H3C H3 Cl C2H50-C0 ~ CH- ~ 52,7 155-160/1 H3C CH3 Cl C2H50-C0 ~ CH~ ~ 57 n25:1,520~

C2H50-C ~ S ~ -Cl 81 nD5:1,5025 Cl C2H50-C0 ~ CH2C\ 71 nD6:1,5359 (b) C2~5~-C ~ CH=C

22.8 g (0.1 mol) of benzylphosphonic acid diethyl ester were dissolved in 400 ml of absolute tetrahydro-furan and the solution was cooled to -70C. 0.11 mol of n-butyl-lithium (as a :5% strength solution in hexane) were added dropwise under a counter-current of nitrogen and whilst stirring we:l; the mixture was then stirred at -70C for a further 15 minutes, and thereafter 18.6 g (0.1 mol) of 2,2-dimethyl-3-formyl-cyclopropanecarboxylic acid ethyl ester were added dropwise at -65C, again still under nitrogen. The reaction mixture was then allowed to come to room temperature and was stirred further for 3 hours at 25C. Thereafter, the reaction batch was poured into 2 litres of water and extracted with 600 ml of ether.
The ether phase was dried over sodium sulphate and the solvent was then stripped off in vacuo. The oily residue was distilled 2t 145-150C/3 mm Hg. 2,2-Dimethyl-3-(2-phenyl-vinyl)-cyclopropanecarboxylic acid ethyl ester having a refractive index n23 of 1.5022 was obtained in 69.6~ yield.

The following could be prepared analogously:

- ~2~422~7 Yield (~ Yhysical theory) data (re-fractive Formula index;
boilin~
point ~ C/mm _ C2H50-C0 CH~C
H ~H ~Cl 70,2 n25:1,5584 49.6 n25:1,5o57 H

C2H5-C~7CC~I~C~[~3 46 150-155/l 3 ~3 1 The cyclopropanecarboxylic acid ethyl esters pre-pared according to Example (a) or (b) were subjected to acid or alkaline saponification, in accordance with known methods, to give the ~rrespondin~ acids. These were converted, in accordance with methods which are also known, into the corresponding salts (for example alkali metal salts or ammonium salts) or acid chlorides.

Claims

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. A 3-phenoxybenzyl 2,2-dimethyl-3-vinyl-cyclopropane carboxylate of the formula (I) in which R, R1 and R2 are the same or different and each independ-ently is hydrogen or halogen, but R and R1 cannot both be hydrogen, R3 is phenyl, phenylthio, or phenyl or phenylthio carrying at least one alkyl group or halogen atom, Y is hydrogen or cyano, n is 1, 2, 3, 4 or 5, and m is 1, 2, 3 or 4.

2. A carboxylate according to claim 1, in which R and R1 each independently is hydrogen or fluorine, R2 is hydrogen, chlorine or bromine, R3 is phenyl, phenylthio, halogenophenyl or C1-6-alkylphenyl, and Y is hydrogen or cyano.

3. 3'-(4-Fluorophenoxy)-.alpha.-cyanobenzyl 2,2-dimethyl-3-(2-phenyl-2-chlorovinyl)-cyclopropane carboxylate of the formula (I) 4. 3'-(4-Fluorophenoxy)-.alpha.-cyanobenzyl 2,2-dimethyl-3-[2-(4-chlorophenyl)-2-chlorovinyl] -cyclopropane carboxylate of the formula 3'-Phenoxy-4'-fluoro-.alpha.-cyanobenzyl 2,2-dimethyl-3-[2-(4-chlorophenyl)-2-chloroviny] -cyclopropane carboxylate of the formula 6. A method of combating arthropods which comprises applying to the arthropods, or to a habitat thereof, an arthro-podicidally effective amount of a carboxylate according to claim 1.

7. A method according to claim 6 wherein the carboxylate is applied in admixture with a suitable diluent or carrier.

8. A method according to claim 6 or 7 wherein the carboxylate is 3'-(4-fluorophenoxy)-.alpha.-cyanobenzyl 2,2-dimethyl-3-(2-phenyl-2-chlorovinyl)-cyclopropane carboxylate.

9. A method according to claim 6 or 7 wherein the carboxylate is 3'-(4-fluorophenoxy)-.alpha.-cyanobenzyl 2,2-dimethyl-3-[2-(4-chlorophenyl)-2-chlorovinyl] -cyclopropane carboxylate.

10. A method according to claim 6 or 7 wherein the carboxylate is 3'-phenoxy-4'-fluoro-a-cyanobenzyl 2,2-dimethyl-3-[2-(4-chlorophenyl)-2-chlorovinyl] -cyclopropane carboxylate.

11. A method of freeing or protecting domesticated animals from ectoparasitical insect or acarid pests which comprises applying to said animals a carboxylate of formula (I) as defined in claim 1, in admixture with a suitable diluent or carrier.

12. A method according to claim 7 or 11 in which a composition is used containing from 0.01 to 10% of the carboxylate, by weight.

13. A method according to claim 7 or 11 in which the carboxylate is the compound of claim 3.

14. A method according to claim 7 or 11 in which the carboxylate is the compound of claim 4.

15. A method according to claim 7 or 11 in which the carboxylate is the compound of claim 5.

16. A process for the preparation of a carboxylate of formula (I) as defined in claim 1, in which (a) a phenoxybenzyl alcohol of the general formula (II) in which R, R1, Y, n and m have the meanings stated in claim 1, is reacted with a cyclopropanecarboxylic acid derivative of the general formula (III) in which R2 and R3 have the meanings stated in claim 1 and R4 represents halogen or C1-4 alkoxy, or (b) a phenoxybenzyl halide of the general formula (IV) in which R, R1, Y, n and m have the meanings stated in claim 1 and Hal represents halogen, is reacted, with a cyclopropanecarboxylic acid derivative of the general formula (V) in which R2 and R3 have the meanings stated in claim 1, the latter being employed in the form of an alkali metal salt, alkaline earth metal salt or ammonium salt or as such in the presence of an acid acceptor.

17. A process for the preparation of the compound of claim 3 which comprises (a) reacting 3'-(4-fluorophenoxy)-.alpha.-cyanobenzyl alcohol with a 2,2-dimethyl-3-(2-phenyl-2-chlorovinyl)-cyclopropane carboxylic acid halide or (C1-4) alkyl ester, or (b) reacting a 3'-(4-fluorophenoxy)-.alpha.-cyanobenzyl halide with 2,2-dimethyl-3-(2-phenyl-2-chlorovinyl)-cyclopropane carboxylic acid in the presence of an acid acceptor, or with an alkali metal, alkaline earth metal or ammonium salt of such carboxylic acid.

18. A process for the preparation of the compound of claim 4 which comprises (a) reacting 3'-(4-fluorophenoxy)-.alpha.-cyanobenzyl alcohol with a 2,2-dimethyl-3-[2-(4-chlorophenyl)-2-chlorovinyl]-cyclopropane carboxylic acid halide or (C1-4) alkyl ester, or (b) reacting a 3'-(4-fluorophenoxy)-.alpha.-cyanobenzyl halide with 2,2-dimethyl-3- [2-(4-chlorophenyl)-2-chlorovinyl]-cyclopropane carboxylic acid in the presence of an acid acceptor, or with an alkali metal, alkaline earth metal or ammonium salt of such carboxylic acid.

19. A process for the preparation of the compound of claim 5 which comprises (a) reacting 3'-(phenoxy-4'-fluoro)-.alpha.-cyano-henzyl alcohol with a 2,2-dimethyl-3-[2-(4-chlorophenyl)-2-chloro-vinyl] -cyclopropane carboxylic acid halide or (C1-4) alkyl ester, or (b) reacting a 3'-(phenoxy-4'-fluoro)-.alpha.-cyanobenzyl halide with 2,2-dimethyl-3-[2-(4-chlorophenyl)-2-chloroviny] -cyclopropane carboxylic acid in the presence of an acid acceptor, or with an alkali metal, alkaline earth metal or ammonium salt of such carboxylic acid.