FR2494266A1 - BENZYL ESTER SUBSTITUTED WITH 2,2-DIMETHYL-3- (2,2-DIHALOVINYL) CYCLOPROPANECARBOXYLIC ACID, PESTICIDAL COMPOSITION CONTAINING THE ESTER AS AN ACTIVE INGREDIENT AND METHOD OF USING THE ESTER AS A PESTICIDE - Google Patents

Abstract

The invention relates to novel pyrethroid compounds, to pesticidal agents comprising the latter as active ingredients, and to a method of controlling pests. The pyrethroid compounds can effectively be used for controlling pests which occur in rice cultures, as well as the brown leaf hopper (Nilaparvata lugens Stal), the smaller brown leaf hopper (Laodelphax striatellus Fallen) and the green rice leaf hopper (Nephotettix cincticeps Uhler), which transmit virus diseases of rice plants. The pyrethroid compounds consist of an alpha -ethynylbenzyl ester of a 2,2-dimethyl-3-(2,2-dihalovinyl)cyclopropanecarboxylic acid, where it is possible for the ring to have a substituent selected from the group comprising halogen, nitro, methyl and trifluoromethyl. In contrast to the pyrethroids known from the prior art, the compounds according to the invention are distinguished by an outstanding activity against leaf hoppers.

Description

dans laquelle X est un atome d'halogène et R est un atome d'hydrogène, un atome d'halogène ou un radical nitro, méthyle ou trifluorométhyle.L'invention est également relative à une composition pesticide contenant ce composé en tant que principe actif et à un procédé de destruction d'organismes nuisibles mettant en oeuvre ce composé pyréthrolde. Substituted benzyl ester of 2,2-dimethyl-3- (2,2-dihalobinyl) cyclopropanecarboxylic acid, pesticidal composition containing this ester as active ingredient and method of using this ester as a pesticide
The invention relates to a novel pyrethroid compound, namely a 2,2-dimethyl-3- (2,2-dihalovinyl) cyclopropanecarboxylic acid substituted benzyl ester, represented by formula (I):

in which X is a halogen atom and R is a hydrogen atom, a halogen atom or a nitro, methyl or trifluoromethyl radical.The invention also relates to a pesticidal composition containing this compound as active principle and a method of destroying harmful organisms using this pyrethroid compound.

Viral diseases of rice include dwarfism, rice streak disease, black-spot dwarfism and yellow dwarfism, caused by viruses transmitted by green leafhopper rice and brown fungus and the mosaic is also known necrotic caused by soil infection. The stunting of rice, which has been reported to predominate in rice growing areas in tropical regions and Asia, is also due to a disease whose virus is harvested by brown fulgoridae. Rice fields attacked by stunting produce low quality rice.To prevent the occurrence and spread of such viral diseases, it is necessary to control over time harmful organisms such as brown fulgoridae, brown fungus and green leafhopper that are virus causing these diseases. However, no currently available pesticide can be effective for brown fungus. So far, no pesticide has been found to be able to act vigorously and effectively on these virus-carrying pests.

Certain benzyl esters of 2,2-dimethyl-3- (2,2-dichlorovinyl) -cyclopropanecarboxylic acid are known. For example, Japanese Patent Application No. 35,332 / 80 discloses a general formula which covers α-substituted or unsubstituted benzyl esters having on the benzene ring a lower alkyl, lower alkenyl, cycloalkenyl, lower alkynyl, benzyl or phenoxy radical. or a halogen atom or halogen atoms.However, the 3-propargyl-α-ethynylbenzyl ester, the 3-allyl-α-ethynylbenzyl ester and the 3,4-dichloro-α-ethynylbenzyl ester (Compound (A) cited below by its structural formula) are the only compounds specifically described which have on the benzene ring an aliphatic hydrocarbon radical or halogen atoms.

Among the other known benzyl esters of cyclopropanecarboxylic acid there may be mentioned Compounds (B), (C), (D), (E), (F), (G), (H), (J), (K) and (L) shown below.

However, the pesticidal activity of each of these compounds is unsatisfactory so that they can be used in practice (see Japanese Patent No. 28,103 / 71, Japanese Patent Application No. 28,632 / 73, Japanese Patent Application
No. 45 674/80 and the Report of the 5th Meeting of Nippon
Noyaku Gakkai (Society of Pesticide Science in Japan)
No. 115.

hereinafter referred to
Compound (A) hereinafter referred to
Compound (B) hereinafter referred to
Compound (C), hereinafter referred to as
Compound (D) hereinafter referred to as
Compound (E) hereinafter referred to as
Compound (F) hereinafter referred to
Compound (G) hereinafter referred to
Compound (H) hereinafter referred to
Compound (J) hereinafter referred to as
Compound (K) hereinafter referred to
Compound (L) It is an object of the invention to provide a new pyrethroid-type compound, more exactly a benzyl ester substituted with a 2,2-dimethyl-3- (2, 2-dihalovinyl) cyclohexyl propanecarboxylic acid, represented by the general formula (I) above, which, applied to rice crops, can effectively regulate the population of pests such as Brown Flycatcher, Lesser Brown Flycatcher and Green Rice Leafhopper, organisms carrying virus causing viral diseases on the rice crop, further provide a pesticidal composition containing this pyrethroid-type compound as the active ingredient and also provide a method for reducing to an acceptable level the population of these pests Another object of the invention is to provide a substituted benzyl ester of general formula (I) which is clearly superior from the point of view of its production. insecticidal activity with regard to the various harmful organisms, compared to the benzyl esters of cyclopropanecarboxylic acid known until now.

Another object of the invention is to provide a substituted benzyl ester represented by the general formula (I) which can be produced at lower cost than the usual pyrethroids, more specifically permethrin and fenvalerate.

The Applicant has found that the substituted benzyl esters of a 2,2-dimethyl-3- (2,2-dihalovinyl) cyclopropanecarboxylic acid, which are represented by the general formula (I), are very effective against fulgorids such as brown and small brown fulgorid, this being demonstrated by utility examples 1 and 2 reported below.
This discovery is quite surprising in view of the fact that existing pyrethromes, specifically permethrin and fenvalerate, have virtually no useful activity against fulgorids.

The substituted benzyl esters of the general formula (I) exert excellent pesticidal effects, not only with regard to the organisms harmful to rice growth, carriers of the viruses causing diseases on the rice crop, but also with regard to pests in agriculture, horticulture or forests that damage paddy (unshelled rice), dry field crops, cotton, fruit trees, forest trees, etc. They have excellent pesticidal effects also with regard to organisms harmful to grains in storage and to domestic organisms. More particularly, the substituted benzyl esters of general formula (I) exert an excellent pesticidal activity against susceptible and resistant strains of pests belonging to the following orders (they are effective against these organisms during all their stages of growth or at least during some of these stages)
Order of THYSANOURES: for example, Ctenolepisma villosa
Escherich;
Order COLLEMBOLA: for example, Anurida trioculata
Kinoshita, Onychiurus pseudarmatus Miyoshi yagii, Sminthurus viridis Linnaeus, Bourletiella hortensis Fitch;
Order of ORTHOPTERES: eg Northern Grasshopper (Homorocoryphus jezoensis Matsumura and Shiraki), Grasshopper Grasshopper (P. sapporensis Shiraki), Field Cricket
Emma (Teleogryllus emma Ohmachi and Matsuura), Doenitz cricket (Loxoblemmus doenitzi Stein), cockroach (Blattella germanica
Linnaeus), Gryllotalpa africana Palisot of Beauvois, Periplaneta fuliginosa Servile;
Order of ISOPTERES: for example, Coptotermes formosanus
Shiraki;
Order of MALLOPHAGA: for example, Menopon gallinae Linnaeus,
Damalinia equi Denny, Trichodectes canis De Geer;
Order of ANOPLURA: for example, Haematopinus eurysternus
Nitzsch;
Order of THYSANOPTERES: for example, tobacco and onion thrips (Thrips tabaci Lindeman), Hercinothrips femoralis
Reuter;
Order of HEMIPTERES: for example, white-backed fulgoridae (Sogatella furcifera Horvàth), brown fulgoridae (Nilaparvata lugens Stál), brown felugidae (Lacdelphax striatel lus Fallén), green leafhopper (Nephotettix cinct - Uhler vines), striped leafhopper in zigzag (Inazuma dorsalis
Motschulsky), black rice bugs (Scotinophara lurida Burmeisterj, rice pentatomids (Lagynotomus elongatus
Dallas), rice stink bug (Leptocori.xa corbetti China), Nezara (liezara viridula Linné), cereal aphid (Rhopalosiphum padi Linné), Japanese cereal aphid (Macrosiphum akebiae Shinji), corn aphid (Rhopalosiphum maidis Fitch), aphid peach tree (Myzus persicae Sulzer), cotton aphid (Aphis gossypii Glover), geranium aphid (Aulacorthum solani Kaltenbach), soybean aphid (Aphis glycines Matsumura), small bean aphid (Chauliops fallax Scott), bean aphid ( Riptortus clavatus Thunberg), common Nezara (Nezara antennata Scott), Piezodorus rubrofasciatus Fabricius, blackthorn bunt (Dolycoris baccarum Linné), eastern lygeid (Cavelerius saccharivorus kajima), sugar cane aphid (Ceratovacuna lanigera
Zehntner), white cabbage aphid (Brevicoryne brassicae Linné), green stink bug (Lygus lucorum Meyer-Dürs, onion aphid (Neotoxoptera formosana Takahashi), dwarf mealybug (Unaspis yanonensis Kuwana), red
California (Aonidiella aurantii Maskell), vine phylloxera (Viteus vitifolii Fitch), grapevine leafhopper (Erythroneura apicalis Nawa), whitefly grapevine (Kuwana Aleurolobus taonabac), Kuwana kunoense eunuchus, chrysanthemum aphid (Macrosiphoniella sanborni Gillette) rose-bush aphid (Macrosiphum ibarae Matsumura), azalea stink bug (Stephanitis pyrioides Scott), fern mealybug (Pinnaspis aspidistrae Signoret);
Order of TRICHOPTERES: for example, Oecetis nigropunctata
Ulmer;
Order of Diptera: for example, rice maggot (Chlorops oryzae Matsumura), rice miner (Agromyza oral Munakat), small rice miner (Hydrellia griseola Failén), wild rice fly (Hydrellia sasaki Yuasa and Ishitani), wheat maggot lMeromY3a saltatrix Linnaeus), miners, wheat midge (Sitodiplosis mosellana Géhin) 1 soybean squeegee (Melanagromyza dolichostigma DE Meijere), soybean midge (Profeltiella soya Monzen), soybean leafminers (Melanagromyza sojae Zehntner), midge midge (Aspondylia sp.), gray seedling fly (Hylemya platura Meigen), onion maggot (Hylemya antiqua
Meigen), leek miner (Phytobia cepae Hering), narcissus fly (Lampetia equestris Fabricius), common fly (Musca domestica vicina), common cousin (Culex pipiens);
Order of APHANIPTERES: for example, Xenopsylla cheopis
Rothschild, Pulex irritans Linnaeus;
Order of the HYMENOPTERES: for example, Dolerus hordei Rohwer, soybean holocampus (Takeuchiella pentagona Malaise);
Order of LEPIDOPTERS: eg, rice stem borers (Chilo suppressalis Walker), yellow rice borer (Tryporyza incertulas Walker), Sesamia inferens Walker, Pelopidas mathias oberthüri Evans, grass budworm (Cnaphalocrocis medinalis Guéée), leafroller rice (Susumia exigua Butler), green rice caterpillar (Naranga aenescens Moore), armyworm (Leucania separata Walker), Ostrinia furvacalis Guénée, sweet potato budworm (Brachmia triannulella Herrich-SchaLfer), leaf bindweed (Bedellia sommulentella)
Zeller), sweet potato leaf worm (Aedia leucomelas
Linnaeus), leafminer (Heliothis viriplaca adaucta Butler), tobacco striped caterpillar (Pyrrhia umbra
Hufnagel), bean caterpillar (Syllepte ruralis Scopli),
Grapholita glycinivorella Matsumura, Matsumuraeses phaseoli
Matsumura, boring lima bean sprouts (Etiellazinckenella Treitschke), borer of oriental tobacco buds (Helicoverpa assulta Guénée), Pyrausta aurata
Scopoli, peacock butterfly, lilac moth (Margaronia nigropunctalis Bremer), stemming of sugar cane roots (Eucosma schistaceana Snellen), cabbage worm (Mamestra brassicae Linné), tobacco agrotis (Plodenia litura Fabricius), common cutworm ( Agrotis fucosa Butler), stonewort (Pieris rapae crucivora Boisduval), cruciferous caterpillar (Mesographe forficalis Linné), cruciferous moth (Plutella maculipennis Curtis), cotton caterpillar (Margaronia indica)
Saunders), Acrolepia alliella Semenov and Kuznetsov, orange borer (Phyllocnistis citrella Stainton), Papilio xuthus Linnaeus, Carposina niponensis Walsingham, Oriental fruit moth (Grapholitha molesta Buszk), summer fruit berry moth (Adoxophyes orana Fischer von Röslerstamm ), bombyx disparate (Lymantria dispar Linnaeus), malacosome (Malacosoma neustria testacea Notschulsky), berry moth (Stenoptilia vitis Sasaki), Stathmopoda flavofasciata
Nagano, white caterpillar (Yphantria cunca Drury), Rusidrina depravata Butler, Pectinophora gossypiella;
Order of the COLEOPTERES: for example, rice galetuque (Oulema.

oryzae Kuwayama), large 28-spotted ladybug (Henosepilachna vigintioctomaculata Motschulsky), 28-spotted ladybug <H. vigintioctopunctata Fabricius), melon weevil (Atrachya menetriesi Faldermann), two-striped gallerum (Paraluperodes nigrobilineatus Motschulsky), bean berry leaflet <Colposcelis signata Motschulsky), bean bean (Eugnathus distinctus Roelofs), Maladera castanea Arrow, soy bean (Anomala rufocuprea Motschulsky), bean sweetmeat (Epicauta gorhami Marseul), mint galley (Chrysolina exanthematica Wiedemann), olive weevil tHylobius cribripennis Matsumura and Kono), vegetable weevil (Listroderes obliquus Klug), cucumber gallerus 5Aulacophora femoralis Motschulsky), Anthonomus grandis Boh., rice weevil (Sitophilus zeamais Motschulsky), rice water weevil (Lissorhoptrus oryzophilus), grain capuchin (Rhizopertha dominica Fabricius), Callosobruchus chinensis
Linnaeus, chrysomata of watercress (Phaedon cochleariae Fab.),
Order of the ACARIANS: for example1 Penthaleus major Dugès; spotted spider (Tetranychus urticae Koch), red spider (Tetranychus telarius Linné) and the like.

The substituted benzyl esters of the general formula (I) have, with respect to the various harmful or parasitic organisms mentioned above, a pesticidal activity which is very much higher than that of the benzyl cyclopropanecarboxylic acid esters known and mentioned above.

dans laquelle R' est un atome d'hydrogène ou un radical nitro ou trifluorométhyle en position méta- ou para- du noyau benzénique, ont une activité insecticide puissante.Among the substituted benzyl esters of general formula (I), the preferred compounds from the point of view of pesticidal activity are those in which R is a hydrogen atom or a halogen atom or a nitro, methyl or trifluoromethyl radical, the substituent R being in the meta- or para position on the benzene ring. In particular, 2,2-dimethyl-3- (2,2-dichloro-vinyl) cyclopropanecarboxylic acid substituted benzyl esters represented by the general formula

wherein R 'is a hydrogen atom or a nitro or trifluoromethyl radical in the meta- or para- benzene ring position, have a potent insecticidal activity.

Other characteristic features of the substituted benzyl esters of the general formula (I) are (1) a high vapor pressure despite good volatility or vaporization, (2) a fast acting effect, (3) a high stability to light or oxidation which, nevertheless, does not lead to environmental residue problems such as those encountered with organochlorine pesticides and, (4) very low toxicity to man and cattle.

In addition, among the substituted benzyl esters of general formula (I), the 4-chloro-α-ethynylbenzyl ester and the 4-trifluoromethyl-α-ethynylbenzyl ester of a trans-2,2-dimethyl-3- acid ( 2,2-dihalovinyl) cyclopropanecarboxylic acid have a characteristic low toxicity to fish at the same time.

Typical examples of substituted benzyl esters of the general formula (I) are given below. These esters include geometric isomers due to different configurations in the acid portion as well as optical isomers due to asymmetric carbon atoms in the acid and alcohol moieties.

<tb> Composite <SEP> Basic SEP Analysis
<tb><SEP> No <SEP> Structural <SEP> Formula <SEP> Found <SEP> (%) <SEP> Calculated <SEP> (%)
<tb><SEP> C
<tb><SEP> C = CH <SEP> C: <SEP> 63.10 <SEP> 63.17
<tb> (1) <SEP> C <SEP><SEP> H: <SEP> 5, u2 <SEP> H: <SEP>, uo <SEP> 4.99
<tb> (2) <SEP>Cl'C = CH <SEP> NO2 <SEP> C: <SEP> 55.36 <SEP> 55.45
<tb><SEP> Cl7COOC1H \ <SEP> H: <SEP> 4.06 <SEP> 4.11
<tb> (3) <SEP> Br <SEP> NO2 <SEP> 2 <SEP> C: <SEP> 44.52 <SEP> 44.67
<tb><SEP> Br <SEP> COOCH <SEP> U <SEP> H: <SEP> 3.24 <SEP> 3.31
<tb><SEP> 4 <SEP> A <SEP> = CH <SEP> NO2 <SEP> C: <SEP> 60.77 <SEP> 60.90
<tb><SEP> (4) COO <SEP> Q <SEP> H <SEP> H: <SEP> 4.55 <SEP> 4.51
<tb><SEP> Cl, <SEP> = CH <SEP> C: <SEP> 55.52 <SEP> 55.45
<tb> (5) <SEP> / <SEP> COOCH <SEP> bi <SEP> H: <SEP> 4.00 <SEP> 4.11
<tb><SEP> C1
<tb> 6 <SEP> BM <SEP> C- = CH <SEP> C: <SEP> 44.52 <SEP> 44.67
<tb><SEP> (6) <SEP> bu <SEP><<SEP> COOCH <SEP> o <SEP> {2 <SEP> H: <SEP> 3.29 <SEP> 3.31
<tb><SEP> Cl
<tb><SEP> CCH <SEP> iX <SEP> CCK <SEP> CF <SEP> C: <SEP> 55-, 30 <SEP> 55.26
<tb> C1- <SEP><SEP> COOCH <SEP> 4 <SEP> H: <SEP> 3.96 <SEP> 3.86
<tb><SEP>, C1
<tb> (8) <SEP> sr- <SEP> X <SEP> j <SEP> mCH <SEP> C: <SEP> 55.34 <SEP> 55.26
<tb><SEP> H: <SEP> aOOCH73 <SEP> H: <SEP> 3.90 <SEP> 3.86
<tb> (9) <SEP><H9F3<SEP> C <SEP> 45.17 <SEP> 45, a3
<tb><SEP> Br <SEP> GOCH <<SEP> 3.08 <SEP> 3.15
<Tb>

<tb><SEP> Br
<tb><SEP> Br \ <SEP> X <SEP> C-CH <SEP> C <SEP>: <SEP> 45.15 <SEP> 45.03
<tb> (10) <SEP> BrS <SEP><<SEP> C = CH <SEP> C <SEP> F3 <SEP> H <SEP>: <SEP> 45.15 <SEP> 45.03
<tb>Br'COOHF3<SEP> H <SEP>: <SEP> 3.21 <SEP> 3.15
<tb> (11) <SEP> C-CH <SEP> CF3 <SEP> C <SEP>: <SEP> 60.26 <SEP> 60.34
<tb><SEP> d <SEP> H <SEP> rgd45 <SEP>: <SEP> 4.25 <SEP> 4.22
<tb><SEP> F
<tb> (12) <SEP> F <SEP> 1 = CH <SEP> C <SEP>: <SEP> 60.30 <SEP> 60.34
<tb><SEP> Ft <SEP> OOCH <SEP> b <SEP> F3 <SEP> H <SEP>: <SEP> 4.27 <SEP> 4.22
<tb><SEP> C1 <SEP> CCH <SEP><SEP> C <SEP>: <SEP> 57.07 <SE> 57.09
<tb> (13) <SEP> C <SEP> OOA <SEP> H <SEP>: <SEQ> 4.18 <SEP> 4.23
<tb><SEP> C <SEP> e
<tb> (14) <SEP> C <SEP>><SEP> CH <SEP> 4 <SEP> H <SEP>: <SEQ> 4.48 <SEP> 4.43
<tb> (15) <SEP> C <SEP><SEP> Y <SEP><SEP> C <SEP>: <SEP> 50.83 <SEP> 50.78
<tb><SEP> Cl <SEQ> LOOCH <SEP> H <SEP>: <SEQ> 3.81 <SEQ> 3.76
<tb> (16) <SEP> FH <SEP> 5 ': <SEP> / 1 <SEP> C <SEP> CtI <SEP>: <SEP> 45.57 <SEP> 45.46
<tb><SEP> C <SEP> COOCE <SEP> H <SEP>: <SEP> 3.43 <SEP> 3.37
<tb><SEP>B'C = CHl <SEP> 45.79 <SEP> 45.72
<tb> (17) <SEP> C-CH <SEP> HC <SEP> C <SEP>: <SEP> 45.79 <SEP> 45.72
<tb><SEP> -COOc, 9s <SEP> H: <SEP> 3.34 <SEP> 3.38
<tb><SEP> (18) <SEP> BX <SEP> X <SEP> ICc = <SEP> t <SEP> C <SEP>: <SEP> 47.41 <SEP> 47.47
<tb><SEP> Br <SEP> OOH <SEP> H <SEP>: <SEP> 3.45 <SEP> 3.52
<Tb>

<tb> (19) <SEP> 9 <SEP> w <SEP> C <SEP>: <SEP> 41.48 <SEP> 41.58
<tb><SEP> B <SEP><SEP> X <SEP>: <SEP> 3.02 <SEP> 3.08
<tb><SEP> Br
<tb> (20) <SEP> r <SEP> ~ Y <SEP> I <SEP> C <SEP> C <SEP> 62.85 <SEP> 62.87
<tb><SEP> F <SEP> 1
<tb><SEP> F <SEP> OOCH <SEP> H <SEP>: <SEQ> 4.60 <SEQ> 4.66
<tb><SEP> F
<tb> (21) <SEP> 1 = -CH <SEP> F <SEP> C <SEP>: <SE> 66.28 <SEP> 66.23
<tb><SEP> F - OOCH <SEP> H <SEP>: <SEQ> 4.95 <SEP> 4.90
<tb> (22) <SEP><SEP> ss <SEP> FC1 = CHr <SEP> C <SEP> 55.42 <SEP> 55.30
<tb><SEP> F <SEP> V <SEP> \ <SEP> COOCH <SEP> t <SEP> H <SEP>: <SEP> 4, D4 <SEP> 4.10
<tb><SEP> C <SEP> \
<tb> (23) <SEP> 1 = CH <SEP> C <SEP> 57.13 <SEP> 57.09
<tb><SEP> ClCOOCHl <SEP> H <SEP>: <SEQ> 4.29 <SEP> 4.23
<tb><SEP> Cl <SEP>
<tb><24)<SEP> X <SEP> X <SEP> Ç = CH <SEP> fCH3 <SEP> C <SEP>: <SEP> 64.08 <SEP> 64.11
<tb><SEP> Cl <SEP> CO <SEP> H <SEP> H <SEP>: <SEQ> 5.44 <SE> 5.38
<tb><SEP> C1 <SEP> \ <SEP> /
<tb> (25) <SEP> 5C1 = -CH <SEP> C <SEP>: <SEP> 64.06 <SEP> 64.11
<tb><SEP> Cl <SEP> COOCHH3 <SEP> H <SEP>: <SEP> 5.30 <SEP> 5.38
<tb><SEP> Br
<tb><SEP>'L<SEP>
<tb> (26) <SEP> u <SEP> = = CH <SEP> CH3 <SEP> C <SEP>: <SEP> 5D, B2 <SEP> 50.73
<tb><SEP>B;<SEP> H <SEP> COO &<SEP>:<SEP> 4.31 <SEQ> 4.26
<tb><SEP> 3r
<tb> (27) <SEP> t <SEP> C-CH <SEP> C <SEP>: <SEP> 50.68 <SEP> 50.73
<tb><SEP> Br <SEP> COOH \ H3 <SEP> H <SEP>: <SEQ> 4.18 <SEQ> 4.26
<Tb>

<tb><SEP> F <SEP> CH <SEP> CH <SEP> C: <SEP> 71.13 <SEP> 71.04
<tb> (28) <SEP> Fy <SEP> CCH <SEP> CH3 <SEP> C: <SEP> 71x13 <SEP> 71.04
<tb><SEP> Ir / <SEP>"3
<tb> (29) <SEP> F) <SEP> CiCH <SEP> C: <SEP> 70.98 <SEP> 71.04
<tb><SEP> F <SEP> COOCH <SEP> b <SEP> H3 <SEP> H: <SEP> 5.92 <SEP> 5.96
<Tb>

dans laquelle R a la même signification que dans la formule générale (I), ou un dérivé fonctionnel de cet alcool avec un acide carboxylique de formule générale

dans laquelle X a la même signification que dans la formule générale (I), ou avec un dérivé fonctionnel de cet acide.The substituted benzyl ester of general formula (I) can be easily prepared by reacting a substituted benzyl alcohol of formula

in which R has the same meaning as in general formula (I), or a functional derivative of this alcohol with a carboxylic acid of general formula

wherein X has the same meaning as in general formula (I), or with a functional derivative of this acid.

Functional derivatives of substituted benzyl alcohol include halides and arylsulfonates. The functional derivative of the carboxylic acid is, for example, a lower alkyl ester, an acid halide, an acid anhydride, an alkali metal salt, a silver salt, or a salt with an organic base. tertiary. Typical embodiments of the above preparation process are described below (Method a) - Reaction of alcohol with a halide
of carboxylic acid.

dans laquelle X a la même signification que dans la formule (I) et X' est un atome d'halogène, de préférence avec un -chlorure d'acide carboxylique, dans un solvant inerte (par exemple benzène, toluène, éther, hexane, chloroforme), en présence d'une amine tertiaire (par exemple pyridine, triéthylamine) en une quantité de 1 à 3 équivalents molaires par mole de l'alcool benzylique substitué, à température ambiante ou en chauffant, de façon à obtenir l'ester benzylique substitué désiré.The substituted benzyl alcohol of formula (II) is reacted with a carboxylic acid halide of general formula

in which X has the same meaning as in formula (I) and X 'is a halogen atom, preferably with a carboxylic acid chloride, in an inert solvent (for example benzene, toluene, ether, hexane, chloroform), in the presence of a tertiary amine (for example pyridine, triethylamine) in an amount of 1 to 3 molar equivalents per mole of the substituted benzyl alcohol, at room temperature or by heating, so as to obtain the benzyl ester substituted substituted.

(Method b) - Reaction of alcohol with an anhydride
of carboxylic acid.

dans laquelle X a la même signification que dans la formule générale (I), dans un solvant inerte, (par exemple benzène, toluène, xylène, hexane ou acétone); de préférence en présence d'un acide (par exemple l'acide sulfurique, l'acide p-toluènesulfonique) ou d'une amine tertiaire (par exemple pyridine, triéthylamine), à température ambiante ou en chauffant, pour fournir l'ester benzylique substitué désiré.The substituted benzyl alcohol of formula (with a carboxylic acid anhydride of general formula

wherein X has the same meaning as in general formula (I), in an inert solvent (for example benzene, toluene, xylene, hexane or acetone); preferably in the presence of an acid (for example sulfuric acid, p-toluenesulfonic acid) or a tertiary amine (for example pyridine, triethylamine), at room temperature or by heating, to provide the benzyl ester substituted substituted.

(Method c) - Reaction of the alcohol with a carboxylic acid e
The substituted benzyl alcohol of formula (II9) is reacted with the carboxylic acid of general formula (III) in an inert solvent (for example benzene, toluene, xylene), in the presence of a dehydration / condensation agent (for example dicyclohexylcarbodiimide, 2-chloro-1-methylpyridinium iodide plus triethylamine), at room temperature or under heating, to obtain the desired substituted benzyl zester.

(Method d) - Reaction of the alcohol with an alkyl ester
lower of the carboxylic acid.

The substituted benzyl alcohol of formula (II) is reacted with a lower alkyl ester of the carboxylic acid of general formula (III) in the presence of an appropriate ester exchange catalyst (for example alkali metal alcohol, sodium hydride, titanium compound such as tetramethyl titanate), by heating in an inert solvent (eg toluene, xylene), and extracting from the reaction system the low boiling alcohol which is formed by means of a fractionation column, to obtain the desired substituted benzyl ester.

(Method e) - Reaction of a halide or an arylsulfonate
of alcohol with an alkali metal salt of acid
carboxylic acid.

A halide or arylsulphonate of the substituted benzyl alcohol of formula (II) is reacted with an alkali metal salt of the carboxylic acid of general formula (III) in a solvent (for example dimethylformamide, benzene, acetone) at room temperature. ambient or under heating, to obtain the desired substituted benzyl ester.

The substituted benzyl alcohol of formula (II), i.e. the alcohol component, can be prepared easily and at low cost, in accordance with the following reaction scheme

<tb><SEP> R <SEP> CCft, <SEP> C = C
<tb> OHC <SEP> U <SEP>><SEP> HO-CH <SEP> U
<tb><SEP> (IV) <SEP> (He)
<tb> wherein R has the same meaning as in the general formula (I).

Thus, a substituted benzaldehyde of formula (IV) is ethynylated with sodium acetylide in ammonia as a solvent, or with ethylmagnesium bromide or ethynyllithium in tetrahydrofuran as a solvent, for provide the substituted benzyl alcohol of formula (II).

On the other hand, 2,2-dimethyl-3- (2,2-dihalovinyl) cyclopropanecarboxylic acid, i.e. the acid component, or lower alkyl esters thereof are known in the art, and the derivatives The functional groups mentioned above may be prepared from a lower alkyl ester of the corresponding carboxylic acid in the usual manner.

In practice, the compound of the invention can be used as it is, without the addition of any other ingredient. However, to facilitate its use as a pesticide, it is generally convenient to formulate it with a carrier and to apply the resulting composition, if necessary after adequate dilution.For the preparation of the composition, the compound of the invention is mixed according to usual methods with a carrier in the form of a liquid, a solid or a liquefied gas, optionally using a surfactant which serves as an emulsifying and / or dispersing agent and / or foaming agent to provide any desired composition in the form of an emulsifiable concentrate, a wettable powder, powder, granules, micro-granules, oily preparation, aerosol, thermal fumigant (by for example, smoke coil, electric smoke cloth), fog, non-thermal smoke or partridge for example. The composition may be selectively applied depending on the intended use thereof. When water is used as a carrier, for example an organic solvent may be used as a co-solvent or auxiliary solvent.

Suitable liquid carriers in most cases include aromatic hydrocarbons (e.g., xylene, toluene, benzene, alkylnaphthalene), chlorinated aliphatic or aromatic hydrocarbons (e.g. chlorobenzene, chloroethylene, methylene chloride), aliphatic hydrocarbons or the like. alicyclic (for example cyclohexane, paraffin (for example mineral oil fraction)), alcohols (for example butanol, glycol) and ethers or esters thereof, ketones (for example acetone, methyl-ethyl-ketone, methyl isobutyl ketone, cyclohexanone), strongly polar solvents (for example dimethylformamide, dimethylsulfoxide, acetonitrile) and water.

The preferable solid carriers are natural mineral powdered materials such as kaolin, clay, talc, lime, quartz, attapulgite, montmorillonite and diatomaceous earth, and synthetic mineral powdered materials such as alumina and silicates.

Liquefied gas supports include liquids which are gases under ordinary temperature and pressure conditions, for example, aerosol propellants such as dichlorodifluoromethane and trichlorofluoromethane.

Preferable examples of the emulsifier and the foaming agent are nonionic and anionic emulsifiers such as polyoxyethylene-aliphatic carboxylic acid esters, polyoxyethylene-aliphatic alcohol ethers (for example alkylaryl polyglycol ether), alkylsulfonates, alkylsulfates, arylsulfonates and albumin hydrolyzate. Preferable examples of dispersing agents are lignosulphite residues and methylcellulose.

Natural and synthetic macromolecules in the form of powders, granules or latices, for example, gum arabic, carboxymethylcellulose, polyvinyl alcohol and polyvinyl acetate, can be used as binding agents in the compositions. In addition, mineral pigments (for example iron oxide, titanium oxide) and organic dyes (for example alizarin dyes, azo dyes, metal-phthalocyanine dyes).

Unlike the usual chrysanthemumic acid esters, the compounds of the invention have a very high stability in light, heat and oxidation. However, if it is considered necessary under extreme oxidizing conditions, a suitable amount of an antioxidant and / or an ultraviolet absorbing agent can be added as a stabilizer to obtain a pesticidal composition. which has a more stabilized activity. As a stabilizing agent there may be mentioned, for example, a phenol derivative (for example 2,6-di-tert-butyl-4-methylphenol or
BHT), 2,6-di-tert-butylphenol), a bisphenol derivative, an arylamine (eg, phenyl-α-naphthylamine, phenyl-naphthylamine, phenetidine-acetone condensate), or a benzophenone compound.

The pesticidal composition according to the invention should contain not less than 1 x 10 7% by weight of substituted benzyl ester of the general formula (I). In general, however, the composition contains from 0.01 to 95% by weight, preferably from 0.1 to 90% by weight of the compound according to the invention.

The compound of the invention can be applied either in the form of one of the various compositions mentioned above, or in various forms of applications which can be obtained by using such compositions additionally to obtain the desired goal. . In such embodiments, the content of the compound of the invention may vary within a very wide range. Thus, the concentration of said compound in one form of application can be from 1 x 10 7 to 100% by weight, preferably from 0.001 to 10% by weight.

The pesticidal composition according to the invention can be applied using the usual methods appropriate for each form of application.

In the following description, the synthesis examples, test examples, formulation examples and utility examples further illustrate the invention and are given by way of non-limiting example. In the example compositions, all parts are by weight. The compounds referred to by numbers correspond respectively to the substituted benzyl esters
Nos. 1 to 29 mentioned above and represented by the general formula (I).

EXAMPLE SYNTHESIS 1
In 20 ml of dry benzene, 2.28 g (0.01 mol) of cis-2,2-dimethyl-3- (2,2-dichlorovinyl) cyclopropanecarbonyl chloride and 1.77 g (0, 01 mol) of α-ethynyl-3-nitrobenzyl alcohol. 1.58 g (0.02 mol) of pyridine are then added dropwise to this solution at room temperature. The mixture is left overnight at room temperature with stirring. The reaction mixture is then poured into water and extracted with diethyl ether, and the extract is washed with dilute hydrochloric acid and saturated aqueous sodium chloride solution. The organic layer is dried over anhydrous magnesium sulfate and the low-boiling fraction is distilled off under reduced pressure. The remaining viscous oil is purified by high performance liquid chromatography on silica gel (solvent system: n-hexane / isopropyl ether = 85/15 by volume) and 3.30 g (yield 908) of cis-2,2-dimethyl-3- (2, 2-dichlorovinyl) cyclopropanecarboxylate of α-Sthy- n-3-nitrobenzyl (Compound (2), cis-isomer).

Substituting 2.28 g (0.01 mole) of trans-2,2-di-methyl-3- (2,2-dichlorovinyl) cyclopropanecarbonyl chloride for cis-2,2-dimethyl-3- (2-dichloro) chloride. 2-dichlorovinyl) cyclopropanecarbonyl (0.01 mol) and using the above procedure, 3.39 g (92% yield) of trans-2,2-dimethyl-3- (2,2-dichlorovinyl) are obtained. cyclopropanecarboxylate dl-ethynyl-3-nitrobenzyl (Compound (2), trans isomer).

The RtN spectra for the cis isomer and the trans isomer of the compound (2) as obtained above are as follows:
NMR Spectrum (90 MHz) SHDsl3
cis isomer: 1.13-1.26 (m, 6H); 1.79-2.21 (n, 2H);
2.67-2.72 (m, 1H); 6.13, 6.17 (each, 1H);
6.45-6.53 (m, 1H); 7.68 (d, 2H);
8.22 (d, 2H)
trans isomer: 1.10-1.28 (m, 6H); 1.62, 1.64 (each,
1H);
2.10-2.33 (m, 1H); 2.67-2.76 (m, 1H);
5.58, 5.60 (each, 1H);
6.48-6.57 (m, 1H); 7.43-8.44 (m, 4H).

EXAMPLES OF SYNTHESIS 2 to 6
Following the procedure of Synthesis Example 1, the cis isomer and the trans isomer of Compound (3), the cis isomer and the trans isomer of Compound (5) and the cis isomer are obtained.
Compound (6). The yield and the NMR spectrum for each product obtained are reported in Table 1 below.

TABLE I Product Ex. Rend- NMR spectrum (90 MHz) # CDCl3 synthesis% HMNS
Compound (3) 88 1.13-1.27 (m, 6H),
cis isomer 1.79-2.14 (m, 2H),
2.67-2.74 (m, 1H),
6.44-6.53 (m, 1H),
6.59-6.77 (m, 1H),
7.43-8.44 (m, 4H),
Compound (3) 91 1.13-1.28 (m, 6H);
trans isomer 1.64, 1.66 (each, 1H);
2.02-2.30 (m, 1H);
2.67-2.77 (m, 1H);
6.13, 6.14 (each, 1H);
6.47-6.57 (m, 1H);
7.43-8.45 (m, 4H);
Compound (5) 87 1.13-1.26 (m, 6H);
cis isomer 1.79-2.21 (m, 2H);
2.67-2.72 (m, 1H);
6.13, 6.17 (each, 1H);
6.45-6.53 (m, 1H);
7.68 (d, 2H); 8.22 (d, 2H)
Compound (5) 90 1.10-1.27 (m, 6H);
trans isomer 1.62, 1.64 (each d, 1H);
2.08-2.36 (m, 1H);
2.67-2.74 (m, 1H);
5.57, 5.59 (each, 1H);
6.47-6.54 (m, 1H);
7.67 (d, 2H); 8.19 (d, 2H)
Compound (6) 90 1.14-1.27 (m, 6H),
cis isomer 1.77-2.12 (m, 2H),
2.66-2.72 (m, 1H),
6.43-6.52 (m, 1H),
6.58-6.76 (m, 1H),
7.68 (d, 2H), 8.21 (d, 2H)
EXAMPLE OF SYNTHESIS 7
In 20 ml of dry benzene, 2.28 g (0.01 mole) of cis-2,2-dimethyl-3- (2,2-dichlorovinyl) cyclopropanecarbonyl chloride and 2.00 g (0%) are dissolved. 01 mol) of α-ethynyl-3-trifluoromethylbenzyl alcohol. 1.58 g (0.02 mol) of pyridine are then added dropwise to this solution at room temperature. The mixture is left overnight at room temperature with stirring. Then, the reaction mixture is poured into water and extracted with diethyl ether and the extract is washed with dilute hydrochloric acid and saturated aqueous sodium chloride solution. The organic layer is dried over anhydrous magnesium sulfate and the low boiling fraction is distilled off under reduced pressure. The remaining viscous oil is purified by high performance liquid chromatography on silica gel (solvent system: n-hexane / isopropyl ether = 85/15 by volume) and 3.53 g (90% yield) of cis- Α-Ethynyl-3-trifluoromethylbenzyl 2, 2-dimethyl-3- (2, 2-dichlorovinyl) cyclopropane carboxylate (Compound (7), cis-isomer).

Using 2.28 g (0.01 mole) of trans-2,2-di-methyl-3- (2,2-dichlorovinyl) cyclopropanecarbonyl chloride instead of 0, 1 mol of cis-2,2-chloride. dimethyl-3- (2,2-dichloro-vinyl) cyclopropanecarbonyl and using the above procedure, 3.60 g (92% yield) of trans 2,2-dimethyl-3- (2,2-dichlorovinyl) are obtained; cyclopropanecarboxylate of α-ethynyl-3-trifluoromethylbenzyl (Compound (7), trans isomer).

NMR spectra for the cis isomer and the trans isomer
Compound (7) as obtained above are as follows
NMR Spectrum (90 MHz) aCDCl3
HMS
cis isomer: 1.10-1.27 (m, 6H); 1.76-2.15 (m, 2H);
2.60-2.68 (m, 1H); 6.17, 6.20 (each, 1H);
6.40-6.52 (m, 1H); 7.36-7.84 (m, 4H)
trans isomer: 1.08-1.29 (m, 6H); 1.61, 1.59 (each d, 1H);
2.11-2.37 (m, 1H); 2.60-2.70 (m, 1H);
5.56, 5.58 (each, 1H);
6.46-6.55 (m, 1H); 7.34-7.86 (m, 4H)
A 40/60 mixture of the cis isomer and the trans isomer of
Compound (7) has a boiling point of 1570C at 1.4 mm Hg.

EXAMPLES OF SYNTHESIS 8 to 13
Following the procedure of Synthesis Example 7, the cis isomer and the trans isomer of Compound (8), the trans isomer of Compound (9), the cis isomer of Compound (10) are obtained, and the cis isomer and the trans isomer of Compound (1). The yield and the NMR spectrum for each product obtained are reported in Table 2 below.

TABLE 2
Example of Rende-CDCl3 synthesis Product% NMR Spectrum (90 MHz) #HMS
Compound (8) 92 1.10-1.27 (m, 6H);
cis isomer 1.74-2.15 (m, 2H);
2.58-2.63 (m, 1H);
6.14, 6.18 (each, 1H)
Compound (8) 946.40-6.48 (m, 1H);
trans isomer 7.62 (s, 4H);
1.07-1.27 (m, 6H);
1.58, 1.60 (each, 1H);
2.10-2.33 (m, 1H);
2.59-2.67 (m, 1H);
5.54, 5.56 (each, 1H);
6.44-6.51 (m, 1H);
7.62 (s, 4H)
Compound (9) 90 1.09-1.27 (m, 6H);
trans isomer 1.60, 1.62 (each d, 1H);
2.03-2.26 (m, 1H);
2.58-2.67 (m, 1H);
6.08, 6.10 (each d, 1H);
6.43-6.52 (m, 1H);
7.34-7.83 (m, 4H)
Compound (10) 92 1.12-1.27 (m, 6H);
cis isomer 1.74-2.08 (m, 2H);
2.58-2.65 (m, 1H);
6.40-6.53 (m, 1H);
6.60-6.79 (m, 1H);
7.64 (s, 4H)
Compound (1) 92 1.08-1.21 (m, 6H);
cis isomer 1.70-2.11 (m, 2H);
2.51-2.59 (m, 1H);
6.18, 6.20 (each, 1H);
6.35-6.45 (m, 1H);
7.23-7.56 (m, 5H)
Compound (1) 91 1.04-1.26 (m, 6H);
trans isomer 1.54, 1.56 (each, 1H);
2.08-2.33 (m, 1H);
2.54-2.61 (m, 1H);
5.51, 5.53 (each, 1H);
6.39-6.47 (m, 1H);
7.23-7.59 (m, 5H)
EXAMPLE OF SYNTHESIS 14
In 20 ml of dry benzene, 2.28 g (0.01 mol) of
trans-2,2-dimethyl-3- (2,2-dichlorovinyl) cyclo-
propanecarbonyl and 1.67 g (0.01 mole) of 3-chloro alcohol
Has éthynylbenzylique. Then add drop by drop to
this solution, at room temperature, 1.58 g (0.02 mol) of pyridine.The mixture is left overnight at room temperature with stirring. Then, the reaction mixture is poured into water and extracted with diethyl ether, and the extract is washed with dilute hydrochloric acid and saturated aqueous sodium chloride solution. The organic layer is dried over anhydrous magnesium sulfate and the low boiling fraction is distilled off under reduced pressure. The remaining viscous oil is purified by high performance liquid chromatography on silica gel (solvent system n-hexane / isopropyl ether: 90/10 by volume) and 3.30 g (yield 928) of 3-chloro trans-2,2-dimethyl-3- (2,2-dichlorovinyl) cyclopropanecarboxylate are obtained. -α-ethynylbenzyl (Compound (13), trans isomer).

Using 2.28 g (0.01 mole) of cis-2,2-dimethyl-3- (2,2-dichlorovinyl) cyclopropanecarbonyl chloride instead of 0.01 mole of trans-2,2 chloride. dimethyl-3- (2,2-dichloro-vinyl) cyclopropanecarbonyl and by carrying out the above procedure, 3.21 g (90% yield) of cis-2,2-dimethyl-3- (2, 3-chloro-α-ethynylbenzyl 2-dichlorovinyl) cyclopropanecarboxylate (Compound (13), cis-isomer).

NMR spectra for the cis isomer and the trans isomer
Compound (13) as obtained above are as follows:
NMR Spectrum (90 MHz) 5CDCl3
HMS
cis isomer: 1.10-1.24 (m, 6H); 1.74-2.13 (m, 2H);
2.57-2.64 (m, 1H);
6.17, 6.19 (each, 1H);
6.32-6.40 (m, 1H); 7.19-7.54 (m, 4H)
trans isomer: 1.08-1.28 (m, 6H);
1.58, 1.60 (each, 1H);
2.09-2.32 (m, 1H); 2.57-2.66 (m, 1H);
5.58, 5.60 (each, 1H);
6.35-6.42 (m, 1H); 7.20-7.56 (m, 4H)
A 40/60 mixture of the cis isomer and the trans isomer of
Compound (13) has a boiling point of 1750C at 1.3 mm Hg.

EXAMPLES OF SYNTHESIS 15 to 29
Following the procedure of Synthesis Example 14, the cis isomer and the trans isomer of Compound (14), the cis isomer and the trans isomer of Compound (15), the 50/50 mixture of the cis isomer and the trans isomer of Compound (16), the trans isomer of Compound (18), the trans isomer of Compound (19), the cis isomer and the trans isomer of Compound (23) , the cis isomer and the trans isomer of Compound (24), the cis isomer and the trans isomer of Compound (25), the trans isomer of Compound (26) and the trans isomer of Compound (27) . Performance and spectrum
NMR of each of the products obtained are reported in the
Table 3 below.

TABLE 3
Ex. De - 6CDCl3 Synthesis Product Rende% NMR Spectrum (90 MHz)
% HMS
Compound (14) 93 1.10-1.23 (m, 6H);
cis isomer 1.74-2.13 (m, 2H);
2.57-2.63 (m, 1H);
6.16, 6.18 (each, 1H);
6.33-6.44 (m, 1H);
6.86-7.45 (m, 4H)
Compound (14) 92 1.07-1.27 (m, 6H);
trans isomer 1.58, 1.60 (each d, 1H);
2.08-2.33 (m, 1H);
2.58-2.65 (m, 1H);
5.53, 5.55 (each, 1H);
6.38-6.46 (m, 1H);
6.85-7.45 (m, 4H)
Compound (15) 90 1.10-1.24 (m, 6H);
cis isomer 1.74-2.13 (m, 2H);
2.58-2.65 (m, 1H);
6.18, 6.20 (each, 1H);
6.30, 6.41 (m, 1H);
7.09-7.70 (m, 4H)
Compound (15) 91 1.03-1.26 (m, 6H);
trans isomer 1.55, 1.57 (each d, 1H);
2.06-2.30 (m, 1H);
2.58-2.67 (m, 1H);
5.52, 5.54 (each, 1H);
6.34-6.43 (m, 1H)
7.03-7.69 (m, 4H) Compound (16) 88 1.10-1.27 (m, 6H);
(50/50 mixture 1.50-2.34 (m, 2H);
cis isomer 2,60-2,64 (m, 1H);
and isomer 5.53, 5.55, 6.18, 6.20
trans) (each d, 1H);
6.28-6.40 (m, 1H);
6.96-8.04 (m, 4H) Compound (18) 90 1.08-1.28 (m, 6H);
trans isomer 1.60, 1.62 (each d, 1H);
2.01-2.25 (m, 1H);
2.57-2.64 (m, 1H);
6.09, 6.11 (each, 1H);
6.37-6.46 (m, 1H);
6.85-7.46 (m, 4H) Compound (19) 90 1.07-1.27 (m, 6H);
trans isomer 1.58, 1.60 (each d, 1H);
2.00-2.24 (m, 1H);
2.56-2.63 (m, 1H);
6.10 (d, 1H);
6.34-6.43 (m, 1H);
7.07-7.69 (m, 4H) Compound (23) 92 1.08-1.24 (m, 6H);
cis isomer 1.72-2.12 (m, 2H);
2.54-2.62 (m, 1H);
6.15, 6.18 (each, 1H);
6.32-6.46 (m, 1H);
7.19-7.52 (m, 4H) Compound (23) 94 1.07-1.28 (m, 6H);
trans isomer 1.56, 1.58 (each 4, 1H);
2.07-2.32 (m, 1H);
2.56-2.63 (m, 1H);
5.53, 5.55 (each, 1H);
6.37-6.45 (m, 1H);
7.21-7.53 (m, 4H) 24 Compound (24) 91 1.10-1.24 (m, 6H);
cis isomer 1.74-2.10 (m, 2H);
2.33 (s, 3H);
2.54-2.60 (m, 1H);
6.20, 6.22 (each d, 1H);
6.33-6.40 (n, 1H);
7.04-7.34 (m, 4H) Compound (24) 93 1.05-1.26 (m, 6H);
trans isomer 1.56, 1.58 (each d, 1M);
2.07-2.35, 2.32 (m, s, 4H);
2.53-2.60 (n, 111);
5.52, 5.54 (each, 1H);
6.37-6.43 (m, 1E);
7.03-7.34 Sm, 4E) Compound (25) 92 1.10-1.23 (m, 6H);
cis isomer 1.72-2.10 (m, 2H);
2.30 (s, 3H);
2.52-2.58 (m, 1H);
6.19, 6.21 (each, 1H);
6.33-6.40 (m, 1H);
7.12 (d, 2H); 7.38 (d, 2H) Compound (25) 94 1.03-1.25 (m, 6H);
trans isomer 1.55, 1.57 (each d, 1H);
2.07-2.32, 2.30 (m, s, 4H);
2.52-2.59 (m, 1H);
5.51, 5.53 (each, 1H);
6.37-6.43 (m, 1H);
7.13 (d, 2H); 7.39 (d, 2H) Compound (26) 89 1.06-1.27 (m, 6H);
trans isomer 1.59, 1.61 (each d, 1H);
2.02-2.36, 2.32 (m, s, 4H);
2.54-2.62 (m, 1H);
6.08, 6.10 (each d, 1H);
6.37-6.44 (m, 1H);
7.04-7.37 (m, 4H) Compound (27) 90 1.06-1.27 (m, 6H);
trans isomer 1.58, 1.60 (each d, 1H);
2.00 - 2.34, 2.30 (m, s, 4H);
2.54-2.62 (m, 1H);
6.07-6.09 (each d, 1H);
6.37-6.44 (m, 1H);
7.14 (d, 2H); 7.39 (d, 2H)
EXAMPLE TEST # 1
Mortality test on houseflies (Musca domestica) by a topical application method.

Each of the compounds of the invention and control compounds (Table 4 below) are accurately weighed and dissolved in acetone to prepare a predetermined concentration solution. Adult female houseflies (Musca domestica) are anesthetized with ether and a microliter of the above solution is micropipetted onto the dorsal prothoracic region of each insect. The insects are then placed in a high-walled container with food and the container is covered with a wire mesh lid, the container being maintained at a temperature of 250C. Test insects-are used in groups of 30 individuals each.

Insects are examined 24 hours later to check how many insects have died and calculate the mortality rate. The results are collated in Table 4 below.

47 0 0 0
0 0 10 0 Phénoilirine 100 30 Alléthrine 57 0
EXEMPLE D'ESSAI 2
Essai de mortalité sur l'agrotis du tabac (Prodenia litura
Fabricius) par une méthode d'appl-ication topique.Table 4
% mortality
Test compound 1 pg / female 0.1 vg / female
Compound (2) 100 87
Compound (3) 100 70
Compound (5) - 100 83
Compound (7) 1080
Compound - (9) 100 60
Compound (23) 100 73
Compound (A) 100 0
Compound (B) 67 0
Compound (D) 63 0
Compound (E) 53 0
Compound (G) 20 0
Compound (H) 20 0
Compound (K) 10 0
Compound (L) 53 0

47 0 0 0
0 0 10 0 Phenoilirine 100 30 Allethrin 57 0
EXAMPLE OF TEST 2
Mortality test on tobacco agrotis (Prodenia litura
Fabricius) by a method of topical application.

Each of the compounds according to the invention and each of the control compounds (Table 5 below) are accurately weighed and dissolved in acetone to prepare a predetermined concentration solution. Using a micro-syringe, 0.5 μl of the above solution is dripped onto the thoracic abdominal region of each third-growth larva of tobacco agrotis (Prodenia litura Fabricius). The larvae are then released with food on a filter paper in a dish 9 cm in diameter and kept at a temperature of 250C. The test larvae are used in groups of 20 individuals each.

24 hours later, the number of dead insects is determined and the mortality rate is calculated. The results are collated in Table 5.

0 0

30 0 0 0 45 0
Phénothrine 100 25
EXEMPLE DE COMPOSITION 1
On prépare 30 parties de chacun des composés (1) à (29).Table 5
% mortality
Test compound 1 ilg / larva 0.1 pg / larva
Compound (2) 100 65
Compound (3) 100 75
Compound (7) 100 95
Compound (9) 100 80
Compound (13) 100 65
Compound (16) 100 70
Compound (A) 80 20
Compound (C) 0 0
Compound (D) 40 0
Compound (G) 20 0
Compound (K) 65 0
Compound (L) 30 0

0 0

30 0 0 0 45 0
Phenothrin 100 25
EXAMPLE OF COMPOSITION 1
30 parts of each of the compounds (1) to (29) are prepared.

To each of them are added 50 parts of xylol and 20 parts of an anionic surfactant (New Kargen ST-50: an alkylaryl sulfonate, manufactured by Takemoto Oil & Fat Co., Ltd).

Each mixture is well stirred and thus preparing concentrates emulsifiable to 30% of the respective active compounds.

EXAMPLE OF COMPOSITION 2
30 parts of each of the compounds (1) to (29) are prepared.

To each of them are added 50 parts of xylol and 20 parts of a nonionic surfactant (Sorpol SM-200: a mixture of about 45% by weight of an alkylaryl sulphonate anionic surfactant and about 55% by weight of a nonionic surfactant which comprises a mixture of long chain and short chain polyoxyethylene glycol alkylaryl ethers and a polyoxyethylene ester of a fatty acid manufactured by Toho Chemical Co., Ltd.). Each mixture is well stirred and thus 30% emulsifiable concentrates of each of the respective active compounds are prepared.

EXAMPLE OF COMPOSITION 3
0.5 parts of each of the compounds (1) to (29) are respectively dissolved in 20 parts of acetone and then 99.5 parts of clay are added. After vigorous stirring, the acetone is evaporated from each mixture and the residue is subsequently stirred in a triturator; a 0.5% powder of each of the active compounds is thus prepared.

EXAMPLE OF COMPOSITION 4
0.2 parts of each of the compounds (1) to (29) are dissolved in kerogen with stirring to obtain 100 parts.

In this way, oily preparations of each of the active compounds are obtained.

EXAMPLE OF COMPOSITION
To 20 parts of each of the compounds (1) to (29) are added 5 parts of nonionic surfactant (Sorpol SM-200 mentioned above). After vigorous stirring, 75 parts of talc are added to each mixture and suitably mixed in a pulper. In this way, wettable powders of each of the active compounds are obtained.

EXAMPLE OF USE 1
A 30% emulsifiable concentrate of each of the test compounds, as prepared as described in Composition Example 1, was diluted in water to give a test dilution of 40 ppm. Rice shoots four weeks after sowing (grown in a 6 cm diameter pot, 7 plants) are sprayed with 7 ml per pot of the test dilution and, after drying in the air, a glass cylinder is placed on the pot. 20 adult fulgorids are then released into the cylinder and the cylinder is covered with a gauze. The pot is kept in a constant temperature chamber at 250C. 24 hours later, the number of dead insects is counted and mortality is determined. The insecticidal activity of each compound is evaluated according to the criterion described below.

The results obtained are collated in Table 6 below.

Evaluation criteria :
A ... Mortality: not less than 90%
B ... Mortality: less than 90% but not lower
at 60%
C ... Mortality: less than 60% but not lower
at 30%
D ... Mortality: no greater than 308
Table 6
Insecticide activity test compound
Compound (1) A
Compound (2) A
Compound (7) A
Compound (8) A
Compound 9) B
Compound <13) A
Compound 14) A
Compound (18) A
Compound (23) A
Compound (24) A
Compound (25) B
Compound (A) C
Compound (B) D
Compound (C) D
Compound (D) D
Compound (E) D
Compound (F) D
Compound (G) C
Compound (H) C
Compound (J) D
Compose (K) D
Compound (L) D

(Propaphos)
EXEMPLE D'UTILISATION 2
On dilue dans de l'eau un concentré émulsifiable à 30% de chaque composé d'essai tel que préparé comme décrit dans l'exemple de composition 1 pour préparer une dilution d'essai d'une concentration de 40 ppm. Des pousses de riz, quatre semaines après l'ensemencement (cultivées dans un pot de 6 cm de diamètre, 7 plants) sont aspergées à raison de 7 ml par pot de la dilution d'essai et, après les avoir fait sécher à l'air, on place un cylindre de verre sur le pot.Phenothrin D
Permethrin C
Fenvalerate - D

(Propaphos)
EXAMPLE OF USE 2
A 30% emulsifiable concentrate of each test compound as prepared as described in Composition Example 1 was diluted in water to prepare a test dilution of 40 ppm concentration. Rice shoots four weeks after sowing (grown in a 6 cm diameter pot, 7 plants) are sprayed at 7 ml per pot of the test dilution and, after drying at air, place a glass cylinder on the pot.

We then release in the cylinder 20 small adult brown fulgorids and cover the cylinder with a gauze. The pot is kept in a constant temperature chamber at 250C. 24 hours later, the number of dead insects is counted and mortality is determined. The insecticidal activity of each compound is evaluated according to the criterion described in the use example 1. The results obtained are collated in Table 7.

Table 7
Test compound Insecticide activity
Compound (7) A
Compound (8) A
Compound (9) A
Compound (13) A
Compound (15) A
Compound (18) A
Compound (23) A
Compound (24) A
Compound (A) B
Compound (H) C
Compound (K) C
Fenvalerate C
EXAMPLE OF USE 3
A 30% emulsifiable concentrate of each prepared compound as prepared by the procedure described in Composition Example 1 is diluted with water to obtain a test dilution of 40 ppm concentration. Rice shoots, four weeks after sowing (grown in a 6 cm diameter pot, 7 plants), are sprayed at 7 ml per pot of the test dilution and, after drying at air, place a glass cylinder on the pot. Green leafhoppers of the adult rice are then released into the cylinder and the cylinder is covered with gauze. The pot is kept in a constant temperature chamber at 250C. 24 hours later, we count the number of dead insects and calculate the mortality rate.

The insecticidal activity of each compound is evaluated according to the criterion described in the use example 1. The results obtained are collated in Table 8.

Table 8
Insecticide activity test compound
Compound (1) A
Compound (2) A
Compound (7) A
Compound (8) A
Compound (9) A
Compound (13) A
Compound (14) A
Compound (15) A
Compound (16) A
Compound (18) A
Compound (19) A
Compound (23) A
Compound (24) A
Compound (25) A
Compound (A) C
Compound (F) D
Compound (G) C
Compound (K) C
Compound (L) D

EXAMPLE OF USE 4
A 30% emulsifiable concentrate of each test compound as prepared by the procedure of Composition Example 2 is diluted in water to a concentration of 20 ppm.

Cabbage leaves are dipped in the dilution, air-dried and placed in a plastic container (about 6 cm in diameter, with a capacity of about 60 cm3). Then 10 larvae of ringworm cruciferous (3rd and 4th stage of growth) are released into the container. The container is stored in a constant temperature chamber at 250C. Two days later, the number of dead larvae is determined and the mortality rate is calculated. Two containers are used for each test compound. The results obtained are collated in Table 9.

Table 9
Test compound Mortality (%)
Compound (1) 95
Compound (2) 100
Compound (7) 100
Compound t8) 100
Compound (13) 95
Compound (14) 100
Compound (15) 90
Permethrin 90
EXAMPLE OF USE 5
A 30% emulsifiable concentrate of each test compound, as prepared as described in Composition Example 2, is diluted in water to a concentration of 20 ppm.

Leaves of a tea plant are dipped in the dilution, air dried and placed in a plastic container (about 6 cm in diameter, capacity about 60 cm3).

Ten larvae of small tea budworm (3rd-4th stage of growth) are then released into the container. The container is kept in a constant temperature chamber at 250C. Two days later, we count the number of dead larvae. Two containers are used for each test compound. The results obtained are collated in Table 10.

Table 10
Test compound Mortality (%)
Compound (7) 100
Compound (8) 90
Permethrin 85
Fenvalerate 65
EXAMPLE OF USE 6
A 30% emulsifiable concentrate of each test compound, as prepared by the procedure of Composition Example 2, is diluted with water to a concentration of 20 ppm. Cabbage leaves are dipped in the dilution, air dried and placed in a plastic container (about 6 cm in diameter, capacity about 60 cm3).

10 larvae of agrotis are then released into the container at the 3rd stage of growth. The container is stored in a constant temperature chamber at 250C. Two days later, the number of dead larvae is counted and the mortality rate is calculated. Two containers are used for each test compound. The results obtained are collated in Table 11.

Table 11
Test compound Mortality (%)
Compound (7) 90
Compound (8) 100
Permethrin 90
Fenvalerate 95
TEST EXAMPLE 3
Fish toxicity test on carp (Cyprinus carpio L).

An acetone solution of a test compound selected from the trans isomer of Compound (8), the trans isomer of
Compound (23), permethrin and fenvalerate, and a nonionic surfactant (Tween-20: polyethylene sorbitan monolaurate). In a glass container containing 50 liters of water (30 cm in height), the acetone solution above is added. The mixture is vigorously stirred to prepare an aqueous solution containing the test compound in a predetermined concentration. This solution is used as test water. In each test water maintained at 21 ° C, five carp (Cyprinus carpio L) weighing approximately 6 g and measuring approximately 6 cm were released. 48 hours later, it is examined whether test fish are dead. The average tolerance limit is determined in ppm (TLm). During the test, the water is moderately aerated. The results are collated in Table 12.

Table 12
TLm test compound (ppm)
Compound (8)> 1
Compound (23)> 1
Permethrin 0.015
Fenvalerate 0.0032

Claims (33)

 wherein X is halogen and R is hydrogen, halogen, nitro, methyl or trifluoromethyl.

Claims 1. Substituted benzyl ester of a 2,2-dimethyl-3 (2,2-dihalovinyl) cyclopropanecarboxylic acid, represented by the general formula: 2. substituted benzyl ester according to claim 1, represented by the general formula

 wherein X is a halogen atom. 3. Substituted benzyl ester according to claim 1, represented by the general formula

 in which X is a halogen atom and R "is a halogen atom or a nitro, methyl or trifluoromethyl radical, the substituent R 'being in the meta or para position of the benzene ring. 4. Substituted benzyl ester according to claim 1, represented by the general formula:

 wherein R 'is a hydrogen atom or a nitro or trifluoromethyl radical in the meta or para position of the benzene ring. 5. Substituted benzyl ester according to claim 4, corresponding to the nomenclature 2,2-dimethyl-3-12,2-dichlorovinyl) cyclopropanecarboxylate of a-ethynylbenzyl. 6. substituted benzyl ester according to claim 4, corresponding to the nomenclature 2,2-dimethyl-3- (2,2-dichlorovinyl) cyclopropanecarboxylate dl-ethynyl-3-nitrobenzyl or nomenclature 2,2-dimethyl-3- (2-ethynyl-4-nitrobenzyl) 2,2-dichlorovinyl) cyclopropanecarboxylate, 7. substituted benzyl ester according to claim 4, corresponding to the nomenclature of 212-dimethyl-3- (2,2-dichloro-vinyl) cyclopropanecarboxylate a-ethynyl-3-trifluoromethyl or 2,2-dimethyl-3 nomenclature - alpha-ethynyl-4-trifluoromethylbenzyl (2,2-dichlorovinyl) cyclopropanecarboxylate.  8. substituted benzyl ester according to claim 1, nomenclature of trans-2,2-dimethyl-3-12,2-dihalovinyl) cyclopropanecarboxylate 4-ethynyl-chlorobenzyl. 9. Substituted benzyl ester according to claim 1, of trans-2,2-dimethyl-3- (2,2-dihalovinylcyclopropanecarboxylate) nomenclature of alpha-ethynyl-4-trifluoromethylbenzyl. 10. Pesticidal composition, characterized in that it comprises (i) as active ingredient a substituted benzyl ester of a 2,2-dimethyl-3- (2,2-dihalovinyl) cyclopropanecarboxylic acid represented by the general formula

 wherein X is a halogen atom and R is a hydrogen atom, a halogen atom or a nitro, methyl or trifluoromethyl radical, and (ii) a carrier for this ester. 11. Pesticidal composition according to claim 10, characterized in that the active ingredient is a substituted benzyl ester of a 2,2-dimethyl-3- (2,2-dihalovinyl) cyclopropanecarboxylic acid represented by the general formula

 wherein X is a halogen atom. 12. Pesticidal composition according to claim 10, characterized in that the active ingredient is a substituted benzyl ester of a 2,2-dimethyl-3- (2,2-dihalovinyl) cyclopropanecarboxylic acid represented by the general formula

 in which X is a halogen atom and R "is a halogen atom or a nitro, methyl or trifluoromethyl radical, the substituent R" being in the meta or para position of the benzene ring. 13. Pesticidal composition according to claim 10, characterized in that the active principle is a substituted benzyl ester of 2,2-dimethyl-3- (2,2-dichlorovinyl) -cyclopropanecarboxylic acid represented by the general formula:

 wherein R 'is a hydrogen atom or a nitro or trifluoromethyl radical in the meta or para position of the benzene ring. 14. Pesticidal composition according to claim 13, characterized in that the ester is α-ethynylbenzyl 2,2-dimethyl-3- (2,2-dichlorovinyl) cyclopropanecarboxylate. 15. The pesticidal composition as claimed in claim 13, characterized in that the ester is α-ethynyl-3-nitrobenzyl 2,2-dimethyl-3- (2,2-dichloro-vinyl) cyclopropanecarboxylate or α- ethynyl-4-nitrobenzyl. 16. The pesticidal composition as claimed in claim 13, characterized in that the ester is α-ethynyl-3-trifluoromethylbenzyl or α-thynyl 2,2-dimethyl-3- (2,2-di chlorovinyl) cyclopropanecarboxylate; -4-trifluoromethylbenzyl. 17. Pesticidal composition according to claim 10, characterized in that the active ingredient is α-ethynyl-4-chlorobenzyl trans-2,2-dimethyl-3- (2,2-dihalovinyl) cyclopropanecarboxylate. 18. Pesticidal composition according to claim 10, characterized in that the active ingredient is a trans-2,2-dimethyl 3- (2,2-dihalovinyl) cyclopropanecarboxyls of a-ethynyl-4-trifluoromethylbenzyl. 19. Pesticidal composition according to any one of claims 10 to 18, characterized in that the content of active ingredient is not less than 1 x 10 7% by weight based on the total weight of the composition. 20. The pesticidal composition according to claim 19, characterized in that the content of active ingredient is from 0.01 to 95% by weight. 21. The pesticidal composition according to claim 20, characterized in that the content of active ingredient is from 0.1 to 90% by weight. 22. A method of destroying pests, characterized in that an effective amount of a substituted benzyl ester of a 2,2-dimethyl-3- (2,2- -dihalovinyl) cyclopropanecarboxylic acid represented by the general formula

 wherein X is halogen and R is hydrogen, halogen, nitro, methyl or trifluoromethyl. 23. Process according to claim 22, characterized in that an ester represented by the general formula is used

 wherein X is a halogen atom. 24. Process according to claim 22, characterized in that an ester represented by the general formula

 in which X is a halogen atom and R "is a halogen atom or a nitro, methyl or trifluoromethyl radical, the substituent R" being in the meta or para position of the benzene ring 25. The method of claim 22, characterized in that an ester represented by the general formula is used

 in which R 'is a hydrogen atom or a nitro or trifluoromethyl radical in the meta or para position of the benzene ring. 26. The method of claim 25, characterized in that the ester used is 2, 2-dimethyl-3- (2, 2-dichlorovinyl) cyclopropanecarboxylate a-ethynylbenzyl. 27. Method according to claim 25, characterized in that the ester used is 2-2-dimethyl-3- (2, 2-dichlorovinyl) -cyclopropanecarboxylate a-ethynyl-3-nitrobenzyl or a-ethynyl -4-nitrobenzyl. 28. Process according to claim 25, characterized in that the ester used is 2,2-dimethyl-3- (2,2-dichlorovinyl) cyclopropanecarboxylate dga-ethynyl-3-trifluoromethylbenzyl or dl-ethynyl-4-trifluoromethylbenzyl. 29. The method of claim 22, characterized in that the ester used is an ethynyl-4-chlorobenzyl trans-2,2-dimethyl-3- (2,2-dihalovinyl) cyclopropanecarboxylate. 30. The method of claim 22, characterized in that the ester used is a trans-2, 2-dimethyl-3- (2, 2-dihalovinyl) cyclopropanecarboxylate a-ethynyl-4-trifluoromethylbenzyl. 31. Process according to any one of claims 22 to 30, characterized in that the ester is applied in a concentration of 1 x 10 7 to 100% by weight. 32. The method of claim 31, characterized in that the ester is applied in a concentration of 0.001 to 10% by weight. 33. Method according to any one of claims 22 to 32, characterized in that the ester is applied to a rice field.