GB1579514A

GB1579514A - Optionally substituted phenoxybenzyl esters of-haloalkenyl isovalenic acids and pesticidal compositions containing them

Info

Publication number: GB1579514A
Application number: GB9425/78A
Authority: GB
Original assignee: Kuraray Co Ltd
Current assignee: Kuraray Co Ltd
Priority date: 1977-03-11
Filing date: 1978-03-09
Publication date: 1980-11-19
Also published as: FR2382901A1; FR2422629A1; DE2810031A1; IT1115597B; IT7821130A0; FR2382901B1; FR2422629B1; CH640697A5; NL7802626A

Abstract

The pesticidal composition contains, as active ingredient, an alpha - or beta -substituted isovaleric ester of the formula <IMAGE> in which Z<1> denotes hydrogen, <IMAGE> or <IMAGE>, Z<2> denotes <IMAGE> or <IMAGE>, if Z<1> denotes hydrogen, or denotes hydrogen, if Z<1> denotes <IMAGE> or <IMAGE>, A denotes cyano or ethynyl if Z<1> denotes <IMAGE> or, if not, hydrogen, cyano or ethynyl, and X and Y are identical or different and denote chlorine or bromine.

Description

(54) OPTIONALLY a-SUBSTITUTED PHENOXYBENZYL ESTERS OF (a OR p)-HALOALKENYL ISOVALERIC ACIDS AND PESTICIDAL COMPOSITIONS CONTAINING THEM (71) We, KURARAY CO. LTD., a company organised under the laws of Japan, of 1621, Sakazu, Kurashiki-city, Japan, do hereby declare the invention, for which we pray that a patent may be granted to us and the method by which it is to be performed, to be particularly described in and by the following statement:- This invention relates to pesticidal compositions. The compositions of the present invention contain, as an active ingredient, an isovaleric acid ester substituted in the a- or p-position and having the general formula:

in which Z' is hydrogen and Z2 is CX2 = CII-CH2-I or CX2 = CH-CHY-, or is CX2 = CH- or CX2 = CH-CH2- and Z2 is hydrogen; when Z' is CX2 = CH-; and each X and Y, which may be the same or different, represents chlorine or bromine.

The isovaleric acid esters substituted in the a- or p-position as represented by general formula (I) comprise the four types of substituted isovaleric acid esters which may be designated by the following general formulae (I-A), (I-B), (I-C) and (l-D), respectively.

Since the discovery of BHC and dichlorodiphenyltrichloroethane, there has been an amazing development of insecticides containing, as an active ingredient, such compounds as organophosphorus compounds, carbamates and chlorinated organic compounds. Such insecticides have been used in farming and gardening and their use had resulted in marked increases in the yields of crops, thus enabling a stabilized supply of crops to be secured without being intiuenced by climatic conditions. However, this success has been more or less offset by the fact that such agricultural and horticultural insecticides have not only high toxicity to human beings and domesticated animals but also a high tendency to cause environmental pollution. Thus, the chronic toxicity and accumulation of such poisons have become major concerns of our times. Furthermore, in many geographical areas, agricultural pests such as green-rice leafhoppers and plant hoppers have been acquiring resistance to the common pesticides comprising organic phosphorus compounds or carbamates, and the development of substitutes for those chemicals is a pressing need today. Pyrethroid pesticides, such as allethrin, phthalthrin, resmethrin, furamethrin and pyrethrin, which have hitherto been used for the purpose of controlling household pests, not only are low in toxicity to man and domestic animals but also have excellent pesticidal activities and fast-acting properties against noxious insects, which acquire resistance to such compounds only with difficulty. However, because of their extremely low stability to light and low residual activity, these compounds cannot be used as agricultural or horticultural pesticides replacing organophosphorus or carbamate pesticides.

Under the circumstances, there have been some developments in agricultural and horticultural pesticides that take advantage of the characteristics of pyrethroids, which are not possessed by the conventional agricultural pesticides.

Among the pesticides recently developed are 3 - phenoxybenzyl (+) - cis, trans - 2,2 - dimethyl - 3 - (2,3 - dichlorovinyl)cyclopropanecarboxylate (Permethrin, U.S.P. No. 4,024,163), which has the structural formula:

and a - cyano - 3 - phenoxybenzyl a - (4 - chlorophenyl)isovalerate (Fenvalerate, U.S.P. No. 3,996,244) which has the structural formula:

However, because of their high toxicity to fish, the applicability of these compounds is considerably restricted in geographical areas where, if used, they would contaminate natural waters such as river water.

Further, 3 - phenoxybenzyl a - (2,2 - dichlorovinyl)isovalerate, which has the structural formula:

and a - (allyl or 3,3 - dimethylallyl)isovaleric acid esters, which have the following structural formula:

(where A' is hydrogen, alkynyl or cyano) are reported to have pesticidal activity against agricultural, horticultural and household pests. (Published examined Japanese Patent Application No. 125723/1976 and U.S.P. No.4,042,710). However, none of these compounds possesses fully satisfactory pesticidal activity.

With a view to developing a pesticide that would have the characteric properties of pyrethroids and yet would display a higher residual activity than pyrethroids, a number of isovaleric acid esters having a substituent in the a- or position were synthesized and their pesticidal activity was investigated. The investigation revealed that certain a- or p-substituted isovaleric acid esters of the general formula (I) above possessed a markedly increased pesticidal activity as compared with the commonly used allethrin, as well as excellent resistance to light and hydrolysis and excellent residual activity, with many of such compounds being low in toxicity to fish. The present invention is based on the above discoveries.

It has been found that a- or p-substituted isovaleric acid esters of general formula (I) not only are pesticidally active against pests injurious to such plants as paddy rice plants, dry-field crop plants, cotton plants and orchard trees, which pests include green rice hoppers (Nephotettia cinticeps U,HLER), plant hoppers (e.g.

Sogatella furcifera HORVATH, Nilaparvata lugens STAL and Laodelphax stiatellus FALLEN), rice-stem borers (Chilo suppressalis WALKER), cabbage armyworm (Mamestra brassica LINE), diamond-back moth (Plutella maculi-pennis CURTIS), owlet moths and underwings, common cabbage worm (Pieris rapae crucivora BOISDUVAL), Japanese giant silk moth (Dictyoploca japonica BUTLER), bean web worm (Syllepte ruralis SCOPOLI), aphids, scale, mustard beetles (Phaedon cochleariae Fab.), boll weevils, pink bollworms (Pectinophora gossypiella Saund), tobacco budworms and mites, but also display excellent pesticidal activity against household pests such as houseflies, mosquitoes, and cockroaches (Blatella germanica). It should be understood that where the a- or p-substituted isovaleric acid ester of general formula (I) is a racemate, excellent effects will still be obtained if the racemate is resolved.

Among the compounds of general formula (I), those of general formulae (I-A) and (I-B) have particularly good pesticidal activity against the aforementioned variety of pests: they also have more potent killing effects upon agricultural and horticultural pests such as green rice leafhoppers than the known compound 3 - phenoxybenzyl a - (2,2 - dichlorovinyl)isovalerate. The a - (cyano or ethynyl) - 3 - phenoxybenzyl esters of a - (2,2 - dihalogenovinyl or 3,3 dihalogenoallyl)isovaleric acids have especially excellent killing effects upon agricultural and horticultural pests.

Regarding the compounds of general formula (I-C) and (I-D), the 2 phenoxybenzyl esters have good pesticidal activity against household pests such as houseflies, while the a - (cyano or ethynyl) - 3 - phenoxybenzyl esters have potent killing effects upon agricultural and horticultural pests such as green rice leafhoppers. Most of the a- or p-substituted isovaleric acid esters are extremely low in toxicity to fish and have promising applications as pesticides in localities where river water pollution and contamination are liable to take place. Thus, notwithstanding their varied pesticidal activities, the a- or p-substituted isovaleric acid esters of general formula (I) are low in toxicity to man and animals, with most of then being sparingly toxic to fish, are invariably highly resistant to light and hydrolysis, and have excellent residual activity.

Furthermore, the a- or p-substituted isovaleric acid esters of general formula (I) are not only insecticidal but also have promising repelling activity against mites, or/and produce synergistic effects with other biologically active compounds. Thus, the compounds (I) can be made available at low cost as control agents against agricultural and horticultural insects, forest insects, insects injurious to harvested crops, household insects, mites and other pests belonging to the following families: Tettigoniidae, Gryllidae, Gryllotalpidae, Blattidae, Reduviidae, Pyrrocoridae, Cimicidae, Delphacidae, Aphididae, Diaspididae, Pseudococcidae, Scarabaeidae, Dermestidae, Coccinellidae, - Tenebrionidae, Chrysomelidae, Bruchidae, Tineidae, Noctuidae, Lymantriidae, Pyralidae, Culicidae, Tipulidae, Stomoxydae, Trypetidae, Muscidae, Calliphoridae, Pulicidae, Tetranychidae and Dermanyssidae.

The following are examples of the a- or ,B-substituted isovaleric acid esters of general formula (I) according to this invention.

Compound No. Structural formula

a-Cyano-3-phenoxybenzyl a-(2,2-dichlorovinyl) isovalerate

a-Ethynyl-3-phenoxybenzyl a-(2,2-dichlorovinyl) isovalerate

a-Cyano-3-phenoxybenzyl a-(2,2-dibromovinyl) isovalerate

a-Ethynyl-3-phenoxybenzyl a-(2,2-dibromovinyl) isovalerate

3-Phenoxy benzyl a-(3,3-dichloroallyl)isovalerate

a-Cyano-3-phenoxybenzyl a-(3,3-dichlorallyl) isovalerate Compound No. Structural formula

a-Ethynyl-3-phenoxybenzyl a-(3,3-dichlorallyl) isovalerate

3-Phenoxybenzyl a-(3 ,3-dibromoallyl) isovalerate

a-Cyano.3.phenoxybenzyl a-(3,3-dibromoallyl) isovalerate

a-Ethynyl-3-phenoxybenzyl a-(3 ,3-dibromoallyl) isovalerate

3-Phenoxybenzyl p-(3,3dichlorallyl) isovalerate

a-Cyano-3-phenoxybenzyl p-(3,3-dichlorallyl) isovalerate Compound No. Structural formula

a-Ethylynyl-3-phenoxybenzyl P(3,3-dichlorallyl) isovalerate

3-Phenoxy benzyl p-(3,3-dibromoallyl) isovalerate

a-Cyano-3-phenoxybenzyl p-(3,3-dibromoallyl) isovalerate

a-Ethylynyl-3-phenoxybenzyl p-(3,3-dibromoallyl) isovalerate

3-Phenoxybenzyl p-(1,3,3-trichloroallyl) isovalerate

a-Cyano-3-phenoxybenzyl P-(l ,3,3-trichloroallyl) isovalerate Compound No. Structural formula

a-Ethynyl-3-phenoxybenzyl P-(l ,3,3-trichloroallyl) isovalerate

3-Phenoxybenzyl p-(I-chloro-3,3-dibromoallyl) isovalerate

a-Cyano-3-phenoxybenzyl -(1-chloro-3,3- dibromoallyl)isovalerate

a-Ethynyl-3-phenoxybenzyl p-(1-chloro-3,3- dibromoallyl)isovalerate

3-Phenoxybenzyl -(I-bromo-3,3-dichloroallyl) isovalerate

a-Cyano-3-phenoxybenzyl -(1-bromo-3,3- dichloroallyl) isovalerate Compound No. Structural formula

a-Ethynyl-3-phenoxybenzyl p-(1-bromo-3,3- dichloroallyl) isovalerate

3-Phenoxybenzyl 3-(1,3,3-tribromoallyl) isovalerate

a-Cyano-3-phenoxybenzyl p-(1,3,3-tribromoallyl) isovalerate

a-Ethynyl-3-phenoxybenzyl P-(l ,3,3-tribromoallyl) isovalerate Among the a- or p-substituted isovaleric acid esters of general formula (I), the a-substituted isovaleric acid esters of general formula (I-A), the a-substituted isovaleric acid esters of general formula (I-B) and the p-substituted isovaleric acid esters of general formula (I-C) are novel compounds, and according to the results of researches made by the present inventors, can each be easily produced by the following processes (i) to (iii).

CX3Y Treatment x + X aY with base COOR COOR JCOOR (1L) (ill) Xy Reduction XX Hydrolysis )C COOR X COOR x HOCHq (IV) X Hciogenoting X HOCHQ ('V) xM COOH Halogenoti x cov Tertiary amne (I"-A) (I"'-A ) Ester inter change X < XCOOC A t (l-A) LCOOR Xx#VY(vli COOR or COOR COOR X (Vii) (Vl I" ccooR (V) Treatment with X Hydrolysis base > (VI11) \ < COOH; X COOR x (lxi ii, - I X X ondor XyCŎHH H x (X) (1-B) HoCAH I Ester interchange COO COUCH H (I-B)

(i-1) Ozonolysis ( 93 P/CXL COOR i;ni cxrrl y X yCOOR COOR (I' -B) (iii) OH H CH3C(ORi3 E a,, mQCOOR 3 CHX3 H Catclyst Ixm (rev) #COOR HX XM#COOR X 3C Treatment with base (XV) ( 1' -C) H)iHy I Ester interchange X A O (iii -1) yCOOR Ozonolysis,, oHc gCOOR 3 4 P/Cx (Xvii X > < XzC OOR I x tr-c

(where R is lower alkyl; X and Y are the same or different and each means chlorine or bromine; A is hydrogen, cyano or ethynyl).

The a-substituted isovaleric acid esters of general formula (I-A) are produced by the above process (i). First, a compound of general formula (II) and a tetrahalomethane, e.g. tetrachloromethane (carbon tetrachloride), tetrabromomethane (carbon tetrabromide) or monobromotrichloromethane, are heated to SO--1500C in the presence of a radical initiator such as benzoyl peroxide (BPO), azobisisobutyronitrile (AIBN), acetyl peroxide or t-butyl perbenzoate to obtain a compound of general formula (III), which is then treated with a base such as 1,5 diazabicyclo[3,4,Oinonene - 5(DBN), 1,5 - diazabicyclo[5,4,Oiundecene - 5 (DBU), sodium ethoxide, potassium t-butoxide or sodium hydroxide, and the resultant product is reduced to a compound of general formula (I'-A). The above treatment with a base is desirably carried out in a solvent such as chloroform, tetrachloromethane, benzene, toluene, methanol, ethanol, tetrahydrofuran or n-hexane at a temperature of 0 C to 1000C. The reduction reaction is preferably carried out in an atmosphere of hydrogen gas and in the presence of a reduction catalyst, e.g.

palladium-on-carbon, palladium-on-barium-sulphate or palladium black, using a solvent such as methanol, ethanol or n-hexane at a temperature which may range from room temperature to 1000C. Then, the compound of general formula (l'-A) is hydrolysed in a conventional manner to the free carboxylic acid (I"-A) which, in turn, is treated with a halogenating agent such as thionyl chloride, thionyl bromide, phosphorus trichloride, phosphorus tribromide, phosphorus oxychloride or phosphorus oxybromide to obtain the corresponding carboxylic acid halide (I"--A). This carboxylic acid halide (l"'-A) is further reacted with an alcohol of general formula (IV) in the presence of a tertiary amine such as pyridine or triethylamine. By the above procedure is obtained the a-substituted isovaleric acid ester of general formula (I-A). An a-substituted isovaleric acid ester of general formula (I-A) may also be produced from a compound of general formula (I'-A) or a free carboxylic acid of general formula (I"-A) by several other alternative processes known per se, viz. (a) transesterification by reacting a compound of general formula (I'-A) directly with an alcohol of general formula (IV), (b) an esterification reaction involving a dehydrative condensation by reacting a free carboxylic acid of general formula (I"-A) with an alcohol (IV), (c) an esterification reaction in which a salt of free carboxylic acid (I"-A) with an alkali metal, silver or organic tertiary base is reacted with a sulfoxylate or halide of an alcohol (IV) or a quaternary ammonium salt thereof and (d) an esterification reaction by reacting the acid anhydride of a free carboxylic acid (I"-A) with an alcohol (IV).

The a-substituted isovaleric acid esters of general formula (I-B) can be produced by the above process (ii). First, a lower alkyl ester of isopropylmalonic acid of general formula (V) is reacted with a halogen compound of general formula (VI) or (VII), such as 1,1 - dichloro - 3 - bromo - 1 - propene, 1,1 - dibromo - 3 chloro - I - propene, 1,1,3 - trichloro - 1 - propene, 1,1,3 - tribromo - propene, 3,3,3 - trichloro - 1 - propene or 3,3,3 - tribromo - 1 - propene in the presence of a basic reagent at a temperature in the range 0 to 1000C to prepare a compound of general formula (VIII). As examples of said basic reagent may be mentioned sodium methoxide, sodium ethoxide, sodium t-butoxide, potassium tbutoxide, sodium hydride, sodium amide, butyllithium, sodium hydroxide, potassium hydroxide, sodium carbonate, 1,5 - diaazabicyclo[5,4,0]undecene 5[DBU] and 1,5 - diazabicyclo[3,4,0]nonene - 5(DBN). Then, the compound of general formula (VIII) is saponified, e.g. with potassium hydroxide or sodium hydroxide, and then neutralized with acid. By this hydrolytic treatment, which is conventional per se, the monoester of general formula (IX) and/or dicarboxylic acid of general formula (X) can be obtained. Thus, depending on the conditions of hydrolysis, including the relative amount of potassium hydroxide or sodium hydroxide based on the compound of general formula (VIII), and the time and temperature of reaction, a compound of general formula (IX), a compound of general formula (X), or a mixture of (IX) and (X) is obtained. The mono-ester of general formula (IX) and/or the dicarboxylic acid of general formula (X) are/is subjected to decarboxylation reaction by heating at a temperature in the range of 120 to 2500C, whereby a compound of general formula (I'-B) and/or a free carboxylic acid of general formula (I"-B) is obtained. Where the compound of general formula (I'-B) and the free carboxylic acid of general formula (I"-B) are obtained as a mixture; these compounds may be separated from each other, e.g.

by distillation, or, alternatively, the mixture may be hydrolysed so as to convert the compound of general formula (I '-B) to the free carboxylic acid (I"-B). The compound of general formula (I'-B) can also be easily produced by the process (ii-l).

Thus, ozone gas is bubbled into a solution of the y,b-unsaturated carboxylic acid ester of general formula (XI) in a solvent such as methanol or n-hexane at -200C to -10"C, whereby an aldehyde of general formula (XII) is obtained. This compound of general formula (XII) is subjected to the so-called Wittig's reaction, that is to say, reacted with the phospholane as formed from triphenylphosphine and carbon tetrahalide (U.S.P. No. 4,024,163), whereby a compound of general formula (I'-B) can be easily obtained. the carbon tetrahalide mentioned above is preferably carbon tetrachloride or carbon tetrabromide. The Wittig reaction is expediently accomplished in the solvent used in the preparation of phospholane, although it may be conducted in any other solvent that does not interfere with the Wittig reaction, such as methylene chloride or benzene. The asubstituted isovaleric acid ester of general formula (I-B) can be obtained by subjecting either the compound of general formula (I '-B) or the free carboxylic acid of general formula (I"-B) to an ester interchange reaction similar to the above-mentioned process (i).

The p-substituted isovaleric acid ester of general formula (I-C) can be produced by the above process (iii). Thus, in the first place, an orthocarboxylic acid ester (XIII) acts upon 3 - methyl - 2 - buten - I - owl in the presence of an acidic catalyst such as propionic acid, butyric acid, valeric acid, p-toluenesulfonic acid, phenol or hydroquinone at a temperature in the range 120 to 1600C. to produce the v,-unsaturated carboxylic acid ester (XIV) (Published unexamined Japanese Patent Applications Nos. 65710/1976 and 86410/1976). This y,X-unsaturated carboxylic acid ester (XIV) is then reacted with chloroform in the presence of a catalyst, for example in the presence of a radical initiator such as azobisisobutyro nitrile (AIBN), benzoyl peroxide (BPO), acetyl peroxide, di-t-butyl peroxide, t butyl peracetate, t-butyl perbenzoate, t-butyl perphthalate or t-butyl hydroperoxide at a temperature in the range 60 to 1500C, whereby the addition compound (XV) is obtained. This addition compound (XV) is then treated with a base such as sodium methoxide, sodium ethoxide, sodium t-butoxide, potassium t butoxide, sodium isoamylate, 1,5 - diazabicyclo[5,4,0]undecene - 5 (DBU), 1,5 diazabicyclo[3,4,0] noriene - 5 (DBN), sodium hydroxide, potassium hydroxide, sodium amide, sodium hydride or butyllithium at a temperature in the range -70" to +1500C, whereby a compound of general formula (I'-C) is obtained. The compound of general formula (I'-C) can also be produced by the method (iii-l).

This process can be effected by the same procedure as that of process (ii-l) except that the compound of general formula (XVI) is used in lieu of the compound of general formula (XI). By an ester interchange reaction of the compound of general formula (I'-C) in a manner analogous to that of the above process (i), the p substituted isovaleric acid ester of general formula (I-C) can be obtained.

The psubstituted isovaleric acid ester of general formula (I-D) is known only as an intermediate compound in the synthesis of 2,2 - dimethyl - 3 - (2,2 dichlorovinyl)cyclopropanecarboxylic acid, which is the acid residue of the aforementioned permethrin. (Published unexamined Japanese Patent ADplications Nows. 98248/1976, 125251/1976 and 125252/1976). The p-substituted isovaleric acid esters'of general formula (I-D) can be easily produced, for example by the following process (iv).

(iv) x xCOY xf Halogenating agent 0 x y o (Xvlt) (T"'-D) HCACIH (1 A $CCOCAIH H X Y O Tertiary amine X y OU (I - D) (where X and Y are the same or different and each is chlorine or bromine and A is hydrogen, cyano or ethynyl).

Thus, in the first place a y-lactone of general formula (XVII) is reacted with a halogenating agent to prepare a carboxylic acid halide of general formula (I"'-D).

When the halogenating agent is thionyl chloride, phosphorus pentachloride or phosphorus oxychloride, there is obtained a compound of general formula (I"'-D) in which Y is a chlorine, while a compound of general formula (I"'-D) in which Y is bromine is obtained when thionyl bromide or phosphorus pentabromide, for instance, is used as halogenating agent (Published unexamined Japanese Patent Application No. 12160-1977). The carboxylic acid halide of general formula (I"'-D) can also be produced by the method that we have previously discovered, that is to say by reacting a y-lactone of general formula (XVII) with a thionyl halide in the presence of a Lewis acid catalyst, e.g. zinc chloride or tin tetrachloride, and a hydrogen halide. Then, in an inert solvent, the carboxylic acid halide of general formula (I"'-D) is reacted with an alcohol of general formula (IV) in the presence of a tertiary amine such as pyridine or triethylamine, whereby a -substituted isovaleric acid ester of general formula (I-D) is easily obtained. (Published unexamined Japanese Patent Application No. 125150/1977).

The a- or -substituted isovaleric acid ester of general formula (I) (hereinafter referred to as the active compound) can be used in the form of conventional formulations such as solutions, emulsifiable concentrates, wettable powders, suspensions, dusts, granules, microfine granules, powders, coatings, aerosols, mosquito incense coils, (these are helical coils of paper impregnated with insecticide and incense, which are stood on a saucer and burn away very slowly), fumigants, slow-acting fumigants, electric mosquito incense mats and capsules.

These formulations may be prepared by conventional procedures, for example by admixing the active compound with a volume-builder, such as a liquid, solid or liquefied gas diluent or carrier (optionally with a surfactant, i.e. an emulsifier and/or a dispersing agent and/or a foaming agent). Where water is used as the volume building, an organic solvent may be used as a co-solvent.

Suitable liquid diluents usually include aromatic hydrocarbons such as xylene, toluene, benzene and alkylnaphthalenes; chlorinated aromatic or aliphatic hydrocarbons such as chlorobenzene, chloroethylene and methylene chloride; aliphatic or alicyclic hydrocarbons such as cyclohexane and paraffin (e.g. mineral oil distillate); alcohols such as butanol and glycol; glycol ethers and esters; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; highly polar solvents such as dimthylformamide, dimethylsulfoxide and acetonitrile; and water.

By "liquified gas diluent" is meant a material that is gaseous at normal temperature and pressure but can be liquified under pressure, such as aerosol propellants e.g. dichlorodifluoromethane and trichlorofluoromethane.

Preferred examples of solid diluent or carrier are finely divided naturally occurring minerals such as kaolin, clay, talc, chalk, quartz, attapulgite, montmorillonite and diatomaceous earth; and finely divided synthetic minerals such as alumina and silicates.

As preferred examples of emulsifiers and foaming agents may be mentioned nonionic and anionic emulsifying agents such as polyoxyethylene-aliphatic carboxylic acid esters; polyoxyethylene-aliphatic alcohol ethers such as alkyl aryl polyglycol ether; alkylsulfonates, alkylsulfates, arylsulfonates and albumin hydrolysate. Preferred examples of the dispersing agents include spent lignosulfite liquor and methylcellulose.

Adhesive agents such as carboxymethylcellulose; powdery, granular or latextype naturally occurring or synthetic high-molecular-weight compounds such as gum Arabic, polyvinyl alcohol and polyvinyl acetat (resmethrin), 5 - propargylturturyl chrysanthemate(turamethrin) 5 - propargyl 2 - methyl - 3 - furylmethyl chrysanthemate(proparthrin), 3 - phenoxybenzyl chrysanthemate(phenothrin), a - ethynyl - 3 - phenoxybenzyl chrysanthemate, 3 phenoxy - benzyl 2,2 - dimethyl - 3 - (2,2 - dichlorovinyl)cyclopropanecarboxylate(permethrin), a - ethynyl - 3 - phenoxybenzyl 2,2 - dimethyl - 3 - (2,2 dichlorovinyl)cyclopropanecarboxylate and a - cyano - 3 - phenoxybenzyl 2,2 dimethyl - 3 - (2,2 - dichlorovinyl)cyclopropanecarboxylate; and substituted acetic acid esters such as a - cyano - 3 - phenoxybenzyl a - (4 - chlorophenyl)isovalerate and a - ethynyl - 3 - phenoxybenzyl a - (4 - chlorophenyl)isovalerate.

In each formulation, the active compound is generally incorporated at the level of 0.01 to 95 weight percent, preferably 0.1 to 90 weight percent.

The active compound of this invention can be used in any of the aforementioned varied types of formulations or as further formulated into various application forms. The content of the active compound in such an application form may be varied over a broad range. The concentration of active compound in such an application form may range from 0.0000001 to 100 weight percent, preferably from 0.001 to 10 weight percent.

The pesticides containing any of the active compounds according to this invention can be put to use by routine procedures suited to modes of application.

The following examples of synthesis, testing examples, formulation examples and examples of effects are further illustrative of this invention. In the formulation examples and effect examples, all parts are by weight. The compound numbers correspond to the a- or -substituted isovaleric acid esters (I) to (28) of the general formula (I) mentioned hereinbefore.

Example of Synthesis-l To a mixture of 4.4 g of ethyl a-isopropylacrylate and 40 g of monobromotrichloromethane was added 0.14 g of t-butyl perbenzoate and the entire mixture was heated at 1200C for 12 hours. The reaction mixture was distilled to remove the low-boiling fraction and then further subjected to distillation under reduced pressure to recover 8.5 g. of ethyl a-bromo-a-(2,2,2-trichloroethyl)isovalerate, b.p.

132--136"C/0.8 mmHg (yield 81%).

In 20 g of chloroform was dissolved 6.ü g of the ethyl a-bromo-a-(2,2,2-tri- chloroethyl)isovalerate and, after the addition of 3.5 g of 1,5-diazabicylco[5,4,0]- undecene-5 (DBU), the solution was stirred at room temperature for 2 hours. The reaction mixture was then diluted with diethyl ether, washed with water and dilute aqueous hydrogen chloride and dried over anhydrous magensium sulfate. The lowboiling fraction was removed by distillation, whereupon 4.6 g of oily product was obtained. Based on its NMR spectrum and .gc-mass spectrum, this product was identified to be ethyl a-isopropyl-p-trichloromethylacrylate containing a certain amount of ethyl a-bromo-a-(2,2,-dichlorovinyl) isovalerate. In 50 ml of ethanol was dissolved 4.6 g of the oily product obtained above and, following the addition of 0.4 g of 5% palladium-on-carbon, the solution was stirred in an atmosphere of hydrogen gas at 550C for 6 hours. Thereafter, the reaction mixture was filtered to remove the catalyst and the ethanol was distilled off. By the above procedure was obtained 3.9 g of ethyl a-(2,2-dichlorovinyl)isovalerate as oil. then, 3.9 g of this ethyl a-(2,2-dichlorovinyl)isovalerate was dissolved in 20 ml of ethanol and a solution of 2.0 g of sodium hydroxide in 10 ml of water was added to the above ethanol solution. The mixture was stirred at room temperature for 10 hours, at the end of which time the ethanol was distilled off. The residue was neutralized with aqueous hydrogen chloride and extracted with diethyl ether. The ethereal solution yielded 2.9 g of a-(2,2-dichlorovinyl)isovaleric acid having the following NMR spectrum [yield: 84% based on ethyl a-bromo-a-(2,2,2-trichloroethyl)isovaleratei.

NMR spectrum (60 MHz) a TCMIs: 0.97(d, J = 7Hz), l.03(d, J = 7Hz), 6H; 1.83--2.36(m)ln; 3.23(d, J = t0Hz), 3.35(d, J = 10Hz)lH; 6.04(d, J = 10Hz)lH.

In 15 ml of dry benzene was dissolved 1.8 g of a-(2,2-dichlorovinyl)isovaleric acid, followed by the addition of 3.5 g of thionyl chloride. The mixture was refluxed for 5 hours and, then, distilled to remove the low-boiling fraction. By the above procedure was obtained a-(2,2-dichlorovinyl)isovaleroyl chloride. This chloride was dissolved in 20 ml of benzene, and 2.0 g of a-ethynyl-3-phenoxybenzyl alcohol was added. This was followed by the addition of 2.9 g of pyridine and the mixture was stirred at room temperature for 8 hours. The resultant reaction mixture was diluted with diethyl ether, washed with water and dilute aqueous hydrogen chloride and dried over anhydrous magnesium sulfate. The low-boiling fraction was then distilled off and the residue was chromatographed on a column of silica gel (benzene/n-hexane = 1:1 v/v). By the above procedure was obtained 2.6 g of cu- ethynyl-3-phenoxybenzyl a-(2,2-dichlorovinyl)isovalerate[compound (2)] [yield: 71% based on a-(2,2-dichlorovinyl)isovaleric acid].

NMR spectrum (60 MHz) a CDCl3 TMS 0.78--1.06(m)6H, 1.80--2.47(m)lH, 2.61(d, J=2Hz)lH, 3.29 (dd, J=7Hz & 10Hz)lH, 6.00(d, J = l0Hz)lH, 6.44(d, J = 2Hz) 1H, 6.85-7.55(m)9H Elemental analysis (calcd. in parentheses): C% 65.65(65.52) H% 5.09 (5.00) Example of Synthesis-2.

In 20 ml of dry benzene was dissolved 2.0 g of a-(2,2-dichlorovinyl)isovaleric acid, followed by the addition of 6.0 g of thionyl chloride. The mixture was refluxed overnight. It was then distilled to remove the low-boiling fraction, whereby a-(2,2dichlorovinyl)isovaleroyl chloride was obtained. This a-(2,2-dichlorovinyl)- isovaleroyl chloride was dissolved in 25 ml of dry benzene, followed by the addition of 2.3 g of zr-cyano-3-phenoxybenzyl alcohol and, then, 2.4 g of pyridine.

The mixture was stirred at room temperature overnight. The resultant reaction mixture was diluted with diethyl ether, washed with water and dilute aqueous hydrogen chloride, dried over anhydrous magnesium sulfate and distilled to remove the low-boiling fraction. Column chromatography was carried out on the residue to obtain 3.2 g of a-cyano-3-phenoxybenzyl e-(2,2-dichlorovinyl)isovalerate [Compound (I)] which was shown to have the properties given below [yield: 78% based on a-(2,2-dichlprovinyl)isovaleric acid].

NMR spectrum (60 MHz) 8 CDCl3 TMS 0.78--1.04(m)6H, 1.74--2.40(m)lH, 3.31(dd, J=7Hz & lûHz)lH 5.95(d, J = lOHz)lH, 6.33(s)lH, 6.87-7.53(m)9H Elemental analysis (calcd. in parentheses): C% 62.28(62.39) H% 4.70(4.74) Example of Synthesis-3 10.5 g of sodium hydride (ca. 50%) was washed with n-hexane and suspended in 430 g of benzene with stirring. To this suspension was added 36.8 g of diethyl isopropylmalonate and the mixture was refluxed for about 40 minutes. The reaction mixture was then allowed to stand and cool for about 20 minutes, after which 37.9 g of I,I.dichloro-3-bromo-l-propene was added in several instalments. The mixture was then stirred under reflux for 1.5 hours. After cooling, the reaction mixture was washed with water and dilute hydrochloric acid, dried over anhydrous magnesium sulfate and distilled to remove the low-boiling fraction. The resultant oil was further distilled under reduced pressure to obtain 52.3 g of diethyl isopropyl-(3,3dichloroallyl)malonate which was shown to have the tollowlng NMK spectrum [yield: 92% based on diethyl isopropylmalonate].

NMR spectrum (60 MHz) 8 CHCM4s: HMS 0.94(d, J = 7Hz)6H, 1.22(t, J = 7Hz)6H, 2.04-2.44(m)lH, 2.64 (d, J = 7Hz)2H, 4. 16(q, J = 7Hz)4H, 5.90(t, J = 7Hz)l H In 20 g of ethanol was dissolved 8.8 g of the above diethyl isopropyl-(3,3 dichloroallyl)malonate and a solution of 6.4 g of potassium hydroxide in 10 g of water was added to the above ethanol solution. The mixture was refluxed overnight. Then, the reaction mixture was distilled to remove the ethanol and a sufficient amount of dilute hydrochloric acid was added to make the residue acidic.

The residue was extracted with diethyl ether and the ethereal layer was dried over anhydrous magnesium sulfate and distilled to remove the low-boiling fraction. By this procedure was obtained a mixture of isopropyl-(3,3-dichloroallyl)malonic acid and monoethyl isopropyl-(3,3-dichloroallyl)malonate. This mixture was subjected to decarboxylation reaction at 180 to 2300C under a reduced pressure. of 35 to 60 mmHg, whereupon 6.0 g of a mixture of a-(3,3-dichloroallyl)isovaleric acid and ethyl a-(3,3-dichloroallyl)isovalerate was obtained. In 20 g of ethanol was dissolved 6.0 g of the above decarboxylated mixture and a solution of 1.2 g of sodium hydroxide in 10 g of water was added to the above solution. The mixture was refluxed for 4 hours, after which the ethanol was distilled off. The residue was made acidic with dilute hydrochloric acid and extracted with diethyl ether. The ethereal layer was dried over anhydrous magnesium sulfate and distilled to remove the lowboiling fraction. By the above procedure was obtained 4.2 g of a-(3,3-dichloroallyl)isovaleric acid, the NMR spectrum of which appears below [yield: 70% based on diethyl isopropyl-(3,3-dichloroallyl)malonate].

NMR spectrum (60 MHz) a CHCM4s: HMS 1.01(d, J=7Hz)6H, 1.67--2.67(m) 4H, 5.94(t, J=7Hz)lH To 2.1 g of a-(3,3-dichloroallyl)isovaleric acid was added 3.0 g of thionyl chloride as well as 10 g of benzene and the mixture was refluxed for 5 hours.

Then, the reaction mixture was distilled to remove the low-boiling fraction.

By this procedure was obtained cw-(3,3-dichloroallyl)isovaleroyl chloride. This chloride was dissolved in 30 g of dry benzene, followed by the addition of 2.0 g of 3-phenoxybenzyl alcohol. Then, 2.0 g of pyridine was added dropwise and the mixture was stirred at room temperature overnight. The reaction mixture was then diluted with diethyl ether, washed with dilute hydrochloric acid and water, dried over anhydrous magnesium sulfate and distilled to remove the low-boiling fraction.

The residual viscous oil was purified by column chromatography to recover 3.1 g of 3-phenoxybenzyl a-(3,3-dichloroallyl)isovalerate[Compound (5)] having the following properties [yield: 79% based on a-(3,3-dichloroallyl)isovalerylic acid].

NMR spectrum (60 MHz) a CDCI, 0.94(d, J = 7Hz)6H, 1.65--2.66(m)4H, 5.14(s)2H, 5.87(t, J = 7Hz)lH, 6.83-7.60(m)9H Elemental analysis (calcd. in parentheses): C% 64.20(64.13) H% 5.58(5.64) Examples of Synthesis-4 & 5.

The procedure of Example of Synthesis-3 was repeated except that 2.3 g of a- cyano-3-phenoxybenzyl alcohol or 2.3 g of a-ethynyl-3-phenoxybenzyl alcohol was used in lieu of 2.0 g of 3-phenoxybenzyl alcohol. By these procedures were obtained the corresponding a-(3,3-dichloroallyl)isovaleryl acid esters [Compound (6) and Compound (7)], respectively. The yields, NMR spectra and elemental analyses of these esters are shown below.

Compound (6): yield 3.5 g (84%) NMR spectrum (60 MHz) a TCMSCii: 0.78-I .05(m)6H, I .63-2.52(m)4H, 5.60--5.94(m)lH, 6.38(s)lH, 6.85-7.55(m)9H Elemental analysis (calcd. in parentheses): C% 63.09 (63.17) H% 4.95(5.06) Compound (7): yield 3.0 g (72%) NMR spectrum (60 MHz) a CDCl3 TMS 0.81-I .05(m)6H, 1 .62-2.55(m)4H, 2.63(d, J = 2Hz) 1 H, 5.67--5.98(m)1H, 6.47(d, J = 2Hz)lH, 6.87-7.55(m)9H Elemental analysis (calcd. in parentheses): C% 66.31(66.20) H% 5.38(5.31) Example of Synthesis-6 In 100 g of methanol was dissolved 10.0 g of ethyl a-allylisovalerate [general formula (XI) where R = -CH2CH3] and, under cooling at -20--100C and stirring, ozone gas was bubbled into the solution for 8 hours. Then, at room temperature, the reaction mixture was added to 100 g of dimethyl sulfide and the mixture was stirred at that temperature overnight. The reaction mixture was then distilled under reduced pressure to remove the low-boiling fraction and the residue was diluted with 50 g of diethyl ether. Following the addition of 4 g of calcium chloride, HCI gas was bubbled into the mixture at room temperature for 10 minutes. Then, 5 g of anhydrous potassium carbonate was added and the mixture was thoroughly stirred.

The diethyl ether solution was taken, washed with water, dried over anhydrous magnesium sulfate and distilled under reduced pressure to remove the low-boiling fraction. By the above procedure was obtained 9.0 g of ethyl 2 - isopropyl - 3 formyl - propionate[general formula (XII) wherein R=-CH2CH3][yield: 89% based on ethyl a-allylisovalerate; the NMR spectrum of the aldehyde (60 MHz) a HMS : 9 9.74] In 240 g of methylene chloride was dissolved 12.5 g of carbon tetrabromide, followed by the addition of 19.8 g of triphenylphosphine. The mixture was thoroughly stirred. To this mixed solution was added 5.0 g of the ethyl 2 isopropyl - 3 - formyl - propionate prepared above and the mixture was stirred at room temperature overnight. Thereafter, the low-boiling fraction was distilled off under reduced pressure and the residue was stirred well with diethyl ether and water. The diethyl ether layer was taken and distilled under reduced pressure to remove the low-boiling fraction. To the residue was added petroleum ether and, after thorough stirring, the petroleum ether solution was taken and further distilled under reduced pressure to remove the low-boiling fraction. The resultant oily residue was purified by distillation under reduced pressure. By the above procedure was obtained 4.6 g of ethyl sr-(3,3-dibromoallyl)isovalerate[yield: 48% based on ethyl 2 - isopropyl - 3 - formyl - propionate] NMR spectrum (60 MHz) a CDCI, HMS 0.88(d, J = 6.5Hz)6H, 1.20(t, J = 7Hz)3H, 1.65--2.38(m)4H, 4.09(q, J = 7Hz)2H, 6.35(t, J = 7Hz)lH In a mixture of 7 g of water and 20 g of ethanol was dissolved 1.1 g of sodium hydroxide and 4.6 g of the ethyl a-(3,3-dibromoallyl)isovalerate obtained above was added to the above solution. The mixture was stirred at room temperature overnight and, then, refluxed for 3 hours. The reaction mixture was then distilled to remove the ethanol and the residue was made acidic by the addition of dilute hydrochloric acid and extracted with diethyl ether. The ethereal layer was dried over anhydrous magnesium sulfate and the low-boiling fraction was distilled off. By the above procedure was obtained 3.7 g of a-(3,3-dibromoallyl)isovaleric acid, the NMR spectrum of which is shown below [yield: 88% based on ethyl a-(3,3dibromoallyl)isovalerate] .

NMR spectrum (60 MHz) a CDCI, HMS 0.92(d, J = 6.5Hz)6H, 1.67--2.42(m)4H, 6.39(t, J = 7Hz) 1H, 10.63(s)lH In 20 g of benzene was dissolved 2.0 g of cg-(3,3-dibromoallyl)isovaleric acid, followed by the addition of 4.7 g of thionyl chloride and 2 drops of N,N-dimethylformamide. The mixture was refluxed overnight and, then, distilled to remove the low-boiling fraction. As the residue was obtained a-(3,3-dibromoallyl)isovaleroyl chloride. This a-(3,3-dichloroallyl)isovaleroyl chloride was dissolved in 30 g of dry benzene and 1.5 g of a-ethynyl-3-phenoxybenzyl alcohol was added. This was further followed by the dropwise addition of 1.6 g of pyridine and the mixture was stirred at room temperature overnight. Thereafter, the reaction mixture was further stirred at 40--500C for 2 hours, after which it was diluted with diethyl ether, washed with dilute hydrochloric acid and water, dried over anhydrous magnesium sulfate and distilled to remove the low-boiling fraction. The resultant viscous oil was purified by column chromatography to recover 2.0 g of a-ethylnyl-3-phenoxybenzyl a-(3,3-dibromoallyl)isovalerate [Compound (10)] which was shown to have the properties indicated below. [yield: 59% based on a-(3,3-dibromoallyl)isovaleric acid] NMR spectrum (60 MHz) a CDCl3 HMS 0.74--1.03(m)6H, 1.60--2.43(m)4H, 2.53--2.63(m)1H, 6.12--6.50(m)2H, 6.84-7.50(m) Elemental analysis (calcd. in parentheses): C% 54.66(54.57) H% 4.40(4.38) Examples of Synthesis-7 & 8.

The procedure described in Example of Synthesis-6 was followed except that 1.4 g of 3-phenoxybenzyl alcohol or 1.5 g of a-cyano-3-phenoxybenzyl alcohol was used in lieu of 1.5 g of a-ethynyl 3-phenoxybenzyl alcohol. By these procedures were obtained the corresponding a-(3,3-dibromoallyl)isovaleric acid esters compound (8) and Compound (9)], respectively. The yields, NMR spectra and elemental analyses of these esters are given below.

Compound (8): yield 2.6 g (81%) NMR spectrum (60 MHz) a TCMCsl3: 0.91(d, J=6.5Hz)6H, 1.65--2.50(m)4H, 5.09(s)2H, 6.35(t, J=7Hz)lH, 6.87-7.50(m)9H Elemental analysis (calcd. in parentheses): C% 52.18(52.31) H%4.55(4.60) Compound (9): yield 2.2 g (65%) Elemental analysis (calcd. in parentheses): C% 51.97(52.10) H% 4.12(4.17) Example of Synthesis-9 A pressure-resistant tubular reactor was charged with a mixture of 20.0 g of ethyl 3,3-dimethyl-4-pentenate, 200 g of chloroform and 1.0 g of t-butyl perbenzoate and, after the tube was sealed, the contents were heated at 12 C for 20 hours. Then, the reaction mixture was distilled to remove the low-boiling fraction and further subjected to distillation under reduced pressure. By the above procedure was obtained 27.2 g of ethyl p-(3,3,3-trichloropropyl)isovalerate(ethyl 6,6,6-trichloro-3,3-dimethylhexanoate) (yleld: 77%).

b.p. 90-920C/0.6 mmHg NMR spectrum (60 MHz) a CDCl3: TMS 1.07(s), 1.26(t, J = 7Hz)9H; 1.67--2.03(m)2H; 2.24(s)2H; 2.60--2.95(m)2H; 4.17(q, J = 7Hz)2H In 50 g of ethanol was dissolved 2.5 g of sodium metal and 20.0 g of the above ethyl p-(3,3,3-trichloropropyl)isovalerate was added to the solution. The mixture was refluxed for 8 hours. The reaction mixture was neutralized with a solution of hydrogen chloride in dry ethanol and concentrated to about one-twentieth of its original volume. To this concentrate was added 100 g of ice-water and the mixture was extracted with diethyl ether. The ethereal layer was dried over anhydrous magnesium sulfate and distilled to remove the low-boiling fraction. By the above procedure was obtained 13.7 g of ethyl p-(3,3-dichloroallyl)isovalerate (ethyl 6,6dichloro-3,3-dimethyl-5-hexenoate), the NMR spectrum of which is given below.

(yield: 79 /O) NMR spectrum (60 MHz) a CHCM4s: HMS 0.99(s)6H, 1.20(t, J = 7.5Hz)3H, 2.09-2.35(m)4H, 4.07(q, J = 7.5Hz)2H, 5.94 (t, J = 7.5Hz)lH To a solution of 2.2 g of sodium hydroxide in 15 g of water was added 10.0 g of the above ethyl p-(3,3-dichloroallyl)isovalerate as well as 20 g of ethanol, and the mixture was refluxed for 4 hours. The reaction mixture was distilled to remove the ethanol, made acidic with aqueous hydrogen chloride and extracted with diethyl ether. The ethereal layer was dried over anhydrous magnesium sulfate and distilled to remove the low-boiling fraction. By the above procedure was obtained 8.2 g of P- (3,3-dichloroallyl)isovaleric acid (6,6-dichloro-3,3-dimethyl-5-hexanoic acid), the NMR spectrum of which is given below. (yield: 93%) CCl NMR spectrum (60 MHz) a HMS : 1.04(s)6H, 2.14-2.34(m)4H, 5.94(t, J = 7.5Hz)lH To 2.1 g of p-(3,3-dichloroallyl)isovaleric acid was added 3.0 g of thionyl chloride and 10 g of benzene, and the mixture was refluxed for 5 hours. The reaction mixture was then distilled to remove the low-boiling fraction and recover ,B-(3,3-dichloroallyl)isovaleroyl chloride as the residue. This -(3,3-dichloroallyl)- isovaleroyl chloride was dissolved in 30 g of dry benzene and 2.0 g of 3-phenoxybenzyl alcohol was added to the solution. This was further followed by the dropwise addition of 1.6 g of pyridine and the mixture was stirred at room temperature overnight. Thereafter, the reaction mixture was diluted with diethyl ether, washed with dilute aqueous hydrogen chloride and water, dried over anhydrous magnesium sulfate and distilled to remove the low-boiling fraction. The resulting oily residue was purified by column chromatography to obtain 2.8 g of 3-phenoxybenzyl P-(3,3- dichloroallyl)isovalerate [Compound (I I)] having the following properties. [yield: 71% based on p(3,3-dichloroallyl)isovalen.c acid] NMR spectrum (60 MHz) a HCM4s: HMS 0.93(s)6H, 2.03-2.23(m)4H, 4.98(s)2H, 5.88(t, J = 7.5Hz) 1H, 6.76-7.50(m)9H Elemental analysis (calcd. in parentheses): C /O 64.08(64.13) H% 5.60(5.64) Examples of Synthesis-lO & II.

The procedure described in Example of Synthesis-9 was repeated except that 2.2 g of a-cyano-3-phenoxybenzyl alcohol or 2.2 g of a-ethynyl-3-phenoxybenzyl alcohol was used in lieu of 2.0 g of 3-phenoxybenzyl alcohol. By these procedures were obtained the corresponding esters of p-(3,3-dichloroallyl)isovaleric acid [Compound (12) and Compound (13)], respectively. The yields, NMR spectra and elemental analysis of these esters are given below.

Compound (12): Yield 3.4 g (81%) NMR spectrum (60 MHz) a TMS 3 TMS 1.01(s)6H; 2.19(d, J = 8Hz), 2.30(s)4H; 5.89(t, J = 8Hz)lH; 6.38(s)1H: 6.907.50(m)9H Elemental analysis (calcd. in parentheses): C% 62.98(63.17) H% 5.06(5.06) Compound (13) Yield 3.3 g(79%) NMR spectrum (60 MHz) a CDCl3 TMS 0.96(s)6H, 2.07-2.28(m)4H, 2.53(d, J=2Hz)lH, 5.87(t, J=8Hz)lH, 6.44(d, J=2Hz)lH, 6.83-7.50(m)9H Elemental analysis (calcd. in parentheses): C% 66.05(66.20) H% 5.19(5.31) Example of Synthesis-12.

In 150 g of benzene was dissolved 62.7 g of 3,3-dimethyl-4-(2,2-dichlorovinyl)4-butanolide and, at room temperature, hydrogen chloride gas was bubbled into the solution for one hour. Then, 3.0 g of zinc chloride was added and the mixture was refluxed. While the introduction of hydrogen chloride gas was continued, 107.0 g of thionyl chloride was added dropwise over a period of one hour. The mixture was further heated at that temperature for one hour. The mixture was further heated at that temperature for 4 hours, after which time the excess of thionyl chloride and benzene were distilled off under reduced pressure. The residue was subjected to distillation under reduced pressure to recover 49.1 g of 3,3-dimethyl4,6,6-trichloro-5-hexanoyl chloride which was shown to have the following properties. (yield: 62%) b.p. 798laC/0.65 mmHg NMR spectrum (60 MHz) # CCl4 : HMS 1.14(s)3H, 1.17(s)3H, 2.87(d, J= 17Hz)lH, 3.22(d, J= 17Hz)lH, 4.83(d, J= l0.5Hz)lH, 6.04(d, J= 10.5Hz)lH In 30 g of dry benzene was dissolved 2.6 g of 4,6,6-trichloro-3,3-dimethyl-5- hexanoyl chloride and 2.0 g of 3-phenoxybenzyl alcohol was added to the solution.

This was followed by the dropwise addition of 2.4 g of pyridine and the mixture was stirred at room temperature overnight. The reaction mixture was then diluted with diethyl ether, washed with dilute aqueous hydrogen chloride and water, dried over anhydrous magnesium sulfate and distilled to remove the low-boiling fraction. The residual viscous oil was purified by column chromatography. By the above procedure was obtained 3.9 g of 3-phenoxybenzyl -(1,3,3-trichloroallyl)- isovalerate [3-phenoxybenzyl 4,6,6-trichloro-3,3-dimethyl-5-hexanoate, Compound (17)], the NMR spectrum and elemental analysis of which are given below. (yield: 91%) NMR spectrum (60 MHz) a CCl4 HMS I.03(s)6H, 2.18(d, J= 15Hz)lH, 2.52(d, J= 15Hz)lH, 4.87 (d, J= 10.5Hz)lH, 5.02(s)2H, 6.02(d, J= 10.5Hz)lH, 6.807.50(m)9H Elemental analysis (calcd. in parentheses): C% 58.85(58.97) H% 5.02 (4.97) Examples of Synthesis-13 & 14.

The procedure described in Example of Synthesis-12 was repeated except that 2.3 g of a-cyano-3-phenoxybenzyl alcohol or 2.3 g of a-ethynyl-3-phenoxybenzyl alcohol was used in lieu of 2.0 g of 3-phenoxybenzyl alcohol. By the above procedures were obtained the corresponding esters of p-(1,3,3-trichloroallyl)- isovaleric acid [Compound (18) and Compound (19)], respectively. The yields, NMR spectra and elemental analyses of these esters are as follows.

Compound (18): Yield 3.8 g (84%) CDCl NMR spectrum (60 MHz) a TMS 1.08(s)6H; 2.33(bd, J = 15Hz), 2.66(bd, J = 15Hz)2H; 4.80(d, J = 10.5Hz)lH; 6.02(d, J=10.5Hz)1H; 6.36(s)1H; 6.92-7.58(m)9iH Elemental analysis (calcd. in parentheses): C% 58.45(58.36) H% 4.41(4.45) Compound (19): Yield 3.6 g (80%) NMR spectrum (60 MHz) a CDCl3: TMS 0.94(s)6H; 2.11(d, J=l5Hz), 2.14(d, J= 15Hz), 2.38 (d, J=l5Hz), 2.41(d, J = 15Hz), 2.45(d, J = 2Hz)3H; 4.69(d, J = 11Hz), 4.72(d, J = I 1Hz)1H; 5.86(d, J= IlHz)lH; 6.30(d, J=2Hz)lH; 6.77.25(m)9H Elemental analysis (calcd. in parentheses): C% 61.25(61.14) H

TABLE 1

Mortality ("/o) Test compound No. 10 pg"fly Ig?ly (1, 100 100 (2) 100 100 (5) 100 100 (6) 100 100 (7) 100 90 (8) 100 100 (9) 100 100 (10) 100 100 (11) 100 100 (12) 100 (13) 100 (17) 100 100 (18) 100 (19) 100 Allethrin 100 50 X,:ooCH, O 0 5!$COOCH2 - 0 Test Example 2.

A killing test against green rice leafhoppers by the topical application method Each test compound was accurately weighed and a 0.1% solution in acetone was prepared. Female adults of green rice leafhopper (Nephotettix cincticeps UHLER) were anaesfhetized w'ith carbon dioxide gas and 0.5 y1 of the above solution was micropipetted onto the thoracic abdominal part of each leafhopper.

Then, the test leafhoppers were kept at 25 (: with access to rice plant seedlings.

Each group comprised 15 green rice leafhoppers. After 24 hours, the leafhoppers were inspected for deaths and the mortality (%) was calculated for each compound.

The results are set forth in Table 2.

TABLE 2

Test compound No. | Mortality (No) (1) Not less than 90% (2) (6) (7) (9) (leo) (12) (13) Ass's 40% c S co0cH242 40% ot Test Example 3.

A killing test against cockroaches by the topical application method Each test compound was accurately weighed and made in a 1% solution in acetone. ?hen, I y1 of the above solution was micropipetted onto the abdominal part of each female cockroach (Blattella germanica Linne) under ether anaesthesia.

The roaches were released in a high-walled dish together with feed and, after the dish was covered with a metal wire net, it was maintained at 250C. Fifteen roaches per group were used. After 24 hours, the test roaches were inspected for deaths and the mortality (%) for each group was calculated. The results are set forth in Table 3.

TABLE 3

Test compound No. Mortality (%) (1) 100 (2) 80 (6) 100 (7) 80 Test Example 4.

Light stability test In 2.0 ml ol acetone was dissolved 80 mg of each test compound. A 5 y1 portion of the solution was taken and spread on a glas plate (Micro Standard Cover Glass, 18m/mO No. 1, 200 pcs, Matsunami Glass Ind., Ltd) and the acetone was evaporated. Then, a similar glas plate was superimposed on the above plate in such a manner that the test solution was sandwiched. The specimen was exposed to direct sunlight at an atmospheric temperature of 12"C. for a predetermined exposure time. As an unexposed control, a similar specimen was covered with an aluminum foil. The test solution was washed away with 1.0 ml of methanol containing 0.04% of dioctyl phthalate as an internal reference and high-speed liquid chromatography was carried out on the washings to determine the residual amount of the test compound. The percent residue (%) is shown in Table 4. The residue (%) was calculated with the value for the aluminum-foil-covered control specimen as the standard.

Table 4.

Residue (%) 4 hours 8 hours Test compound No. Exposure Exposure 93 90 2 97 100 5 99 98 6 92 92 7 96 96 10 97 97 11 100 96 12 92 90 13 100 100 17 100 100 18 98 97 19 97 92 Allethrin 35 17 Test Example 5.

Hydrolysis resistance test In about 8 ml of acetone was dissolved 100 mg of each test compound and, then, 1.0 g of water was added to this solution to prepare a mixed solution. This mixed solution was refined for 2 days, after which the acetone was distilled off.

After concentration to about one half of the original volume and with the addition of dioctyl phthalate as an internal reference, the residual amount of the compound was determined by high-speed liquid chromatography. The residue (%) was then calculated. The results are set forth in Table 5.

Table 5.

Test compound No. Residue (%) (2) more than 90 (6) (7) (11) (12) (18) Test Example 6.

Fish Toxicity test To 51 of water was added 250 mg of Sorpol SM-200 (registered trademark.

Toho Chemical Co., Ltd.) or Tween-20 (registered trademark) as an emulsifier (surfactant) as well as 2.5 ml of an acetone solution containing one of the test compounds in a predetermied concentration. The mixture was stirred well to prepare a test water. Ten female guppies from 3 to 4 months of age were released into the test water and kept at 250 C. The concentration of the test compound at which 90% or more of the guppies were killed during the ensuring 48 hours was determined. (This concentration is referred to as LCgo). The results are set forth in Table 6.

TABLE 6

Test compound No. LC90 (2) Not less than 10 ppm (5) (7) (8) (10) (11) (12) (13) (17) (18) (19) Allethrin Not more than 0.5 ppm Permethrin Fenvalerate Formulation Example 1.

0.2 part of each of Compounds (1), (2), (5) to (13) and (17) were prepared and 0.8 part of piperonyl butoxude was added to each of them. To this mixture was added a sufficient amount of kerosene to make 100 parts, followed by stirring. By this procedure was obtained an oil preparation of each Compound.

Formulation Example 2.

To 0.1 part of each of Compounds (1) to (17) was added 0.1 part of resmethrin, followed by the addition of a sufficient amount of kerosene to make 100 parts. The mixture was stirred to obtain an oil preparation of each compound.

Formulation Example 3.

To 0.1 part of each of Compounds (1) to (28) was added 0.08 part of permethrin, followed by the addition of a sufficient amount of kerosene to make 100 parts. The mixture was stirred to obtain an oil preparation of each compound.

Formulation Example 4.

To 0.2 part of each of Compounds (1), (2), (5) to (13) and (17) to (19) was added 0.2 part of 2-isopropoxyphenyl N-methylcarbamate and 5 parts of xylene. The composition was dissolved in a sufficient amount of kerosene to make 100 parts. In the above manner, an oil preparation of each compound was obtained.

Formulation Example 5.

To 30 parts of each of Compounds (1), (2), (5) to (13) and (17) to (19) was added 50 parts of xylene and 20 parts of Sorpol SM-200 (a surfactant, trade mark of Toho Chemical Co., Ltd.). The mixture was stirred well and dissolved to obtain a 30% emulsifiable concentrate.

Formulation Example 6.

To 20 parts of each of Compounds (1), (2), (5) to (9) and (Il) to (13) wad added 20 parts of 0,0 - dimethyl - 0 - 4 - cycanophenyl phosphorothioate [Thianox, trademark of Sumitomo Chemical Co., Ltd.], 20 parts of Sorpol SM-200 (a surfactant, trade mark of Toho Chemical Co., Ltd.) and 40 parts of xylene. The mixture was stirred well to dissolve, whereby an emulsifiable concentrate of each compound was obtained.

Formulation Example 7.

To 20 parts of each of Compounds (1), (2), (5) to (13), (17) to (19) and (2)) ways added 5 parts of Sorpol SM-200 (a surfactant, trade mark of Toho Chemical Co., Ltd.), followed by thorough mixing. With the addition of 75 parts of 300-mesh talc, the mixture was thoroughly stirred in a triturator. By the above procedure was obtained a wettable powder of each compound.

Formulation Example 8.

To 15 parts of each of Compounds (1), (2) and (5) to (13) was added 15 parts of l-naphthyl N-methylcarbamate and 5 parts of Sorpol SM-200 (a surfactant, trade mark of Toho Chemical Co., Ltd.), followed by thorough mixing. With the addition of 65 parts of 300-mesh talc, the mixture was thoroughly stirred in a triturator to obtain a settable powder of each compound.

Formulation Example 9.

To one part of each of Compounds (1), (2), (5) to (13) and (17) to (20) was added 5 parts of piperonyl butoxide and the mixture was dissolved in 20 parts of acetone. With the addition of 94 parts of 300-mesh diatomaceous earth, the mixture was stirred well and mixed in a triturator and the acetone was evaporated off. By the above procedure was obtained a powder containing each compound.

Formulation Example 10.

To 0.4 part of each of Compounds (I) to (19) was added 0.1 part of resmethrin, 1.5 parts of octachlorodipropyl ether and 28 parts of refined kerosene. The solution thus obtained was dispensed into aerosol containers and, after the valve was attached, each container was filled with 70 parts of propellant (liquefied petroleum gas). By this procedure was obtained an aerosol preparation of each compound.

Formulation Example 1 1 To 0.3 part of each of Compounds (1), (2) and (5) to (13) was added 0.3 part of DDVP and the mixture was dissolved in a mixture of xylene and refined kerosene to make a total of 15 parts. Each solution was dispensed into aerosol containers and, after the valve was attached, each container was filled with 85 parts of a propellant (liquified petroleum gas) through the filling valve. By the above procedure was obtained an aerosol preparation of each compound.

Formulation Example 12.

To 0.5 part of each of Compounds (1) to (13) was added 0.5 part of BHT and 99.0 parts of moxquito incense coil materials including pyrethrum marc, sawdust and starch. The mixture was evenly blended and processed into a moxquito coil in the manner conventional per se.

Formulation Example 13.

To 0.05 g of each of Compounds (1), (2), (5), (8), (10) and (11) was added 0.02 g of furamethrin, 0.15 g of piperonyl butoxide and 0.1 g of BHT and the mixture was dissolved in an appropriate amount of chloroform. This solution was adsorbed uniformly on the surface of an asbestos mat having a size of 2.5 cm x 1.5 cm and a thickness of 0.3 mm, and another asbestos mat of the same size and thickness was superimposed on the treated surface. By this procedure was obtained a fibrous fumigation pesticidal composition (mat) for heating on a hot plate.

Effect Example 1.

The emulsifiable concentrate prepared from Compounds (1), (2), (6), (7), (9), (10), (12) and (13) in Formulation Example 5 were each diluted 300-fold with water.

Then, each of the dilutions was sprayed over rice seedlings 25 days after sawing at the rate of 10 ml/pot. The pot was covered with a wire-net and 15 green rice leafhoppers were released under the net. After 24 hours, the leafhoppers were examined for deaths. The mortality (%) was not less than 90% for each of Compounds (1), (2), (6), (7), (9), (10), (12) and (13).

Effect Example 2.

By the settling mist method, a killing test against houseflies (Musca domestica) was carried out using the oil preparations obtained according to Formulation Example I from Compounds (1), (2), (5), to (11) and (17). After 24 hours, the flies were examined for deaths. The mortality (%) was not less than 90 for each of Compounds (1), (2), (5), to (11) and (17).

Effect Example 3.

By the settling mist method, a killing test against houseflies was carried out using the oil preparations made in Formulation Example 2 from Compounds (I), (2), (5), to (11) and (17). After 24 hours, the flies were examined for deaths. The mortality (%) was not less than 90% for each of Compounds (1), (2), (5), to (11) and (17).

Effect Example 4.

By the settling mist method, a killing test against houseflies was carried out using the oil preparations obtained in Formulation Example 3 from Formulation Example 3 from Compounds (1), (2), (5) to (11) and (17). After 24 hours, the flies were axamined for deaths. The % mortality (%) was not less than 90% for each of Compounds (1), (2), (5), to (11) and (17).

WHAT WE CLAIM IS:- 1. A pesticidal composition containing as an active ingredient an a- or substituted isovaleric acid ester of the general formula:

in which Z' is hydrogen and Z2 iS CX2 = CH-CH2 or CX2 = CH-CHY-, or Zt iS CX2 = CH- or CX2 = CH-CH2- and Z2 iS hydrogen; A is hydrogen, cyano or ethynyl, except that A is not hydrogen when Z' is CX2 = CH-; and each X and Y, which may be the same or different, represents chlorine or bromine.

2. A pesticidal composition as claimed in Claim 1 in which the active ingredient is an a-substituted isovaleric acid ester of the general formula:

where A is cyano or ethynyl and X is chlorine or bromine.

3. A pesticidal composition as claimed in Claim 2 in which the active ingredient is a-cyano-3-phenoxybenzyl a-(2,2-dichlorvinyl)isovalerate.

4. A pesticidal composition as claimed in Claim 2 in which the active ingredient is a-ethynyl-3-phenoxybenzyl a-(2,2-dichlorovinyl)isovalerate.

5. A pesticidal composition as claimed in Claim 1 in which the active ingredient is an a-substituted isovaleric acid ester of the general formula:

**WARNING** end of DESC field may overlap start of CLMS **.

Claims

**WARNING** start of CLMS field may overlap end of DESC **. examined for deaths. The mortality (%) was not less than 90% for each of Compounds (1), (2), (6), (7), (9), (10), (12) and (13). Effect Example 2. By the settling mist method, a killing test against houseflies (Musca domestica) was carried out using the oil preparations obtained according to Formulation Example I from Compounds (1), (2), (5), to (11) and (17). After 24 hours, the flies were examined for deaths. The mortality (%) was not less than 90 for each of Compounds (1), (2), (5), to (11) and (17). Effect Example 3. By the settling mist method, a killing test against houseflies was carried out using the oil preparations made in Formulation Example 2 from Compounds (I), (2), (5), to (11) and (17). After 24 hours, the flies were examined for deaths. The mortality (%) was not less than 90% for each of Compounds (1), (2), (5), to (11) and (17). Effect Example 4. By the settling mist method, a killing test against houseflies was carried out using the oil preparations obtained in Formulation Example 3 from Formulation Example 3 from Compounds (1), (2), (5) to (11) and (17). After 24 hours, the flies were axamined for deaths. The % mortality (%) was not less than 90% for each of Compounds (1), (2), (5), to (11) and (17). WHAT WE CLAIM IS:-

1. A pesticidal composition containing as an active ingredient an a- or substituted isovaleric acid ester of the general formula:

where A is cyano or ethynyl and X is chlorine or bromine.

where A and X are as defined in Claim 2.

6. A pesticidal composition as claimed in Claim 5 in which the active ingredient is a-ethynyl-3-phenoxybenzyl a-(3,3-dibromoallyl)isovalerate.

7. A pesticidal composition as claimed in Claim 5 in which the active ingredient is a-cyano-3-phenoxybenzyl a-(3,3-dichloroallyl)isovalerate

8. A pesticidal composition as claimed in Claim 1 in which the active ingredient is a p-substituted isovaleric acid ester of the general formula:

where A and X are as defined in Claim 2.

9. A pesticidal composition as claimed in Claim I in which the active ingredient is a a-substituted isovaleric acid ester of the general formula:

where A and X are as defined in Claim 2.

10. An a-substituted isovaleric acid ester of the general formula:

where A is cyano or ethynyl and X is chlorine or bromine.

11. a-Cyano-3-phenoxybenzyl a-(2,2-dichlorovinyl)isovalerate.

12. a-Ethynyl-3-phenoxybenzyl a-(2,2-dichlorovinyl)isovalerate.

13. An a-substituted isovaleric acid ester of the general formula:

where A and X are as defined in Claim 2.

14. a-Ethynyl-3-phenoxybenzyl a-(3,3-dibromoallyl)isovalerate.

15. a-Cyano-3-phenoxybenzyl a-(3,3-dichloroallyl)isovaleraSte.

16. A p-substituted isovaleric acid ester of the general formula:

where A and X are as defined in Claim 2.

17. A composition as claimed in any one of Claims 1 to 9 in the form of solutions, emulsifiable concentrates, wettable powders, suspensions, dusts, granules, microfine granules, powders coatings. aerosols, mosquito incense coils, fumigants, slow-acting fumigants, electric mosquito incense mats or capsules.

18. A composition as claimed in Claim 1 substantially as hereinbefore described in any one of the Formulation Examples.