GB2035314A

GB2035314A - Heterocyclic carboxylates

Info

Publication number: GB2035314A
Application number: GB7937098A
Authority: GB
Original assignee: Sumitomo Chemical Co Ltd
Current assignee: Sumitomo Chemical Co Ltd
Priority date: 1978-10-27
Filing date: 1979-10-25
Publication date: 1980-06-18
Also published as: IT7950679A0; AU5212979A; DE2943394A1; FR2439780A1; NL7907888A

Abstract

A carboxylate has the formula <IMAGE> wherein R1 and R2 are independently H, CH3 or Hal, A is O or S or methylene R is O or-CH = CH-, R4 is H or ethynyl or cyano and R3 is <IMAGE> in which R5is hal, when A is O or S and R is -CH = CH-; when A is methylene, R is -CH = CH-; and R4 is H or when A is methylene, R is O and R4 is H or ethynyl, (2) when A is methylene, R is -CH = CH-; and R4 is ethynyl R3 is <IMAGE> in which R6 is H or CH3, when R6 is H, R7 is <IMAGE> or -CH = N-OCH3 (in which R8 is H, CH3 or methoxycarbonyl and R9 is hal or CH3, and when R6 is CH3, R7 is CH3, and (3) when A is methylene and R4 is cyano, R3 is <IMAGE> in which R10 is H or CH3, when R10 is H, R11 is <IMAGE> or -CH = N-OCH3 (in which R12 is Hal or methyl, methoxycarbonyl or methoxymethyl and R13 is H, Hal or CH3 and when R10 is methyl, R11 is methyl. The carboxylates are useful insecticides and/or acaricides.

Description

SPECIFICATION Carboxylates, their production and insecticide and acaricide compositions containing them The present invention relates to carboxylates, their production and insecticide and acaricide compositions containing them.

Of the insecticides now in common use, pyrethrum extracts (containing Pyrethrin) and synthetic Allethrin, which is a homologue of the active ingredient of pyrethrum extracts, are insecticides which have a particularly rapid effect, are not toxic to mammals and therefore can be used safely. Pyrethrum extracts, however, tend to be limited in use because, even though they give excellent results, they are relatively expensive.

We synthesized many carboxylates and examined their biological activity. As a result, we found a carboxylate useful as a low-cost insecticide and/or acaricide which is low in toxicity to mammals and strong in insecticidal and acaricidal effect and which can be used in environmental sanitation, agriculture and household horticulture. It has excellent insecticidal activity against not only harmful insanitary insects such as flies, but also insects harmful to agricultural crops, particularly the green rice leafhopper (Nephotettix cincticeps), diamond-back moth (Plutella xylostella), armyworms and cutworms.

The carboxylate is of the formula

wherein R1 and R2, which may be the same or different, are each a hydrogen atom, a methyl group or a halogen atom, A is an oxygen or sulfur atom or a methylene group, R is an oxygen atom, or a group of the formula -CH = CH-, R4 is a hydrogen atom or an ethynyl or cyano group, and

in which R5 is a halogen atom, when A is an oxygen or sulfur atom and R is a group of the formula -CH = CH-; when A is a methylene group, R is a group of the formula -CH = CH-, and R4 is a hydrogen atom; or when A is a methylene group, R is an oxygen atom and R4 is a hydrogen atom or an ethynyl group, (2) when A is a methylene group, R is a group of the formula -CH = CH-, and R4 is an ethynyl group, R3 its a group of the formula (III),

in which R6 is a hydrogen atom or a methyl group, when R6 is a hydrogen atom, R7 is a group of the formula (lav),

(in which R8 is a halogen atom or a methyl or methoxy-carbonyl group and Rg is a halogen atom or a methyl group), and when R6 is a methyl group, R7 is a methyl group, and (3) when A is a methylene group and R4 is a cyano group, R3 is a group of the formula (V),

in which Ra0 is a hydrogen atom or a methyl group, when R1O is a hydrogen atom, R11 is a group of the formula (VI),

(in which R12 is a halogen atom or a methyl, methoxy-carbonyl or methoxymethyl group and R3 is a hydrogen or halogen atom or a methyl group) and when Ra0 is a methyl group, R11 is a methyl group. The halogen atom referred to herein means a chlorine or bromine atom for the groups R1 and R2, and a chlorine, bromine or fluorine atom for the groups Rs, R8 and Rg.

Carboxylates within the present invention (hereinafter called "the present compounds") have wide application in the prevention of epidemics. Since, however, they have also excellent insecticidal activity and residual effect against insects harmful to stored cereals, agricultural crops, trees in woods or forests and domestic animals, they are very useful for controlling these insects. Parcitularly, because of their low toxicity, they can be used for crops before harvest, greenhouse cultivation, household horticulture and food-packing materials. Examples of the insects described above will be shown hereinafter.

(1) Sanitary pests: Mosquitoes; (for example, Culexpipiens molestus, Culexpipienspallens, Aedes aegypti, Anopheles stephensi) Flies; (for example, Musca domestica, Lucilia caesar, Boettcherisca peregrine) Cockroaches; (forexample, Periplaneta americana, P. fulginosa, Blattella germanica) Gnats; (for example, Prosimulium hirtipes, Simullum aokii) Fleas; (for example, Pulex irritans) Lice; (for example, Pedimulus humanus, Phthirus pubis) (2) Stored crops: Coleoptera; (for example, Sitophilus zeamais, Tribolium castaneum, Tenebrio molitor) Lepidoptera; (for example, Ephestia cautella) Acarina; (for example, Tyrophagus dimidiatus) (3) In paddy field: Hemiptera; Delphacidae (planthoppers, delphacids) (for example, Sogatella furcifera, Nllaparvata lugens, Laodelphax striatellus) Deltocephalidae (leafhoppers) (for example, Nephotettix cinditiceps, Tettigella viridis) Aphididae (aphids) (for example, Rhopalosiphum rufiabdominalis, Rhopalosiphumpadi) Pentatomidae (stink bugs, shield bugs) (for example, Nezara antennata, Leptocorixa corbettl) Lepidoptera (moths and butterflies); (for example, Chilo suppressalis, Craphalocrocis medinalis, Sesamia inferens, Parnara guttata) (4) Vegetables, fruit trees, woods: Lepidoptara; (for example, Plutella xylostella, Spodoptera litura, Spodoptera exigua, Mamestera brassicae, Leucania separata, Ostrinia nubilalis, Pieris rapae, Papilio xuthus) Hemiptera; (for example, Myzus persicae, Apis gossypii) Coleoptera (beetles); (for example, Phaeddn brassicae) Diptera (flies); (for example, Hylemya platus, Hylemya antiqua) Isoptera (termites); (for example, Coptotermes formosanus, Leucotermes speratus) Tetranychidae (spider mites); (for example, Tetranychus cinnavarinus, T. ulticae, T. kanzawai, Pan on ych us citri, P. ulmi, Aculus pelekassi) (5) In forest: For example, Den drolim us spectabilis, Monochamus alternatus, Archips fumiferana, Oligonychus hon do en sis.

(6) Livestock: For example, Boophilus microplus.

The carboxylates (I) of the present invention do not appear to have been previously disclosed in the literature.

The synthesis of the carboxylates will be explained hereinafter.

A carboxylate of the formula (I) can be obtained by reacting an alcohol or halide of the formula (VII),

wherein R1, R2, A, R and R4 have the same meanings as above and X' is a hydroxyl group or a halogen atom, with a carboxylic acid of the formula (VIII),

wherein R3 has the same meaning as above, or a reactive derivative thereof in the presence of a suitable reaction assistant if necessary. The reactive derivative referred to herein means acid halides, acid anhydrides and alkali metal or organic tertiary base salts of the acid.

Also, the carboxylate of the formula (I) of which the group R4 is a cyano group, can be obtained by reacting an aldehyde of the formula (IX),

wherein R1, Fl2, A and R have the same meanings as above, with a carboxylic acid halide of the formula (X),

wherein R3 has the same meaning as above and Y is a halogen atom, and an alkali metal cyanide.

These synthetic methods will be explained in more detail.

Firstly, there is given a case wherein the group X' in the formula (VII) is a hydroxyl group. In this case, the esters of the formula (I) are obtained by reacting an alcohol of the formula (XI),

wherein R1, Fl2, A, R and R4 have the same meanings as above, with a carboxylic acid of the formula (VIII) or an acid halide or acid anhydride thereof.

When the carboxylic acid is used, the reaction is achieved in dehydration conditions. That is, an ester of the formula (I) can be obtained by reacting an alcohol of the formula (Xl) with a carboxylic acid of the formula (VIII) at -30" to 100"C for 0.5 to about 20 hours in a solvent (e.g. benzene, toluene, xylene, mixtures thereof) in the presence of a dehydrating agent or condensing agent (e.g. decyclohexylcarbodiimide).

When the acid halide is used, the reaction proceeds sufficiently well even at room temperature by reacting an alcohol of the formula (Xl) with the acid halide using an organic tertiary base (e.g. pyridine, triethylamine) as an acid-binding agent.

The acid halide used in this reaction is not particularly limited, but generally an acid chloride is used. In this reaction, the use of a solvent is favourable to allow the reaction to proceed smoothly, and generally inert solvents such as benzene, toluene, xylene, ether, hexane and heptane are used. The reaction temperature may be from -30" to 1000C and the reaction time from 0.5 to 10 hours.

When the acid anhydride is used, the process can be carried out by reacting an alcohol of the formula (XI( with the acid an hydride at 200 to 100O without a reaction assistant. The use of a solvent (e.g. benzene, toluene, xylene, hexane, acetone) is favourable to allow the reaction to proceed smoothly, but it is not essential.

Secondly, there is given a case wherein the group X in the formula (VII) is a halogen atom. In this case, an ester of the formula (I) is obtained by reacting a halide of the formula (XII),

wherein Fl1, Fl2, A, R and R4 have the same meanings as above, and Z is a halogen atom, with an alkali metal salt or organic tertiary base salt of the carboxylic acid of the formula (VIII).

When the organic tertiary base is triethylamine or trimethylamine, the desired ester can be obtained by converting a carboxylic acid of the formula (VIII) into a salt with the base in an inert solvent (e.g. benzene, toluene, acetone, dioxane) and then reacting the resulting salt with a halide of the formula (VII) at 0 to 1500C for 0.5 to 10 hours.

When the alkali metal salt is used, the desired ester can be obtained by carrying out the reaction at 0 to 15000 for 0.5 to 20 hours in a two-phase system comprising an inert solvent (e.g. benzene, toluene, xylene, heptane) and water using 1 to 10 mole % of a phase transfer catalyst such as tetra-n-butyl-ammonium bromide or benzyltriethylammonium chloride.

The group Z in the formula (XII) is not particularly limited, but generally it is a chlorine or bromine atom.

Thirdly, there is given a case wherein an aldehyde of the formula (IX) is reacted with a carboxylic acid halide of the formula (X) and an alkali metal cyanide. When the reaction is carried out in a non-aqueous system comprising an inert solvent, crown ethers are preferably used as a catalyst. When the reaction is carried out in a two-phase system comprising an inert solvent and water, phase transfer catalysts such as organic quaternary ammonium salts are preferably used. In either case, the desired compounds can be obtained in a high yield.

The alkali metal cyanide used in this reaction includes sodium cyanide and potassium cyanide. The inert solvent includes aromatic hydrocarbons (e.g. benzene, toluene, xylene), aliphatic hydrocarbons (e.g.

hexane, heptane, octane), halogenated aromatic hydrocarbons (e.g. chlorobenzene) and halogenated aliphatic hydrocarbons (e.g. dichloromethane, chloroform, carbon tetrachloride). Crown ethers are, for example, large-ring polyethers such as dibenzo-1 8-crown-6 and dicyclohexyl-1 8-crown-6.

The organic quaternary ammonium salt includes benzyltriethylammonium chloride, tetra-nbutylammonium bromide and the like. The amount of catalyst is generally 1 to 10 mole %. The reaction can be achieved at - 100 to 500C in 0.5 to 20 hours.

Examples of synthesis will be shown by standard procedures.

A. Method by reaction between alcohol and carboxylic acid halide 0.05 Mole of the alcohol is dissolved in dry benzene of three times by volume, and 0.075 mole of pyridine is added thereto. 0.053 Mole of the carboxylic acid chloride is dissolved in dry benzene of three times by volume and added dropwise, at 5"C or less, to the above solution with stirring and ice-cooling. After addition is finished, stirring is continued overnight at 25 C.

A little water is added to the reaction solution to dissolve the deposited pyridine hydrochloride, followed by phase separation. The organic layer is washed with 5% aqueous hydrochloric acid, sodium bicarbonate-saturated water and then with sodium chloride-saturated water, dried over anhydrous sodium sulfate and freed from the solvent by evaporation. The residue obtained is purified by column chromatography on silica gel to obtain the objective ester.

B. Method by reaction between alcohol and carboxylic acid anhydride 0.05 Mole of the alcohol is dissolved in toluene of three times by volume, and 0.05 mole of the carboxylic acid an hydride is added thereto. After stirring for 3 hours at room temperature, the reaction mixture is heated under reflux for 1 hour, allowed to cool and then extracted with 5% aqueous sodium hydroxide to transfer the carboxylic acid as by-product to the aqueous layer. The organic layer is washed with a sodium chloride-saturated water, dried over anhydrous sodium sulfate and freed from the solvent by evaporation.

The residue obtained is purified by column chromatography on silica gel to obtain the objective ester.

C. Method by reaction between alcohol and carboxylic acid 0.05 Mole of the alcohol and 0.05 mole of the carboxylic acid are dissolved in dry benzene of three times by volume, and 0.08 mole of dicyclohexylcarbodiimide is added thereto. After stirring overnight at 25"C, the reaction solution is filtered to remove dicyclohexylurea, and the filtrate is concentrated. The residue obtained is purified by column chromatography on silica gel to obtain the objective ester.

D. Method by reaction between alcohol halide and organic tertiary base salt of carboxylic acid 0.05 Mole of a halide of the alcohol and 0.06 mole of the carboxylic acid are dissolved in acetone of three times by volume. While, 0.08 mole of triethylamine is dissolved in acetone of three times by volume, and added dropwise to the above solution at 15 to 20 C with stirring. After the addition is finished, the reaction solution is heated under reflux for 2 hours, allowed to cool and filtered to remove the deposited triethylamine hydrochloride.After removing acetone from the filtrate by evaporation, the residue is added to benzene of three times by volume, and in the same manner as in the standard procedure A, the resulting organic layer is washed, dried, concentrated and column chromatographed on silica gel to obtain the objective ester.

E. Method by reaction between alcohol halide and alkali metal salt of carboxylic acid 0.05 Mole of the halide and 0.055 mole of the sodium salt of the carboxylic acid are dissolved in toluene of four times by volume and water of three times by volume, respectively. The two solutions are mixed, and 1.3 mole of tetra-n-butylammonium bromide is added thereto. After stirring at 70 to 80 C for 4 hours, the reaction solution is allowed to cool, washed with a sodium chloride-saturated water, dried over anhydrous sodium sulfate and then freed from the solvent by evaporation. The residue obtained is purified by column chromatography on silica gel to obtain the objective ester.

F. Method by reaction among aldehyde, alkali metal cyanide and carboxylic acid halide F-i. 0.075 Mole of sodium cyanide and 0.8 g of dibenzo-1 8-crown-6 are suspended in 100 ml of dry benzene. Then, 0.05 mole of the aldehyde and 0.0525 mole of the carboxylic acid chloride are dissolved in 50 ml of dry benzene, and added dropwise to the above suspension at room temperature with stirring. After addition is finished, stirring is continued overnight at 25"C. The reaction solution is washed with a sodium chloride-saturated water and freed from the solvent by evaporation. The residue is purified by column chromatography on silica gel to obtain the objective ester.

F-2. 0.075 Mole of sodium cyanide and 2.5 mmole of tetra-n-butylammonium bromide are dissolved in 20 ml of water. While, 0.05 mole of the aldehyde and 0.0525 mole of the carboxylic acid chloride are dissolved in 40 ml of toluene, and added dropwise to the above solution at 25 C over 3 hours with stirring.

After addition is finished, stirring is continued for 3 hours. The reaction solution is washed with a sodium chloride-saturated water, dried over an hydrous sodium sulfate and then freed from the solvent by evaporation. The residue is purified by column chromatography on silica gel to obtain the objective ester.

Typical examples of the carboxylates (I) according to the present invention are given below, but said ester is not of course limited to these examples.

Among the esters of the formula (I), there are stereoisomers owing to the steric configuration of the carboxylic acid and optical isomers owing to asymmetric carbon atoms on the carboxylic acid and the alcohol, but all these isomers are included in the scope of the present invention.

Compound Structure and name Acid moiety Method Yield Refractive No. (%) index (1) # de-cis-trans A 94.2 nD23.0 1.5729 isomer 3-(2-Thienyloxy)benzyl 2,2-dimethyl 3-(2,2-dichlorovinyl)cyclopropane 1-carboxylate (2) # de-cis-trans C 89.6 nD19.5 1.5736 isomer 3-(2-Thienyloxy)benzyl 2,2-dimethyl 3-(2,2-dichlorovinyl)cyclopropane 1-carboxylate (3) # de-cis-trans A 91.5 nD21.0 1.5747 isomer α-Ethynyl-3-(2-thienyloxy)benzyl 2,2-dimethyl-3-(2,2-dichlorovinyl) cyclopropane-1-carboxylate (4) # de-cis-trans A 90.3 nD21.5 1.5758 isomer α;-Ethynyl-3-(2-thienyloxy)benzyl 2,2-dimethyl-3-(2,2-dichlorovinyl) cyclopropane-1-carboxylate

Compound Structure and name Acid moiety Method Yield Refractive No. (%) index (5) # de-cis-trans F-1 83.9 nD21.5 1.5720 isomer α-Cyano-3-(2-thienyloxy)benzyl 2,2-dimethyl-3-(2,2-dichlorovinyl) cyclopropane-1-carboxylate (6) # de-cis-trans F-2 87.4 nD22.5 1.5723 isomer (7) α;-Cyano-3-(2-thienyloxy)benzyl 2,2-dimethyl-3-(2,2-dichlorovinyl) cyclopropane-1-carboxylate (8) # de-cis-trans F-2 88.8 nD25.5 1.5705 isomer 3-(2-Thenyl)benzyl 2,2-dimethyl-3 2,2-dichlorovinyl)cyclopropane-1 carboxylate (9) # de-cis-trans B 95.0 nD23.5 1.5701 isomer 3-)3-Thenyl)benzyl 2,2-dimethyl 3-(2,2-dichlorovinyl)cyclopropane 1-carboxylate

Compound Structure and name Acid moiety Method Yield Refractive No. (%) index (10) # de-cis-trans A 92.7 nD24.0 1.5710 isomer α-Ethylnyl-3-(2-thenyl)benzyl 2,2 dimethyl-3-(2,2-dichlorovinyl) cyclopropane-1-carboxylate (11) # de-cis-trans A 91.6 nD25.0 1.5692 isomer α-Ethylnyl-3-(2-thenyl)benzyl 2,2 dimethyl-3-(2,2-dichlorovinyl) cyclopropane-1-carboxylate (12) # de-cis-trans D 89.1 nD25.0 1.5709 isomer (13) α;-Cyano-3-(2-thenyl)benzyl 2,2- d-cis isomer D 88.1 nD27.0 1.5716 dimethyl-3-(2,2-dichlorovinyl) cyclopropane-1-carboxylate (14) # de-cis-trans E 90.5 nD29.0 1.5689 isomer α-Cyano-3-(2-thenyl)benzyl 2,2 dimethyl-3-(2,2-dichlorovinyl) cyclopropane-1-carboxylate

Compound Structure and name Acid moiety Method Yield Refractive No. (%) index (15) # d-trans A 93.8 nD21.5 1.5676 isomer α-Ethynyl-3-(2-thenyl)benzyl chrysanthemate (16) # A 91.9 nD23.5 1.5518 α-Ethynyl-3-(2-thenyl)benzyl 2,2,3,3 tetramethylcyclopropanecarboxylate (17) # F-2 91.0 nD25.5 1.5498 α-Cyano-3-(3-thenyl)benzyl 2,2,3,3 tetremethylcyclopropanecarboxylate (18) # d-trans A 90.1 nD24.5 1.5746 isomer α-Ethynyl-3-(3-thenyl)benzyl pyrethrate (19) # d-trans F-2 88.7 nD27.0 1.5513 isomer α;-Cyano-3-(3-thenyl)benyl)benzyl 2,2 dimethyl-3-(2,2-difluorovinyl) cyclopropane-1-carboxylate

Compound Structure and name Acid moiety Method Yield Refractive No. (%) index (20) # d-cis isomer F-2 90.5 nD24.0 1.5905 α-Cyano-3-(3-thlenyloxy)benzyl 2,2 dimethyl-3-(2,2-dibromovinyl) cyclopropane-1-carboxylate (21) # d-cis isomer F-1 87.5 nD23.0 1.5902 α-Cyano-3-(2-thlenyloxy)benzyl 2,2 dimethyl-3-(2,2-dibromovinyl)cyclo propane-1-carboxylate (22) # d-trans E 90.8 nD23.0 1.5536 isomer α;-Cyano-3-(2-thlenyloxy)benzyl 2,2-dimethyl-3-methoxyimino methylcyclopropane-1-carboxylate (23) # d-trans D 88.7 nD24.0 1.5727 isomer α-Cyano-3-(2-thlenyloxy)benzyl 2,2 dimethyl-3-(2methoxymethyl-1 propenyl)cyclopropane-1-carboxylate

Compound Structure and name Acid moiety Method Yield Refractive No. (%) index (24) # de-cis-trans B 88.3 nD21.0 1.6035 isomer α-Ethynyl-3-(2-thienylthio)benzyl 2,2-dimethyl-3-(2,2-dichlorovinyl) cyclopropane-1-carboxylate (25) # de-cis-trans F-1 83.7 nD23.0 1.5993 isomer α-Cyano-3-(3-thienylthio)benzyl 2,2-dimethyl-3-(2,2-dichlorovinyl) cyclopropane-1-carboxylate (26) # de-cis-trans F-1 90.4 nD27.0 1.5528 isomer α-Cyano-3-(5-bromo-2-thienyloxy) benzyl 2,2-dimethyl-3-(2,2 dichlorovinyl)cyclopropane-1 carboxylate (27) # F-2 89.6 nD25.0 1.5598 α ;-Cyano-3-(5-chloro-2-thienyloxy) benzyl 2,2-dimethyl-3-(2,2-dichloro vinyl)cyclopropane-1-carboxylate

Compound Structure and name Acid moiety Method Yield Refractive No. (%) index (28) # A 92.4 nD25.0 1.5501 α;-Cyano-3-(5-methyl-2-thenyl)benzyl 2,2,3,3-tetramethylcyclopropane carboxylate (29) # de-cis-trans A 90.6 nD22.5 1.5581 isomer (30) [5-(2-Thenyl)-2-furyl]methyl d-trans A 92.3 nD25.5 1.5563 2,2-dimethyl-3-(2,2-dichlorovinyl)- isomer cyclopropane-1-carboxylate (31) # de-cis-trans A 91.3 nD23.0 1.5579 isomer (32) [5-(3-Thenyl)-2-furyl]methyl d-cis-isomer A 90.1 nD25.5 1.5586 2,2-dimethyl-3-(2,2-dichlorovinyl) cyclopropane-1-carboxylate (33) # de-cis-trans F-1 79.5 nD22.5 1.5568 isomer [5-(2-Thenyl)-2-furyl]cyanomethyl 2,2-dimethyl-3-(2,2-dichlorovinyl) cyclopropane-1-carboxylate

Compound Structure and name Acid moiety Method Yield Refractive No. (%) index (34) # de-cis-trans F-2 84.9 nD22.5 1.5551 isomer [5-(3-Thenyl)-2-furyl]cyanomethyl 2,2-dimethyl-3-(2,2-dichlorovinyl) cyclopropane-1-carboxylate (35) # de-cis-trans B 84.6 nD21.0 1.5582 isomer 1-[5-(2-Thenyl)-2-furyl]propargyl 2,2-dimethyl-3-(2,2-dichlorovinyl) cyclopropane-1-carboxylate (36) # de-cis-trans C 85.6 nD25.0 1.5569 isomer [2-(2-Thenyl)-4-furyl]methyl 2,2 dimethyl-3-(2,2-dichlorovinyl) cyclopropane-1-carboxylate (37) # de-cis-trans A 83.7 nD22.0 1.5553 isomer [2-(2-Thenyl)-4-furyl]cyanomethyl 2,2-dimethyl-3-(2,2-dichlorovinyl) cyclopropane-1-carboxylate

Compound Structure and name Acid moiety Method Yield Refractive No. (%) index (38) # de-cis-trans D 72.6 nD22.5 1.5576 isomer [4-(2-Thenyl)-2-furyl]methyl 2,2 dimethyl-3-(2,2-dichlorovinyl) cyclopropane-1-carboxylate (39) # de-cis-trans A 95.1 nD24.5 1.5568 isomer [2-(3-Thenyl)-4-furyl]methyl 2,2 dimethyl-3-(2,2-dichlorovinyl) cyclopropane-1-carboxylate (40) # d-trans A 91.4 nD22.0 1.5748 isomer [5-(2-Thenyl)-2-furyl]methyl 2,2 dimethyl-3-(2,2-dichlorovinyl) cyclopropane-1-carboxylate (41) # d-cis isomer A 94.2 nD22.0 1.5748 [5-(3-Thenyl)-2-furyl]methyl 2,2 dimethyl-3-(2,2-dichlorovinyl) cyclopropane-1-carboxylate

Compound Structure and name Acid moiety Method Yield Refractive No. (%) index (42) # F-2 80.4 nD21.0 1.5367 [5-(2-Thenyl)-2-furyl]cyanomethyl 2,2,3,3-tetramethylcyclopropane carboxyiate (43) # d-trans A 92.2 nD25.0 1.5717 isomer [5-(2-Thenyl)-2-furyl]methyl 2,2 dimethyl-3-methoxyiminomethyl cyclopropane-1-carboxylate

The aldehydes of the formula (IX), novel compounds, used as intermediates for producing the present compounds (I) can be produced by the following methods.

The first is a method which comprises reacting an alcohol of the formula (XIII),

wherein R1, R2, A and R have the same meanings as above, with an oxidizing agent.

The alcohols of the formula (XIII) are disclosed in the form of a general formula,

wherein R; and R2, which may be the same or different, are each a halogen atom or a lower alkyl group, m and n are each an integer of 0 to 3 and A is an oxygen or sulfur atom, in Published Unexamined Japanese Patent Application No. 125523/1974. They are also disclosed in Published Unexamined Japanese Patent Application Nos. 58712/1976 and 30632/1973 in the form of general formulae,

respectively.

The oxidizing agent includes manganese dioxide, chromium trioxide/pyridine, pyridinium chlorochromate, chromium trioxide/graphite, potassium chromate/sulfuric acid, lead tetracetate/pyridine, dimethyl sulfoxide and the like.

The solvent, reaction time and reaction temperature vary with the kind of oxidizing agent. Generally, however, the desired aldehydes can be obtained by carrying out the reaction at 20 to 200 C for 1/3 to 20 hours using a solvent such as aromatic hydrocarbons (e.g. benzene, toluene, xylene), halogenated hydrocarbons (e.g. dichloromethane, chloroform, carbon tetrachloride, dichloroethane, chlorobenzene), hexane, ether or petroleum ether. These solvents may be used alone or in combination.

The second is a method which comprises producing a compound of the formula (IX) of which the group A is an oxygen or sulfur atom by reacting a thiophene halide of the formula (XIV),

wherein R has the same meaning as above, and E is a halogen atom, with an alkali metal salt of the aldehvde of the formula (XV),

wherein R2 and A have the same meaning as above, or an alkali metal salt of the acetal thereof in an inert solvent in the presence of a copper catalyst with heating.

The halogen atom, E, in the formula (XIV) includes chlorine, bromine and iodine atoms of which bromine and iodine atoms are preferred. The copper catalyst includes copper powder, cuprous chloride, cupric chloride, cupric bromide and the like. The solvent includes toluene, xylene, naphthalene, pyridine, nitrobenzene, dinitrobenzene, chlorobenzene, dichlorobenzene, N,N-dimethylformamide, dimethyl sulfoxide and the like. These solvents may be used alone or in combination. A reaction temperature of 100"two 200 C, preferably 120 to 170 C, and a reaction time of 1 to 30 hours are sufficient to obtain the desired aldehydes.

When the acetal is used, it should be converted after reaction, to the aldehyde by acid treatment. As the acetal, dimethyl acetal and diethyl acetal are used generally. The acid includes hydrochloric acid, sulfuric acid, nitric acid, acetic acid, formic acid and the like.

The third is a method for producing a compound of the formula (IX) of which the group A is a methylene group by reacting an alkali metal salt of thiophene of the formula (XVI),

wherein R1 has the same meaning as above, and G is an alkali metal or a group of the formula, MgJ in which J is a halogen atom, with an acetal of the haloaldehvde of the formula (XVII),

whereR2 and R have the same meanings as above, and L is a halogen atom.

The alkali metal, G, in the formula (XVI) includes lithium, sodium and potassium atoms. The halogen atom, J, in the group MgJ includes bromine and iodine atoms, and the same, L, in the formula (XVII) includes chlorine, bromine and iodine atoms. The acetal generally includes dimethyl acetal and diethyl acetal. The solvent includes ether, tetrahydrofuran, dioxane, 1 ,2-dimethoxyethane, bis(2-methoxyethyl) ether, pentane, hexane, heptane, benzene and the like. These solvents may be used alone or in combination. The reaction temperature is preferably -70'to 70"C when G is an alkali metal, and -20'to 120"C when G is MgJ.This condensation reaction may come to an end at any time within a period of 0.5 to 20 hours, and the resulting acetal is converted to the aldehyde in the same manner as that described above to obtain the desired compound.

The fourth is a method which comprises producing a compound of the formula (IX) of which the group A is a methylene group by reacting a halomethyl derivative of thiophene of the formula (XVIII),

wherein R1 has the same meaning as above, and Q is a halogen atom, with a Grignard reagent of h::uln::Udrhv(is3 S Pt: nf tI,p fnrmx (XIXI

wherein R2 and R have the same meanings as above, and J is a halogen atom.

The halogen atom, J, in the formula (XIX) includes chlorine, bromine and iodine atoms, and the same, Q, in the formula (XVIII) include generally bromine and iodine atoms. The acetal is generally dimethyl acetal and diethyl acetal. The reaction solvent is the same as described in the third method. This reaction may be carried out at -20" to 120 C and may come to an end at any time within a period of from 0.5 to 20 hours, and after reaction, the resulting acetal is converted to the aldehyde to obtain the desired compound.

In the methods 3 and 4, the use of a catalyst can allow the reaction to proceed smoothly, but it is not always essential. The catalyst includes AgBr, Cull2, CrO3 and the like, and its amount is preferably 0.1 to 10%.

The synthesis of the aldehydes of the formula (IX) will be shown with reference to the following examples, but the present invention is not limited to these examples.

Synthetic Example 1: 3-(3-Thienyloxy)benzaldehyde 3-(3-Thienyloxy)benzyl alcohol (20.6 g), manganese (IV) oxide (26.1 g) and chloroform (100 ml) were mixed and heated under reflux for 3 hours. After cooling to room temperature, the reaction solution was filtered through celite layer which was then thoroughly washed with chloroform (200 ml). The filtrate and washings were combined and washed with 10% aqueous hydrochloric acid (30 ml) and then with sodium chloride-saturated water (30 ml). The chloroform layer was then dried over magnesium sulfate, and chloroform was concentrated. The residue obtained was vacuum distilled (b.p. 108 - 11 3'O/0.4 mmHg) to obtain 19.1 g of a colourless liquid (yield 93.6%).

Synthetic Example 2: 3-(2-Thienyloxy)benzaldehyde 66.5% Sodium hydride (4.0 g) diluted with nujol was freed from the nujol by washing with n-hexane, and then pyridine (80 ml) was added thereto. 3-Hydroxy-benzaldehyde (14.7 g) was added to the solution over 20 minutes with ice-cooling, followed by stirring at 250C for further 30 minutes. Thereafter, 2-bromothiophene (16.3 g) and copper (I) chloride (1.0 g) were added, and after replacement with nitrogen gas, the mixture was heated under reflux for 15 hours. After cooling to room temperature, the reaction solution was poured into ice water (300 ml) containing conc. hydrochloric acid (100 ml), and extracted with two 200 portions of ether.The ether layer was washed with two 100 ml portions of 10% aqueous hydrochloric acid, sodium bicarbonate-saturated water (50 ml) and then with sodium chloride-saturated water (50 ml), and dried over magnesium sulfate. After concentrating the ether, the residue obtained was vacuum distilled (b.p. 98 104"C/0.2 mmHg) to obtain 8.3 g of a colourless liquid (yield 40.7%).

Synthetic Example 3: 3-(2-Thenyl)benzaldehyde To a Grignard solution prepared from 2-bromothiophene (19.6 g) and magnesium (3.2 g) in ether (80 ml), was added copper (I) oxide (1.0 g). After replacement with nitrogen gas, a solution of 3chloromethylbenzaldehyde diethylacetal (22.9 g) in ether (40 ml) was added dropwise thereto over 1 hour with ice-cooling. After addition was finished, the solution was heated under reflux for 2 hours. After cooling to room temperature, the reaction solution was poured into ice water (150 ml) containing ammonium chloride (10 g), and extracted with two 100 ml portions of ether. The ether layer was washed with water (40 ml) and dried over magnesium sulfate.After concentrating the ether, the residue obtained was vacuum distilled (b.p. 117 - 1 23"C/0.12 mm Hg) to obtain 19.0 g of a colourless liquid (yield 68.8%). This product was 3-(2-thenyl)benzaldehyde diethylacetal.

This acetal (10.0 g) was added to a mixed solvent of 5% aqueous hydrochloric acid (100 ml), toluene (30 ml) and tetrahydrofuran (30 ml), followed by stirring at 25"C for 15 hours. After phase separation, the aqueous layer was extracted with toluene (100 ml). The organic layers were combined, washed with sodium bicarbonate-saturated water (30 ml) and then with sodium chloride-saturated water (30 ml), and dried over magnesium sulfate. The solvent was concentrated to obtain 6.9 g of a colourless liquid (yield 94.2%).

Synthetic Example 4: 5-(3-Thenyl)furfural A solution of 3-bromothiophene (16.3 g) in ether (40 ml) was cooled to -70 C or less after replacement with nitrogen gas, and a n-hexane solution (69 ml) containing 1.6 mole/e of n-butyl lithium was added dropwise thereto over 2 hours. The mixture was stirred at -70 C for further 30 minutes. Thereafter, a toluene solution (31.2 g) containing 70% of 5-chloromethyl-furfural diethylacetal was dissolved in ether (70 ml) and added dropwise to the mixture over 2 hours. After stirring at -70O for further 1 hour, the temperature was gradually returned to room temperature, followed by stirring for further 1 hour at room temperature. The reaction solution was poured into 5% aqueous hydrochloric acid (150 ml), followed by stirring for 2 hours.

After phase separation, the aqueous layer was extracted with ether (100 ml). The organic layers were combined, washed with sodium bicarbonate-saturated water (30 ml) and then with sodium chloridesaturated water (30 ml), and dried over sodium sulfate. The ether was concentrated, and the residue obtained was purified by chromatography on silica gel to obtain 5.1 g of the objective compound (yield 26.6%).

Synthetic Example 5: 3-(3-Thenyl)benzaldehyde A Grignard solution was prepared from 3-bromobenzaldehyde diethylacetal (33.7 g) and magnesium (2.9 g) in tetrahydrofuran (60 ml). Separately from this, a solution comprising 3-chloromethylthiophene (13.3 g), copper (I) chloride (1.0 g) and tetrahydrofuran (30 ml) was prepared, and after replacement with nitrogen gas, it was cooled to -10 C.The Grignard solution was added dropwise to this solution over 1.5 hours. After addition was finished, the mixture was heated under reflux for 1 hour. After cooling to room temperature, the reaction solution was poured into ice water (150 ml) containing ammonium chloride (10 g), and then extracted with two 100 ml portions of ether. The ether layer was washed with water (40 ml) and dried over magnesium sulfate.After concentrating the ether, the residue obtained was vacuum distilled (b.p. 116 122 C/0.2 mmHg) to obtain 15.2 g of a colourless liquid (yield 57.6%). This product was 3-(3thenyl)benzaldehyde diethylacetal.

This acetal (10.0 g) was added to a mixed solution comprising 5% aqueous hydrochloric acid (100 ml), toluene (30 ml) and tetrahydrofuran (30 ml), followed by stirring at 25 C for 15 hours. After phase separation, the aqueous layer was extracted with toluene (100 ml). The organic layers were combined, washed with sodium bicarbonate-saturated water (30 ml) and then with sodium chloride-saturated water (30 ml), and dried over magnesium sulfate. The solvent was concentrated to obtain 6.8 g of a colourless liquid (yield 93.3%).

In applying the compound of this invention as an insecticide or acaricide, it can be employed as such without blending with other ingredients, but generally it is used in the form of pesticidal composition by biending with a carrier to improve its handling quality as a pest controlling agent; and such a composition may be further diluted prior to use, if necessary.

In preparing pesticidal compositions, the compound of this invention may be formulated in a manner similar to that used in customary pesticides by use of techniques well known to those skilled in the art and no other special precautions are necessary. The compound of this invention may be employed for the intended use in any of the forms such as emulsifiable concentrate, wettable powder, dust, granule, fine granule, oil preparation, aerosol, heating fumigant (mosquito coil, electrically heating mosquito mat), fuming preparation such as fogging, non-heating fumigant, poisonous bait, etc.

The compounds of this invention may be used in combinations of two or more members to enhance the insecticidal and acaricidal activity. The activity may also be enhanced by incorporating with synergists for pyrethroids, such as a-[2-(2-butoxyethoxy)ethoxy]-4,5-methylenedioxy-2-propyltoluene (referred to as "piperonyl butoxide"), 1 ,2-methylenedioxy-4-[2-(octylsulfinyl )-propyl] benzene, 4-(3,4- methyl ened ioxyp henyl)-5-m ethyl-l ,3-di oxane, N-(-2-ethylhexyl)-bicyclo[2,2,1 ihepta-5-ene-2,3- dicarboxyimide, octachlorodipropyl ether, isobornyl thiocyanoacetate, and other known synergists effective for allethrin and pyrethrin.

Although highly resistant to light, heat and oxidation, the compound of this invention may be further stabilized against severe oxidative conditions by incorporating with a suitable amount of stabilizers. Suitable stabilizers are antioxidants and ultraviolet absorbers including phenol derivatives and bisphenol derivatives such as BHT (2,6-di-tert-butyl-4-methylphenol) and BHA (2-tert-butyl-4-methoxyphenol); arylamines such as phenyl-cl-naphthylamine, phenyl- -naphthylamine and phenetidineacetone condensate; and benzophenone compounds.

The compound of this invention may be formulated to provide multipurpose compositions with desirable activities and, in some cases, even synergistic activities by mixing with various physiologically active substances including, for example, allethrin, N-(chrysanthemoxymethyl)-3,4,5,6-tetrahydrophthalimide, 5-benzyl-3-furylmethyl ch rysanthemate (referred to as "Chrysron"), 3-phenoxybenzyl chrysanthemate, 5-propargylfurfuryl chrysanthemate, 2-methyl-5-propargyl-3-furylmethyl chrysanthemate, d-trans-, d-cis, trans-chrysanthemates thereof, pyrthrum extract, d-trans- or d-cis, trans-ester of d-allethrolone, other known cyclopropane-carboxylate esters; organophosphorus insecticides such as O,O-dimethyl-O-(3-methyl-4- nitrophenyl) phosphorothioate (referred to as "Sumithion"), 0,0-dimethyl-0-4-cyanophenyl phosphorothioate, and O,O-dimethyl-0-(2,2-dichlorovinyl) phosphate (referred to as dichlorvos); carbamate insecticides such as 1-naphthyl-N-methylcarbamate, 3,4-dimethyl-phenyl-N-methylcarbamate, m-tolyl-Nmethylcarbamate, O-sec-butyl phenyl-N-methylcarbamate, O-isopropoxyphenyl-N-methylcarbamate, 3 methyl-4-dimethylaminophenyl-N-monomethylcarbamate, and 4-dimethylamino-3,5xylylmethylcarbamate; other insecticides, fungicides, nematocides, acaricides, herbicides, plant growth regulators, fertilizers, microbial pesticides described in E.S. Raun et al., J. Eco.Ento., 59(3), 620 (1966), insect hormones, and other agricultural chemicals.

The insecticidal and/or acaricidal composition according to this invention contain 0.001 to 80.0%, preferably 0.01 to 50% by weight of an active ingredient Practical embodiments of the insecticidal or acaricidal composition acocrding to this invention are illustratively shown in the following examples, wherein parts and percents are by weight.

Formulation Example 1 Each 10 parts of the compounds (1) to (43) of this invention were mixed with 15 parts of "Sorpol 3005X" (a mixture of nonionic surfactant (polyoxyethylene phenyl phenol derivative and anionic surfactant (alkyl aryl sulfate)) and 75 parts of xylene. The mixture was thoroughly stirred, mixed, and dissolved to obtain respective 10% emulsifiable concentrates.

Formulation Example 2 Each 0.3 part of the compound (1), (2), (3) and (4) of this invention was dissolved in 20 parts of acetone, admixed with 99.7 parts of 300-mesh clay, stirred thoroughly, and freed from the acetone by evaporation to yield 0.3% dust preparations of each compound.

Formulation Example 3 Each 50 parts of the compound (1), (2), (3), (4) and (6) of this invention was well mixed with 5 parts of "Sorpol 5029-0" (anionic surfactant or registered trademark of the product sold by Toho Chemicals), admixed with 45 parts of 300-mesh diatomaceous earth, and thoroughly mixed in a grinding mill to obtain 50% wettable powder of each compound.

Formulation Example 4 Each 10 parts of the compounds (1), (2), (3), (4) and (6) of this invention was admixed with 5 parts of "fenitrothion", mixed thoroughly with 5 parts of "Sorpol 5029-0", admixed with 80 parts of 300-mesh diatomaceous earth, and throug hly blended in a grinding mill to obtain 15% wettable powder of each compound.

Formulation Example 5 To each 2 parts of the compounds (1), (5), (6), (7), (26) and (41) of this invention, was added 2 parts of sodium ligninsulfonate (a binder) followed by adding 96 parts of ciay (an extender). The mixture was thoroughly blended in a grinding mill, admixed with water in an amount of 10% of the resulting mixture, again mixed thoroughly, then granulated by means of a granulator, and dried in air stream to obtain 2% granule of each compound.

Formulation Example 6 0.2 Part of the compounds (1), (4), (5), (6), (7) and (41) of this invention was dissolved in illuminating kerosene to make a total of 100 parts to obtain a 0.2% oil spray.

Formulation Example 7 A mixture of 0.1 part of the compound (5) of this invention and 0.5 part of piperonyl butoxide was dissolved in purified kerosene to make a total of 100 parts to obtain a 0.1% oil spray.

Formulation Example 8 A mixture of 0.1 part of the compound (6) of this invention and 0.2 part of "Dichlorvos" was dissolved in purified kerosene to make a total of 100 parts to obtain a 0.3% oil spray.

Formulation Example 9 Each 0.1 part of the compounds (5) and (6) of this invention, 0.2 part of "resmethrin" [(1-cyclohexene-1,2dicarboximido)-methyl dt,cis,trans-chrysanthemate], 7 parts of xylene and 7.7 parts of deodorized kerosene were mixed to form a solution. An aerosol container was filled with the above solution and fitted with a valve portion through which 85 parts of a propellant (liquefield petroleum gas) was filled under pressure into the container to obtain an aerosol preparation containing 0.3% of active ingredient.

Formulation Example 10 Each 0.4 part of the compounds (12) of this invention, 0.5 part of "fenitrothion", 7 parts of xylene and 7.1 parts of deodorized kerosene were mixed to form a solution. In the same manner as in Formulation Example9, an aerosol preparation containing 0.9% of active ingredient was obtained from the above solution.

Formulation Example 11 0.4 Part of the compound (26) of this invention, 2.0 parts of piperonyl butoxide, 6.2 parts of xylene and 7 parts of deodorized kerosene were mixed to form a solution. An aerosol preparation containing 0.4% active ingredient was obtained in the same manner as in Formulation Example 9.

Formulation Example 12 To 0.5 g of the present compound (19) was added 0.5 g of BHT, and the mixture was dissolved in 20 ml of methanol. The solution was uniformly mixed, with stirring, with 99.0 g of a mosquito coil carrier containing Tabu powder, Pyrethrum marc and wood powder in a ratio of 3: 5:1, and then methanol was evaporated.

To the residue was added 150 ml of water and the mixture was well kneaded, shaped into a mosquito coil and dried. Thus, the mosquito coil of the compound was obtained.

Formulation Example 13 To 0.15 g of each of the present compounds (6) and (17) was added 0.2 g of the d-trans chrysanthemic ester of Allethrin, and the mixture was dissolved in 20 ml of methanol. The solution was uniformly mixed with 99.65 g of a mosquito coil carrier (described above) with stirring, and then methanol was evaporated. To the residue was added 150 ml of water and the mixture was well kneaded, shaped into a mosquito coil and dried.

Thus, the mosquito coil of each compound was obtained.

Formulation Example 14 To 0.1 g of each of the present compounds (5), (6) and (7) were added 0.1 g of BHT and 0.1 g of piperonylbutoxide, and the mixture was dissolved in a suitable amount of chloroform. The solution was uniformly adsorbed in a filter paper of 3.5 cm x 1.5 cm x 0.3 cm (thick).

Thus, a fibrous fumigant for heating on a hot plate was obtained. As the fibrous carrier, those having the same effect as pulp plate (e.g. filter paper), for example asbestos may be used. Formulation Example 15 To 0.02 g of each of the present compounds (5), (6), (7) and (13) were added 0.05 g of 5-propargylfurfuryl d-cis-trans-chrysanthemate and 0.1 g of BHT, and the mixture was dissolved in a suitable amount of chloroform. The solution was then uniformly adsorbed in a filter paper of 3.5 cm x 1.5 cm x 0.3 cm (thick).

Thus, a fibrous fumigant for heating on a hot plate was obtained.

The outstanding insecticidal and acaricidal activity of carboxylates within this invention are illustrated below with reference to Test Examples. In Text Examples, reference compositions were prepared similarly to the test compositions using known compounds shown in Table 2.

No. Structure Literature (A) < /cw,-o-c-cH--cH /CI Brit. Pat. No. 1,413,491 CR3 CR3 CI (B) clH24 0 /ccH=czCI CI Brit. Pat. No. 1,413,491 CCl II C'Cl= C 0 Ci"'3%l3 CI (C) to' 2 iC4H~CH,-o-E-CH--CH Brit. Pat. No. 1,413,491 CC 0 C C-C Ci;3 \ CR3 Cl3 CN (D) < 3cu240Y 8 ,xC XCH=Cz Brit. Pat. No. 1,413,491 Cl3 O CI (E) Pyrethrins F.B. LaForge et al; "J. Am. Chem. Soc., 58, 1777 (1936)" CH3 T. Iwata et al; CH3NHCOO- Cl3 "J. Econ. Entomol., 65 (3), 643 (1972)"

F. Mungeretal; "J. Econ. Entomol., 53 (3), 384(1960)" Test example 1 The present compounds (1), (4), (5), (6), (7), (8), (12), (13), (20),(25), (29), (30), (33), (37), (41) and (43) and the reference compound were each formulated into oil sprays of four or five different concentrations using deodorized kerosene.

Five milliliters of the oil spray was sprayed using the Campbel's turn table [Soap and Sanitary Chemicals, Vol. 14, No. 6, 119 (1938)]. Twenty seconds after spraying, the shutter was opened and about 100 housefly adults (Musca domestica) per group were exposed to the descending mist for 10 minutes. Thereafter, the adults were transferred to a wire-screen cage and left as they were at 26"C. After 24 hours, median lethal concentration [LC50 (mg/100 ml)] was calculated from mortality at each concentration (three replications).

Test compound LC50 after 24 hours (mg/100 ml) Present compound (1) 35 (4) 24 (5) 12 (6) 15 (7) 8 (8) 60 (12) 51 (13) 27 (20) 9 (25) 15 (29) 73 (30) 36 (33) 30 (37) 77 (41) 29 (43) 69 Reference compound (E) 280 Test Example 2 The present compounds (3), (4) and (5) were each diluted to four or five difference concentrations with acetone.

A circle of 12 cm in diameter was drawn on aluminium foil, and 1 ce of the above dilute acetone solution was coated within the circle. After acetone was evaporated, ten male adult german cockroach (Blattella germanica) were released and covered with a polyethylene cup of 12 cm in diameter After 48 hours, median lethal dose [LD50 (mg/m2)] was calculated from mortality at each concentration (three replications).

Test compound LD50 (mg/m2) Present compound 3 0.6 4 0.8 5 0.4 Reference compound (A) 2.0 " (B) .051 5.0 (c) > 5.0 (D) > 5.0 Test Example 3 Each of the emulsifiable concentrates, described in Formulation Example 1, containing the present compounds (3), (4), (5), (6), (7), (12), (13), (14), (20), (21), (25) (26), (29) and (33) was diluted with water to an active ingredient content of 1 ppm. One hundred miliiliters of each emulsion was placed in a 180-ml plastic cup and 30 third-instar larvae of yellow fever mosquito (Aedes aegypti) were released in each cup. After 24 hours, 100% mortality was observed in every cup (three replications).

Test Example 4 Each of the emulsifiable concentrates, described in Formulation Example 1, containing the present compounds (1) - (43) was diluted with water to an active ingredient content of 500 ppm.

Butter was coated on the whole inside wall of a polyethylene cup (diameter 5.5 cm), and on the bottom of the cup was placed a piece of filter paper of the same size. 0.5 Ml of each diiute solution was dropped on the filter paper, and 20 larvae, 10th day after hatch, of german cockroach (Blattella germanica) were released in the cup which was then covered with a lid. After 24 hours, the dead and alive were counted to obtain mortality by the tests repeated three times.

Mortality Test compound after 24hr(%) Present compound (1) 100 (2) 100 (3) 100 (4) 100 (5) 100 (6) 100 (7) 100 (8) 100 (9) 100 (10) 100 tut (11) 100 (12) 100 (13) 100 (14) 100 (15) 95 (16) 85 (17) 85 (18) 80 (19) 100 (20) 100 (21) 100 (22) 100 (23) 90 (24) 100 (25) 100 (26) 100 (27) 100 (28) 90 (29) 100 (30) 100 (31) 100 (32) 100 (33) 100 (34) 100 (35) 100 (36) 95 (37) 100 (38) 95 (39) 90 (40) 100 (41) 100 (42) 100 (43) 95 Untreated O Test Example 5 The insecticidal activity on housefly adults (Musca domestica) of each aerosol obtained in Preparation examples 9, 10 and 11 was tested by the aerosol test method (Soap and Chemical Specialities, Blue Book, 1965) using a (6 ft)3 Peet Grady's chamber.As a result, with any aerosol, more than 80% of the flies could be knocked down 15 minutes after spraying, and 100% of the flies were killed by the next day (three replications).

Test Example 6 About 50 adults of northern house mosquito (Culex pipiens pallens) were released in a (70 cm)3 glass chamber in which a battery-type small electric fan (wing diameter 13 cm) was placed and driven.

0.1 Gram of each of the mosquito coils obtained in Preparation examples 12 and 13 was ignited at one end and placed at the centre of the bottom of the chamber. With any mosquito coil, more than 90% of the adults could be knocked down within 20 minutes, and more than 80% of the adults were killed after 24 hours (three replications).

Test Example 7 Each ofthewettable powders containing the present compounds (1) - (4) and (6), described in Formulation Example 3, was diluted with water to an active ingredient content of 400 ppm. The diluted preparation was applied to rice plant grown in a 180-mi cup at a rate of 15 cc/2 cups. After air-drying, the plant was covered with a wire-screen cage and 15 female adults of smalier brown plant hopper (Laodelphax striatellus) were released in the cage. After 24 hours, the dead and alive were observed and a mean mortality of three repeated tests was obtained (three replications).

Compound Mortality (%) Compound of this invention (1) 100 (2) 100 (3) 100 (4) 100 (6) 100 Reference compound (C) 10 Untreated O Test Example 8 The emulsifiable concentrate containing the present compound (1), (2), (3), (4), (5), (6), (8), (9), (12), (14), (26), (29) or (33), described in Formulation Example 1, was diluted with water to an active ingredient content of 500 ppm. Five rice seedlings, 10 days after sowing, were dipped in the preparation for one minute and air dried. The treated seedlings and 10 third-instar larvae of rice stem borer (Chilo suppressalis) were placed in a plastic cup of 5cm in diameter. After 10 days, 100% mortality was observed in every case (three repiications).

Test Example 9 Each of the emulsifiable concentrates containing the present compounds (1) - (9), (12), (14), (26), (29) and (33), described in Formulation Example 1, was diluted with water to an active ingredient content of 500 ppm.

Kidney bean plant leaves were immersed in the emulsion for one minute, air-dried and placed in a polyethylene cup of 10 cm in diameter and 4.5 cm high, together with 10 third-instar larvae of tobacco cutworm (Spodoptera litura). After 2 days, 100% kill was observed in every case (three replications).

Test Example 10 Each of the dust preparations described in Formulation Example 2 was applied at a rate of 3 keg/1 0 are to rice plant grown in a 1/10,000 are Wagner pot. The plant was covered with a wire-screen cage and 15 female adults of green rice leafhopper (Nephodettix cincticeps) resistant to carbamate compounds were released in the cage. The pot was kept in a greenhouse and after 24 hours, the dead and alive were observed. Mortalities in mean values of three repeated tests for each compound were as shown below (three replications).

Compound Mortality (%) Compound of this invention (1) 100 (2) 100 (3) 100 (4) 100 Reference compound (F) 30 Untreated O Test Example 11 Each of the emulsifiable concentrates containing the present compounds of (2), (6), (12) and (14) described in Formulation Example 1, was diluted with water to an active ingredient content of 500 ppm. The emulsion (50 cc) was sprayed over a mandarin orange seedling planted in a 9-cm pot and parasitized by citrus red mite (Panonychus citri) resistant to kelthene (Reference compound G) in every growth stage. After 10 days, the number of female adults on the plant was counted and rated according to the following criteria: ++ : 0-9 female adults are parasitic on one plant, + : 10-30 female adults are parasitic on one plant, - . 31 or more female adults are parasitic on one plant.

(three replications).

Compound Rating Compound of this invention (2) ++ (6) ++ (12) ++ (14) ++ Reference compound (B) (C) ~ (G) Untreated Test Example 12 Each of the emulsifiable concentrates containing the present compounds, described in Formulation Example 1, was diluted with water to an active compound content of 100 ppm. Each of the two leaves of kidney bean plants (Phaseolus vulgaris) at the primordial leaf stage was trimmed into a circle of 3 cm in diameter. Each of them was dipped into test solutions for one minute. After agglutinant was painted on the stem, about thirty adults of carmine mite (Tetranychus cinnabarinus) were released on the treated leaf.After 48 hrs the number of mites on both the leaves was counted. "Leaving Percentage" for a test compound was calculated by the following equation, Leaving percentage =

Na1: number of mites on the untreated leaf of experimental plot, Na2: number of mites on the treated leaf of experimental plot; Nb1: number of mites on the unreleased leaf of untreated plot; Nb2: number of mites on the released leaf of untreated plot (three replications).

Compound Left mites (%) Compound of this invention (6) 95 (9) 80 (12) 90 Reference compound (G( Test Example 13 (Residual activity test) The emulsifiable concentrate containing the present compound (2) and (4), described in Formulation Example 1, was diluted with water to an active ingredient content of 400 ppm. Rice plant grown in a Wagner pot was sprayed with 20 cc of the emulsion. After air-drying, the plant was covered with a wire-screen cage and 15 female adults of green rice leafhopper (Nephotettix cincticeps) were released in the cage. The mortality after 24 hours was determined. In order to test the residual activity, the pot with grown rice plant was treated in the same manner as mentioned above and left standing for 7 days. In the same manner as mentioned above, the test insect was released and the mortality after 24 hours was determined. The above tests were carried out in a greenhouse (three replications).

Mortality (%) Compound Immediately 7 Days after after treatment treatment Present compound (2) 100 100 (4) 100 100 Reference compound (F) 70 0 Untreated O 0 Test Example 14(Mammalian toxicity test) Male mice (18 - 22 g) were orally administered with each of the corn oil solutoins of the present compounds (1), (2), (3) and (29), the dosage having 0.2 ml/1 0 g body weight.

The mortality after 24 hours was observed and median lethal dose [LD50 (mg/kg)] was calculated (three replications).

Compound LD50 (mg/kg) Compound of this invention (1) > 800 (2) > 800 (3) > 800 (29) > 800 Reference compound (A) 650 (E) 370 (F) 60

Claims

CLAIMS 1. A carboxylate of the formula,

wherein R1 and R2, which may be the same or different, are each a hydrogen atom, a methyl group or a halogen atom, A is an oxygen or sulfur atom or a methylene group, R is an oxygen atom or a group of the formula -CH = CH-, R4 is a hydrogen atom or an ethynyl or cyano group, and (1) R3 is a group of the formula

in which R5 is a halogen atom, when A is an oxygen or sulfur atom and R is a group of the formula -CH = CH-; when A is a methylene group, R is a group of the formula -CH = OH- and R4 is a hydrogen atom; or when A is a methylene group, R is an oxygen atom and R4 is a hydrogen atom or an ethynyl group, (2) when A is a methylene group, R is a group of the formula -CH = CH-, and R4 is an ethynyl group, R3 is a group of the formula

in which R6 is a hydrogen atom or a methyl group, when R6 is a hydrogen atom, R7 is a group of the formula

or -CH = N - OCH3 (in which R8 is a halogen atom or a methyl or methoxycarbonyl group and Rg is a halogen atom or a methyl group), and when R6 is a methyl group, R7 is a methyl group, and (3) when A is a methylene group and R4 is a cyano group, R3 is a group of the formula

in which R1O is a hydrogen atom or a methyl group, when R1O is a hydrogen atom, R11 is a group of the formula

or-CH=N-OCH3 (in which R12 is a halogen atom or a methyl, methoxy-carbonyl or methoxymethyl group and Ra3 is a hydrogen or halogen atom or a methyl group) and when R10 is a methyl group, R11 is a methyl group.
2. A carboxylate according to Claim 1, wherein each of R1 and R2 is a hydrogen atom, R is a group of the formula -CH = CH-, R4 is a cyano group and R3 is a group ofthe formula

in which R5 is as defined in Claim 1.
3. A carboxylate according to Claim 1, wherein each of R1 and R2 is a hydrogen atom, A is a methylene group, R is a group of the formula -CH = CH-, R4 is a cyano group and R3 is a group of the formula
4. A carboxylate according to Claim 1 which is a-cyano-3-(2-thienyloxy)benzyl 2,2-dimethyl-3-(2,2 dichlorovinyl)cyclopropane-1 -carboxylate.
5. A carboxylate according to Claim 1 which is a-cyano-3-(3-thienyloxy)benzyl 2,2-dimethyl-3-(2,2 dichlorovinyl)cyclopropane-1 -carboxylate.
6. A carboxylate according to Claim 1 which is a-cyano-3-(2-thenyl)benzyl 2,2-dimethyl-3-(2,2dichlorovinhyl)cyclopropane-1-carboxylate.
7. A carboxylate according to Claim 1 which is a-cyano-3-(3-thenyl)benzyl 2,2-dimethyl-3-(2,2 dichlorovinyl)cyclopropane-1 -carboxylate.
8. A carboxylate according to Claim 1 which is a-cyano-3-(3-thienyloxy)benzyl 2,2-dimethyl-3-(2,2 dibromovinyl)cyclopropane-1 -carboxylate.
9. A carboxylate according to Claim 1 which is α-cyano-3-(2-thienyloxy)benzyl, 2,2-dimethyl-3-(2,2dibromovinyl)cyclopropane-1 -carboxylate.
10. A process for producing a carboxylate of the formula given and defined in Claim 1,which process includes

wherein R1, R2, A, Rand R4 are as defined in Claim 1, with a carboxylic acid halide of the formula

wherein Rs is as defined in Claim 1, and Y is a halogen atom, in an inert solvent in the presence of an organic tertiary base, or (2) reacting an alcohol oftheformula

wherein R1, R2, A, R and R4 are as defined in Claim 1, with a carboxylic acid an hydride of the formula

wherein R3 is as defined in Claim 1, in an inert solvent, or (3) reactina an alcohol of the formula

wherein R1, R2, A, Rand R4 are as defined in Claim 1, with a carboxylic acid of the formula

wherein R3 is as defined in Claim 1, in an inert solvent in the presence of a dehydrating agent or a condensing agent, or (4) reactina a halide of the formula

wherein Fl1, R2, A, R and R4 are as defined in Claim 1, and X is a halogen atom, with a carboxylic acid of the formula

wherein R3 is as defined in Claim 1, in an inert solvent in the presence of an organic tertiary base, or (5) reactina a halide of the formula

wherein Fl1, R2, A, Rand R4 are as defined in Claim land X is a halogen atom, with an alkali metal salt of a carboxylic acid represented by the formula

wherein R3 is as defined in Claim 1, and M is an alkali metal, in the presence of a phase transfer catalyst in a I two-phase system comprising water and an inert solvent sparingly soluble in water.
11. A process for producing a carboxylate of the formula given and defined in Claim 1, in which the group R4 is specifically a cyano group, which process includes (1) reacting an aldehvde of the formula

wherein R1, R2, A and R are as defined in Claim 1 with a carboxylic acid halide of the formula

wherein R3 is as defined in Claim 1 and Y is a halogen atom, and an alkali metal cyanide in an inert solvent in the presence of a phase transfer catalyst, or (2) reacting an aldehyde of the formula

wherein R1, R2, A and R are as defined in Claim 1, with a carboxylic acid halide of the formula

wherein R3 is as defined in Claim 1 and Y is a halogen atom, and an alkali metal cyanide in the presence of a phase transfer catalyst in a two-phase system comprising water and an inert solvent sparingly soluble in water.
12. An aldehydeoftheformula

wherein R, R2, A and R are as defined in Claim 1.
13. An aldehyde according to Claim 12, wherein each of R1 and R2 is a hydrogen atom, A is an oxygen or sulfur atom and R is a group of the formula -CH = CH-.
14. An aldehyde according to Claim 12, wherein each of R1 and R2 is a hydrogen atom, A is a methylene group and R is a group of the formula -CH = CH-.
15. An aldehyde according to Claim 12, wherein each of R1 and r2 is a hydrogen atom, A is a methylene group and R is a oxygen atom.
16. A process for producing an aldehyde of the formula given and defined in Claim 12, which process includes reacting an alcohol of the formula

wherein R1, R2, A and Rare as defined in Claim 1, with an oxidizing agent in an inert solvent.
17. A process for producing an aldehyde ofthe formula given and defined in Claim 12, which process includes reacting a thiophene halide of the formula

wherein R1 is as defined in Claim 1, and E is a halogen atom, with an alkali metal salt of an aldehyde of the formula

wherein R2 and A are as defined in Claim 1, or an alkali metal salt of the acetal thereof in an inert solvent and when the acetal is used, converting the resulting acetal to the aldehyde.
18. A process for producing an aldehyde of the formula given and defined in Claim 12, which process includes reacting a metallic salt of a thiophene represented by the formula

wherein R1 is as defined in Claim land G is an alkali metal our a group of the formula MgJ in which J is a halogen atom, with an acetal of the aldehyde of the formula

wherein R2 and R are as defined in Claim 1, and L is a halogen atom, in an inert solvent and then converting the resulting acetal to the aldehyde.
19. A process for producing an aldehyde of the formula given and defined in Claim 12, which process includes reacting a Grignard reagent of the formula

wherein R1 is as defined in Claim 1, and J is a halogen atom, with an acetal of the haloaldehyde of the formula

wherein R2 is as defined in claim 1, and Q is a halogen atom, in an inert solvent and then converting the resulting acetal to the aldehyde.
20. An insecticidal and/or acaricidal composition which comprises, as active ingredient, a compound of the formula given and defined in claim 1 and an inert carrier.
21. A method of knocking down or killing an insect and/or acarid which comprises applying to the insect and/or acarid a compound of the formula given and defined in claim 1.
22. Use of a compound of the formula given and defined in claim 1 for knocking down an insect and/or acarid.
23. The carboxylates of the formula given and defined in claim 1, other than those specifically claimed in claims 4 to 9, which are specifically disclosed herein.
24. Processes according to claim 10 or claim 11, for preparing a carboxylate, which processes are substantially as herein described and exemplified.
25. Carboxylates of the formula given and defined in claim 1 whenever prepared by a process according to any one of claims 10,11 and 24.
26. Insecticidal and/or acaricidal compositions according to claim 20 substantially as herein described and exemplified.
27. Processes according to any one of claims 16 to 19 for producing an aldehyde, which processes are substantially as herein described and exemplified.
28. Aldehydes whenever prepared by a process according to any one of claims 16 to 19 and 27.