US3661926A - Physiologically active oxadiazoline and thiadiazoline derivatives of phosphoric acid and thiophosphoric acid - Google Patents

Abstract

OXADIAZOLINE OR THIADIAZOLINE DERIVATIVES OF PHOSPHORIC OR THIOPHSPHORIC ACID OF THE FORMULA

R1-P(=X3)(-R1)-N<(-C(=X2)-X1-C(-R2)=N-)

WHEREIN X1,X2 AND X3 ARE OXYGEN AND SULFUR AND R1 AND R2 ARE ORGANIC MOIETIES. THESE COMPOUNDS ARE USEFUL AS INSECTICIDES AND ACARACIDES. AN EXAMPLE IS (5-(P-CHLOROPHENYL) - 1,3,4 - OXADIAZOLONE (2)) BIS(DIETHYLAMIDO) PHOSPHORIC ACID.

Description

United States Patent Oifice 3,661,926 Patented May 9, 1972 U.S. Cl. 260-307 A Claims ABSTRACT OF THE DISCLOSURE Oxadiazoline or thiadiazoline derivatives of phosphoric or thiophosphoric acid of the formula wherein X X and X are oxygen and sulfur and R and R are organic moieties. These compounds are useful as insecticides and acaracides. An example is [S-(pchlorophenyl) 1,3,4 oxadiazolone (2)] bis(dimethylarnido) phosphoric acid.

It has been found that compounds of the general formula in which X is an oxygen atom or sulphur atom,

R is an alkoxy group or alkylthio group each having 1 to 5 carbon atoms, an amino group, an alkylamino group having 1 to 5 carbon atoms or a dialkylamino group, each alkyl group containing 1 to 5 carbon atoms, and

R is a hydrogen atom, a substituted or non-substituted alkyl group having 1 to carbon atoms, a substituted or nonsubstituted phenyl group, a thiophene group, a substituted or nonsubstituted phenyl alkyl group having 7 to 10 carbon atoms, a cyclic alkyl group or a group COOA1k, in which Alk represents an alkyl group containing 1 to 5 carbon atoms, have insecticidal and acaricidal activities. Because of these properties the compounds, after having been worked up into the usual compositions, such as wettable powder, miscible oil and granule, are suitable to be used in combating insects and acarides in agricultural and horticultural plants. The compounds, in addition, not being phytotoxic, their use in agricultural and horticultural plants is particularly interesting. It has been found that very good results are obtained especially with compounds corresponding to the formula in which R is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkyl group having 1 to 10 carbon atoms and containing 1-3 substituents which may be identical or diflierent and are chosen from the group comprising halogen atom, cyano group and the --COOAlk group, in which latter group Alk is an alkyl group having 1 to 5 carbon atoms, a phenyl group, a phenyl group containing 1 or 2 substituents chosen from the group comprising halogen atom, nitro group, alkyl group having 1 to 5 carbon atoms, and alkoxy group having 1 to '5 carbon atoms, a phenylalkyl group having 7 to 10 carbon atoms or a cyclic alkyl group.

A. very good activity was formed with compounds which are characterized by the formula in which R, is a hydrogen atom, an alkyl group containing 1 to 5 carbon atoms or a benzyl group.

Of the compounds according to the invention reference is notably made to the substances which satisfy the following formulae:

It has been found that the compounds indicated by 1, 2, 3 and 4 are most active and can be used as active constituents in compositions for combating, for example, the room fly (Musca domestica) in its various stages of development from larva to adult insects, the yellow fever mosquito (Aedes egyptei), plant lice such as the bean aphis (Aphis fabae) and red spider, such as Tetrdnychus cinnabarinus.

Compounds according to the invention may be worked up in the usual manner into means for combating insects and acarides such as, for example, dusts, Wettable powders, miscible oils and granules. To this end, the compounds are either dissolved or dispersed in liquid carrier materials, such as hydrocarbon oils, organic solvents, such as pumice, chalk, marble, coffee-grounds, Walnut particles, granite, mirgle, dolomite, kaolin, attapulgite and bentonite, frequently with the use of, for example, dispersing agents, for example in manufacturing wettable powders and miscible oils, of wetting agents, for example in manufacturing wettable powders of surface-active substances, or binders and stabilisers, for example in manufacturing granules. For the manufacture of a plurality of compositions reference can be made to the examples.

Granular compositions and dusts can be used without further treatments in combating harmful organisms; wettable powders and miscible oils are formulations in concentrated form and made ready for use by mixing with a diluent and preferably with water. In certain cases such as, for example, in aircraft application where a small volume of a liquid combating agent is distributed over a comparatively large surface area, the active compound can be used Without further dilution, but preferably a solution of the active compound in a fetty oil, such as castor oil, is used possibly with the addition of an auxiliary solvent. The amount of active substance which :must be applied per unit surface to the area to be treated in order to ensure effective combatment of the harmful organisms depends inter alia upon the vintage, the degree of infestation of the plants and the soil, weather conditions, and the type of insect or acaride that has to be combated.

Although the dosages will be divergent, it may be stated that a dosage from 0.5 kg. to 3 kgs. of active material per ha. will produce the desired effect.

In an advantageous embodiment of the invention the composition, when used in the field is applied to the plants to be treated in the form of an aqueous dispersion or emul sion such as, for example, an aqueous emulsion of a miscible oil, the concentration of the active constituent in the emulsion or dispersion varying from 0.02 to 0.1% by weight.

Furthermore, it is to be noted that the means according to the invention can be combined with other insecticides, acaricides or fungicides for widening the total activity spectrum of the composition or for obtaining synergistic effects.

For such a combination use may be made of the following biocidal compounds:

Insecticides such as organic phosphor compounds, for example, 0,0-diethyl-O-p-nitrophenyl phosphorusthioate, 0,0-dimethyl S-1,2-di(ethoxycarbamyl)ethyl phosphorus dithioate and 0,0-diethyl O-2-(ethylthio)ethyl phosphorus thioate, chlorinated hydrocarbons, for example: 2,2-bis(p-chlorophenyl)-1,l,1-trichloroethane and hexachloroepoxy octahydro dimethanonaphthalene, carbamates, for example N-methyl-l-naphthylcarbamate, dinitrophenols, for example, 2-methyl-4,6-dinitrophenol and 2- 2-butyl) -4,6-dinitrophenyl 3,3-dimethylacrylate.

Acaricides such as diphenylsulphides and derivatives thereof, for example p-chlorobenzyl-p-chlorophenyl sulphide and 2,4,4,S-tetrachloridphenyl sulphide, diphenyl sulphonates, for example p-chloro-phenyl-benzene sulphonate, methylcarbinols, for example ethyl 4,4-dichlorobenzilate.

Fungicides such as organic mercury compounds, for example phenylmercuro-acetate and methylmercuro-cyanoguanidine, organic tin compounds, for example triphenyltin hydroxide and triphenyltin acetate, dialkyldithiocarbamates, for example zinc dimethyldithiocarbamate, alkylenebisdithiocarbamates, for example zincethylenebisdithiocarbamate, zincpropylenebisdithiocarbamate, manganeseethylenebisdithiocarbamate and combination compositions of zincand manganeseethylenebisdithiocarbamate, dinitrophenols, for example, 2,4-dinitro-6-(2-octyl) phenylcrotonate and 2,4-dinitro-6-sec. butyl-phenyl acrylate, and further l-[bis(dimethylamino)phosphoryl]3- phenyl-S-amino-1,2,4-triazol, 6-methyl-chin0xaline-2,3-dithiocarbonate, 1,4-dithia-anthraquinone-Z,3-dicarbonitrile, N-trichloromethylthiophthalimide, N-trichloromethylthiotetrahydrophthalimide, N-( l, l ,2,2-tetrachloroethylthio tetrahydrophthalimide, N dichlorofiuormethylthio N- phenyl-N'-dimethyl-sulphonyldiamide and tetrachloroisophthalonitrile.

The compounds according to the invention are new substances which may be manufactured by methods which are known per se for the manufacture of similar compounds.

Thus, compounds according to the invention can be obtained by reacting a compound of the formula in which X is an oxygen atom or sulphur atom Y is a hydrogen atom or an alkalimetal atom and R is a hydrogen atom, a substituted or non-substituted alkyl group having 1 to 10 carbon atoms, a substituted or nonsubstituted phenyl group, a thiophene group, a substituted or non-substituted phenyl alkyl group having 7 to 10 carbon atoms, a cyclic alkyl group or a COOAlk-group, in which Alk is an alkyl group containing 1 to carbon atoms,

with a phosphoric-acid halide or thiophosphoric-acid halide or thiophosphoric-acid halide of the formula Hlg-P X in which X is an oxygen atom or sulphur atom Hlg is a halogen atom and preferably a chlorine atom and R is an alkoxy group or alkylthio group each having 1 to 5 carbon atoms, an amino group, an alkylamino group having 1 to 5 carbon atoms or a dialkylamino group, each alkyl group containing 1 to 5 carbon atoms, where in the case that Y is a hydrogen atom, an acid binder such as an inorganic or organic base, for example soda, collidine or pyridine, is also present.

The reaction process may be carried out with the reagents in themselves, but is preferably carried out in the presence of a solvent, such as an organic solvent, for example aliphatic or aromatic hydrocarbons, alcohols, ethers and acetonitrile. The reaction temperature is allowed to vary between 0 C. and the boiling point of the solvent.

More particularly interesting compounds according to the invention may be obtained by reacting the alkalimetal salt of 1,3,4-oxadiazolon, which may be substituted at the 2-position, with diethoxythiophosphorylchloride in the presence of a solvent, such as benzene or acetonitrile. The substituent of the 1,3,4-oxadiazolon is preferably chosen from the group consisting of alkyl having 1 to 10 carbon atoms and phenylalkyl having 7 to 10 carbon atoms.

Particularly interesting substituents are methyl, isopropyl, pentyl and benzyl. The heterocyclic initial product of this reaction may be obtained by reacting in a first reaction step, a compound of the formula where R is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or a phenylalkyl group having 7 to 10 carbon atoms, with carbonyldichloride in the presence of an acid binder, such as soda, pyridine or collidine, and a solvent, for example water, aromatic and aliphatic hydrocarbons, alcohols and ethers to convert the resulting product subsequently into the alkali-metal salt thereof by treatment with a solution of an alkali-metal in a suitable solvent, such as, for example, sodium in methanol.

EXAMPLES (I) Manufacture of [S-pentyl-l,3,4-oxadiazolon(2)] diethoxythiophosphoric acid (A) Manufacture of 5-pentyl-1,3,4-oxadiazolon(2): 13 gs. of phosgene are introduced, while stirring and cooling, to a solution of 13 gs. (0.1 mol.) or caproylhydrazide in 200 mls. of dry acetonitrile within a period of approximately /2 hour. The temperature is maintained at approximately 10 C. After the phosgene has been introduced completely there is stirred at room temperature till a clear solution is obtained.

The acetonitrile is distilled olf and the residue dissolved in ether. The ethereal solution is washed successively with 2 N HCl and with water until the solution is neutral. After drying on sodiumsulphate the solvent is evaporated and the residual oil distilled. Yield 11 gs. (71%) of the colourless oil. Boiling trajectory 113 to 115/0.3 mm.

(B) 4.7 gs. (0.03 mol.) of 5-pentyl-1,3,4-oxadiazolon (2) are added to a solution of 0.69 gs. (0.03 g.at.) of sodium in approximately 30 mls. of methanol. The solution is evaporated under water-jet vacuum and the residue dissolved in 30 mls. of anhydrous acetonitrile, whereafter 5.7 gs. of diethoxythiophosphorylchloride are added.

The mixture is then boiled for 2 hours and, after cooling, dissolved in ether. The ethereal solution is washed successively with water, a cold 5% soda solution and again with water until the solution is neutral. After drying on sodium sulphate, the solvent is evaporated. The residue is dissolved in petroleum ether and filtered over norite, whereafter the solvent is evaporated. Yield 6 gs. (65%) of a colourless oil.

Analysis.Calculated (percent): C, 42.86; H, 6.82; S, 10.39. Found (percent): C, 42.32; H, 6.96; S, 10.01.

(H) Manufacture of [S-isopropyl-1,3,4-oxadiazolon(2)] diethoxythiophosphoric acid (A) The manufacture of -isopropyl-1,3,4-oxadiazo1on proceeded in a similar manner as described under IA, except that isobutyrylhydrazide instead of caproylhydrazide 'was used as the initial material. Boiling trajectory of '5-isopropyl-1,3,4-oxadiazolon: 141 to 143/ (B) 3.8 gs. (0.03 mol.) of S-isopropyl-1,3,4-oxadiazolon are added to a solution of 0.69 gs. (0.03 g.at.) of sodium in approximately rnls. of methanol. The solution is evaporated to dryness and the residue then suspended in rnls. of anhydrous acetonitrile. After adding 5.7 gs. of diethoxythiophosphoryl chloride, the mixture is boiled for 3 hours and then dissolved in ether. The ethereal solution is washed successively with water, a cold 5% soda solution and again with Water until it is neutral. After drying on sodium sulphate the solvent is evaporated. The residue is an oil, which is distilled under high vacuum. Yield 5.5 gs. (68%), boiling trajectory 109 to 110/0.1 mm.

(III) Manufacture of [S-methyl-l,3,4-oxadiazolon(2)] diethoxythiophosphoric acid The initial produdct for manufacturing the above compound, namely S-methyl-1,3,4-oxadiazolon(2), is manufactured by suspending 30 gs. (0.4 mol) of aceethydrazide in 350 mls. of dry acetonitrile and then introducing 50 gs. of phosgene into the suspension while stirring and cooling with ice. The phosgene is added within a period of 1% hours while maintaining the temperature of the suspension at from 50 C. to 10 C. After the phosgene has been introduced completely there is stirred at room temperature for 1 hour. The white deposit produced is worked up in the usual manner. Yield after crystallisation 30 gs. (75%). Melting point 212 Koflier. 5 gs. of the resulting S-methyl-1,3,4-oxadiazolon are dissolved in 30 mls. of methanol and added to a solution of 1:15 gs. of sodium in 30 mls. of methanol.

The mixture is evaporated to dryness under water-jet vacuum and the residue suspended in 70 mls. of anhydrous acetonitrile, whereafter 9.4 gs. of diethoxyphosphorylchloride are added. The mixture is boiled for 20 hours, and, after cooling, dissolved in 20 mls. of ether to be subsequently transferred into a separating funnel. The ethereal solution is washed successively with water, a cold 5% soda solution and again with water until it is neutral. After drying on sodium sulphate, the solvent is evaporated. The residual oil is distilled. Yield 9 gs. (71%). Boiling trajectory 113 to 116/35 mm.

(IV) Manufacture of [S-benzyl-1,3,4-oxadiazolon(2)] diethoxythiophosphoric acid (A) Manufacture of S-benzyl-1,3,4-oxadiazolon(2): l5 gs. (0.1 mol.) of phenylacethydrazide are suspended in 200 rnls. of anhydrous acetonitrile. 12 gs. of phosgene are introduced into this suspension, while stirring and cooling by ice, within a period of approximately /2 hour, followed by stirring for 1 hour. The acetonitrile is evaporated and 2 N HCl is added to the residue. An oil is separated which is extracted using methylene chloride. After drying, the methylene-chloride solution is evaporated to dryness. The residual solid substance is crystallised from a mixture consisting of 2 parts of benzene and 1 part of petroleum ether (40 to yield 50 gs. (83%). Melting point 49 Koflier.

(B) Manufacture of [S-benzyl-l,3,4-oxadiazolon(2)1 diethoxy-thiophosphoric acid: A solution of 8.8 gs. (0.05 mol.) of S-benzyl-1,3,4-oxadiazolon in 50 mls. of methanol is added to a solution of 1.15 gs. of sodium (0.05 g.at.) in 30 rnls. of methanol. The mixture is evaporated to dryness under water-jet vacuum and the dry residue suspended in 100 mls. of anhydrous acetonitrile, whereafter 9.4 gs. of diethoxythiophosphorylchloride are added. The whole is boiled for 3 hours.

After cooling, the reaction mixture is dissolved in 200 mls. of ether and transferred into a separating funnel, followed by washing successively with water, a cold 5% soda solution and again with Water until neutral. The ethereal solution is dried on sodium sulphate and then evaporated to dryness. The residual oil is dissolved in a mixture consisting of approximately 3 parts of petroleum ether (40 to 60 C.) and 1 part of ether. The solution is filtered over norite and the solvent evaporated. Yield 13 gs. of a colourless oil.

Analysis.Calculated (percent): C, 47.55; H, 5.22; S, 9.77. Found (percent): C, 46.91; H, 5.53; S, 10.06.

(V) Manufacture of [5-(p-chlorophenyl)-1,3,4-oxadiaz0lon(2) ]bis(dimethylamido) phosphoric acid (A) Manufacture of 5 (p chlorophenyl)-1,3,4-oxadiazolon(2). 17 gs. of p-chlorobenzoylhydrazine are suspended in 200 mls. of anhydrous acetonitrile, whereafter 12 gs. of phosgene are introduced while stirring and cooling by ice within a period of approximately /2 hour. After the phosgene has been introduced completely there is stirred further for 1 hour.

Subsequently mls. of water are carefully added to the reaction mixture. The deposit produced is sucked off, washed with water and dried. Yield 18 gs. (94%). Melting point 227 Koffier.

(B) Manufacture of [S-(p-chlorophenyl) 1,3,4- oxadiazolon(2)] bis(dimethylamido)phosphoric acid: A solution of 5.9 gs. of 5-(pachlorophenyl)-oxadiazolon-l,3,4 in methanol is added to a solution of 0.69 gs. of sodium (0.03 g.at.) in approximately 30 mls. of methanol. The resulting solution is evaporated to dryness and the dry sodium salt suspended in approximately 50 mls. of anhydrous acetonitrile, whereafter 5.1 gs. of bis(dimethylamido) phosphoryl chloride are added. The mixture is boiled for 1 hour, then filtered and subsequently evaporated to dryness. The residual solid substance is recrystallized from benzene. Yield 7.5 gs. (76%). Melting point 159 Kofller.

(VI) Manufacture of [5-pentyl-1,3,4-oxadiazolon(2)] diethoxyphosphoric acid The initial product, S-pentyl-1,3,4-oxadiazolon(2), for the manufacture of the above-mentioned phosphorus compound is obtained in the manner as has been described in Example IA.

4.7 gs. (0.03 mol.) of 5-pentyl-1,3,4-oxadiazolon(2) are added to a solution of 0.69 gs. of sodium in approximately 30 mls. of methanol. The solution is evaporated to dryness and the resulting dry sodium salt suspended in 50 rnls. of anhydrous acetonitrile, whereafter 5.2 gs. of diethoxyphosphorylchloride are added. The mixture is boiled for 1 hour and, after cooling, dissolved in ether. The ethereal solution is Washed successively with water, a cold 5% sodium solution and again with Water until the solution is neutral. After drying, the ether is evaporated and the residual oil dissolved in petroleum ether. The solution is subsequently filtered over norite and the solvent evaporated. Yield 8 gs. (91%) of a colourless oil.

Analysis.Calculated (percent): C, 45.20; H, 7.24. Found (percent): C, 44.28; H, 7.62.

(VII) Manufacture of [5-methyl 1,3,4-oxadiazo1thion(2)] diethoxy-thiophosphoric acid (A) Manufacture of 5-methyl-l,3,4-oxadiazolthion(2): A mixture consisting of 17 mls. of thiophosgene and 60 mls. of ether is dropped within approximately /2 hour while stirring and cooling by ice into a solution con- 9 sisting of 15 gs. (0.02 mol.) of aceethydrazide in 200 mls. of water. The resulting mixture is stirred for 20 hours. \A small amount of solid substance is separated. After filtration, the combined water-ether layers are evaporated under water-jet vacuum. The temperature of the bath is maintained at approximately 60 C.

The residue is crystallised from benzene. Yield 7 gs. (30%). Melting point 73 Kofiler.

(B) Manufacture. of [5 methyl 1,3,4 oxadiazolthion(2)] diethoxythiophosphoric acid: 3.5 gs. of S-methyl-oxadiazolthion 1,3,4 (0.03 mol.) are added to a solution of 0.69 Igs. (0.03 g.at.) of sodium is approximately 30 mls. of methanol. The solution is evaporated to dryness and the dry sodium salt suspended in approximately 50 mls. of anhydrous acetonitrile, whereafter 5.7 gs. of diethoxythiophosphoryl chloride are added. The mixture is stirred at room temperature for 20 hours and then dissolved in ether. The ethereal solution is washed successively with water, a cold 5% soda solution and again with water until neutral. After drying on sodium sulphate, the ether is evaporated, the residual oil dissolved in a mixture of ether and petroleum (1:1) and then purified chromatographically. Yield 3 gs. (40%).

(VIII) Manufacture of [S-phenyl-1,3,4-thiadiazolon(2)] diethoxythiophosphoric acid (A) Manufacture of 5-phenyl-1,3,4-thiadiazolon(2): 6.4 gs. (0.03 mol.) of thiobenzoylthioacetic acid and 3.4 gs. of semicarbazide HCl are dissolved in 100 mls. of 1 N NaOI-I of C. The resulting solution is stored at a temperature of 0 C. for 20 hours and then acidified with 2 N hydrochloric acid. The resulting deposit is sucked off, washed with water and, after drying, cyclised by heating at approximately 180 C. for minutes.

The resulting product is recrystallized from little alcohol. Yield 3.5 gs. "(6 6%). Melting point 146 Koflier.

(B) Manufacture of [5-phenyl-l,3,4-thiadiazolon(2)] diethoxythiophosphoric acid. 3.6 gs. (0.02 mol.) of 5- phenyl-1,3,4-thiadiazolon (2) are added to a solution of 0.46 gs. of sodium in approximately 30 mls. of methanol. The resulting solution is evaporated to dryness and the dry residue suspended in 30 mls. of anhydrous acetonitrile, whereafter 3.2 mls. (3.8 gs.) of diethoxythiophosphoryl chloride are added. The whole is boiled for 3 hours.

[After cooling, the reaction mixture is dissolved in ether, and washed successively with water, a cold 5% soda solution and again with water until neutral. After drying and evaporation of the ether, 5 gs. (81%) of a substantially colourless oil are obtained.

(XI) Manufacture of miscible oil Of the compounds mentioned in col. 2, the substances 1, 2, 3 and 4 are formed into miscible oils by dissolving 50 parts by weight of one of the substances, together with 5 parts by weight of a mixture (1:1) of alkylphenolpolyglycol ether and calciumdodecylbenzene sulphonate, in 45 parts by weight of xylene.

(X) Manufacture of wettable powder The compounds specified in Example IX were formed into Wettable powders by mixing 25 parts by weight of each substance with 40 parts by weight of attaclay, 30 parts by weight of kaoline, 2 parts by weight of sodiumoleyl-tN-methyltaurate and 3 parts by weight of sodiumlignine sulphonate.

Test methods: The compounds were tested in the laboratory by the test methods specified hereinafter. Various test solutions and suspensions or emulsions of the active compound were used in which the concentration of the active material continuously decreased according to the series 3.10 l0- 3.10 10 (I) Test on representatives of the insect order Diptera (a) Musca domestica (home fly) adult: One ml. of an acetonic test solution or suspension having the desired concentration of the active substance is transferred into a Petri box of 9 cms. in diameter. After evaporation of the solvent, 5 male' and 5 female flies from three to four days of age are introduced into the Petri box. The box is maintained at room temperature and is placed with its underside upright to avoid dropped flies from constantly contacting the insecticide tfilm. After 21 hours the mortality percentage is determined, making allowance for the natural mortality according to Abbott. The test is carried out threefold.

'(b) Musca donrestica, larva: 15 mls. of an agar foodstuff which contains inter alia 2% of agar, 8% of milk powder and 8% of malt yeast and in which the active compound is dispersed in the desired concentration are transferred into a plastic beaker.

T he agar layer is inoculated with 20 grub's each 1 day of age and subsequently covered with 2 ccs. of moist sawdust. The plastic beakers are closed at the top and maintained at a temperature of 25 C. at a relative humidity degree from 60% to 70%. After 14 days, when untreated animals have become adults, the mortality percentage is determined, making allowance for natural mortality according to Abbott. The test is carried out threefold.

(c) Aedes egyprei (yellow fever mosquito), larva: The active compound is dispersed in water in the desired concentration, whereafter the aqueous dispersion is inoculated with 20 larvas 1 day of age, of the yellow fever mosquito and maintained at a temperature of 25 C. The larvas are fed with malt yeast. After 6 days, when untreated animals have become adults, the mortality percentage is determined, making allowance for the natural mortality.

(II) Test on representatives of the insect family aphidid'ae (a) Aphis fabae (bean aphis), residual activity: Pot bean plants are treated with a solution or suspension of the test compound in the desired concentration. The plants are dried and then placed in a cage so that the lice deposited on the plants cannot be lost.

Finally, the plants are infested with 10 young adult lice and maintained at a temperature of 24 C. at a relative humidity degree from 60% to 70%. After 5 days, the mortality is determined.

(b) A phis fabae (bean aphis), system activity: The required amount of active material is added, together with the nutritious solution, to bean plants growing in a Water culture. One day after the addition of the active material the plants are placed in a cage and infested with 10 young adult lice. The plants are maintained at a temperature of 24 C. at a relative humidity degree from 60% to 70%. After 5 days the mortality is determined.

(III) Test of representatives of the insect order Coleoptera (a) Leptz'notarsa decemlineata (Colorado beetle), lanva: Potato foliage is dipped in a test solution or suspension containing the aotive compound in the desired concentration and then transferred into glass pots. The foliage is dried and surrounded by a cage in such manner that larvas deposited on the foliage cannot walk away, to be finally infested with 10 larvas. The foliage is maintained at a relative humidity degree from 60% to 70% at a temperature of 24 C. for 5 days, whereafter the mortality percentage is determined, making allowance for the natural mortality. The test is carried out threefold.

(IV) Test on representatives of the insect order Lepidoptera (a) Pieris brassica (cabbage butterfly), larva: Cauliflower plants are dipped in a test solution or suspension containing the active material in the desired concentration and then transferred into glass pots. After drying, the

plants are surrounded by a cage to prevent caterpillars deposited in the plants from walking away. Finally the plants are infested with 10 caterpillars and maintained at a humidity degree from 60% to 70% at a temperature of 24 C. for 5 days.

The test is carried out threefold. The mortality percentage is determined with a correction for the natural mortality according to Abbott.

(V) Test on representatives of Acarides, family Tetranychidae (red spider) (a) T etranychus cinnabarinus, adult: Potted bean plants (French beans) showing 2 well-developed leaves are dipped in a test solution or suspension containing the active compound in the desired concentration. The leaves are dried and provided with a small plastic cage into which 10 young female spint mites are introduced. The plants are maintained at a temperature of 24 C. at a humidity degree of 60% to 70% for 5 days, whereafter the mortality is determined, making allowance for the natural mortality. The test is carried out threefold.

(b) T etranychus cinnabarinus, ovicide test: Series A- Small plastic cages containing 7 or 8 young female animals are placed on the leaves of potted bean plants (French beans). After 2 days, the cages with the animals are removed and the deposited eggs counted. The plants are then dipped in a test solution or suspension containing the active material in the desired concentration and maintained at a temperature of 24 C. at a humidity degree from 60% to 70%. Each test is carried out sixfold. Ten days after the infestation the mortality percentage is determined with a correction for the natural mortality.

Series BThe plants of Series B are treated with the test solution and dried, whereafter eggs are allowed to be deposited on the dry residue of the active material.

The treatment of the B-plants is otherwise similar to that of the A-plants.

12 What is claimed is: 1. A compound of the formula wherein R is a moiety selected from the group consisting of hydrogen, thiophene, alkyl of 1-10 carbon atoms inclusive, trifiuoromethyl, phenyl, monosubstituted phenyl substituted with a substituent selected from the group consisting of halo, nitro, alkyl of 1-5 carbon atoms inclusive and alkoxy of 1-5 carbon atoms inclusive, phenylalkyl of 7-10 carbon atoms inclusive, cycloalkyl of 5-7 carbon atoms inclusive and --COOA1k wherein Alk is alkyl of 1-5 carbon atoms inclusive.

2. A compound of claim 1 wherein R is selected from the group consisting of hydrogen, alkyl of 1-5 carbon atoms inclusive and benzyl.

3. A compound of claim 2 wherein R is alkyl selected from the group consisting of isopropyl, methyl and pentyl.

4. A compound of claim 2 wherein R is benzyl.

5. A compound of claim 2 wherein R is hydrogen.

References Cited UNITED STATES PATENTS 2,151,380 3/1939 Flint et a1. 260461 2,385,713 9/1945 Kosolapoif 260-461 3,523,951 8/1970 Rufenacht 260'--306.7

ALEX MAZEL, Primary Examiner R. V. RUSH, Assistant Examiner U.S. Cl. X.R.