GB2088369A - Pesticidal Substituted Benzyl Esters of 2,2-Dimethyl-3-(2,2- dihalovinyl) Cyclopropanecarboxylic Acid - Google Patents

Abstract

Novel compounds of the formula: <IMAGE> wherein each X is halogen and R is hydrogen, halogen, nitro, methyl trifluoromethyl possess pesticidal activity, especially against planthoppers.

Description

SPECIFICATION Substituted Benzyl Esters of 2,2-Dimethyl-3-(2,2-dihalovinyl) Cyclopropanecarboxylic Acid, Pesticidal Composition Containing Said Esters as Active Ingredients and Methods of Controlling Pests with Said Esters and Compositions Background of the Invention Field of the Invention This invention relates to a novel pyrethroid compound, namely a substituted benzyl ester of a 2,2dimethyl-3-(2,2-dihalovinyl)cyclopropanecarboxylic acid, represented by the formula (I)

wherein each X is a halogen atom and R is a hydrogen or halogen atom or a nitro, methyl or trifluoromethyl group, a pesticidal composition containing the same as an active ingredient, and a method for controlling pests using said pyrethroid compound.

Description of the Prior Art As virus diseases on rice plants, dwarf, stripe, black-streaked dwarf and yellow dwarf, being carried by the green rice leafhopper and smaller brown planthopper, have been known, and necrotic mosaic caused by a soil infection has been known. Grassy stunt, the prevalence of which in rice cultivating areas in the tropics and Asia has recently been reported, is also a virus disease which is carried by the brown planthopper. Rice plants attacked by grassy stunt produce rice of inferior quality.

For preventing the outbreak and spreading of such virus diseases, it is necessary for timely control of such pests as the brown planthopper, smaller brown planthopper and green rice leafhopper, which are carriers of viruses causing the diseases. However none of the currently available pesticides can efficiently control the brown planthopper, and pesticides capable of controlling these virus-carrying pests thoroughly and efficiently have not as yet been found.

Some benzyl esters of 2,2-dimethyl-3-(2,2-dichlorovinyl)cyclopropanecarboxylic acid are known.

For example, Japanese Unexamined Patent Publication No. 35332/80 carries a general formula which covers alpha-substituted or unsubstituted benzyl esters having on the benzene ring a lower alkyl, lower alkenyl, cycloalkenyl, lower alkynyi, benzyl or phenoxy group or a halogen atom or halogen atoms.

However, 3-propargyl-alpha-ethynylbenzyl ester, 3-allyl-alpha-ethynylbenzyl ester and 3,4-dichloroalpha-ethynylbenzyl ester [Compound (A) given below by structural formula] are the only compounds specifically disclosed, which have on the benzene ring an aliphatic hydrocarbon group or halogen atoms. Other known cyclopropanecarboxylic acid benzyl esters include Compounds (B), (C), (D), (E), (F), (G), (H), (J), (K) and (L) shown below. However, the pesticidal activity of each of these compounds is not satisfactory for practical use thereof (cf. Japanese Patent Publication No. 281 03/71, Japanese Unexamined Patent Publication No. 28632/73, Japanese Unexamined Patent Publication No.

45674/80, and 5th Meeting of Nippon Noyaku Gakkai (Pesticide Science Society of Japan) Abstracts of Papers, No. 11 5).

[Hereinafter referred to as Compound (A)] [Hereinafter referred to as Compound (B)] [Hereinafter referred to as Compound (C)] [Hereinafter referred to as Compound (D)]

[Hereinafter referred to as Compound (E)] [Hereinafter referred to as Compound (F)] [Hereinafter referred to as Compound (G)] [Hereinafter referred to as Compound (H)] [Hereinafter referred to as Compound (J)j [Hereinafter referred to as Compound (K)] [Hereinafter referred to as Compound (L)] Summary of the Invention An object of the invetnion is to provide a novel pyrethroid compound, namely a substituted benzyl ester of a 2,2-dimethyl-3-(2,2-dihalovinyl)cyclopropanecarboxylic acid, represented by the above general formula (I), which can efficiently control such pests to rice cultivation as the brown planthopper, smaller brown planthopper and green rice leafhopper, which are carriers of viruses causing virus diseases of the rice plant, and further to provide a pesticidal composition containing said pyrethroid compound as an active ingredient as well as a method for controlling said pests to rice cultivation with said pyrethroid compound.

Another object of the invention is to provide a substituted benzyl ester represented by the above general formula (I) which is markedly superior in pesticidal activity against various pests as compared with the so-far known cyclopropanecarboxylic acid benzyl esters.

A further object of the invention is to provide a substituted benzyl ester represented by the above general formula (I) which can be produced at lower cost as compared with the conventional pyrethroids, typically permethrin and fenvalerate.

Detailed Description of the Invention It has now been found that substituted benzyl esters of a 2,2-dimethyl-3-(2,2dihalovinyl)cyclopropanecarboxylic acid, which are represented by general formula (I), are very effective against planthoppers such as the brown planthopper and smaller brown planthopper, as evidenced by Utility Examples 1 and 2 to be mentioned later. This finding is very surprising in view of the fact that the existing pyrethroids, typically permethrin and fenvalerate, have no practically usefui activity against planthoppers.

The substituted benzyl esters of general formula (I) exert excellent pesticidal effects not only against pests to rice raising, which are carriers of viruses causing virus diseases of the rice plant, but also against agricultural, horticultural or forest pests which cause damage to paddy, dry field crop, cotton, fruit trees, forest, etc. They exhibit excellent pesticidal effects also against pests to grain storage and household pests.More particularly, the substituted benzyl esters of general formula (I) display excellent pesticidal activity against both the susceptible and resistant strains of pests belonging to the following orders (same are effective against such pests during all or at least some of their growth stages), amongst others: Order THYSANURA: e.g., Ctenolepisma villosa Escherich: Order COLLEMBOLA: e.g., Anurida trioculata Kinoshita, Onychiurus pseudarmatus yagi Miyoshi, Sminthurus viridis Line, Bourletiella hortensis Fitch; Order ORTHOPTERA: e.g., Northern cone-headed long horn grasshopper (Homorocoryphus Jezoensis Matsumura et Shiraki), Vegetable grasshopper (P. sapporensis Shiraki), Emma field cricket (Teleogryllus emma Ohmachi et Matsuura), Doenitz cricket (Loxoblemmus doenitzi Stein), cockroach (Blattella germanica Lint6), Gryllotalpa africana Palisot de Beauvois, Periplaneta fuliginosa Serville; Order IS OP TERA: e.g., Coptotermes formosanus Shiraki; Order MALL OPHA GA: e.g., Menopon gallinae Anne', Damalinia equi Denny, Trichodectes canis De Geer; Order ANOPLURA: e.g., Haematopinus eurysternus Nitzsch; Order THYSANOPTERA: e.g., Onion thrips (Thrips tabaci Lindeman), Hercinothrips femoralis Reuter; Order HEMIPTERA: e.g., White-backed planthopper (Sogatella furcifera Horváth), Brown planthopper (Nilaparvata lugens Stgl), Small brown planthopper (laodelphax striatellus Fallen), Green rice leafhopper (Nephotettix cincticeps Uhler), Zigzag-striped leafhopper (Inazuma dorsalis Motschulsky), Black rice bug (Scotinophara lurida Burmeister), Rice stink bug (Lagynotomus elongatus Dallas), Corbett rice bug (Leptocorixa corbetti China), Southern green stink bug (Nezara viridula Linné), Grain aphid (Rhopalosiphum padi Line'), Japanese grain aphid (Macrosiphum akebiae Shinji), Corn leaf aphid (Rhopalosiphum maidis Fitch), Green peach aphid (Myzus persicae Sulzer), Cotton aphid (Aphis gossypii Glover), Foxglove aphid (Aulacorthum solani Kaltenbach), Soy bean aphid (Aphis glycins Matsumura), Small bean bug (Chauliops fallax Scott), Bean bug (Riptortus clavatus Thunberg), Common green stink bug (Nezara antennata Scott), Unibanded stink bug (Piezodorus rubrofasciatus Fabricius), Sloe bug (Dolycoris baccarum Line'), Oriental chinch bug (Cavelerius saccharivorus Okajima), Sugarcane cottony aphid (Ceratovacuna lanigera Zehntner), Cabbage aphid (Brevicoryne brassicate LinnB), Small green plant bug (Lygus lucorum Meyer-Dijr), Onion aphid (Neotoxoptera formosana Takahashi), Arrowhead scale (Unaspis yanonensis Kuwana), California red scale (Aonidiella aurantii Maskell), Viteus vitifolii Fitch, Grape leafhopper (Erythroneura apicalis Nawa), Grape whitefly (Aleurolobus taonabae Kuwana), Ume globose scale (Eulecanium kunoense Kuwana), Chrysanthemum aphid (Macrosiphoniella sanborni Gillette), Rose aphid (Macrosiphum ibarae Matsumura), Azalea lacewing bug (Stephanitis pyrioides Scott), Fern scale (Pinnaspis aspidistrae Signoret); Order TRICHOPTERA: e.g., Oecetis nigropunctata Ulmer; Order DIPTERA: e.g., Rice steam maggot (Chiorops oryzae Matsumura), Rice leaf miner (Agromyza oryzae Munakata), Small rice leaf miner (Hydrellia griseola Fallen), Paddy steam maggot (Hydrellia sasaki Yuasa et Ishitani), Wheat thigh chloropid fly (Meromyza saltatrix Lint6), Leaf miner, Wheat blossom midge (SitodiPlosis mosellana GBhin), Soy bean root miner (Melanagrnmyza dolichostigma DE Meijere), Soy bean steam midge (Profeltiella soya Monzen), Soy bean stem miner (Melanagromyza sojae Zehntner), Soy bean pod gall midge (Aspondylia sp.), Seed maggot (Hylemya platura Meigen), Onion maggot (Hylemya antiqua Meigen), Stone leek leaf miner (Phytobia cepae Hering), Narcissus bulb fly (Lampetia equestris Fabricius), House fly (Musca domestica vicina), Mosquito (Culex pipiens); OrderAPHANIPTERA: e.g., Xenopsylla cheopis Rothschild, Pulex irritans Anne'; Order HYMENOPTERA: e.g., Dolerus hordei Rohwer, Soy bean sawfly (Takeuchiella pentagona Malaise); Order LEPIDOPTERA: e.g., Rice stem borer (Chilo suppressalis Walker), Yellow rice borer (Tryporyza incertulas Walker), Pink borer (Sesamia inferens Walker), Pelopidas mathias oberthüri Evans, Grass leaf roller (Cnaphalocrocis medinalis Guénée), Rice leaf roller (Susumia exigua Butler), Rice green caterpillar (Naranga aenescens Moore), Armyworm (Leucania separata Walker), Corn borer (Ostrinia furvacalis Guénée), Sweetpotato leaf folder (Brachmia triannulella Herrich-Schäffer), Bindweed leaf miner (Bedellia sommulentella Zeller), Sweetpotato leaf worm (Aedia leucomelas Line'), Flax budworm (Heliothis viriplaca adaucta Butler), Tobacco striped caterpillar (Pyrrhia umbra Hufnagel), Bean webworm (Syllepte ruralis Scopli), Soy bean pod borer (Grapholitha glycinivorella Matsumura), Azuki pod worm (Matsumuraeses phaseoli Matsumura), Lima-bean pod borer (Etiella-zinckenella Treitschke), Oriental tobacco budworm (Helicoverpa assulta Gu'en6e), Peppermint pyrausta (Pyrausta aurata Scopoli), Peacock butterfly, Lilac pyralid (Margaronia nigropunctalis Bremer), Sugarcane shoot borer (Eucosma schistaceana Snellen), Cabbage armyworm (Mamestra brassicae Linné), Tobacco cutworm (Plodenia litura Fabricius), Common cutworm (Agrotis fucosa Butler), Common cabbageworm (Pieris rapae crucivora Boisduval), Crucifer caterpillar (Mesographe forficalis Lint6), Diamond-back moth (Plutella maculipennis Curtis), Cotton caterpillar (Margaronia indica Saunders), Stone leek miner (Acrolepia alliella Semenov et Kuznetsov), Citrus leaf miner (Phyllocnistis citrella Stainton), Smaller citrus dog (Papilio xuthus Line'), Peach fruit moth (Carposina niponensis Walsingham), Oriental fruit moth (Grapholitha molesta Busck), Summer fruit tortrix (Adoxophyes orana Fischer von Röslerstamm), Gypsy moth (Lymantria dispar Linné), Tent caterpillar (Malacosoma neustria testacea Motschulsky), Small grape plume moth (Stenoptilia vitis Sasaki), Persimmon fruit moth (Stathmopoda flavofasciata Nagano), Fall webworm (Hyphantria cunea Drury), Japanese lawn grass cutworm (Rusidrina depravata Butler), Pectinophora gossypiella; Order COLEOPTERA: e.g., Rice leaf beetle (Oulema oryzae Kuwayama), Large 28-spotted lady beetle (Henosepilachna vigintioctomaculata Motschulsky), 28-spotted lady beetle (H.

vigintioctopunctata Fabricius), False melon beetle (Atrachya menetriesi Faldermann), Two-striped leaf beetle (Paraluperodes nigrobilineatus Motschulsky) Bean leaf beetle (Colposcelis signata Motshculky), Bean frosted weevil (Eugnathus distinctus Roelofs), Castaneous garden beetle (Maladera castanea Arrow), Soy bean beetle (Anomala rufocuprea Motschulsky), Bean blister beetle (Epicauta gorhami Marseul), Peppermint leaf beetle (Chrysolina exanthematica Wiedemann), Olive engraved weevil (Hylobius cribripennis Matsumura et Kono), Vegetable weevil (Listroderes obiiquus Klug), Cucurbit leaf beetle (Aulacophora femoralis Motschulsky), Boll weevil (Anthonomus grandis Boh.), Rice weevil (Stiophilus zeamais Motschulsky), Rice water weevil (Lissorhoptrus oryzophilus), Lesser grain borer (Rhizopertha dominica Fabricius), Azuki bean weevil (Callosobruchus chinensis Lint6), Mustard beetle (Phaedon cochleariae Fab.); OrderACARINA: e.g., Winter grain mite (Penthaleus major Dugs), Two-spotted spider mite (Tetranychus urticae Koch) and Carmine mite (Tetranychus telarius Line').

The substituted benzyl esters of general formula (I) have markedly superior pesticidal activity against the various above-mentioned pests as compared with the previously mentioned cyclopropanecarboxylic acid benzyl esters known in the art.

Among the substituted benzyl esters of general formula (I), those preferred from the viewpoint of pesticidal activity are the compounds in which R is a hydrogen atom or a halogen atom or a nitro, methyl or trifluoromethyl group, said R substituent being at them orp-position of the benzene ring. In particular, substituted benzyl esters of 2,2-dimethyl-3-(2,2-dichlorovinyl)cyclopropanecarboxylic acid, represented by the general formula (I'):

wherein R' is a hydrogen atom our a nitro or trifluoromethyl group at the m- or p-position of the benzene ring, have potent pesticidal activity.

Other characteristic features of the substituted benzyl esters of general formula (I) are (1) high vapor pressure, hence good volatility or vaporizability, (2) fast-acting effect, (3) high stability against light or oxidation, which nevertheless does not result in such environmental residue problem as encountered with organochlorine pesticides, and (5) very low toxicity to man and beast.

Furthermore, among the substituted benzyl esters of general formula (I), the 4-chloro-alphaethynylbenzyl ester and 4-trifl uoromethyl-alpha-ethynylbenzyl ester of a trans-2 ,2-dimethyl-3-(2,2dihalovinyl)cyclopropanecarboxylic acid are at the same time characteristically low in toxicity to fish.

Typical examples of the substituted benzyl ester of the above general formula (I) are the following (these esters include geometric isomers due to different configurations in the acid moiety as well as optical isomers due to asymmetric carbon atoms in the acid and alcohol moieties):

Elemental analysis Found(%) Calcd.(%) Compound No. Structural formula C} \/ C~CH C: 63.10 63.17 (1) COOCH CH H: 5.02 4.99 Cl X CZECH NO2 C: 55.36 55.45 (2) CI COOCH H: 4.06 4.11 Br g CacH NO2 C: 44.52 44.67 (3) Br COOCH H: 3.24 3.31

Elemental analysis Found(%) Calcd. { /OJ Compound No. Structural formula F =CH NO2 C: 60.77 60.90 F COOCH/ H: 4.55 4.51 (5) ) < CZECH C: 55.52 55.45 (5) Cl < CooCHt3No2 H: 4.00 4.11 Br C-CH C: 44.52 44.67 (6) srKcoocH < 3NO2 NO2 H: 3.29 3.31 (6) COOCH (7) {M C-=CH CF3 C: 3.96 535 826 COOCH H: 3.96 3.86 (8) I Csa:CH Dr4D 53 55.26 CI -coOcH- CF3 H: 3.90 3.86 Br C=-CH CF3 C: 45.17 45.03 Br COOCH/\ H: 3.08 3.15 Br (10) < CZECH C: 45.15 45.03 Br COOCH < cF3 H: 3.21 3.15 (11) C=CH 3CH CF3 C: 60.26 60.34 F COOCHt H: 4.25 4.22 F y CATCH C: 60.30 60.34 (12) F COOCHCF3 H: 4.27 4.22 (13) clt C="-CHC C: 57.07 57.09 Cl COOCHC H: 4.18 4.23 Cl V CATCH C: 59.90 59.84 (14) COOCH H: 4.48 4.43 Cl \X/ C=CH Br C: 50.83 50.78 (15) fizz COOCH H: 3.81 3.76

Elemental analysis Found(%) Calcd.(%) Compound No. Structural formula CciIM C-C H (16) C: COOCH < H: 3.43 COOCH H: 3.43 3.37 Br CZECH C: CI C 45.79 45.72 (17) Br = \ L COOCH < H: 3.34 3.38 Br \t 5 CH F C 47.41 47 -4747.47 (18) Br < COOCH < H: 3.45 3.52 (79) Br C=H Br C:41.48 41.58 Br Br) = COOCH H: 3.02 3.08 F C=CH /CI Cl (20) 1 > < COOCH q5 H 4 60 4.66 F COOCH- F > 4 C acHfi CZECH F (21) F COOCH < = 2 C: 66.28 66.23 F COOH H: H: 4.95 4.90 F \t /Br C: 55.42 (22) fuzz < COOCH < H: 4.04 4.10 --coocHH CI C=CH (23) Cl 1 2 t to CH C: 57.13 57.09 Cl J\ COOCH < C H: 4.29 4.23 (24) cCiI&num; C=-CH CH3 C: 64.08 64.11 CM COUCH H: H: 5.44 5.38 (25) C-1=CH C: CH CH3 64.06 3 0 64.11 CI COOCH - CH3 H: 5.30 5.38 (26) bur CH} v CH3 C: 50.82 50.73 Br by > COOCH < H: 4.31 4.26 Br =-CH C: 50.68 50.73 (27) Br < COOCH < CH3 H: 4.18 4.26

Elemental analysis Found { /OJ Calcd. { /OJ Compound No. Structural formula FC=-CH CH3 C:71.13 71.04 (28) F < COOCHX H. 6 06 5.96 F V CZECH C: 70.98 71.04 (29) F < COOCH4CH3 H: 5.92 5.96 The substituted benzyl ester of general formula (I) can easily be produced by reacting a substituted benzyl alcohol of the formula (all):

wherein R has the same meaning as in general formula (I), or a functional derivative thereof with a carboxylic acid of the general formula (III):

wherein X has the same meaning as in general formula (I), or a functional derivative thereof. The functional derivative of the substituted benzyl alcohol includes 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 tertiary base. Typical embodiments of the above production method are as follows: [Process a] Reaction of Alcohol with Carboxylic Acid Halide The substituted benzyl alcohol of formula (II) is reacted with a carboxylic acid halide of the general formula (Ill A)::

wherein X has the same meaning as in general formula (I) and X' is a halogen atom, preferably a carboxylic acid chloride, in an inert solvent (e.g. benzene, toluene, ether, hexane or chloroform), in the presence of a tertiary amine (e.g. pyridine or triethylamine) in an amount of 1-3 molar equivalents per mole of said substituted benzyl alcohol, at room temperature or with heating, to give the desired substituted benzyl ester.

[Process b] Reaction of Alcohol with Carboxylic Acid Anhydride The substituted benzyl alcohol of formula (II) is reacted with a carboxylic acid anhydride of the general formula (Ill B):

wherein X has the same meaning as in general formula (I), in an inert solvent (e.g. benzene, toluene, xylene, hexane or acetone), preferably in the presence of an acid (e.g. sulfuric acid orp-toluenesulfonic acid) or a tertiary amine (e.g. pyridine or triethylamine), at room temperature or with heating, to give the desired substituted benzyl ester.

[Process c] Reaction of Alcohol with Carboxylic Acid The substituted benzyl alcohol of formula (Il) is reacted with the carboxylic acid of general formula (Ill) in an inert solvent (e.g. benzene, toluene, xylene), in the presence of a dehydrating/condensing agent (e.g. dicyclohexylcarbodiimide, or 2-chloro-1 -methylpyridinium iodide plus triethylamine), at room temperature or with heating, to give the desired substituted benzyl ester.

[Process d] Reaction of Alcohol with Carboxylic Acid Lower Alkyl Ester 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 (e.g. alkali metal alkoxide, sodium hydride, titanium compound such as tetramethyl titanate), with heating in an inert solvent (e.g. toluene, xylene), while the low-boiling alcohol which forms is removed from the reaction system by means of a fractionating column, to give the desired substituted benzyl ester.

[Process e] Reaction of Halide or Arylsulfonate of Alcohol with Alkali Metal Salt of Carboxylic Acid A halide or arylsulfonate 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 (e.g. dimethylformamide, benzene, acetone), at room temperature or with heating, to give the desired substituted benzyl ester.

The substituted benzyl alcohol of formula (II), which is the alcohol component, can be produced easily and at low cost in accordance with the following reaction scheme:

wherein R has the same meaning as in general formula (I).

Thus, a substituted benzaldehyde of formula (IV) is ethynylated with sodium acetylide in liquid ammonia solvent, or with ethynylmagensium bromide or ethynyllithium in tetrahydrofuran solvent, to give the substituted benzyl alcohol of formula (II).

On the other hand, the 2,2-dimethyl-3-(2,2-dihaiovinyl)cyclopropanecarboxylic acid, which is the acid component, or a lower alkyl ester thereof, is known in the art, and the above-mentioned functional derivatives can be prepared from a lower alkyl ester of the corresponding carboxylic acid in a conventional manner.

In practical application, the compound of the invention may be used by itself without adding any other ingredients. For ease in use as a pesticide, however, it is a general practice to formulate it with a carrier and apply the resulting formulation, if necessary after adequate dilution. In formulation, the compound of the invention is mixed, in accordance with conventional formulation technology, with a carrier in the form of a liquid, solid or liquefied gas, optionally using a surfactant, which serves as an emulsifying and/or dispersing and/or foaming agent, to give any desired formulation in the form of emulsifiable concentrate, wettable powder, dust, granular formulation, microgranular formulation, oil preparation, aerosol, thermal fumigant (e.g. fumigation coil, electric fumigation mat), fogging formulation, non-thermal fumigant or bait, for instance.The formulation can be selectively applied depending on the intended use thereof. When water is used as the carder, an organic solvent, for instance, may be used as a cosolvent or auxiliary solvent.

Aromatic hydrocarbons (e.g. xylene, toluene, benzene, alkylnaphthalene), chlorinated aromatic or aliphatic hydrocarbons (e.g. chlorobenzene, chloroethylene, methylene chloride), aliphatic or alicyclic hydrocarbons [e.g. cyclohexane, paraffin (e.g. mineral oil fraction)], alcohols (e.g. butanol glycols and ethers or esters thereof, ketones (e.g. acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone), strongly polar solvents (e.g. dimethylformamide, dimethyl sulfoxide, acetonitrile) and water are suitable liquid carriers in most cases.

Preferred solid carriers are pulverized natural minerals, such as kaolin, clay, talc, chalk, quartz, attapulgite, montmorillonite and diatomaceous earth, and pulverized synthetic minerals, such as alumina and silicates.

The liquefied gas carrier includes liquids which are gases at ordinary temperature and pressure, for example, aerosol propellants, such as dichlorodifluoromethane and trichiorofluoromethane.

Preferable examples of the emulsifier and foaming agent are nonionic and anionic emulsifiers, such as polyoxyethylenealiphatic carboxylic acid esters, polyoxyethylene-aliphatic alcohol ethers (e.g.

alkylaryl polyglycol esters), alkylsulfonates, alkylsulfates, arylsulfonates and albumin hydrolyzate.

Preferred examples of the dispersing agent are ligninsulfite waste and methylcellulose.

Natural and synthetic macromolecules in the form of powders, granules or latexes, for example, gum arabic, carboxymethylcellulose, polyvinyl alcohol and polyvinyl acetate, may be used as binding agents in the formulations. Furthermore, inorganic pigments (e.g. iron oxide, titanium oxide) and organic dyes (e.g. alizarin dyes, azo dyes, metalphthalocyanine dyes) may also be used as colorants in the formulations.

Unlike the usual chrysanthemumic acid esters, the compounds of the present invention are highly stable against light, heat and oxidation. However, if deemed necessary under extreme oxidative conditions, an adequate quantity of an antioxidant and/or ultraviolet absorber may be added as a stabilizer so as to obtain a pesticidal composition with more stabilized activity. Such stabilizer is, for example, a phenol derivative (e.g. 2,6-di-tert-butyl-4-methylphenol (BHT), 2,6-di-tert-butylphenol), a bisphenol derivative, an arylamine (e.g. phenyl-alpha-naphthylamine, phenyl-beta-naphthylamine, phenetidine-acetone condensate), or a benzophenone compound.

The pesticidal composition of the present invention may contain not less than 1 x10-7 weight percent of the substituted benzyl ester of the above general formula (I). Generally, however, the formulation contains 0.01 to 95 weight percent, preferably, 0.1 to 90 weight percent, of the compound of the invention.

The compound of the invention may be applied either in the form of a variety of formulations such as mentioned above or in various application forms obtainable by processing such formulations further to suit the purpose. In such application forms, the content of the compound according to this invention may vary in a very wide range. Thus, the concentration of said compound in an application form may be 1 x10-7 to 100 weight percent, preferably 0.001 to 10 weight percent.

The pesticidal composition of the present invention can be applied by the conventional method suited to each application form.

The following Synthesis Examples, Test Examples, Formulation Examples and Utility Examples are intended to further illustrate the invention and should by no means be construed as limiting the scope of the invention. In the Formulation Examples, all parts are by weight. The compounds referred to by numbers respectively correspond to the previously mentioned substituted benzyl esters (1) to (29), represented by general formula (I).

Synthesis Example 1 In 20 ml of dried benzene were dissolved 2.28 g (0.01 mole) of cis-2,2-dimethyl-3-(2,2dichlorovinyl)cyclopropanecarbonyl chloride and 1.77 g (0.01 mole) of alpha-ethynyl-3-nitrobenzyl alcohol. Then, 1.58 g (0.02 mole) of pyridine was added dropwise to this solution at room temperature.

The mixture was stirred at room temperature overnight. Thereafter, the reaction mixture was poured into water and extracted with diethyl ether, and the extract was washed with diluted hydrochloric acid and saturated aqueous sodium chloride solution. The organic layer was dried over anhydrous magnesium sulfate, and the low-boiling fraction was distilled off under reduced pressure. The remaining viscous oil was purified by high performance liquid chromatography on silica gel (solvent system: n-hexane/isopropyl ether=85/1 5 by volume) to give 3.30 g (90% yield) of alpha-ethynyl-3nitrobenzyl cis-2,2-dimethyl-3-(2,2-dichlornvinyl)cycloprnpanecarboxylate [Compound (2), cis-isomer].

Substituting 2.28 g (0.01 mole) of trans-2,2-dimethyl-3-(2,2-dichlorovinyl)cyclopropanecarbonyl chloride for 0.01 mole of cis-2,2-dimethyl-3-(2,2-dichlorovinyl)cyclopropanecarbonyl chloride and, repeating the above procedure, there were obtained 3.39 g (92% yield) of alpha-ethynyl-3-nitrobenzyl trans-2,2-dimethyl-3-(2,2-dichlorovinyl)cyclopropanecarboxylate [Compound (2), trans-isomer].

The NMR spectra for the cis-isomer and the trans-isomer of Compound (2) as obtained in the above are as follows: NMR spectrum (90 MHz) AHDMC3: Cis-isomer: 1.13-1.26 (m, 6H); 1.79-2.21 (m, 2H); 2.67-2.72 (m, 1 H); 6.13, 6.17 (each d, 1 H); 6.45-6.53 (m, 1 H); 7.68 (d, 2H); 8.22 (d, 2H) Trans-isomer: 1.10-1.28 (m, 6H); 1.62, 1.64 (each d, 1 H); 2.10-2.33 (m, 1 H); 2.67-2.76 (m, 1 H); 5.58, 5.60 (each d, 1 H); 6.48-6.57 (m,1 H); 7.43-8.44 (m, 4H) Synthesis Examples 2-6 Following the procedure of Synthesis Example 1, there were obtained the cis-isomer and the trans-isomer of Compound (3), the cis-isomer and the trans-isomer of Compound (5), and the cisisomer of Compound (6). The yield and NMR spectrum for each product are shown in Table 1.

Table 1 Synthesis Example Product Yield (%) NMR spectrum (90 MHz) #HMSCDCl3 2 Compound (3) 88 1.13-1.27 (m, 6H), (Cis-isomer) 1.79-2.14 (m, 2H), 2.67-2.74 (m, 1 H), 6.44-6.53 (m, 1 H), 6.59-6.77 (m, 1H), 7.43-8.44 (m, 4H) 3 Compound (3) 91 1.13-1.28 (m, 6H); (Trans-isomer) 1.64, 1.66 (each d, 1H); 2.02-2.30 (m, 1 H); 2.67-2.77 (m, 1H); 6.13, 6.14, (each d, 1H); 6.47-6.57 (m, 1H); 7.43-8.45 (m, 4H) 4 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 d, 1H); 6.45-6.53 (m, 1H); 7.68 (d, 2H); 8.22 (d, 2H) 5 Compound (5) 90 1.10-1.27 (m, 6H); (Trans-isomer) 1.62, 1.64 (each d, 1 H); 2.08-2.36 (m, 1H); 2.67-2.74 (m, 1H); 5.57, 5.59 (each d, 1 H); 6.47-6.54 (m, 1H); 7.67 (d, 2H); 8.19 (d, 2H) 6 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) Synthesis Example 7 In 20 ml of dried benzene were dissolved 2.28 g (0.01 mole) of cis-2,2-dimethyl-3-(2,2dichlorovinyl)cyclopropanecarbonyl chloride and 2.00 g (0.01 mole) of alpha-ethynyl-3trifluoromethylbenzyl alcohol. Then, 1.58 g (0.02 mole) of pyridine were added dropwise to this solution at room temperature. The mixture was stirred at room temperature overnight.Thereafter, the reaction mixture was poured into water and extracted with diethyl ether, and the extract was washed with diluted hydrochloric acid and saturated aqueous sodium chloride solution. The organic layer was dried over anhydrous magnesium sulfate, and the low-boiling fraction was distilled off under reduced pressure. The remaining viscous oil was purified by high performance liquid chromatography on silica gel (solvent system: n-hexane/isopropyl ether=85/15 by volume), to give 3.53 g (90% yield) of alphaethynyl-3-trifluoromethylbenzyl cis-2,2-dimethyl-3-(2,2-dichlorovinyl)cyclopropanecarboxylate [Compound (7), cis-isomer].

Substituting 2.28 g (0.01 mole) of trans-2,2-dimethyl-3-(2,2-dichlorovinyl)cyclopropanecarbonyl chloride for 0.01 mole of cis-2,2-dimethyl-3-(2,2-dichlorovinyl)cyclopropanecarbonyl chloride and repeating the above procedure, there were obtained 3.60 g (92% yield) of alpha-ethynyl-3trifluoromethylbenzyl trans-2,2-dimethyl-3(2,2-dichlorovinyl)cyclopropanecarboxylate [Compound (7), trans-isomer].

The NMR spectra for the cis-isomer and the trans-isomer of Compound (7) as obtained in the above are as follows: NMR spectrum (90 MHz) #HMSCDCl3: 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 d, 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, 1 H); 5.56, 5.58 (each d, 1 H); 6.46-6.55 (m, 1 H); 7.34-7.86 (m, 4H) And a 40:60 mixture of the cis-isomer and the trans-isomer of Compound (7) has a boiling point of 157 C/1.4 mmHg.

Synthesis Examples 8-13 Following the procedure of Synthesis Example 7, there were obtained the cis-isomer and the trans-isomer of Compound (8), the trans-isomer of Compound (9), the cis-isomer of Compound (10), and the cis-isomer and the trans-isomer of Compound (1). The yield and NMR spectrum for each product are shown in Table 2.

Table 2 Synthesis Example Product Yield(%) NMR spectrum (90 MHz) #HMSCDCl3 8 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 d, 1 H) 9 Compound (8) 94 6.40-6.48 (m, 1 H); (Trans-isomer) 7.62 (s, 4H); 1.07-1.27 (m, 6H); 1.58,1.60 (each d, 1H); 2.10-2.33 (m, 1H); 2.59-2.67 (m, 1H); 5.54, 5.56 (each d, 1 H); 6.44-6.51 (m, 1H); 7.62 (s, 4H) 10 Compound (9) 90 1.09-1.27 (m, 6H); (Trans-isomer) 1.60, 1.62 (each d, 1 H); 2.03-2.26 (m, 1 H); 2.58-2.67 (m, 1 H); 6.08,6.10 (each d, 1H); 6.43-6.52 (m, 1 H); 7.34-7.83 (m, 4H) 11 Compound (10) 92 1.12-1.27 (m, 6H);; (Cis-isomer) 1.74-2.08 (m, 2H); 2.58-2.65 (m, 1 H); 6.40-6.53 (m, 1H) 6.60-6.79 (m, 1 H); 7.64 (s, 4H) 12 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 d, 1 H); 6.35-6.45 (m, 1 H); 7.23-7.57 (m, 5H) 13 Compound (1) 91 1.04-1.26 (m, 6H); (Trans-isomer) 1.54,1.56 (each d, 1 H); 2.08-2.33 (m, 1H); 2.54-2.61 (m, 1H); 5.51,5.53 (each d, 1 H); 6.39-6.47 (m, 1H);; 7.23-7.59 (m, 5H) Synthesis Example 14 In 20 ml of dried benzene were dissolved 2.28 9 (0.01 mole) of trans-2,2-dimethyl-3-(2,2dichlorovinyl)cyclopropanecarbonyl chloride and 1.67 g (0.01 mole) of 3-chloro-alphaethynylbenzyl alcohol. Then, 1.58 g (0.02 mole) of pyridine were added dropwise to this solution at room temperature. The mixture was stirred at room temperature overnight. Thereafter, the reaction mixture was poured into water and extracted with diethyl ether, and the extract was washed with diluted hydrochloric acid and saturated aqueous sodium chloride solution. The organic layer was dried over anhydrous magnesium sulfate, and the low-boiling fraction was distilled off under reduced pressure.

The remaining viscous oil was purified by high performance liquid chromatography on silica gel (solvent system: n-hexane/isopropyl ether=90/10 by volume) to give 3.30 g (92% yield) of 3-chloroalpha-ethynlybenzyl-trans-2,2-dimethyl-3-(2,2-dichlorovinyl)cyclopropanecarboxylate [Compound (13), trans-isomer].

Substituting 2.28 g (0.01 mole) of cis-2,2-dimethyl-3-(2,2-dichlorovinyl)cyclopropanecarbonyl chloride for 0.01 mole of trans-2,2-dimethyl-3-(2,2-dichlorovinyl)cyclopropanecarbonyl chloride, and repeating the above procedure, there were obtained 3.21 9 (90% yield) of 3-chloro-alphaethynylbenzyl cis-2,2-dimethyl-3-(2,2-dichlorovinyl)cyclopropanecarboxylate [Compound (13), cisisomer].

The NMR spectra for the cis-isomer and the trans-isomer of Compound (13) as obtained in the above are as follows: NMR spectrum (90 MHz) #HMSCDCl3 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 d, 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 d, 1H); 2.09-2.32 (m, 1H); 2.57-2.66 (m, 1 H); 5.58, 5.60 (each d, 1 H); 6.35-6.42 (m, 1 H); 7.20-7.56 (m, 4H).

And a 40:60 mixture of the cis-isomer and the trans-isomer of Compound (1 3) has a boiling point of 1750C/1.3 mmHg.

Synthesis Examples 15-29 Following the procedure of Synthesis Example 14, there were obtained 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 cisisomer 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). The yield and NMR spectrum for each product are shown in Table 3.

Table 3 Synthesis Example Product Yield(%) NMR spectrum (90 MHz) #HMSCDCl3 15 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 d, 1H); 6.33-6.44 (m, 1H); 6.86-7.45 (m, 4H) 16 Compound (14) 92 1.07-1.27 (m, 6H); (Trans-isomer) 1.58, 1.60 (each d, 1 H); 2.08-2.33 (m, 1H); 2.58-2.65 (m, 1H); 5.53, 5.55 (each d, 1 H); 6.38-6.46 (m, 1H); 6.85-7.45 (m, 4H) 17 Compound (15) 90 1.10-1.24 (m, 6H)M (Cis-isomer) 1.74-2.13 (m, 2H); 2.58-2.65 (m, 1H); 6.18, 6.20 (each d, 1 H); 6.30, 6.41 (m, 1 H); 7.09-7.70 (m, 4H) 18 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 d, 1 H); 6.34-6.43 (m, 1H);; 7.03-7.69 (m, 4H) 19 Compound (16) 88 1.10-1.27 (m, 6H); (50:50 mixture 1.50-2.34 (m, 2H); of cis-isomer 2.60-2.64 (m, 1 H); and trans-isomer) 5.53, 5.55, 6.18, 6.20 (each d, 1 H); 6.28-6.40 (m, 1 H); 6.96-8.04 (m, 4H) 20 Compound (18) 90 1.08-1.28 (m, 6H); (Trans-isomer) 1.60, 1.62 (each d, 1 H); 2.01-2.25 (m, 1H); 2.57-2.64 (m, 1H); 6.09, 6.11 (each d, 1 H); 6.37-6.46 (m, 1H); 6.85-7.46 (m, 4H) Table 3 (cont.) 21 Compound (19) 90 1.07-1.27 (m, 6H); (Trans-isomer) 1.58, 1.60 (each d, 1 H); 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) 22 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 d, 1 H);; 6.32-6.46 (m, 1H); 7.19-7.52 (m, 4H) 23 Compound (23) 94 1.07-1.28 (m, 6H); (Trans-isomer) 1.56, 1.58 (each d, 1 H); 2.07-2.32 (m, 1H); 2.56-2.63 (m, 1H); 5.53, 5.55 (each d, 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, 1 H); 6.33-6.40 (m, 1H); 7.04-7.34 (m, 4H) 25 Compound (24) 93 1.05-1.26 (m, 6H); (Trans-isomer) 1.56, 1.58 (each d, 1H); 2.07-2.35, 2.32 (m, s, 4H); 2.53-2.60 (m, 1H); 5.52, 5.54 (each d, 1H); 6.47-6.43 (m, 1H); 7.03-7.34 (m, 4H) 26 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 d, 1H); 6.33-6.40 (m, 1H); 7.12 (d, 2H); 7.38 (d, 2H) 27 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 d, 1 H); 6.37-6.43 (m, 1H); 7.13 (d, 2H); 7.3 (d, 2H) 28 Compound (26) 89 1.06-1.27 (m, 6H); (Trans-isomer) 1.59,1.61 (eachd, 1H); 2.02-2.36, 2.32 (m, s, 4H); 2.54-2.62 (m, 1H); 6.08, 6.10 (each d, 1 H); 6.37-6.44 (m, 1H); 7.04-7.37 (m, 4H) 29 Compound (27) 90 1.06-1.27 (m, 6H); (Trans-isomer) 1.58, 1.60 (each d, 1 H); 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) Test Example 1 Mortality Test with Houseflies (Musca Domestica) by Topical Application Method Each of the compounds according to this invention and the control compounds (Table 4) was accurately weighed and dissolved in acetone to prepare a solution of predetermined concentration.

Female adult houseflies (Musca domestica) were anesthetized with ether and 1 yl of the above solution was micropipetted onto the prothoracic dorsal region of each insect. The insects were then put in a high-walled dish together with feed and the dish was covered with a wire-mesh cover and kept at a temperature of 250C. The test insects were used in groups of 30 individuals each. After 24 hours, the insects were examined for deaths and the percentage mortality was calculated. The results are set forth in Table 4.

Table 4

% Mortality Test compound 1 g/Female 0.1 yg/Female Compound (2) 100 87 Compound (3) 100 70 Compound (5) 100 83 Compound (7) 100 80 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 C OCHZbCg Ci CN Cl 1e2t \ COOCH I 0 0 Cl CN 1 0 0 CI COOCH NQ V CZECH COOCH --Br Phenothrin 100 30 Allethrin 57 0 Test Example 2 Mortality Test with Tobacco Cutworms (Prodenia Litura Fabricius) by Topical Application Method Each of the compounds according to this invention and the control compounds (Table 5) was accurately weighed and dissolved in acetone to prepare a solution of predetermined concentration.

Using a microsyringe, 0.5 yl of the above solution was dripped onto the thoracic abdominal region of each of 3-instar tobacco cutworm (Prodenia litura Fabricius) larvae. Thereafter, the larvae were released together with feed on a filter paper in a dish 9 cm in diameter and kept at a temperature of 25"C. The test larvae were used in groups of 20 individuals each. After 24 hours, the insects were examined for deaths and the percentage mortality was calculated. The results are shown in Table 6.

Table 5

% Mortality Test compound 1 Mg/Larva 0.1 yg/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 Cl V CN CF3 C 0 0 COOCH C IIMCOOCH2CF3 30 0 F 0 < COOCH X 45 Phenothrin 100 25 Formulation Example 1 Thirty (30) parts each of Compounds (1) to (29) were prepared. To each of them were added 50 parts of xylol and 20 parts of anionic surfactant (New Kargen ST-50: an alkylaryl sulfonate, manufactured by Takemoto Oil 8 Fat Co., Ltd.). Each mixture was stirred well to prepare 30% emulsifiable concentrates of the respective active compounds.

Formulation Example 2 Thirty (30) parts each of Compounds (1) to (29) were prepared. To each of them were added 50 parts of xylol and 20 parts of nonionic surfactant (Sorpol SM-200: a mixture of about 45 wt% of an alkylaryl sulfonate anionic surfactant and about 55 wt% of a nonionic surfactant which comprises a mixture of long and short chain alkylaryl ethers of polyoxyethylene glycol and a polyoxyethylene ester of a fatty acid, manufactured by Toho Chemical Co., Ltd.). Each mixture was stirred well to prepare 30% emulsifiable concentrates of the respective active compounds.

Formulation Example 3 Five-tenths (0.5) parts each of Compounds (1) to (29) were respectively dissolved in 20 parts of acetone, followed by the addition of 99.5 parts of clay. After thorough stirring, the acetone was evaporated from each mixture and the residue was further stirred well in a trituratbr to prepare a 0.5% dust of the respective active compounds.

Formulation Example 4 Two-tenths (0.2) parts each of Compounds (1) to (29) were dissolved in kerosene with stirring to make 1 00 parts. The above procedure yielded oil preparations of the respective active compounds.

Formulation Example 5 To 20 parts each of Compounds (1) to (29) were added 5 parts of nonionic surfactant (Sorpol SM-200 as mentioned hereinbefore). After thorough mixing, 75 parts of talc were added to each mixture and stirred well in a triturator. The above procedure yielded wettable powders of the respective active compounds.

Utility Example 1 A 30% emulsifiable concentrate of each test compound as prepared by the procedure described in Formulation Example 1 was diluted with water to prepare a test dilution having a concentration of 40 ppm. Rice plants, 4 weeks after sowing (cultivated in a pot 6 cm in diameter, 7 seedlings) were sprayed with 7 ml per pot of the test dilution, and, after allowing them to dry in the air, a glass cylinder was placed on the pot. Then, 20 adult brown planthoppers were released into the cylinder, and the cylinder was covered with a gauze. The pot was kept in a constant-temperature chamber at 250C.

After 24 hours, the insects were examined for deaths and the mortality was determined. The insecticidal activity of each compound was evaluated according to the following criteria. The results obtained are shown in Table 6.

Criteria for evaluation: A... Mortality: not less than 90% B ... Mortality: less than 90% but not less than 60% C ... Mortality: less than 60% but not less than 30% D . Mortality: not more than 30%.

Table 6

Insecticidal Test compound activity 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 Compound (K) D Compound(L) D Cl < COOCH < D C1)I LCI D COOCHX D Table 6 (cont.)

C--CH Br COOCH D CZECH D )OCH-- CH3 Phenothrin D Permethrin C Fenvalerate D < CN NCOOA)Oi̇ D HF2CO (AC-222705) XI CN CN H5C2 COO MY D (NK-8116) CH3NHCOO) C CH3CHC2H5 (BPMC) o (CH3CH2CH2O)2 F-O C (Propaphos) Utility Example 2 A 30% emulsifiable concentrate of each test compound as prepared by the procedure described in Formulation Example 1 was diluted with water to prepare a test dilution having a concentration of 40 ppm. Rice plants, 4 weeks after sowing (cultivated in a pot 6 cm in diameter, 7 seedlings) were sprayed with 7 ml per pot of the test dilution, and, after allowing them to dry in the air, a glass cylinder was placed on the pot. Then, 20 adult smaller brown planthoppers were released into the cylinder, and the cylinder was covered with a gauze. The pot was kept in a constant-temperature chamber at 250C.

After 24 hours, the insects were examined for deaths and the mortality was determined. The insecticidal activity of each compound was evaluated according to the criteria as described in Utility Example 1. The results obtained are shown in Table 7.

Table 7 Insecticidal Test compound 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 Table 7 (cont.) Compound (A) B Compound (H) C Compound (K) C Fenvalerate C Utility Example 3 A 30% emulsifiable concentrate of each test compound as prepared by the procedure described in Formulation Example 1 was diluted with water to prepare a test dilution having a concentration of 40 ppm. Rice plants, 4 weeks after sowing (cultivated in a pot 6 cm in diameter, 7 seedlings) were sprayed with 7 ml per pot of the test dilution, and, after allowing them to dry in the air, a glass cylinder was placed on the pot. Then, 20 adult green rice leafhoppers were released into the cylinder, and the cylinder was covered with a gauze.The pot was kept in a constant-temperature chamber at 250C. After 24 hours, the insects were examined for deaths and the mortality was determined. The insecticidal activity of each compound was evaluated according to the criteria as described in Utility Example 1.

The results obtained are shown in Table 8.

Table 8

Insecticidal Test compound activity 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 O YADy F D CZECH Br I D COO CH MCOO{IMC CH3 C Utility Example 4 A 30% emulsifiable concentrate of each test compound as prepared by the procedure of Formulation Example 2 was diluted with water to a concentration of 20 ppm. Leaves of cabbage were dipped in the dilution, air-dried, and placed in a plastics container (about 6 cm in diameter, about 60 cm3 in capacity). Then, 10 diamond-back moth larvae (3rd 4th stage) were released into the container. The container was kept in a constant-temperature chamber at 250 C. After 2 days, the larvae were examined for deaths, and the mortality was determined. Two containers were used for each test compound. The results obtained are shown in Table 9.

Table 9 Test compound Mortality {%) Compound (1) 95 Compound (2) 100 Compound (7) 100 Compound (8) 100 Compound (13) 95 Compound (14) 100 Compound (15) 90 Permethrin 90 Utility Example 5 A 30% emulsifiable concentrate of each test compound as prepared by the procedure of Formulation Example 2 was diluted with water to a concentration of 20 ppm. Leaves of a tea-plant were dipped in the dilution, air-dried, and placed in a plastics container (about 6 cm in diameter, about 60 cm3 in capacity). Then, 1 0 smaller tea tortrix larvae (3rd-4th stage) were released into the container. The container was kept in a constant-temperature chamber at 250C. After 2 days, the larvae were examined for deaths. Two containers were used for each test compound. The results obtained are shown in Table 10.

Table 10 Test compound Mortality (%) Compound (7) 100 Compound (8) 90 Permethrin 85 Fenvalerate 65 Utility Example 6 A 30% emulsifiable concentrate of each test compound as prepared by the procedure of Formulation Example 2 was diluted with water to a concentration of 20 ppm. Leaves of cabbage were dipped in the dilution, air-dried, and placed in a plastics container (about 6 cm in diameter, about 60 cm3 in capacity). Then, 1 0 3-instar tobacco cutworm larvae were released into the container. The container was kept in a constant-temperature chamber at 250C. After 2 days, the larvae were examined for deaths, and the mortality was determined. Two containers were used for each test compound. The results obtained are shown in Table 11.

Table 11 Test compound Mortality { /OJ Compound (7) 90 Compound (8) 100 Permethrin 90 Fenvalerate 95 Test Example 3 Fish Toxicity Test with Carp (Cyprinus Carpio L) An acetone solution of one test compound selected from the group consisting of the trans-isomer of Compound (8), the trans-isomer of Compound (23), permethrin and fenvalerate, and nonionic surfactant (Tween-20: a polyethylene sorbitan monolaurate) was prepared. To 50 liters of water (30 cm deep) in a glass tank was added the above acetone solution. The mixture was stirred thoroughly to prepare an aqueous solution containing the test compound in a predetermined concentration. This was used as a test water. Five carps (Cyprinus carpio L) with a body weight of about 6 g and a body length of about 6 cm were released into each test water which was maintained at 21 + 1 OC. After 48 hours, the test fish were examined for deaths. The TLm (median tolerance limit, ppm) was determined. The test water was moderately aerated. The results are set forth in Table 12.

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

Claims (36)

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

   wherein each X is a halogen atom and R is a hydrogen or halogen atom or a nitro, methyl or trifluoromethyl group.
2. 2. The substituted benzyl ester according to Claim 1, which ester is represented by the general formula (IA):

   wherein each X is a halogen atom.
3. 3. The substituted benzyl ester according to Claim 1, which ester is represented by the general formula (IB):

   wherein each X is a halogen atom and R" is a halogen atom or a nitro, methyl or trifluoromethyl group, said R" substituent being at them orp-position of the benzene ring.
4. 4. The substituted benzyl ester according to Claim 1, which ester is represented by the general formula (I'),

   wherein R' is a hydrogen atom or a nitro or trifluoromethyl group at the m- or p-position of the benzene ring.
5. 5. The substituted benzyl ester according to Claim 4, which ester is alpha-ethynylbenzyl 2,2 dimethyl-3-(2,2-dichlorovinyl)cyclopropanecarboxylate.
6. 6. The substituted benzyl ester according to Claim 4, which ester is alpha-ethynyl-3-nitro or 4nitrobenzyl 2,2-dimethyl-3-(2,2-dichlorovinyl)cyclopropanecarboxylate.
7. 7. The substituted benzyl ester according to Claim 4, which ester is alpha-ethynyl-3trifluoromethyl or 4-trifluoromethylbenzyl 2,2-dimethyl-3-(2,2-dichlorovinyl)cyclopropanecarboxylate.
8. 8. The substituted benzyl ester according to Claim 1, which ester is alpha-ethynyl-4-chlorobenzyl trans-2,2-dimethyl-3-(2,2-dihalovinyl)cyclopropanecarboxylate.
9. 9. The substituted benzyl ester according to Claim 1 , which ester is alpha-ethynyl-4trifluoromethylbenzyl trans-2,2-dimethyl3-(2,2-dihalovinyl)cyclopropanecarboxylate.
10. 1 0. A pesticidal composition comprising (i) as an active ingredient thereof a substituted benzyl ester of a 2,2-dimethyl-3-(2,2-dihalovinyl)cyclopropanecarboxylic acid, represented by the general formula (I):

    wherein each X is a halogen atom and R is a hydrogen or halogen atom or a nitro, methyl or trifluoromethyl group and (ii) a carrier therefor.
11. 11. The pesticidal composition according to Claim 10 wherein said active ingredient is a substituted benzyl ester of a 2,2-dimethyl-3-(2,2-dihalovinyl)cyclopropanecarboxylic acid, represented by the general formula (IA):

    wherein each X is a halogen atom.
12. 12. The pesticidal composition according to Claim 10 wherein said active ingredient is a substituted benzyl ester of a 2,2-dimethyl-3-(2,2-diha lovinyl)cyclopropanecarboxylic acid, represented by the general formula (IB):

    wherein each X is a halogen atom and R" is a halogen atom or a nitro, methyl or trifluoromethyl group, said R" substituent being at the or p-position of the benzene ring.
13. 1 3. The pesticidal composition according to Claim 10 wherein said active ingredient is a substituted benzyl ester of 2,2-dimethyl-3-(2,2-dichlorovinyl)cyclopropanecarboxylic acid, represented by the general formula (I'):

    wherein R' is a hydrogen atom or a nitro tor trifluoromethyl group at the m- or p-position of the benzene ring.
14. 1 4. The pesticidal composition according to Claim 1 3 wherein said ester is alpha-ethynylbenzyl 2,2-dimethyl-3-(2,2-dichlorovinyl)cyclopropanecarboxylate.
15. 1 5. The pesticidal composition according to Claim 13, wherein said ester is alpha-ethynyl-3-nitro or 4-nitrobenzyl 2,2-dimethyl-3-(2,2-dichlorovinyl )cyclopropanecarboxyiate.
16. 1 6. The pesticidal composition according to Claim 13, wherein said ester is alpha-ethynyl-3trifluoromethyl or 4-trifluoromethylbenzyl 2,2-di methyl-3-(2,2-dichlorovinyl)cyclopropanecarboxylate.
17. 1 7. The pesticidal composition according to Claim 10, wherein said active ingredient is alphaethynyl-4-chlorobenzyl trans-2,2-di methyl-3-(2,2-diha lovinyl)cyclopropa necarboxylate.
18. 1 8. The pesticidal composition according to Claim 10, wherein said active ingredient is alphaethynyl-4-trifluoromethylbenzyl trans-2,2-dimethyl-3-(2,2-diha lovinyl)cyclopropanecarboxylate.
19. 1 9. The pesticidal composition according to any of Claims 10 to 1 8, wherein the content of said active ingredient is not less than 1 x10-7 weight percent based on the total weight of said composition.
20. 20. The pesticidal composition according to Claim 1 9, wherein said content of active ingredient is 0.01 to 95 weight percent.
21. 21. The pesticidal composition according to Claim 20, wherein said content of active ingredient is 0.1 to 90 weight percent.
22. 22. A method for controlling pests which comprises applying to a habitat of the pests an effective amount of a substituted benzyl ester of a 2,2-dimethyl-3-(2,2-diha lovinyl)cyclopropanecarboxylic acid, represented by the general formula (I):

    wherein each X is a halogen atom and R is a hydrogen or halogen atom or a nitro, methyl or trifluoromethyl group.
23. 23. The method according to Claim 22, wherein said ester is represented by the general formula (IA):

    wherein each X is a halogen atom.
24. 24. The method according to Claim 22 wherein said ester is represented by the general formula (IB):

    wherein each X is a halogen atom and R" is a halogen atom or a nitro, methyl or trifluoromethyl group, said R" substituent being at them orp-position of the benzene ring.
25. 25. The method according to Claim 22 wherein said ester is represented by the general formula (1'):

    wherein R' is a hydrogen atom or a nitro or trifluoromethyl group at the m- or p-position of the benzene ring.
26. 26. The method according to Claim 25, wherein said ester is alpha-ethynylbenzyl 2,2-dimethyl-3 (2,2-dichlorovinyl)cyclopropanecarboxylate.
27. 27. The method according to Claim 25, wherein said ester is alpha-ethynyl-3-nitro or 4nitrobenzyl 2,2-dim ethyl-3-(2,2-dichlorovinyl)cyclopropanecarboxylate.
28. 28. The method according to Claim 25, wherein said ester is alpha-ethynyl-3-trifluoromethyl or 4-trifluoromethylbenzyl 2,2-dimethyl-3-(2,2-dichlorovinyl)cyclopropanecarboxylate.
29. 29. The method according to Claim 22, wherein said ester is alpha-ethynyl-4-chlorobenzyl trans 2,2-dimethyl-3-(2,2-dihalovinyl)cyclopropanecarboxylate.
30. 30. The method according to Claim 22, wherein said ester is alpha-ethynyl-4 trifluoromethylbenzyl trans-2,2-dimethyl-3-(2,2-dihalovinyl)cyclopropaneca rboxylate.
31. 31. The method according to any of Claims 22 to 30, wherein the application concentration of said ester is 1 x 10-7 to 100 weight percent.
32. 32. The method according to Claim 31 , wherein said application concentration is 0.001 to 10 weight percent.
33. 33. The method according to any of Claims 22 to 32, wherein said ester is applied to a rice paddy.
34. 34. A substituted benzyl ester according to claim 1, substantially as herein described with reference to any of the specific examples.
35. 35. A pesticidal composition according to claim 10, substantially as herein described with reference to any of the specific examples.
36. 36. A method according to claim 22, substantially as herein described with reference to any of the specific examples.