Alkanesulfonate derivatives and their use as insecticides, acaricides or nematicides

Abstract

Disclosed herein is a compound of the formula: ##STR1## wherein Ar is pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, isoquinoline ring or thiazole ring, and those rings may be substituted by 1.about.3 of substituents selected from the group consisting of halogen, C.sub. 1 .about.C.sub.4 -alkyl, C.sub.1 .about.C.sub.4 -alkoxy, CF.sub.3 and nitro,R.sup.1 is C.sub.1 .about.C.sub.8 -alkyl; C.sub.1 .about.C.sub.7 -alkyl which is substituted by 1.about.3 of F, Cl or Br, C.sub.1 .about.C.sub.4 -alkoxy or C.sub.1 .about.C.sub.4 -alkylthio; C.sub.3 .about.C.sub.7 -cycloalkyl which may be substituted by 1.about.4 of F, Cl or methyl; C.sub.3 .about.C.sub.6 -cycloalkylmethyl which may be substituted by 1.about.4 of F, Cl, Br or methyl; allyl, propargyl, phenyl or benzyl; R.sup.2 is C.sub.1 .about.C.sub.4 -alkyl which may be substituted by 1.about.3 of F or Cl,x is integer of 0, 1 or 2, excepting wherein Ar is pyridine ring which is substituted by R.sup.1 --S(O)x and --O--SO.sub.2 R.sup.2 at 2- and 6-position and the R.sup.1 is C.sub.1 .about.C.sub.7 -alkyl and the pyridine ring is not further substituted or substituted by 1.about.3 of halogen.

Description

DETAILED DESCRIPTION OF THE INVENTION

This invention relates to a compound of the formula: ##STR2## wherein Ar is pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, isoquinoline ring or thiazole ring and those rings may be substituted by 1-3 of substituents selected from the group consisting of halogen, C.sub.1 -C.sub.4 -alkyl, C.sub.1 -C.sub.4 -alkoxy, CF.sub.3 and nitro,

R.sup.1 is C.sub.1 -C.sub.8 -alkyl; C.sub.1 -C.sub.7 -alkyl which is substituted by 1-3 of F, Cl or Br, C.sub.1 -C.sub.4 - alkoxy or C.sub.1 -C.sub.4 -alkylthio; C.sub.3 -C.sub.7 -cycloalkyl which may be substituted by 1-4 of F, Cl or methyl; C.sub.3 -C.sub.6 -cycloalkylmethyl which may be substituted by 1-4 of F, Cl, Br or methyl; allyl; propargyl; phenyl or benzyl; R.sup.2 is C.sub.1 -C.sub.4 -alkyl which may be substituted by 1-3 of F or Cl,

x is integer of 0, 1 or 2, excepting wherein Ar is pyridene ring which is substituted by R.sup.1 --S(O).sub.x and -O-SO.sub.2 R.sup.2 at 2- and 6-positions and the R.sup.1 is C.sub.1 -C.sub.7 -alkyl and the pyridine ring is not further substituted or is substituted by 1.about.3 of halogen.

The compounds of the present invention can be utilized as an insecticide, acaricide or nematicide in paddy fields, uplands, orchards, forests or the like.

Certain alkanesulfonate derivatives are known to be useful as an active ingredient of an insecticide or a nematicide.

For example, 3-n-butylthiophenyl methanesulfonate and 3-ethylthiophenyl methanesulfonate are described to be useful as an insecticide in Japanese Patent Publication No. 3898/1968 and Japanese Patent Laid-Open No. 98025/1973, respectively. Further, it is reported in J. Agr. Food Chem. 18(1), 57(1970) that 6-chloro-2-pyridyl methanesulfonate has a nematicidal activity.

Alkanesulfonate derivatives of the prior art have an insufficient insecticidal effect on insect pests which have acquired a resistance to organic phosphate or carbamate insecticides or the like, and on insect pests exhibiting a high susceptibility, so that a compound which can prevent such insects with a low dosage has been desired.

The present inventors have found that a compound having a high insecticidal, acaricidal or nematicidal activity can be obtained by substituting the pyridine, pyridazine, pyrimidine, pyrazine, isoquinoline or thiazole rings, with one alkylthio, alkylsulfin alkylsulfonyl groups as well as with an alkanesulfonyloxy group, as shown by the aforementioned formula (I).

An alkanesulfonate derivative represented by the general formula (I) can be prepared by reacting a compound represented by the general formula: ##STR3## wherein Ar, R.sup.1 and x are as defined above and Y.sup.1 is a hydrogen, alkali or alkaline earth metal atom, or a compound represented by the general formula: ##STR4## wherein Z.sup.2 is hydrogen, halogen, C.sub.1 .about.C.sub.4 -alkyl which may be substituted by halogen, with a sulfonyl halide represented by the general formula:

Z.sup.1 --SO.sub.2 --R.sup.2 (III) wherein R.sup.2 is as defined above, and Z.sup.1 is halogen, or a sulfonic acid anhydride represented by the general formula: (R.sup.2 SO.sub.2).sub.2 O (IV) wherein R.sup.2 is as defined above, in a solvent, if necessary, in the presence of an acid binding agent at a temperature of -10.degree. to 100.degree. C., preferably 0.degree. to 40.degree. C., for 0.5 to 10 hours.

Examples of the solvent to be used include water; aromatic hydrocarbons such as benzene, toluene and xylene; aliphatic hydrocarbons such as hexane, heptane and petroleum benzine; halogenated hydrocarbons such as chloroform and dichloromethane; aprotic polar solvents such as dimethylformamide and dimethylsulfoxide; ethers such as diisopropyl ether, diethyl ether, 1,2-dimethoxyethane, tetrahydrofuran and dioxane; nitriles such as acetonitrile and propionitrile; ketones such as acetone, diisopropyl ketone and methyl ethyl ketone. Examples of the acid binding agent of bases include alkali metal hydroxides such as NaOH and KOH; alkaline earth metal hydroxides such as Ca(OH).sub.2 and Mg(OH).sub.2 ; alkali metal hydrides; alkali metal alcoholates such as sodium alcoholate; alkali metal oxides such as Na.sub.2 O and K.sub.2 O; alkali metal carbonates such as soda ash; sodium amide; aliphatic or aromatic tertiary amines such as triethylamine, dialkyl anilines, pyridines. In addition, silver oxide may be used as an acid binding agent.

Furthermore, a phase transfer catalyst, for example, tetra-n-butylammonium bromide or triethylbenzylammonium chloride, may be also used to obtain the objective alkanesulfonate derivatives in a favorable yield.

Alternatively, a compound represented by the general formula (I) wherein x is 1 or 2 can be prepared as follows:

A compound represented by the general formula: ##STR5## wherein Ar, R.sup.1 and R.sup.2 are as defined above, which corresponds to the general formula (I) wherein x is zero by means of the above-mentioned manner, and then the compound of the formula (V) is treated with an oxidizing agent such as hydrogen peroxide to produce the compound of the formula (I). That is, when the compound represented by the general formula (V) is treated in acetic acid containing 1.0 to 3.0 times by mol as much hydrogen peroxide, preferably at 0.degree. to 60.degree. C. for 3 to 7 hours, a compound represented by the general formula (I) wherein x is 1 can be obtained, while when the compound represented by the general formula (V) is treated in acetic acid containing 2.0 to 5.0 times by mol as much hydrogen peroxide, preferably at 15.degree. to 90.degree. C. for 2 to 24 hours, a compound represented by the general formula (I) wherein x is 2 can be obtained in a high yield. In this treatment, alcohols such as t-butanol, acetone, water or the mixture thereof can be used as a solvent in place of acetic acid.

Examples of the oxidizing agent to be used in oxidizing a compound represented by the general formula (I) wherein x is zero into the corresponding compound of the general formula (I) wherein x is 1 include sodium bromite, organic peroxides, organic halides such as N-bromo-succinimide, bromine, iodine, periodates, nitrogen oxides, ozone, metal oxides, and singlet oxygen as well as hydrogen peroxide. Additionally, this oxidation can be carried out by air or anodic oxidation.

Examples of the oxidizing agents to be used in oxidizing a compound represented by the general formula (I) wherein x is zero or 1 into the corresponding compound represented by the general formula (I) wherein x is 2 include peroxy acid, hydrogen peroxide, halogen, halogenating agents, ozone, oxygen and transition metal catalysts, potassium peroxysulfate, potassium permanganate; dinitrogen tetraoxide sodium metaperiodate, osmium oxide (Os.sup.VIII) ruthenium oxide (Ru.sup.III), sodium dichromate and nitric acid as well as hydrogen peroxide. Additionally, the oxidation with electrode is possible.

The intermediate represented by the general formula (II), for example, wherein Ar is pyridine, can be prepared by the process indicated in U.S. Pat. No. 3,335,146, which can be also applied to the intermediate represented by the general formula (II) wherein Ar is defined as other than pyridine. Further, the other processes shown by the following Course of Reactions are very effective as an alternative synthesis. ##STR6## In order to obtain the compound (VII) from (VI), an alcohol represented by the formula R.sup.3 OH, for example, benzylalcohol is treated by about equivalent mol of sodium hydride in the same solvent as is used in the synthesis of the abovementioned compound (I) to produce the sodium alcoholate (benzylalcoholate), then to which an equivalent mol of the compound (VI) is added, and agitated at 20.degree. to 100.degree. C., preferably at 50.degree. to 90.degree. C. for 3 to 10 hours to produce the compound (VII) in a high yield. In order to obtain the compound (IX) from the compound (VII), the compound (VII) and an equivalent mol of R.sup.1 SH in form of its alkali or alkaline earth metal salt are dissolved in the same solvent as is used in the synthesis of the above-mentioned compound (I), preferably in aprotic polar solvents such as N,N-dimethylacetamide, dimethylformamide and dimethylsulfoxide, and stirred at 20.degree. to 170.degree. C., preferably at 60.degree. to 120.degree. C., for 3 to 10 hours to prepare the compound (IX) in a high yield. Via another route to the compound (IX), the compound (VIII) can be prepared from the compound (VI) in a high yield in a similar manner to the compound (IX) from the compound (VII) aforementioned, and also the compound (IX) from the compound (VIII) is similar to the compound (VII) from the compound (VI). In every process until the above stage, the target compound can be prepared also by utilizing the reaction of double layer system with a phase transfer catalyst in an excellent yield. The compound (X) can be obtained, for example, by treating the compound (IX) with an excess of 47% HBr under stirring at 70.degree. to 100.degree. C. for 3 to 7 hours. In place of HBr, hydrogen iodide (possibly in the presence of red phosphorus), trifluoroacetic acid, concentrated hydrochloric acid, magnesium iodide etherate, aluminium chloride, aluminium bromide, boron tribromide, boron trichloride or boron triiodide may be used. The compound (XI) or (XII) can be prepared from the compound (X), or from the compound (X) or (XI), respectively in a high yield in similar manner to the oxidation process of the compound (V) above.

The intermediate represented by the general formula (II)', thiazolone derivatives, can be also prepared by a well-known method from rhodanines and alkyl halides. [C.A. 75-35864K: Khim. Geterotsikl Soedin, 7(2), 189.about.191 (1971)].

Examples of the pyridine, pyridazine, pyrimidine, pyrazine, isoquinoline and thiazole rings which is Ar in the general formula (I) of the present invention include ##STR7## wherein X is a halogen, Y is C.sub.1 .about.C.sub.4 -alkyl, C.sub.1 .about.C.sub.4 -alkoxy, CF.sub.3 or nitro, Z.sup.2 is hydrogen, halogen, C.sub.1 .about.C.sub.4 -alkyl which may be substituted by halogen, C.sub.1 .about.C.sub.4 -alkoxy, CF.sub.3 or nitro, m is 0, 1, 2 or 3 in case of pyridine, or is 0, 1 or 2 in case of pyridazine, pyrimidine or pyrazine, respectively, and n and 1 are 0, 1 or 2, except that R.sup.1 --S(O)x-- and --O--SO.sub.2 -R.sup.2 are substituted in 2- and 6-positions, R.sup.1 is C.sub.1 .about.C.sub.7 -alkyl, m is 0, 1, 2 or 3 and n is zero when Ar is pyridine.

Examples of the halogen include fluorine, iodine, chlorine and bromine; examples of the C.sub.1 .about.C.sub.4 -alkyl include methyl, ethyl, n-propyl, isopropyl and t-butyl; examples of the C.sub.1 .about.C.sub.4 -alkoxy include methoxy, ethoxy, n-propoxy, isopropoxy and n-butoxy. Examples of the C.sub.1 .about.C.sub.8 -alkyl in R.sup.1 include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, n-pentyl, isopentyl, s-pentyl, 2,2-dimethylpropyl, 1,2-dimethylpropyl, n-hexyl, 1,2,2-trimethylpropyl and n-heptyl, and those substituents may be further substituted, for example, by 1 to 3 of fluorine, chlorine or bromine and/or C.sub.1 .about.C.sub.4 -alkoxy and C.sub.1 .about.C.sub.4 -alkylthio, wherein examples of the C.sub.1 .about.C.sub.4 -alkyl include methyl, ethyl, n-propyl, isopropyl, n-butyl, s-butyl and t-butyl, and examples of the C.sub.3 .about.C.sub.7 -cycloalkyl or C.sub.3 .about.C.sub.7 -cycloalkylmethyl include cyclopropyl, cyclopropylmethyl, 2,2-dichlorocyclopropylmethyl, 2,2-dibromocyclopropylmethyl, 2,2-dichloro-1-methyl-cyclopropylmethyl, cyclobutyl, cyclobutylmethyl, 2,2,3,3-tetrafluorobutylmethyl, cyclopentyl, cyclopentylmethyl, cyclohexyl and cyclohexylmethyl. Examples of the C.sub.1 .about.C.sub.4 -alkyl in R.sup.2 include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, chloromethyl, fluoromethyl, trifluoromethyl, bromomethyl, 2-chloroethyl, 3 -chloropropyl, 3-bromopropyl and 4-chlorobutyl.

Preferable compounds of the formula (I) in the present invention are those wherein ##STR8## X is halogen, Y.sup.2 is C.sub.1 .about.C.sub.4 -alkyl, C.sub.1 .about.C.sub.4 -alkoxy, CF.sub.3 or nitro, m and n are 0, 1, 2 or 3 provided that (m+n) is 0.about.3, R.sup.1 is C.sub.3 .about.C.sub.5 -alkyl which may be substituted by F or Cl, C.sub.3 .about.C.sub.6 -cycloalkyl or C.sub.3 .about.C.sub.6 -cycloalkylmethyl, R.sup.2 is CH.sub.3, CH.sub.2 Cl or C.sub.2 H.sub.5, x is 0, 1 or 2.

Other preferable compounds of the formula (I) in the present invention are those wherein ##STR9## Z.sup.2 is hydrogen, halogen, C.sub.1 .about.C.sub.4 -alkyl which may be substituted by halogen,

R.sup.1 is C.sub.2 .about.C.sub.5 -alkyl which may be substituted by F or Cl, C.sub.3 .about.C.sub.6 -cycloalkyl or C.sub.3 .about.C.sub.6 -cycloalkylmethyl, allyl, R.sup.2 is CH.sub.3, CH.sub.2 Cl or C.sub.2 H.sub.5 and x is 0, 1 or 2.

More preferable compounds of the formula (I) in the present invention are those wherein ##STR10## R.sup.1 is n-C.sub.3 H.sub.7, iso-C.sub.3 H.sub.7, -sec-C.sub.4 H .sub.9, -n-C.sub.4 H.sub.9, iso-C.sub.4 H.sub.9, iso-C.sub.4 H.sub.9, cyclopentyl or cyclopropylmethyl,

R.sup.2 is CH.sub.3, CH.sub.2 Cl or C.sub.2 H.sub.5, and x is 0, 1 or 2.

Other more preferable compounds of the formula (I) in the present invention are those wherein ##STR11## Z.sup.2 is hydrogen or bromine,

R.sup.1 is C.sub.2 H.sub.5, n-C.sub.3 H.sub.7, iso-C.sub.3 H .sub.7, -n-C.sub.4 H.sub.9, -sec-C.sub.4 H.sub.9, iso-C.sub.4 H.sub.9, --CH.sub.2 CH.sub.2 CH.sub.2 Cl, --CH.sub.2 CH.sub.2 CH.sub.2 F, --CH.sub.2 CH.dbd.CH.sub.2, cyclopentyl or cyclopropylmethyl,

R.sup.2 is CH.sub.3 or CH.sub.2 Cl and x is 0, 1 or 2.

The most preferable compound of the formula (I) in the present invention is one selected from the group consisting of the compound of the formula: ##STR12##

The compounds of the present invention may be used alone according to the purpose of application in their practical use, but they are generally formulated by blending suitable adjuvants to improve or stabilize the effects thereof and used as such or after diluted if necessary. The compounds of the invention can be formulated in the conventional manners well-known in the art in any convenient form such as dust, granule, microgranule, wettable powder, flowable powder, emulsion, microcapsule, oil, aerosol, heating fumigant (e.g. mosquito repellent of an incense type or electric type), fuming agents such as fogging, non-heating fumigant, or toxic feed.

Examples of said adjuvants are carrier (i.e. diluent) and other adjuvants such as spreader, emulsifying agent, wetting agent, dispersing agent, fixing agent or disintegrator. Examples of the liquid carrier are aromatic hydrocarbons such as toluene or xylene; alcohols such as methanol, butanol or glycol; ketones such as acetone; amides such as dimethylformamide; sulfoxides such as dimethyl sulfoxide; methylnaphthalene; cyclohexane; animal or vegetable oils; fatty acids and esters thereof or the like as well as petroleum fractions such as kerosene or gas oil.

Examples of the solid carrier are clay, kaolin, talc, diatomaceous earth, silica, calcium carbonate, montmorillonite, bentonite, feldspar, quartz, alumina or saw dust.

Surfactants are generally used as an emulsifying or dispersing agent. Examples of them are anionic, cationic, non-ionic and ampholytic surfactants such as sodium salt of higher alcohol sulfate, stearyltrimethylammonium chloride, polyoxyethylene alkylphenyl ether or laurylbetaine.

Examples of the spreaders are polyoxyethylene nonylphenyl ether and polyoxyethylene lauryl ether. Examples of the wetting agents are polyoxyethylene nonylphenyl ether and dialkyl sulfosuccinates. Examples of the fixing agents are carboxymethylcellulose and polyvinyl alcohol. Examples of the disintegrators are sodium ligninsulfonate and sodium laurylsulfate.

Furthermore, it is possible to blend two or more compounds of the present invention to obtain an improved insecticidal and acaricidal activities. In addition, it is also possible to use a compound of the present invention simultaneously with other physiologically active substances such as pyrethroids, e.g., allethrin, phthalthrin, permethrin, decamethrin, fenvalerate, or .alpha.-cyano-3-phenoxybenzyl- 2,2-dichloro-1-(4-ethoxyphenyl)cyclopropane-1-carboxylate and various isomers thereof, pyrethrum extract; organophosphorus pesticides, e.g., DDVP, fenitrothion, diazinon or temefos; carbamate pesticides, e.g., NAC, MTMC, BPMC or pirimor; other pesticides, acaricides or fungicides, nematicides, herbicides, plant growth regulators, fertilizers, BT, insect hormones or other pesticides, thereby affording a multipurpose composition which exhibits an improved effect and further a synergistic effect, if things go well.

It is further possible to increase the effect of the composition several times as much by adding synergists for pyrethroids such as piperonyl butoxide sulfoxide or safroxane.

Although the compounds of the present invention are stable to light, heat, and oxidation or the like, antioxidant or ultraviolet absorbers such as phenols, e.g., BHT or BHA; arylamines, e.g., .alpha.-naphthyl amine; or benzophenone compound may be added as a stabilizer to prepare a composition which exhibits a higher stability, if necessary.

The content of active ingredients in the composition of the present invention varies depending on the conditions of use such as formulation form or application method, and is usually from 0.2 to 95% by weight, preferably from 0.5 to 80% by weight, although the active ingredients may be used alone in a special case.

The composition of the present invention may be used in an amount which depends on the conditions such as formulation form, method or season for application. It is usually used in an amount of 10 to 300 g/10 a (a=100 m.sup.2), preferably 15 to 200 g/10 a in terms of the active ingredient for the agricultural and horticultural pesticide and the insecticide for forestry and pasturage, and in an amount of 2 to 200 mg/m.sup.2, preferably 5 to 100 mg/m.sup.2 in terms of the active ingredient for the hygienic insecticide. For example, 15 to 120 g/10 a of the active ingredient is used in the case of dust, 30 to 240 g/10 a thereof is used in the case of granule, and 40 to 250 g/10 a thereof is used the case of emulsion. However, it may be possible, or even necessary, to use the active ingredient in an amount which is outside the range as specified above, in a special case.

The insect pests on which the insecticides, acaricides and nematicides of the present invention are effective are as follows: Hemiptera such as Nephotettix cincticeps, Sogatella furcifera, Niraoarvata lugens, Laodelphax striatellus, Riptortus clavatus, Nezara viridula, Stephanis nashi, Trialeurodes vaporaviorum, Aphis gossypii, Myzus persicae and Vnaspis yanonensis; Lepidoptera such as Phyllonorycter ringoneella, Plutella xylostella, Promalactis inonisema, Adoxophyes orana, Leguminivora glycinivorella, Cnaphalocrocis medinalis, Chilo suppressalis, Ostrinia furnacalis, Mamestra brassicae, Pseudaletia separata, Spodoptera litura, Parnara guttata and Pieris rapae crucivora; Coleoptera such as Anomala cuprea, Popillia japonica, Echinocnemus soqameus, Lissorhoptrus oryzophilus, Anthonomus grandis, Oulema oryzae, Diabrotica undecimpunctata, Leptinotarsa decemlineata, Anthrenus verbasci, Tenebroides mauritanicus, Sitophilus zeamais, Henosepilachna vigintioctopunctata, Callosobruchus chinensis, Monochamus alternatus and Aulacophora femovalis; Hymenoptera such as Athalia rosae japonensis and Arge similis; Diptera such as Culex pipiens fatigans, Aedes aegypti, Asphondylia sp., Hylemya platura, Musca domesti cina, Dacus cucurbitae Agromyza oryzae; Aphaniptera such as Pulex irritans, Xenopsylla cheopis and Ctenocephalides canis; Thysanoptera such as Scirtothrips dorsalis, Thrips tabaci, Thrips palmi and Baliothrips biformis; Anoplura such as Pediculus humanus corporis and Pthirus pubis; Psocopters such as Trogium pulsatorium and Liposcelis bostrychophus; Orthoptera such as Gryllotalpa africana, Locusta migratoria, Oxya yezoensis, Blattella germanica and Periplaneta fuliginosa; and Acarina such as Tetranychus urticae, Panonychus citri, Tetranychus cinnabarinus, Tetranychus kanzawai and Rhizoglyphus echinopus.

The nematodes on which the nematicides of the present invention are effective are Tylenchida such as Heterodera glycines, Heterodera elachist, Meloidogyne incognita, Pratylenchus neglectus, Apohelenchoides besseyi, Aphelenchoides ritzemabosi and Bursa phelenchus lignicolus.

The compounds of the present invention can prevent insect pests effectively by contacting them, or control insect pests on leaves by applying the compounds at the root of plants. Thus, the compound is an excellent insecticide, acaricide or nematicide which has characteristics as a systemic insecticide with scarce phytotoxicity on the host crops.

Now, the present invention will be described by Examples.

SYNTHESIS EXAMPLE

Synthesis Example 1: Synthesis of 6-isobutylthio-2-pyrazyl methanesulfonate (Compound No. 14):

(1) Synthesis of 2-benzyloxy-6-chloropyrazine as an intermediate:

7.6 g of benzylalcohol was dissolved in 65 ml of benzene, and 2.8 g of 60% sodium hydride was added little by little to the solution under stirring not so as to foam too much at room temperature. After the addition, stirring was continued for 10 min. at room temperature, followed by reflux for 1 hour. Subsequently, the solution was cooled to 50.degree. to 60.degree. C., and added dropwise with a solution of 10 g of 2,6-dichloropyrazine in 65 ml of benzene for 10 min. Then, after reflux for 4 hours, the reaction was finished. After cooling below 10.degree. C., about 100 ml of water was added, and the separated benzene layer was collected. The residue obtained by distilling off the solvent was purified by silica-gel column chromatography (developing solvent: n-hexane and ethyl acetate) to obtain 12.8 g of 2-benzyloxy-6-chloropyrazine as a colourless oil (yield: 86.5%) n.sub.D.sup.25 1.5818.

(2) Synthesis of 2-benzyloxy-6-isobutylthiopyrazine as an intermediate:

12.8 g of 2-benzyloxy-6-chloropyrazine obtained by the process described in (1) and 11.2 g of potassium salt of isobutylmercaptane were dissolved in 50 ml of N,N-dimethylacetamide, followed by stirring at 70.degree. to 80.degree. C. for 7 hours. After cooling, the reaction mixture was poured into 500 ml of water and extracted twice by 150 ml of toluene to obtain an organic layer, which was further washed with water and then with saturated aqueous solution of common salt, followed by distilling off the solvent. The obtained residue was purified by silica-gel column chromatography (developing solvent: toluene and n-hexane) to obtain 11.1 g of 2-benzyloxy-6-isobutylthiopyrazine as a pale yellow oil (yield: 69.7%).

n.sub.D.sup.25 1.5790

PMR(CDCl.sub.3).delta.: 1.02[6H, d, -SCH.sub.2 CH(CH.sub.3).sub.2 ], 1.94 [1H, m, --SCH.sub.2 CH(CH.sub.3).sub.2 ], 3.02[2H, d, -SCH.sub.2 CH(CH.sub.3).sub.2 ], 5.40 [2H, s, --OCH.sub.2 Ph], 7.39 [5H, s, proton in benzene ring], 7.90[1H, s, proton in pyrazine ring], 8.03[1H, s, proton in pyrazine ring] ppm.

(3) Synthesis of 2-hydroxy-6-isobutylthiopyrazine as an intermediate:

7.0 g of 2-benzyloxy-6-isobutylthiopyrazine obtained by the process described in (2) and 50 ml of acetic acid were mixed and added with 13.2 ml of 47% hydrobromic acid under stirring. The reaction was finished by stirring at 0.degree. to 90.degree. C. for 4 hours. The reaction mixture was cooled to room temperature and then poured into about 300 ml of chilled water. The pH of the solution was adjusted by 20% aqueous caustic soda and extracted thrice by ether. The ether layer was washed with water and then with saturated aqueous solution of common salt, followed by drying with anhydrous sodium sulfate. To the residue obtained after distilling off the solvent a small amount of the solvent mixture of toluene was added and n-hexane (1:1), was added and the mixture was filtrated to separate 4.0 g of the objective 2-hydroxy-6-isobutylpyrazine as a pale brown crystal (yield: 85.1%).

m.p. 130.degree. to 131.degree. C.

PMR(CDCl.sub.3).delta.: 1.05[6H, d, --SCH.sub.2 CH(CH.sub.3).sub.2 ], 1.93[1H, m, --SCH.sub.2 CH(CH.sub.3).sub.2 ], 2.97[2H, d, -SCH.sub.2 CH(CH.sub.3).sub.2 ], 7.57[1H, s, proton in pyrazine ring], 8.00[1H, s, proton in pyrazine ring], 15.50[1H, bs, ##STR13## ppm. (4) Synthesis of 6-isobutylthio-2-pyrazyl methanesulfonate (Compound No. 14) as an objective compound:

4.0 g of 2-hydroxy-6-isobutylthiopyrazine obtained by the process described in (3) and 2.4 ml of methanesulfonyl chloride were dissolved in 20 ml of N,N-dimethylacetamide and cooled to 0.degree. to 10.degree. C. 5.3 ml of triethylamine was added dropwise to the solution under stirring for 10 min, and then the temperature of the solution was raised gradually to room temperature, followed by stirring for 5 hours to accomplish the reaction. The reaction mixture was poured into 200 ml of water and extracted twice by ethyl acetate. The organic layer was washed with water and distilled to remove the solvent. The obtained residue was purified by silica-gel column chromatography (developer: toluene and n-hexane) to obtain 4.1 g of the objective 6-isobutylthio-2-pyrazyl methanesulfonate as a pale brown crystal (yield: 72.0%).

m.p. 65.degree. to 66.degree. C.

PMR(CDCl.sub.3).delta.: 1.05[6H, d, --SCH.sub.2 CH(CH.sub.3).sub.2 ], 1.98[1H, m, --SCH.sub.2 CH(CH.sub.3).sub.2 ], 3.03[2H, d, --SCH.sub.2 CH(CH.sub.3).sub.2 ], 3.46[3H, s, --OSO.sub.2 CH.sub.3 ], 8.08[1H, s, proton in pyrazine ring], 8.40[1H, s, proton in pyrazine ring] ppm.

Synthesis Example 2: Synthesis of 6-isobutylsulfinyl-2-pyrazyl methanesulfonate (Compound No. 15):

1.2 g of 6-isobutylthio-2-pyrazyl methanesulfonate (Compound No. 14) obtained by the process described in Synthesis Example 1 was dissolved in 10 ml of acetic acid. 1.2 ml of 30% aqueous hydrogen peroxide was added under stirring at room temperature during 30 min. After that, stirring was continued at room temperature for 3 hours and at 50.degree. C. for further 3 hours to accomplish the reaction. The reaction mixture was cooled below room temperature and poured into 150 ml of chilled water. The organic layer obtained by extracting by methylene chloride three times was washed with water and 5% aqueous caustic soda twice, and then with water and saturated aqueous solution of common salt. The residue obtained by distilling off the solvent was purified by silica-gel column chromatography (developer: ethylacetate and n-hexane) to obtain 1.0 g of the objective 6-isobutylsulfinyl-2-pyrazyl methanesulfonate as a pale yellow oil (yield: 79.7%).

n.sub.D.sup.25 1.5308

PMR(CDCl.sub.3).delta.: 1.11, 1.21[6H, d, d, --SOCH.sub.2 CH(CH.sub.3).sub.2 ], 2.36, 2.43[1H, m, m, --SOCH.sub.2 CH(CH.sub.3)], 2.92, 2.95 [2H, d, d, --SOCH.sub.2 CH(CH.sub.3).sub.2 ], 3.51[3H, s, -OSO.sub.2 CH.sub.3 ], 8.63[1H, s, proton in pyrazine ring], 9.15[1H, s, proton in pyrazine ring] ppm.

Synthesis Example 3: Synthesis of 4-isobutylthio-2-pyridyl methanesulfonate (Compound No. 30):

1.3 g of 4-isobutylthio-2-pyridone (m.p. 119 to 120.degree. C.) and 0.7 ml of methanesulfonyl chloride were dissolved in 10 ml of methylene chloride, and cooled below 10.degree. C. 1.5 ml of triethylamine was added dropwise to the solution with stirring. By stirring at room temperature for 4 hours, the reaction was completed. The reaction solution was poured into 100 ml of water, followed by addition of 100 ml of methylene chloride for separation. The methylene chloride layer was washed with water and saturated aqueous solution of common salt, then distilled to remove the solvent. The obtained residue was purified by silica-gel column chromatography (developer: benzene and n-hexane) to obtain 1.7 g of the objective 4-isobutylthio-2-pyridyl methanesulfonate (yield: 91.6%) as a colourless oil, which were allowed to stand to crystallization.

m.p. 34.degree. to 35.degree. C.

PMR(CDCl.sub.3).delta.: 1.06[6H, d, --SCH.sub.2 CH(CH.sub.3).sub.2 ], 1.97[1H, m, --SCH.sub.2 CH(CH.sub.3).sub.2 ], 2.86[2H, d, --SCH.sub.2 CH(CH.sub.3).sub.2 ], 3.49[3H, s, --OSO.sub.2 CH.sub.3 ], 6.88[1H, d, proton in pyridine ring], 7.06[1H, d-d, proton in pyridine ring], 8.08[1H, d, proton in pyridine ring] ppm.

Synthesis Example 4: Synthesis of 4-isobutylsulfonyl-2-pyridyl methanesulfonate (Compound No. 32):

1.7 g of 4-isobutylthio-2-pyridyl methanesulfonate (Compound No. 30) obtained by the process described in Synthesis Example 3 was dissolved in 10 ml of acetic acid, followed by adding 1.5 ml of 30% aqueous hydrogen peroxide below 10.degree. C. and stirring at room temperature for 2 hours. Further, 0.5 ml of 30% aqueous hydrogen peroxide was added to the reaction mixture, which was stirred at 40.degree. C. for 8 hours to accomplish the reaction. After cooling, the reaction solution was poured into 100 ml of chilled water and extracted three times with 100 ml of methylene chloride. The organic layer was washed twice with 5% aqueous caustic soda, then with water and saturated aqueous solution of common salt, followed by distilling off the solvent. The obtained residue was purified by silica-gel column chromatography (developer: ethyl acetate and n-hexane) to obtain 1.3 g of the objective 4-isobutylsulfonyl-2-pyridyl methanesulfonate as a colourless crystal (yield: 68.2%).

m.p. 75.5.degree. to 76.5.degree. C.

PMR(CDCl.sub.3).delta.: 1.10[6H, d, --SCH.sub.2 CH(CH.sub.3).sub.2 ], 2.29[1H, m, --SCH.sub.2 CH(CH.sub.3).sub.2 ], 3.06[2H, d, --SCH.sub.2 CH(CH.sub.3).sub.2 ], 3.55[3H, s, --OSO.sub.2 CH.sub.3 ], 7.59[1H, d, proton in pyridine ring], 7.76[1H, d-d, proton in pyridine ring], 8.65[1H, d, proton in pyridine ring] ppm.

Synthesis Example 5: Synthesis of 5-isobutylthio-3-pyridyl trifluoromethylsulfonate (Compound No. 45):

A mixture of 0.5 g of 5-isobutylthio-3-pyridinol (m.p. 83.degree. to 84.degree. C.) and 0.5 ml of pyridine was cooled to 5.degree. to 10.degree. C. 1 g of trifluoromethanesulfonic anhydride was added with stirring to the mixture, which was stirred at this temperature for 30 min. The reaction was continued at room temperature for further 5 hours. The reaction solution was poured into 100 ml of chilled water and extracted twice by 50 ml of toluene. The toluene layer obtained was washed twice by water. The residue obtained by distilling off the solvent was purified by silica-gel column chromatography (developer: ethylacetate and n-hexane) to obtain 0.9 g of the objective 5-isobutylthio-3-pyridyl trifluoromethanesulfonate as a colourless oil (yield: 95.1%).

n.sub.D.sup.25 1.4875

PMR(CDCl.sub.3).delta.: 1.07[6H, d, --SCH.sub.2 CH(CH.sub.3).sub.2 ], 1.91[1H, m, --SCH.sub.2 CH(CH.sub.3).sub.2 ], 2.87[2H, d, --SCH.sub.2 CH(CH.sub.3).sub.2 ], 7.49[1H, t, proton in pyridine ring], 8.33[1H, d, proton in pyridine ring], 8.53[1H, d, proton in pyridine ring] ppm.

Other compounds of the present invention were synthesized according to the same procedure as the ones described in Synthesis Examples 1 to 5. Typical compounds among the obtained ones shown in Table 1.

TABLE 1__________________________________________________________________________R.sup.1S(O)x[Ar]OSO.sub.2R.sup.2 (I)Compound No. formula m.p. or b.p. (refractive appearance__________________________________________________________________________ ##STR14## (n.sub.D.sup.25 1.5620) colourless oil2 ##STR15## (n.sub.D.sup.25 1.5370) "3 ##STR16## (n.sub.D.sup.25 1.5635) pale yellow oil4 ##STR17## (n.sub.D.sup.25 1.5569) "5 ##STR18## mp 71-72.degree. C. colourless crystal6 ##STR19## mp 116-117.degree. C. "7 ##STR20## mp 61-63.degree. C. "8 ##STR21## (n.sub.D.sup.25 1.5242) colourless oil9 ##STR22## (n.sub.D.sup.25 1.5365) "10 ##STR23## (n.sub.D.sup.25 1.5409) colourless oil11 ##STR24## (n.sub.D.sup.25 1.5331) "12 ##STR25## bp 146-154.degree. C./0.6-0.65 "mHg13 ##STR26## mp 86-87.degree. C. pale yellow crystal14 ##STR27## mp 65-66.degree. C. brown crystal15 ##STR28## (n.sub.D.sup.25 1.5308) pale yellow oil16 ##STR29## (n.sub.D.sup.25 1.5183) "17 ##STR30## mp 98-99.degree. C. pale yellow crystal18 ##STR31## mp 120-121.degree. C. colourless crystal19 ##STR32## mp 64-66.degree. C. "20 ##STR33## mp 100-101.degree. C. "21 ##STR34## mp 106-107.degree. C. "22 ##STR35## mp 116-117.degree. C. pale yellow crystal23 ##STR36## mp 56.5-57.5.degree. C. colourless crystal24 ##STR37## (n.sub.D.sup.25 1.5285) colourless oil25 ##STR38## mp 79.5-80.degree. C. colourless crystal26 ##STR39## mp 88-89.degree. C. yellow crystal27 ##STR40## mp 99-100.degree. C. "28 ##STR41## mp 114-115.degree. C. pale yellow crystal29 ##STR42## mp 46-47.degree. C. colourless crystal30 ##STR43## mp 34-35.degree. C. "31 ##STR44## mp 79-80.degree. C. colourless crystal32 ##STR45## mp 75.5-76.5.degree. C. "33 ##STR46## (n.sub.D.sup.25 1.5371) pale yellow oil34 ##STR47## (n.sub.D.sup.25 1.5440) "35 ##STR48## (n.sub.D.sup.25 1.5229) "36 ##STR49## (n.sub.D.sup.25 1.5470) yellow oil37 ##STR50## mp 87-88.degree. C. colourless crystal38 ##STR51## (n.sub.D.sup.25 1.5434) colourless oil39 ##STR52## mp 65-67.degree. C. colourless crystal40 ##STR53## mp 67-68.degree. C. "41 ##STR54## (n.sub.D.sup.25 1.5390) pale yellow oil42 ##STR55## mp 96-97.degree. C. colourless crystal43 ##STR56## mp 110-111.degree. C. "44 ##STR57## mp 38 -40.degree. C. "45 ##STR58## (n.sub.D.sup.25 1.4875) colourless oil46 ##STR59## (n.sub.D.sup.25 1.5511) "47 ##STR60## (n.sub.D.sup.25 1.5434) colourless oil48 ##STR61## mp 56-57.degree. C. colourless crystal49 ##STR62## mp 79-80.degree. C. "50 ##STR63## mp 86.5-87.degree. C. "51 ##STR64## mp 74-75.degree. C. "52 ##STR65##53 ##STR66##54 ##STR67##55 ##STR68##56 ##STR69##57 ##STR70##58 ##STR71##59 ##STR72##60 ##STR73##61 ##STR74##62 ##STR75##63 ##STR76##64 ##STR77##65 ##STR78##66 ##STR79##67 ##STR80##68 ##STR81##69 ##STR82##70 ##STR83##71 ##STR84##72 ##STR85##73 ##STR86##74 ##STR87##75 ##STR88##76 ##STR89##77 ##STR90##78 ##STR91##79 ##STR92##80 ##STR93##81 ##STR94##82 ##STR95##83 ##STR96##84 ##STR97##85 ##STR98##86 ##STR99##87 ##STR100##88 ##STR101##89 ##STR102##90 ##STR103##91 ##STR104##92 ##STR105##93 ##STR106##94 ##STR107## (n.sub.D.sup.25 1.5507) colourless oil95 ##STR108## (n.sub.D.sup.25 1.5481) "96 ##STR109## m.p. 71-72.degree. C. colourless crystal97 ##STR110## (n.sub.D.sup.25 1.5361) pale yellow oil98 ##STR111##99 ##STR112##100 ##STR113##101 ##STR114##102 ##STR115##103 ##STR116##104 ##STR117##105 ##STR118##106 ##STR119##107 ##STR120##108 ##STR121##109 ##STR122##110 ##STR123##111 ##STR124##112 ##STR125##113 ##STR126##114 ##STR127##115 ##STR128##116 ##STR129##117 ##STR130##118 ##STR131##119 ##STR132##120 ##STR133##121 ##STR134##122 ##STR135##123 ##STR136##124 ##STR137##125 ##STR138##126 ##STR139##127 ##STR140##128 ##STR141##129 ##STR142##130 ##STR143##131 ##STR144##132 ##STR145##133 ##STR146##134 ##STR147##135 ##STR148##136 ##STR149## (n.sub.D.sup.25 1.6028) colourless oil137 ##STR150##138 ##STR151##139 ##STR152##140 ##STR153## (n.sub.D.sup.25 1.5152) colourless oil141 ##STR154## (n.sub.D.sup.25 1.5554) "142 ##STR155##143 ##STR156## mp 81-82.degree. C. colourless crystal144 ##STR157##145 ##STR158##146 ##STR159##147 ##STR160##148 ##STR161##149 ##STR162##150 ##STR163## (n.sub.D.sup.25 1.5402) colourless oil151 ##STR164##152 ##STR165## (n.sub.D.sup.25 1.5144) colourless oil153 ##STR166##154 ##STR167##155 ##STR168##156 ##STR169## mp 47-48.degree. C. colourless crystal157 ##STR170## (n.sub.D.sup.25 1.5322) colourless oil158 ##STR171## mp 59.5-60.5.degree. C. colourless crystal159 ##STR172## mp 116-117.degree. C. colourless crystal160 ##STR173## (n.sub.D.sup.25 1.5325) pale yellow oil161 ##STR174## mp 54-55.degree. C. colourless crystal162 ##STR175## mp 63-65.degree. C. "163 ##STR176## (n.sub.D.sup.25 1.5597) colourless__________________________________________________________________________ oil

Synthesis Example 6: Preparation of 2-n- 4-methylsulfonyloxy-1,3-thiazole (No. 164)

8 g of 2-n-propylthio-1,3-thiazoline-4-one and 4.8 g of anhydrous sodium carbonate were suspended in acetonitrile, followed by stirring. 7.9 g of methanesulfonyl chloride was added dropwise to the suspension below 10.degree. C. After the addition, the reaction was continued under stirring at room temperature for 2 hours. The reaction solution was poured into water and extracted by ether. The ether layer was washed with a saturated aqueous solution of common salt and dried over anhydrous sodium sulfate. The oil obtained by concentration was purified by silica-gel column chromatography by 9.1 g of the objective compound as a yellow oil (yield: 78.8%)

n.sub.D.sup.25 1.5510

PMR(CDCl.sub.3).delta.: 1.05 (t, 3H), 1.78 (m, 2H), 3.12 (t, 2H), 3.32 (s, 3H), 6.76 (s, 1H) ppm.

Synthesis Example 7: Preparation of 2-isopropylthio-4-methylsulfonyloxy-1,3-thiazole (No. 171):

8 g of 2-isopropylthio-1,3-thiazoline-4-one was dissolved in 100 ml of methylene chloride and cooled below 10.degree. C. Then, 7.8 g of methanesulfonyl chloride and 12.6 ml of triethylamine were added dropwise to the solution below 15.degree. C. with attention to out-break of heat. After that, the reaction was continued with stirring at room temperature for 2 hours. Water was added to the reaction mixture and extracted by ether. The ether layer was washed with water and dried over anhydrous sodium sulfate. The oil obtained by concentration was purified by silica-gel column chromatography to obtain 9.1 g of the objective compound as a pale brown crystal (yield: 78.8%).

m.p. 83.degree. to 85.degree. C.

PMR(CDCl.sub.3) .delta.: 1.47 (d, 6H), 3.38 (s, 3H), 3.60.about.3.90 (m, 1H), 6.94 (s, 1H) ppm.

Synthesis Example 8: Preparation of 2-isopropylsulfonyl-4-methylsulfonyloxy-1,3-thiazole (No. 176):

2.5 g of 2-isopropylthio-4-methylsulfonyloxy-1,3-thiazole was dissolved in 10 ml of acetic acid. 2.9 ml of 35% aqueous hydrogen peroxide was added to the solution and the reaction was continued at 70.degree. to 80.degree. C. for 2 hours. The reaction mixture was poured into cold water and neutralized with 5% aqueous sodium hydroxide. The neutral solution was extracted by ethyl acetate and washed with saturated aqueous solution of common salt, followed by drying over anhydrous sodium sulfate to be concentrated to 2.5 g of a white crystal of the objective compound (yield: 88.7%).

m.p. 56.5.degree. to 58.5.degree. C.

PMR (CDCl.sub.3) .delta.: 1.48 (d, 6H), 3.48 (s, 3H), 3.48.about.3.80 (m, 1H), 7.66 (s, 1H) ppm.

Synthesis Example 9: Preparation of 2-sec-butylsulfinyl-4-methylsulfonyloxy-1,3-thiazole (No. 203):

4.0 g of 2-sec-butylthio-4-methylsulfonyloxy-1,3-thiazole was dissolved in 15 ml of acetic acid, and 2.2 ml of 35% aqueous hydrogen peroxide was added to the solution at room temperature, followed by reaction at 30.degree. to 40.degree. C. for 4 hours. The reaction mixture was poured into chilled water, neutralized by 5% aqueous solution of sodium hydroxide, and extracted with ethyl acetate. The extract was washed with a saturated aqueous solution of common salt, dried over anhydrous sodium sulfate and concentrated to obtain an oil, which was purified by silica-gel column chromatography to 2.1 g of the objective compound as a pale yellow oil (yield: 49.7%).

n.sub.D.sup.25 1.5421

PMR(CDCl.sub.3) .delta.: 1.04 to 1.56 (m, 6H), 1.56 to 2.44 (m, 2H), 3.08 to 3.48 (m, 1H), 3.66(s, 3H), 8.07 (s, 1H) ppm.

Synthesis Example 10: Preparation of 2-(3-fluoropropylthio)-4-methylsulfonyloxy-1,3-thiazole (No. 206):

6.2 g of 2-(3-fluoropropylthio)-1,3-thiazoline-4-one was dissolved in 80 ml of methylene chloride and cooled below 10.degree. C. 5.5 g of methanesulfonyl chloride and 8.9 ml of triethylamine were added dropwise to the solution keeping the temperature below 15.degree. C., followed by stirring at room temperature for 2 hours. After addition of water, the reaction mixture was extracted by methylene chloride, then organic layer is washed with water and dried over anhydrous sodium sulfate, followed by concentration to an oil, which is purified by silica-gel column chromatography to obtain 6.0 g of the objective compound as a pale brown oil (yield: 69.1%).

n.sub.D.sup.25 1.5389

PMR(CDCl.sub.3) .delta.: 1.90 to 2.20 (m, 2H), 3.16 to 3.40 (m, 2H), 3.28 (s, 3H), 4.24 (t, 1H), 4.70 (t, 1H), 6.74 (s, 1H) ppm.

Synthesis Example 11: Preparation of 2-isopropylthio-4-methylsulfonyloxy-5-chloro-1,3-thiazole (No. 230):

3.5 g of 2-isopropylthio-4-methylsulfonyloxy-1,3-thiazole (No. 171) was dissolved in 50 ml of methylene chloride. 2 g of sulfuryl chloride was added dropwise to the solution keeping the temperature below 0.degree. C., followed by stirring at room temperature for 2 hours. Then, 20% aqueous solution of sodium carbonate was added to the reaction mixture to cease the reaction, and the methylene chloride layer was separated and washed with water, followed by drying over anhydrous sodium sulfate. The oil obtained by concentration was purified by silica-gel column chromatography to 2 g of the objective compound as a pale yellow oil (yield; 50.4%).

n.sub.D.sup.25 5587

PMR(CDCl.sub.3) .delta.: 1.45 (d, 6H), 3.46 (s, 3H), 3.60 to 4.00 (m, 1H) ppm.

Synthesis Example 12: Preparation of 2-isopropylthio-4-methylsulfonyloxy-5-bromo-1,3-thiazole (No. 233):

3.5 g of 2-isopropylthio-4-methylsulfonyloxy-1,3-thiazole was dissolved in 50 ml of ether, and 0.8 ml of bromine was added dropwise to the solution keeping the temperature below 0.degree. C. After the addition, the solution was stirred at room temperature for 2 hours, then 5% solution of sodium hydrogen sulfite was added thereto to separate ether layer, which was washed with water and dried over anhydrous sodium sulfate, followed by concentration to an oil. The oil was purified by silica-gel column chromatography to obtain 3.7 g of the objective compound as a yellow oil (yield: 80.7%).

n.sub.D.sup.25 1.5763

PMR(CDCl.sub.3) .delta.: 1.45 (d, 6H), 3.45 (s, 3H), 3.60 to 4.00 (m, 1H) ppm.

Other compounds of the present invention were synthesized according to the same procedures as the ones described in Synthesis Examples 6 to 12. Typical compounds among the obtained ones shown in Table 2.

TABLE 2__________________________________________________________________________ ##STR177##Compound yieldNo. R.sup.1 x R.sup.2 R.sup.3 (%) n.sub.D.sup.25 (mp .degree.C.) appearance__________________________________________________________________________164 CH.sub.3 CH.sub.2 CH.sub.2 0 CH.sub.3 H 78.8 1.5510 yellow oil165 CH.sub.3 CH.sub.2 CH.sub.2 1 CH.sub.3 H 65.9 1.5462 pale yellow oil166 CH.sub.3 CH.sub.2 CH.sub.2 2 CH.sub.3 H 88.7 (83-85.degree. C.) colourless crystal167 CH.sub.3 0 CH.sub.3 H 74.6 1.5616 brown oil168 CH.sub.3 2 CH.sub.3 H 73.5 (97-98.5.degree. C.) colourless crystal169 CH.sub.3 CH.sub.2 0 CH.sub.3 H 66.5 1.5594 pale brown oil170 CH.sub.2CHCH.sub.2 0 CH.sub.3 H 77.9 1.5669 pale brown oil171 ##STR178## 0 CH.sub.3 H 78.8 (83-85.degree. C.) pale brown crystal172 CH.sub.3 CH.sub.2 CH.sub.2 CH.sub.2 0 CH.sub.3 H 86.7 1.5450 pale brown oil173 ##STR179## 0 CH.sub.3 H 79.7 1.5440 pale brown oil174 ##STR180## 2 CH.sub.3 H 96.8 (58-60.degree. C.) colourless crystal175 CH.sub.3 CH.sub.2 2 CH.sub.3 H 79.4 (57.5-59.degree. C.) colourless crystal176 ##STR181## 2 CH.sub.3 H 88.7 (56.5-58.5.degree. C.) colourless crystal177 CH.sub.2CHCH.sub.2 2 CH.sub.3 H 11.8 (77-79.degree. C.) colourless crystal178 CH.sub.3 CH.sub.2 CH.sub.2 CH.sub.2 2 CH.sub.3 H 85.7 (75.5-76.5.degree. C.) colourless crystal179 CH.sub.3 1 CH.sub.3 H 56.1 (71.5-73.5.degree. C.) colourless crystal180 CH.sub.3 CH.sub.2 1 CH.sub.3 H 49.8 (63-65.degree. C.) colourless crystal181 CH.sub.3 CH.sub.2 CH.sub.2 CH.sub.2 1 CH.sub.3 H 77.8 (48-49.5.degree. C.) colourless crystal182 ##STR182## 1 CH.sub.3 H 76.7 (46-48.degree. C.) colourless crystal183 ##STR183## 0 CH.sub.3 H 70.6 1.5392 pale brown oil184 CH.sub.3 CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2 0 CH.sub.3 H 79.7 1.5330 pale brown oil185 ClCH.sub.2 CH.sub.2 CH.sub.2 0 CH.sub.3 H 53.8 1.5662 pale brown oil186 ClCH.sub.2 CH.sub.2 CH.sub.2 0 CH.sub.2 CH.sub.3 H 43.3 1.5558 pale brown oil187 CH.sub.3 CH.sub.2 CH.sub.2 0 CH.sub.2 CH.sub.3 H 46.6 1.5452 pale brown oil188 CHCCH.sub.2 0 CH.sub.3 H 77.3 1.5740 pale brown oil189 ##STR184## 0 CH.sub.3 H 73.4 (41-43.degree. C.) pale yellow crystal190 CH.sub. 3 CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2 0 CH.sub.3 H 73.5 (44.5-45.5.degree. C.) pale yellow crystal191 ##STR185## 0 CH.sub.3 H 76.3 1.5388 pale brown oil192 CH.sub.2CHCH.sub.2 1 CH.sub.3 H 35.2 (66-68.degree. C.) pale yellow crystal193 ##STR186## 1 CH.sub.3 H 79.9 (31.5-33.degree. C.) colourless crystal194 ClCH.sub.2 CH.sub.2 CH.sub.2 2 CH.sub.3 H 89.9 (92-94.degree. C.) colourless crystal195 ClCH.sub.2 CH.sub.2 CH.sub.2 2 CH.sub.2 CH.sub.3 H 72.6 1.5312 colourless oil196 CH.sub.3 CH.sub.2 CH.sub.2 2 CH.sub.2 CH.sub.3 H 96.2 1.5225 colourless oil197 ##STR187## 2 CH.sub.3 H 89.8 (40.5-41.5.degree. C.) colourless crystal198 CH.sub.3 CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2 2 CH.sub.3 H 87.6 (60-62.degree. C.) colourless crystal199 ##STR188## 2 CH.sub.3 H 71.5 1.5230 colourless oil200 CH.sub.3 CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2 2 CH.sub.3 H 89.7 (73-74.5.degree. C.) colourless crystal201 ##STR189## 2 CH.sub.3 H 63.8 1.5185 colourless oil202 ClCH.sub.2 CH.sub.2 CH.sub.2 1 CH.sub.3 H 66.9 1.5633 colourless oil203 ##STR190## 1 CH.sub.3 H 49.7 1.5421 pale yellow oil204 ##STR191## 1 CH.sub.3 H 84.1 1.5324 pale yellow oil205 ##STR192## 0 CH.sub.2 CH.sub.3 H 49.9 1.5381 pale brown oil206 FCH.sub.2 CH.sub.2 CH.sub.2 0 CH.sub.3 H 69.1 1.5389 pale brown oil207 FCH.sub.2 CH.sub.2 CH.sub.2 2 CH.sub.3 H 82.6 (88-89.5.degree. C.) colourless crystal208 FCH.sub.2 CH.sub.2 CH.sub.2 0 CH.sub.2 CH.sub.3 H 41.3 1.5307 pale yellow oil209 ##STR193## 0 CH.sub.3 H 57.0 1.6007 pale brown oil210 ##STR194## 2 CH.sub.3 H 81.4 (122-123.degree. C.) colourless crystal211 ##STR195## 0 CH.sub.3 CH.sub.3 61.3 (39.5-41.degree. C.) pale yellow crystal212 ##STR196## 1 CH.sub.3 CH.sub.3 70.8 1.5329 colourless oil213 ##STR197## 2 CH.sub.3 CH.sub.3 77.4 (70-71.5.degree. C.) colourless crystal214 ##STR198## 0 CH.sub.3 H 75.6 (41-42.5.degree. C.) pale brown crystal215 ##STR199## 1 CH.sub.3 H 35.5 1.5572 pale yellow oil216 ##STR200## 2 CH.sub.3 H 84.0 (104- 105.degree. C.) colourless crystal217 ##STR201## 0 CH.sub.3 Cl 56.1 1.5501 pale brown oil218 ##STR202## 1 CH.sub.3 Cl 63.3 (85.5-87.5.degree. C.) colourless crystal219 ##STR203## 2 CH.sub.3 Cl 90.4 (68-69.5.degree. C.) colourless crystal220 ##STR204## 0 CH.sub.3 Br 73.8 1.5709 pale brown oil221 ##STR205## 2 CH.sub.3 Br 87.0 (74-75.5.degree. C.) colourless crystal222 ##STR206## 0 CH.sub.3 *.sup.1 36.5 1.5284 pale yellow oil223 ##STR207## 2 CH.sub.3 *.sup.2 90.6 1.5129 colourless oil224 ##STR208## 0 *.sup.3 H 51.5 1.5302 pale brown oil225 ##STR209## 0 *.sup.4 H 70.4 1.5450 pale brown oil226 ##STR210## 2 *.sup.5 H 79.4 1.5322 colourless oil227 ##STR211## 0 *.sup.6 H 52.4 1.5482 pale brown oil228 ##STR212## 0 CH.sub.3 H 66.2 1.5290 pale brown oil229 ##STR213## 2 CH.sub.3 H 94.5 1.5090 colourless oil230 ##STR214## 0 CH.sub.3 Cl 50.4 1.5587 pale yellow oil231 ClCH.sub.2 CH.sub.2 CH.sub.2 0 CH.sub.3 Cl 48.5 1.5780 pale brown oil232 ##STR215## 0 CH.sub.3 Cl 43.3 (35-37.degree. C.) pale brown crystal233 ##STR216## 0 CH.sub.3 Br 80.7 1.5763 yellow oil234 ClCH.sub.2 CH.sub.2 CH.sub.2 0 CH.sub.3 Br 67.3 (44-46.degree. C.) pale brown crystal235 ##STR217## 0 CH.sub.3 Br 55.8 (44-46.degree. C.) brown crystal236 ##STR218## 0 CH.sub.3 H 76.5 1.5655 pale brown oil237 ##STR219## 1 CH.sub.3 H 78.6 (78.5-80.5.degree. C.) colourless crystal238 ##STR220## 2 CH.sub.3 H 72.3 1.5417 colourless oil239 ##STR221## 0 CH.sub.3 H 64.1 (70-72.degree. C.) pale yellow crystal240 ##STR222## 1 CH.sub.3 H 76.7 (59-61.degree. C.) colourless crystal241 ##STR223## 2 CH.sub.3 H 78.5 1.5335 colourless oil__________________________________________________________________________ Note: *.sup.1 CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.3 *.sup.2 CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.3, *.sup.3 CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.3, *.sup.4 CH.sub. 2 CH.sub.2 CH.sub.2 Cl *.sup.5 CH.sub.2 CH.sub.2 CH.sub.2 Cl, *.sup.6 CH.sub.2 CH.sub.2 CH.sub.3

FORMULATION EXAMPLE

Formulation Example 1: Emulsifiable concentration

20 parts of a compound of the present invention was dissolved in 65 parts of a xylene/methylnaphthalene mixture. 15 parts of a mixture of an alkylphenol/ethylene oxide condensate and calcium alkylbenzenesulfonate in a ratio of 8:2 was mixed with the obtained solution to prepare at emulsifiable concentration. This emulsifiable concentration may be used as a spreading agent by diluting with water.

Formulation Example 2: Wettable powder

20 parts of a compound of the present invention was mixed with 35 parts of kaolin, 30 parts of clay and 7.5 parts of diatomaceous earth. 7.5 parts of a mixture of sodium laurate and sodium dinaphthylmethanesulfonate in a ratio of 1:1 was added to the obtained mixture. The resulting mixture was finely ground to prepare a powder. This powder may be used as a spreading agent by diluting with water.

Formulation Example 3: Dust

1 part of a compound of the present invention was mixed with 97 parts of a mixture of talc and calcium carbonate in a ratio 1:1. The resulting mixture was ground to prepare a homogeneously dispersed mixture. 2 parts of silicic acid anhydride was added to this mixture. The resulting mixture was mixed and ground to prepare a dust. This dust may be used as a spreading agent as such.

Formulation Example 4: Granule

2 parts of a compound of the present invention was mixed with 48 parts of finely powdered bentonite, 48 parts of talc and 2 parts of sodium ligninsulfonate, followed by the addition of water. The resulting mixture was kneaded until it became homogeneous. The mixture was granulated by passing it through an injection molding machine and adjusted to a granular size of 0.1 to 1 mm by passing the granule thus molded through a spherizer, a dryer and sieve. The obtained granule may be directly spreaded on the surface of paddy fields and uplands as such.

Formulation Example 5: Oil

A mixture of 0.1 part of a compound of the present invention and 0.5 part of piperonyl butoxide was dissolved in such amount of illuminating kerosene as to give the total volume of 100 parts to prepare an oil. This oil may be used as such.

Formulation Example 6: Aerosol

0.4 part of a compound of the present invention, 20 parts of piperonyl butoxide, 6 parts of xylene and 7.6 parts of deodorized kerosine were mixed and dissolved. After filling the mixture into an aerosol container, a valve was fitted. 86 parts of Freon was introduced into the container through the valve under pressure to obtain an aerosol.

Formulation Example 7: Heating fibrous fumigant insecticidal composition

0.05 g of a compound of the present invention was dissolved in an appropriate amount of chloroform. The obtained solution was homogeneously adsorbed on the surface of an asbestos (2.5.times.1.5 mm, 0.3 mm in thickness) to prepare a fibrous fumigant insecticidal composition of hot plate heating type.

Formulation Example 8: Mosquito-repellant incense

0.5 g of a compound of the present invention was dissolved in 20 ml of methanol, followed by the addition of 99.5 g of an incense carrier comprising tabu powder, pyrethrum marc and wood powder in a ratio of 3:5:1. The obtained mixture was made homogeneous by stirring. After distilling off the methanol, 150 ml of water was added to the residue and the mixture was sufficiently kneaded, molded and dried to obtain a mosquito-repellent incense.

The effects of the present invention will be described by the following Test Examples.

The compounds used in the Test Examples as a control are the following comparative compounds (A), (B) and (C). These compounds were also tested according to the same method as the one for the test of compounds of the present invention.

______________________________________(A) ##STR224## (Japanese Patent Publication No. 3898/1968)(B) ##STR225## (Japanese Patent Laid-Open No. 98025/1973)(C) ##STR226## (J. Agr. Food Chem., 18(1), 57 (1970).______________________________________

TEST EXAMPLE

Test Example 1: Effects on resistant and susceptible strains of Nephotettix cincticeps, respectively.

The compounds of the present invention and the comparative compounds were formulated according to the same procedures as the ones described in Formulation Examples 1 and 2 into 20% wettable powders when they were crystal, or into 20% emulsifiable concentration when they were oils, and were used for this test. Further, a 50% emulsifiable concentration of BPMC (2-sec-butylphenylmethylcarbamate) and a 40% emulsifiable concentration of Diazinon (diethyl 2-isopropyl-4-methyl-6-pyrimidinylphosphorothioate) were used as a control.

Method: 5 to 6 rice plants in the tri- to tetra-foliate stages were dipped in 200 ppm chemical solutions for 15 seconds. After air-drying, the plants were placed in a glass cylinder (4.5.phi., .times.15 cm). Then, ten female adults of Nephotettix cincticeos, susceptible strain (collected in Ageo) and ten of the strain resistant to both organophosphorus and carbamates (collected in Nakagawara and in Izumi) were transferred in the cylinder. After covering with a wire mesh, the cylinder was left in a glass green-house. After 48 hours' treatment, the numbers of live and dead insects were counted to calculate the mortality. The results shown in Table 3 are averages of the two replications.

TABLE 3______________________________________ Mortality (%)Compound Resistant Resistantfor Susceptible (collected in (collected intest (collected in Ageo) Nakagawara) Izumi)______________________________________CompoundNo. 1 100 100 100 2 100 100 90 3 100 90 100 4 100 100 100 14 100 90 80 23 100 80 100 24 100 100 100 25 100 90 100 29 100 100 100 30 100 100 100 33 100 100 100 36 100 100 100 37 100 100 100 38 100 100 100 39 100 100 90 40 100 100 80 44 100 90 80 46 100 100 100 49 100 100 90 50 100 100 100 97 100 100 100136 100 100 100140 100 90 100141 100 100 100150 100 100 100152 100 100 100156 100 100 90164 100 100 100165 100 100 100169 100 100 100170 100 100 100171 100 100 100172 100 100 100173 100 100 100176 100 80 100177 100 100 100182 100 90 70183 100 80 80185 100 100 100189 100 100 100191 100 100 100192 100 90 80193 100 100 100194 100 100 100195 100 100 100197 100 100 80199 100 90 100201 100 100 100202 100 100 100203 100 100 100204 100 70 70205 100 100 80206 100 100 100208 100 70 90212 100 70 60213 100 80 60214 100 100 100215 100 100 100217 100 80 70220 100 100 70222 100 90 70223 100 70 60230 100 70 60233 100 80 90236 100 100 100237 100 100 100238 100 100 100ControlA 100 40 20B 90 20 10C 60 0 20Control 100 20 0BPMCDiazinon 100 0 30______________________________________

Test Example 2: Effect on Nilaparvata lugens

The compounds of the present invention and the comparative compounds were formulated according to the same procedures as the ones described in Formulation Examples 1 and 2 into 20% wettable powder or into 20% emulsifiable concentration and tested.

Method: The same procedure described in Test Example 1 were repeated, except that 10 female adults of Nilaparvata lugens were used. 48 hours after treatment, the numbers of live and dead insects were counted to calculate the mortality. The results shown in Table 4 are averages of two replications. Nilaparvata lugens, ten susceptible strains (collected in Kaseda) and ten resistant strains (resistant to both organophosphorus and carbamates, collected in Izumi) was used in this test.

TABLE 4______________________________________ Mortality (%) Susceptible ResistantCompound for test (collected in Kaseda) (collected in Izumi)______________________________________Compound No. 1 100 100 2 100 100 3 100 100 4 100 100 7 100 70 21 100 80 24 100 100 29 100 90 30 100 100 33 100 100 36 100 100 37 100 100 41 100 80 44 100 80 45 100 90 49 100 100 50 100 100140 100 100141 100 80150 100 100152 100 100156 100 100160 100 90163 100 100164 100 100165 100 90166 100 80168 100 100169 100 100170 100 70171 100 100172 100 100173 100 100174 100 100175 100 100176 100 100177 100 100178 100 60179 100 60180 100 70181 100 100182 100 100183 100 60184 100 70185 100 90187 100 100189 100 100190 100 100192 100 80193 100 100194 100 80195 100 70196 100 70197 100 60199 100 90201 100 100202 100 100203 100 100204 100 80205 100 90206 100 100207 100 70208 100 80211 100 80214 100 100215 100 100216 100 70217 100 100218 100 80219 100 60220 100 100221 100 70222 100 60223 100 60227 100 70228 100 80230 100 60232 100 70233 100 70235 100 70ControlA 90 40B 90 30C 10 0Control BPMC 100 10Diazinon 100 20______________________________________

Test Example 3: Effects on larvae of Culex pipiens pallens

The compounds of the present invention and the control were formulated into 0.1% acetone solution and tested.

Method: 199.8 ml of well water was placed in a plastic container having a diameter of 9 cm. Twenty larvae of Culex pipiens pallens (third to fourth instar), collected in Ageo, were transferred into the container. 0.2 ml of the above prepared solution was pipetted into the container to give a chemical solution of 1 ppm. After 24 hours, the numbers of live and dead insects were counted to calculate the mortality. The results shown in Table 5 are averages of the two replications.

TABLE 5______________________________________Compound for test Mortality (%)______________________________________Compound No. 1 100 2 100 3 100 4 100 5 100 6 100 14 100 15 100 16 80 17 100 18 100 19 90 20 100 21 100 22 100 23 100 24 100 25 100 26 80 27 80 28 80 29 100 30 100 31 100 32 100 33 100 34 100 35 100 36 100 37 100 42 80 43 80 44 100 45 100 46 100 47 100 48 100 49 100 50 100 51 100 94 100 95 100 96 80 97 100136 100140 100150 100152 100156 100157 100158 100159 100160 100161 100162 100163 100164 100165 100166 100169 100170 100171 100172 100173 100174 100176 100177 80178 100180 80181 100182 100183 100184 100185 100186 100187 100188 70189 100190 100191 100192 100193 100194 100195 90196 100197 100198 100199 100200 100201 100202 100203 100204 100205 100206 100207 100208 100209 100210 100211 100214 100215 100216 100217 100218 100219 100220 100221 100222 70223 70224 90225 70226 80227 100228 100229 100230 100231 100232 100233 100234 100235 100236 100237 100238 100239 100240 100241 100ControlA 70B 30C 0______________________________________

Test Example 4: Effect on larvae of Plutella xylostella

The compounds of the present invention and the comparative compounds were formulated according to the same procedures as the ones described in Formulation Examples 1 and 2 into 20% wettable powders when they were crystals, or into 20% emulsifiable concentration when they were oils, and were used for this test. Further, a 40% emulsifiable concentration of MEP (0,0-diethyl-O-4-nitro-m-tolyl phosphorothioate) was used as a control.

Method: A cabbage leaf of a medium size cut from a cabbage grown to deca-foliate stage was dipped in a 500 ppm chemical solution for 15 seconds. After air-drying, the leaf was placed in a plastic container having a diameter of 9 cm. 15 larvae (third instar) of Plutella xylostella were transferred into the container. After covering with a lid having several pinholes, the container was left in a green house at 25.degree. C. 48 hours after the treatment, the numbers of live and dead insects were counted to calculate the mortality. The results shown in Table 6 are averages of two replications.

TABLE 6______________________________________Compound for test Mortality (%)______________________________________Compound No. 3 100 4 10020 10021 10023 10034 10037 100ControlA 10B 0C 0Control MEP 70______________________________________

Test Example 5: Effect on adults of Tetranychus urticae

The compounds of the present invention and the controls were formulated according to the same procedures as the ones described in Formulation Examples 1 and 2 into 20% wettable powders when they were crystals, or into 20% emulsifiable concentration when they were oils, and were used for this test.

Method: The primary leaf of a kidney bean which was cultivated in an unglazed pot (diameter: 9 cm) was trimmed to a size of approximately 3 cm.times.3 cm. 15 female adult mites susceptible to organophosphorus insecticide were transferred onto the leaf carefully using a small brush. The plants were left in a green-house adjusted at 25.degree. C. After one day from the contact with the adults, dead and abnormal mites were taken out of the leaf. The mites on the leaf were dipped in a 400 ppm chemical solution for 10 seconds. After the treatment, the plant was left in the green-house. 48 hours after the treatment, the numbers of live and dead mites were counted under a stereomicroscope to calculate the mortality. The results are shown in Table 7.

TABLE 7______________________________________Compound for test Mortality (%)______________________________________Compound No. 3 100 7 100 8 100 9 100 18 100 24 100171 100175 100176 100177 100185 100______________________________________

Test Example 6: Effect on the clubroot of tomatoes due to Meloidogine incognita

400 g of soil polluted with Meloidogine incognita was packed in a plastic cup having a diameter of 10 cm. The compounds of the present invention, the comparative compounds and a control compound of DCIP [bis(2-chloromethylethyl)ether] were formulated according to the same procedure as the one described in Formulation Example 3 into 1% dusts. 40% mg of each dust was applied to the soil, followed by entire mixing. 15 seeds (variety: Ponte Rosa) were sown per cup.

40 days after the chemical treatment, the tomatoes were digged up and examined for damage due to chemicals and clubroot index. The results are shown in Table 7.

The clubroot index was calculated by the following expression: ##EQU1##

A: Number of tomato seedlings having at least 31 clubroots.

B: Number of tomato seedlings having 21 to 30 clubroots.

C: Number of tomato seedlings having 11 to 20 clubroots.

D: Number of tomato seedlings having 1 to 10 clubroots. The results are shown in Table 8.

TABLE 8______________________________________Compound for test Clubroot index Phytotoxicity______________________________________Compound No. 3 45 no 4 48 no 7 42 no23 13 no29 40 no32 20 no43 39 noControl (C) 78 noControl DCIP 83 noUntreated 100 --______________________________________

Test Example 7: Effect on larvae of Anomala cuprea in the soil

50 grams of chemical solution diluted with water, were fully mixed with 100 grams of dried soil containing dried leaf mold, and the treated soil was transferred to a plastic cup together with five 1st instar larvae of Cupreous chafer, Anomala cuprea and was kept in temperature controlled room (25.degree. C.). After 2 days, the number of live and dead larvae was counted and mortalities were calculated. The results are shown in Table 9.

TABLE 9______________________________________ Mortality (%) Concentration in soilCompound for test 100 ppm 10 ppm______________________________________Compound No. 3 100 100 4 100 80 10 100 100 14 100 80 29 100 100 30 100 100 31 100 100 32 100 100 34 100 100 36 100 100 37 100 100 46 100 100 48 100 100150 100 100152 100 100164 100 100165 100 100169 100 100170 100 100171 100 80173 100 100176 100 80182 100 100185 100 80189 100 100190 100 60193 100 100206 100 100Untreated 0 0______________________________________

Claims

1. A compound of the formula: ##STR227## wherein Ar is ##STR228## R.sup.1 is C.sub.3 -C.sub.5 -alkyl unsubstituted or substituted with F or Cl, C.sub.3 -C.sub.6 -cycloalkyl, C.sub.3 -C.sub.6 -cycloalkylmethyl, R.sup.2 is CH.sub.3, CH.sub.2 Cl or C.sub.2 H.sub.5 and x is 0, 1 or 2.

2. A compound of the formula (I) according to claim 1, wherein Ar is ##STR229## R.sup.1 n-C.sub.3 H.sub.7, iso-C.sub.3 H.sub.7, sec-C.sub.4 H.sub.9, iso-C.sub.4 H.sub.9, cyclopentyl or cyclopropylmethyl, R.sup.2 is CH.sub.3, CH.sub.2 CI or C.sub.2 H.sub.5, x is 0, 1 or 2.

3. A compound of the formula (I) according to claim 2 which is selected from the group consisting of one of the following formulas: ##STR230##

4. An insecticidal, acaricidal or nematicidal composition which comprises an effective amount of a compound of the formula: ##STR231## wherein Ar is ##STR232## R.sup.1 is C.sub.3 -C.sub.5 -alkyl unsubstituted or substituted with F or Cl, C.sub.3 -C.sub.6 -cycloalkylmethyl, R.sup.2 is CH.sub.3, CH.sub.2 CI or C.sub.2 H.sub.5 and x is 0, 1 or 2.

5. A method for killing insect pests, acarids or nematodes, which comprises applying an effective amount of a compound of the formula: ##STR233## where Ar is ##STR234## R.sup.1 is C.sub.3 -C.sub.5 -alkyl unsubstituted or substituted with F or Cl, C.sub.3 -C.sub.6 -cycloalkyl or C.sub.3 -C.sub.6 -cycloalkylmethyl, R.sup.2 is CH.sub.3, CH.sub.2 Cl or C.sub.2 H.sub.5 and x is 0, 1 or 2.