IL36255A

IL36255A - Phosphoric acid esters,their production and their use as insecticides,acaricides and nematocides

Info

Publication number: IL36255A
Application number: IL36255A
Authority: IL
Original assignee: Bayer Ag
Priority date: 1970-03-25
Filing date: 1971-02-22
Publication date: 1973-10-25
Also published as: CH546538A; PL76515B1; JPS5127736B1; FR2083581B1; CS163778B2; BE764837A; ES416952A1; RO58648A; ES389534A1; CA988532A; HU162354B; DE2111589A1; ZA711190B; CS163779B2; NL7104041A; CS163777B2; IL36255A0; GB1294053A; FR2083581A1; AT304936B

Description

niTin&st ηι»τρκ ,α' ^η '^Bifs ana Phosphoric acid esters, their production and their use as insecticides, acaricides and nematocides j AKD FABni BAYER AKTIEMGE3ELISCHAFT Ib The present invention relates to certain new phosphoric acid esters, to a process for their preparation and to their use as insecticides, acaricides and nematocides.

The present invention provides phosphoric acid esters of the general formula in which X stands for an oxygen or sulphur atom, Y stands for a halogen atom or a lower alkyl, lower allcoxy,. or . lower alkylthiq'/" lower alfcylsulphinyl , ¾.·%*·Θ Θ-3» e-y-e»*o group, and · in is 0, 1, 2 or 3 > each radical Y being selected independently when m is 2 or 3.

Although Y may stand for a fluorine or. iodine atom, the preferred halogens are chlorine and bromine. The "lower" groups include those with an alkyl of 1-4 carbon atoms, namely methyl, ethyl, n- and iso-propyl, and n- iso-, sec- and tert-butyl.

In the cultivation of rice plants the damage caused by , such as the two- r, and mites is a serious problem. Much research has been directed to the control of these harmful creatures but only several pesticides among the commerically available pesticides are effective against them; almost all of these pesticides comprise organic phosphorus compounds. Further, since the same insecticides have been used in great amounts, there has been a tendency for harmful insects to The compounds of the general formula (I) have been, found to exhibit a pronounced pesticidal activity against acarids and nematodes and, especially, against insects.

The compounds of this invention can be used for controlling harmful insects of a broad range such as harmful sucking insects, biting insects and plant parasites. They are effective as insecticides against insects harmful to agriculture, such as insects belonging to the Coleoptera, Lepidoptera, Hemiptera, Orthoptera, Isoptera and Diptera, and are also effective against spider mites and harmful nematodes living, in soil; accordingly, they can be used as agents for protecting plants from such pests.

The compounds of this invention exhibit an especially high insecticidal activity against insects belonging to the Lepidoptera, whose control has been difficult by conventional insecticides. Further, they exhibit a very high insecticidal activity against insects which have acquired resistance to organic phosphorus insecticides of the prior art. Still, yellow further, they are effective for controlling the =bw€—b e &ed rice-borer. The compounds of the invention do not exhibit such an acute toxicity to humans as is possessed by parathion and methylparathion. Nevertheless, the insecticidal activity of the compounds of this invention is comparable or superior to that of parathion and, therefore, they can be used as agricultural chemicals safely.

The present invention provides a process for the preparation of a compound of the formula (I) in which (a) an O-ethyl-S-n-propylhalophosphorothiolate of the general formula in which Hal is a halogen atom, preferably a chlorine atom,, reacted with a benzyl mercaptan of the general formula in which M stands for a hydrogen atom or a salt-forming cation, or (b) an O-ethyl-S-n-propyldithiophosphate of the general formula in which 2 stands for a metal equivalent or an ammonium radical, reacted with a benzyl halide of the general formula in which Hal stands for a halogen atom, or (c) a phosphine of the general formula is reacted with sulphur, or (d) a phosphine of the general formula (VI) above is reacted with hydrogen peroxide.

The symbols X, Y and m have, in the above formulae, the meanings given for formula ( I ) .

In the synthesis of the compounds of this, invention according to any of the above process variants, the reaction is preferably conducted in a solven · (which term includes a mere diluent). For this purpose any inert solvent may be used, for example water; aliphatic, alicyclic and aromatic hydrocarbons (which may be halogenated) such as hexane, cyclohexane, petroleum ether, ligroin, benzene, toluene, xylene, methylene chloride, chloroform, carbon tetrachloride, mono-, di- and tri-chloroethylenes , and chlo-robenzene ; ethers such as diethyl ether, methyl ethyl ether, iso-propyl ether, dibutyl ether, ethylene oxide, dioxane and tetrahydrofuran; ketones such as acetone, methyl ethyl ketone, methyl isbbutyl ketone and methyl isopropyl ketone; nitriles such as acetonitrile , propioni-trile and acrylonitrile ; alcohols such as methanol, ethanol, isopropanol, butanol and ethylene glycol; esters such as ethyl acetate and amyl acetate; acid amides such as dimethyl formamide and dimethyl acetamide ; and sulphoxides and sulphones such as dimethyl sulphoxide and sulphoran.

The reaction of any process variant may be effected at temperatures within a fairly broad range, but generally the reaction is carried out at a temperature of from -20°C to the boiling point of the reaction mixture, preferably at from 10° to 100°C .

The reactants are advantageously used in substantially equimolar proportions.

M , in formula (III), stands preferably for a hydrogen or alkali metal, for example, sodium or potassium, atom. As benzylmercaptans ' hich can be used in reaction variant (a), the following may be cited: benzylmercaptan, 2-(or 4~)chloro-(or .bromo-)benzylmerca tan, 2,4-(or 3,4- or 2 , 6- )dichloro-benzylmercaptan, 2,4, 5-(or 2 , 3, 6-)trichloro-benzylmercaptan, 2,4-(or 2 , 5-)dimethyl-benzylmercaptan, 4-metboxy-benzylmercaptan, 3-chloro-4-meth.oxy-benzylmercapta , 4-methylthio-benzylmercaptan, 4-methylsulphinyl-benzylmercaptan, the sodium or potassium salts of. hese mercaptans.

The reaction of process variant (a) may be carried out in the presence of an acid-binder according to need (usually when A M is a hydrogen atom). Suitable acid-binders include hydroxides, carbonates, bicarbonates and alcoholates of alkali, metals, and tertiary amines such as triethylamine, diethylani- line and pyridine.

When the reaction is carried out in the absence of an acid-binder, the intended product of high purity can be obtained in high yield by first forming a salt, preferably a metal salt, of the appropriate benzylmercaptan and then reacting the. salt with the phosphoric acid diester monohalide.

Process variant (b) results in a compound of the formula (I) in which X is an oxygen atom. In formula (IV) M stands preferably for an alkali metal atom, such as sodium or potassium, or an ammonium group, and in formula (V) Hal stands preferably for a chlorine or "bromine atom. s "benzyl halides which may be used in the reaction of process variant (b), the following may be cited: benzyl chloride (or bromide), 2-(or 4-)chloro(or bromo)benzyl chloride (or bromide), 2,4-(or 3,4- or 2 , 6-)dichlorobenzyl chloride (or bromide), 2,4,5-(or 2,3,6-)trichlorobenzyl chloride (or bromide), 2,4-(or 2 , 5-)dimethylbenzyl chloride (or bromide), 4-methoxybenzyl chloride (or bromide), 3-chloro-4-methoxybenzyl chloride (or bromide), 4-methylthiobenzyl chloride (or bromide), 4-methylsulphinylbenzyl chloride (or bromide), ■4—ey-a»©*>efiey-i--efei-€>i¾.4-e-4. -b^-esiid-e-) Process variant (c) results in compounds of the formula (I) in which X is a sulphur atom whilst process variant (d) gives rise to those in which X is an oxygen atom.

The phosphine of the general formula (VI) is conveniently prepared, by the reaction between the compound of the formula and a benzyl mercaptan of the formula in the presence of an acid-binder and an inert solvent diluent.

When the compounds of this invention are used as pesticides, they are conveniently diluted with water, optionally after they have been mixed with solvents or adjuvants according to need; they may also be mixed with various inert gaseous, liquid or solid diluents or carriers, optionally with adjuvants such as surfactants, emulsifiers, dispersing agents, spreaders and adhesives in any customary manner adopted in the preparation of agricultural chemicals.

The active compounds according to the present invention can be converted into the usual formulations, such as solutions, emulsions, suspensions, powders, pastes and granulates. These may be produced in known manner, for example by mixing the active compounds with extenders, that is, liquid or solid or gaseous diluents or carriers, optionally with the use of surface-active agents, that is, emulsifying agents and/or dispersing agents. In the case of the use of water as an extender, organic solvents can, for example, also be used as auxiliary solvents.

As liquid diluents or. carriers, there are preferably used aromatic hydrocarbons, such as xylenes, toluene, benzene, dimethylnaphthalene or aromatic naphthas, chlorinated aromatic or aliphatic hydrocarbons, such as chlorobenzenes, chloro-methylene, chloroethylene or carbon tetrachloride, aliphatic hydrocarbons, such as cyclohexane or paraffins (for example mineral oil fractions), alcohols, such as methanol or. butanol, ketones, such as acetone, methyl ethyl ketone or cyclohexa-none, or strongly polar solvents, such as dimethyl formamide, dimethyl sulphoxide or acetonitrile ,- as well as water.

As solid diluents or carriers, there are preferably used ground natural minerals, such as kaolins, clays, talc, chalk, a'ttap'u'lgite, montmorillonite or diatom ceous earth or f on 3 synthetic minerals, such s highly-dispersed si"! icic acid, alumina or silicates. ■ · As gaseous diluents or carriers there may' be used aerosol propellants which, are gaseous at normal temperatures an<3 pressures, such as freon.

Preferred example of emulsifying ge ts include non-ionic and anionic emulsifi rs, such - as polyoxyethyH ene- y ty acid esters, polyoxyethylene-fatty alcohol 'ethers , for example alkylarylpol gl col ethers, lk l sulpho.ny.tes and aryl sulpho-nates; . and .preferred examples of " dispersing, agents include lignin, sulphite waste liquors, and methyl cellulose.

It is possible to admix the compoimds of the invention . with other agricultural chemicals such as insecticides ,. nemafco-cides, fungicides (including antibiotic substances), herbicides, growth-adjusting agents, fertilisers and fertilizing substances, according to need.

Thus the present invention also provides an insectlcidal, · acaricidal or nematocidal composition containing as active ingredient a compound of the present invention in admixture with a diluent or carrier. When a liquid diluent- or carrier is used, it preferably contains a surface-active agent.

The compositions of this invention. generally contain 0.1-95% by weight, preferably 0.5 - 90 by weight, of the active component. The concentration of the active component may be varied according to. the preparation form, the application method, the object,- time and place of the application and the degree of the infestation to be countered.

The compounds, of this invention may be used alone but also may be used in the form of the preparations used in the field of agricultural chemicals, such as liquid preparations, emulsi-fiable liquids, concentrated emulsions, wettable powders, soluble powders, oil preparations, aerosol preparations, pastes, fumigating agents, dust, particles, coated particles, tablets, granules and pellets.

The compounds of this invention may be applied to places where harmful insects, acarids or nematodes live directly or by means of a tool in accordance with a spraying, scattering, atomizing, misting, powder-scattering, particle-scattering, mixing, fumigating, injecting or powder-coating method. It is also possible to apply the compounds of this invention in accordance with the so-called "ultra-low-volume" spraying method. In this method it is possible to emplo concentrations of the active component up to 95$, or even to employ the active compound alone In actual application, the concentration of the active compounds in the ready-to-use preparations may be varied within a fairly broad, range, but it is preferred that the concentration of the active compound be 0.0001 - 20$ by weight, especially 0.001 - 5.0$ by weight. The compounds of this invention are generally applied to an area of agriculture in an amount of 15 -1000 g per 10 ares, preferably 40 - 600 g per 10 ares. It is possible, and sometimes necessary, to apply the compounds in' an amount exceeding or below the above range.

The present invention also provides a method of combating insects, acarids or nematodes which comprises applying to the insects, acarids or nematodes or an insect, acarid or nematode habitat, a compound of the present invention alone or in the form of a composition containing as active ingredient a compound of the present invention in admixture with a. diluent or carrier.

The present invention furtherprovides crops protected from damage by insects, acarids and nematodes by being grown . in areas in which immediately prior to and/or during the time of the growing a compound of the present invention was applied alone or in admixture with a diluent or carrier. It will be seen that the usual methods of providing a harvested crop may be improved by the present invention.

' The invention is illustrated in the following examples. In Examples (i)-(iv) and in Examples A-D the compounds are identified by the numbers in Examples 1 -4.

Example 1 24 g of potassium O-ethyl-S-n-propyldithiophosphate are dissolved in 100 ml of alcohol, and 1 9.5 g of 2,4-dichloro-benzyl chloride are added to the solution dropwise, followed by agitation at 70°C for 2 hours. The alcohol is removed from the reaction mixture by distillation, and the residue is dissolved in benzene, washed with water and sodium carbonate, and dried over anhydrous sulphuric acid. Benzene is removed by distillation and the residue is subjected to vacuum distil-lation. There are obtained 30 g of 0-ethyl-S-n-propyl-S-( 2 ,4-dichlorobenz l) phosphorodithiolate of the formula: The product has a boiling point of 1 55 - 1 57°C under 0.02 mm Hg and a refractive index η of 1 . 5791 . This compound is hereinafter designated compound No. .

Example 2 19 g of 3,4-dichlorobenzyl mercaptan are dissolved in 1 00 ml of "benzene and 10 of triethylamine are added to the solution. Then 19 g of -ethyl-S-n-propylchloro-phosphoro-thiolate (boiling at 70°C under 0.5 mm Hg) is added t.o the solution under cooling, following which. agitation is continued at room temperature for a while. Then the mixture is heated at 60 - 65°C to complete the reaction. The reaction mixture is washed with water, 1 hydrochloric acid and then with λ sodium carbonate, and dried over anhydrous sodium sulphate.. Distillation of the benzene gives 27 g of a colourless oil, . 0-ethyl-S-n-propyl-S-(3,4-dichlorobenzyl)phosphorodithiolate of the formula: The product hag a boiling point of 163 - 165°C under 0.3 mm Hg and a refractive index ri 2D0 of 1.5796. This compound is hereinafter designated compound No. 7.

Example 3 8 g of pyridine are added to a solution of 16 g of 4-chlorobenzyl mercaptan in 70 ml of toluene. Whilst nitrogen gas is being introduced into the solution, 19 g of O-ethyl-S-n-propylchloro-phosphite (boiling at 48 - 50°C under 1 mm Hg) are added thereto dropwise at room temperature. After completion of the addition, the mixture is agitated at 40°C for 1 hour, followed by additon of 3.2 g of sulphur. Then the mixture is heated at 90°C for 1 hour and cooled to room temperature. The reaction liquor is diluted with 80 ml of benzene, washed with 1 hydrochloric acid and °/Ό sodium bicarbonate and dried over anhydrous sodium sulphate. Distillation of the solvent gives 24 g of a colourless oil, O-ethyl-S-n-propyl-S- (4-cholorobenzyl)phosphorothionodithiolate of the formula: The product has a boiling point of 186 - 190 C under 0. 1 5 mm Hg and a refractive index n¾P of 1.6029. This compound is hereinafter designated compound No. 4.

Example 4 The following compounds may be synthesized by methods analogous to those of Examples 1-3.

Table 1 Physical Properties Compound No. X Ym Boiling Point Refractive index 1 S (m=0) 166-170°C/0.08 mmHg, n¾° 1 .6028 2 0 2-Cl 1 9-1 51°C/0.2 mmHg, n¾P 1 .5707 3 0 4-C1 1 0-1 3°C/0.1 mmHg, n¾° 1 .5710 6 S 2,4-Cl2 h¾> 1 .6060 8 S 5,4-Cl2 174_177°C/0.1 mmHg, n¾° 1 .6087 9 0 2,6-Cl2 1 6-1 8°C/0.05 mmHg, n¾° 1 .5783 0 2,4,5-Cl5 160-162°C/0.08 mmHg, n 2D0 11 .5863 11 s 2 , , 5-Clj n 2D0 1 .6167 Table 1 Continued Physical Properties Compound No. X Ym Boiling Point Refractive index 12 0 2,3,6-Cl3 161-165°C/0.1 mmHg, n¾° 1.5878 13 s 2,3,6-Cl3 n¾u 1.6067 U 0 4-Br 143-156°C/0.08 mmHg, n¾ 2°0 1.5834 0 2.4- (0H3)2 162-167°C/0.15 mmHg, 16 0 2.5- (OH3)2 163-167UC/0.18 mmHg, n 2¾0 « 0 17 0 4-CH30 18 s 4-CH^O «20 19 0 3-Cl,4-CH,0 nD 0 4-CH,S 21 s 4-CH,S «20 22 4-0H,S- n¾° 1.5897 23 4-0H,S njj0 1.6164 A -Θ- 70-173°C/0.17 mmHg, n¾° 1.5800 174-176°C/0.1 mmHg, njP 1.5721 Example (i) 23 parts of compound No. 34, 80 parts of a mixture of di-atomaceous earth and kaolin and 5 parts of an emulsifier ( "RUNNOX" , a product of Toho Kagaku Kogyo abushiki Kaisha) were ground and- mixed together to form a wettable powder. It was diluted with water before application.

Example (ii) parts of compound No. 5, 30 parts of xylene, 30 parts of "KAWAKAZOL" (a product of Kawasaki Kasei Kogyo Kabushiki Kaisha), and 10 parts of an emulsifier "SORPOL" (a product of Toho Kagaku Kogyo Kabushiki Kaisha) were mixed by -stirring to form an emulsifiable preparation. It was diluted with water before application.

Example (iii) parts of compound No. 20, 10 parts of bentonite, 78 parts of zeeklite and 2 parts of lignin sulphonate were formed into a mixture which was intimately mixed with 25 parts of water. The resulting mixture was finely divided by means of an extruding granulator to obtain particles of 20 - 40 mesh, followed by drying at 40 - 50°G.

Example (iv) 2 parts of compound. No. 3 and 98 parts of a mixture of talc and clay were ground and mixed together to form a dust.

As compared with active compounds of similar structure whic have been described in the literature or known compounds exhibiting similar directions of activity, the novel compounds of this invention exhibit substantially improved effects and very low toxicity to warm-blooded animals. Accordingly, the novel compounds of this invention are of great utility.

Example A Preparation of Sample Formulations Solvent: 3 parts by weight of dimethyl formamide Emulsifier: 0.1 part by weight of alkyl aryl polycol ether In order to prepare a suitable formulation of an active compound, one part by weight of the active compound is mixed with the above amount of the solvent containing the above amount of the emulsifier, and the mixture is diluted with water to form an aqueous formulation containing the active compound at a prescribed concentration.

Test procedure Sweet-potato leaves are dipped in the formulation containing the compound of this invention at the prescribed concentration, dried in air and placed into a 9 cm diameter Petri dish. Then 10 third-instar tobacco cutworm larvae are put into the dish and 'the dish is kept in a thermostat chamber maintained at 28°C. After 24 hours have passed, the number of the dead larvae is counted and the killing ratio is calculated. Test 2 Test of effects against the almond moth: Test Procedure almond moth mature larvae are put into a wire gauze vessel of 7 cm diameter and 0.9 cm height. The vessel is dipped for 10 seconds in an aqueous formulation containing the active compound at a prescribed concentration, which is prepared in the same manner as in Test 1 , and then the vessel is allowed to stand for 24 hours in a thermostat chamber. The number of the dead larvae is counted and the killing ratio is calculated. Test 3 Test of effects against green caterpillars: Test Procedure Cabbage seedling leaves are dipped in an aqueous formu-lation containing the active compound at a prescribed concentration, which, is prepared in the same manner as in Test 1, and dried in air. Then they are placed in a Petri dish of 9 cm diameter, and 10 green caterpillar mature larvae are placed therein. Then the dish is kept for 24 hours in a thermostat chamber maintained at 28°C. The number of the dead larvae is counted and the killing ratio is calculated.

The results of the tests of effects against the tobacco cutworm, almond moth and green caterpillar· are shown in Ta.ble 2, in which results of comparative tests using analogous compounds, identified by the numbers (26)-(36) inclusive, are also shown.

Table 2 Table 2 continued From the results shown in Table 2 it can be seen that the " phosphoric acid esters of the general formula (I) exhibit particularly excellent effects against harmful insects belonging to the Lepidoptera as compared with analogous compounds.

Example B Test of effects against tobacco cutworm: Test Procedure The test is conducted in the same manner as in Test 1 of Example A. The results are shown in Table 3.

Table 3 Results of. Tests of Effects Against the Tobacco Cutworm Killing Ratio ( ) Compound No. 300 ppm 100 ppm 1 ' 100 100 2 100 80 100 90 4 100 95 100 95 6 1.00 80 7 100 87 8 100 70 9 100 90 00 65 11 100 90 12 100 90 13 100 85 14 100 87 100 50 16 100 60 17 100 65 18 100 60 19 100 65 00 85 21 100 .65 Table 3 Continued Notes: (1) Papthion: di ethyldithiophosphorylphenyl- acetic acid ethyl ester (2) Sumithion: dimethyl(3-methyl-4-nitrophenyl ) thiophosphate Example C Test of effects against carmine mites: Test Procedure .

A haricot plant having two developing leaves and planted in a 6 cm diameter pot is infected with 50 - 100 carmine mite imagines and nymphs. Two days after the infection, an aqueoi... formulation of an emulsifiable liquor containing the active compound at a prescribed concentration, which is prepared in the same manner as in Test 1 of Example Λ, is sprayed in an amount of 40 ml per pot. The pot is kept in a greenhouse for 10 days and the control effect is evaluated. The evaluation is expressed by an index rated on the following scale.: Index 3: No living imago, nymph or egg 2:. less than 5 of living imagines, nymphs and eggs based on the untreated control 1 :. 5 - 5 f of living imagines, nymphs and eggs based on the untreated control 0: more than 50 of livin imagines, nymphs and eggs based on the untreated control.

The results are shown in Table 4.

Table 4 Results of Tests of Effects Against Carmine Mites Notes: (1) Fuencapton: diethyl-S-( 2 , 5-dichlorophenylthio- methyl )dithiophosphate (2) Sappiran: . chlorophenylchlorobenzene sulphonate Example D Test of effects against root knot nematodes: Preparation of Sample Formulation 2 parts by weight of the active compound is mixed with 98 parts by weight of talc, and the mixture is ground to form a dust.

Test Procedure The so-prepared formulation is mixed with soil tainted v/ith sweet-potato root knot nematodes in an amount such that a prescribed concentration of the active compound is obtained in the soil. The treated soil is uniformly stirred and mixed, and then it is packed in a pot having an area of 1/5000 are. Then , about 20 tomato seeds (Kurihara variety) are sowed per pot and cultivated for 4 weeks in a greenhouse. Then each root is drawn out from the soil without harming it. The damage degree is evaluated with respect. to 10 roots as one group based on the following scale.

Damage Degree 0 no knot (perfect control). 1 ..... knots are formed slightly. 2' ..... knots are formed appreciably. 3 knots are formed considerably. 4 formation of knots is extreme (same as in untreated control).

The knot index is determined by the following equation: v . T , _ ∑(rank value) x (rank population) x 100 Knot index - (whole population) x 4 The results are shown in Table .

Table 5 Results of Tests of Effects Against Root Knot Nematodes Note : VC: diethyldichlorophenyl-thiophosphate

Claims

we claim is : "

Phosphoric acid esters -of the general formula

in which

X stands for an oxygen or sulphur atom, ■

Y stands for a halogen atom or a. lower alkyl, lower alkoxy, lower alkylthio, lower alkylsulphinyl,

n^^^-er^-^ynrtt) . group, and

m is 0, 1, 2 or 3, each, radical Y being selected

independently when m is 2 or 3·
2. Compounds according to claim -1 in which m is 1 , 2 or 3 and the or each Y stands for a bromine or chlorine : atom or a C1-C4 alkyl, O^-C^ alkoxy, alkylthio, ^-C^ or alkylsulphinyl, nitro or cya.no group.

3. The- compound of the formula

4. The compound of the formula

The compound of the formula

6. The compound of the formula

7. The compound of the formula

'8. The compound of the formula

9. The compound of the formula

10. The compound of the formula

CI

36255/2

1, The compound of the formula

The compound of the formula

13. The compound of the formula

14. A process for the production of a compound according to any of claims 1 to 13 in which

(a) an O-ethyl-S-n-propylhalophosphorothiolate of the general formula

reacted with a benzylmercaptan of the general formula

or (b) an O-ethyl-S-n-propyldithiophosphate of the general formula

is reacted with a benzyl halide of the general formula

or (c) a phosphine of the general formula

is reacted with sulphur or (d) a compound of the general formula (VI) above is reacted with hydrogen peroxide,

in which general formulae

M*' stands for a hydrogen atom or a salt-forming cation, 2

M stands for a metal equivalent or an ammonium radical,

Hal stands for a halogen atom and,

X, Y and m have the meanings stated in claim 1.

15 14

A process according to claim 4-6 (a) in which Hal stands for a chlorine atom.

16 14 15

'-ΐβ-ι A process according to claim +6(a) or in which M stands for a sodium or potassium atom.

17 14 15 i 4-9. A process according to claim -†"6(a) or 4^f~ in which stands for a hydrogen atom, the reaction being effected in the presence of an acid-binder.

18 14 2

-26. A process according to claim -1~6(b) in which stands for a sodium or potassium atom or for an ammonium radical.

19 14 18

-24. A process according to claim 44(b) or -2-0 in which Hal stands for a chlorine or bromine atom.

20 14 to 19

22. A process according to any of claims 16 to 21 in which the reaction is effected in an inert solvent.

21 14 to 20

■2$. A process according to any of claims 1 to 22 in which the reaction is effected at a temperature of from -20°C to the boiling point of the reaction mixture.

22 21

-24. A process according to claim -ί?3 in which the reaction is effected at from 10°C to 100°C or the boiling point of the reaction mixture, whichever is the lower.

23

-2 . A process for the preparation of a compound according to claim 1 substantially as hereinbefore described in any of Examples 1 to 4.

■24-,—Compounds aooording to claim 1 whenever prepared by a process according to any of claims 16 to 25.

24

%. An insecticidal, acaricidal or nematocidal composition containing as active ingredient a compound according to any of claims 1 to †5 and 36 in admixture with a diluent or carrier.

25 24

-2½5. A composition according to claim -2 containing from

0.1 to 95 of the active compound, by weight.

26 25

2-9. A composition according to claim ·8β containing from

0.5 to 0$ of the active compound, by weight.

27

-5©. A method of combating insects, acarids or nematodes which comprises applying to the insects, acarids or nematodes, or an insect, acarid or nematode habitat, a compound according to any

13

of claims 1 to 15 a rl ? alone or in the form of a composition containing as active ingredient a compound according to any of

13

claims 1 to 15 Q-nd 26 in admixture with a diluent or carrier.

28 27

34-. A method according to claim 3Θ- in which a composition is used containing from 0.0001 to 20% of the active compound, by weight.

29 28

3-2·. A method according to claim 34- in which a composition is used containing from 0.001 to 5.0 of the active compound, by weight.

27 to 29

33» A method according to any of claims 30 to 32 in which the compound is applied to an area of agriculture in an amount of 1 5 to 1,000 g per 10 ares.

30

■54. A method accordin to claim 33 in which the compound is applied to an area of agriculture in amount of 40 to 600 g er 10 ares.

2 27 to 31

-55. A method according to any of claims 30 to 34 in which the compound is one of those hereinbefore mentioned in any of

Examples A to D.

33

€, Crops protected from damage by insects, acarids and nematodes by being- grown in areas in which immediately prior to and/ or during the time of the growing a compound according to any

13

of claims 1 to 15 and 26 was applied alone or in admixture with a diluent or carrier.

For the Applicants

DR. EI ED COHM AND PARTNE S,