CS213371B2 - Insecticide means - Google Patents

Description

The invention relates to compounds having insecticidal properties, to a process for the preparation of these compounds, to insecticidal compositions containing said compounds as active ingredients, and to methods of controlling pests using such compounds and compositions.

Commercially available insecticides can generally be divided into four main groups, which are chlorinated compounds such as DDT, camphechlor and BHC, organophosphorus compounds such as parathion, carbamates such as cambaryl and more recently synthetic pyrethroids such as permethrin.

After a period of use of the insecticide, pests often develop resistance to the insecticide and there is therefore a constant demand for new insecticides and in particular for new groups of insecticides.

Although there are often indications in the literature that a group of compounds have pesticidal properties, it is often the case that they are not commercially useful as pesticides.

It has now been found that certain benzophenone hydrazones exhibit insecticidal activity against a wide variety of pests.

Some benzophenone hydrazones are already known. For example, U.S. Patent 3,732,307 discloses compounds of the general formula

H-N-H

in which

X is perfluoroalkyl, perfluoroalkoxy or perfluoroalkylthio having up to 4 carbon atoms each, and

Y is hydrogen, chloro, bromo or fluoro, alkyl, alkoxy, alkylthio, perfluoroalkyl, perfluoroalkoxy or perfluoroalkylthio containing up to 4 carbon atoms in each case.

The compounds described in this US patent clearly differ, for example, from the benzophenone hydrazones described by J. R. DoAmaral et al. in J. Med. Chem. 12, 21 (1969), inter alia, because their NH2 group is not substituted in the hydrazine moiety The compounds in this patent are mainly described as plant growth regulators, although the US patent also mentions that Of the 24 examples contained in the cited US patent specification, 20 examples disclose compounds containing neither an alkylthio group nor a perfluoroalkylthio group, with particular emphasis on compounds substituted with a perfluoroalkyl group, in particular trifluoromethyl group, throughout the above cited US patent specification. and nowhere is there any mention of any of the above-mentioned compounds containing an alkylthio or perfluoroalkylthio group at the 4-position of any of the benzene rings, or those substituted at the 4-position as described above but which additionally contain substituents other than those mentioned in this patent.

The present invention provides compounds corresponding to Formula I

R ^L R ^

either m is 0 and n is 0 or m is 1 and n is 0 or 1, p is 0, 2 or 3, x is 0 or 1,

R ¹ , R ⁵ and R ^{7 are each} independently halogen, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl or C 1 -C 4 alkoxy, or R ¹ and the adjacent radical R ⁵ together with the benzene ring to which they are attached form a naphthyl group,

R ² and R ^4, which may be identical or · different, are hydrogen, alkylo.vou group having 1 to 4 carbon atoms, an ester or a thioester moiety of the formula R ⁸ XCO, where X is oxygen or sulfur and R ⁸ represents alkyl C 1 -C 12, optionally substituted C 1 -C 4 alkoxy, cycloalkyl. C 3 -C 6 -alkyl, halogen, cyano, hydroxyl, N-C 1 -C 4 -alkylcarbamoyloxy, phenoxy optionally substituted by halogen or nitro, and phenyl alone. optionally substituted with halogen, further carboxy, carboxy thoxy or C 1 -C 6 alkanoyloxy, or R ⁸ is C 2 -C 10 alkenyl, optionally substituted with phenyl, which is itself optionally substituted with halogen, or is C 2 alkynyl up to 6 carbon atoms optionally substituted by halogen, a cycloalkyl group having 3 to 7 carbon atoms, a morpholino group, an aryl group in which the aromatic ring contains 6 to 10 carbon atoms or a heteroaryl group in which the aromatic ring contains 5 or 6 atoms and the heteroatoms are selected from the group consisting of oxygen, sulfur and nitrogen, or R ² and R ⁴ are each an acyl group of formula R ⁹ CO wherein R ⁹ represents ethoxykarbonylovoiu group karbamoytovou, hydrogen or · a radical R ^8, or R ² and R ⁴ are each a carbamoyl radical of the formula -CONR 4 R ¹¹ where R ¹⁰ and R ¹¹ are the same or different and are hydrogen, alkyl having 1 to 4 carbon atoms optionally substituted by halogen or ethoxykarbonylovoiu group, an alkanoyl group having 1-4 carbon atoms, optionally substituted by halogen, or phenyl optionally substituted by halogen, or R ² and R ⁴ represent each N-alkyl or NN-dlalkylthiokarbamoylovou group in which the alkyl portion contains 1 to 4 carbon atoms, or R ² and R ⁴ together with the nitrogen atom to which they are attached form a five- to seven-membered ring which may optionally contain oxygen or nitrogen as another heteroatom, and

R ³ is C 1 -C 4 alkyl optionally substituted by halogen, C 2 -C 3 alkenyl, Ν, dial C 1 -C 2 dialkylamino in each alkyl moiety, or phenyl optionally substituted by methyl, or halogen, provided that when p is 0, both R ² and R ⁴ are not hydrogen.

In accordance with one embodiment, p has an O value of ¹ so that one of the benzene rings is substituted with an SR ³ moiety and the amine function of the hydrazine residue must be substituted. It is particularly surprising that substitution of this amine function with, for example, R ⁴ , which is an alkyl or especially acyl group as defined above, an ester or thioester moiety or a carbamoyl or thiocarbamoyl group, yields useful compounds.

In accordance with another embodiment, p is 2 or 3. It is understood that the substituent - (OJ2SR ³ ) is a grouping

O

-k = «

o and - (O) 3SR ³ is a grouping

O — O — SR ³ .

II o

These compounds wherein p is 3 _; they are particularly preferred substances according to the invention. It should be noted at this point that these substituents are completely different from all substituents mentioned in U.S. Patent 3,732,307.

As used herein, halogens are fluorine, chlorine, bromine or iodine atoms, preferably fluorine, chlorine or bromine atoms.

Preferred compounds in accordance with the first embodiment are those compounds of formula I wherein p, n and x are each 0, m is 1,

R ¹ represents a halogen atom,

R ² is hydrogen,

R ⁵ represents a defined alkyl group and

R ⁴ represents an acyl or alkoxycarbonyl group as defined above.

Preferred compounds in accordance with the latter embodiment are those compounds of formula I wherein p is 3, x is 0,

R ² is hydrogen,

R ¹ and R ⁵ represent halogen atoms,

R ⁴ represents a hydrogen atom, an acyl or alkoxycarbonyl group, as defined above, and

R ³ represents an alkyl or optionally substituted phenyl group as defined above.

In the general formula I, R @ ¹ , R @ ⁵ and R @ ⁷ are preferably halogen atoms, especially chlorine. When one of these symbols represents an alkyl or alkoxy group having 1 to 4 carbon atoms, it is preferably a methyl or methoxy group. In general, it is preferred that the value of 1 and n is 0. The preferred haloalkyl group having from 1 to 4 carbon atoms, optionally present in the meaning of any of the above, is trifluoromethyl.

R @ ² is preferably hydrogen and R @ ⁴ is preferably other than hydrogen, and is usually a carbonyl derivative. The alkyl groups R ² and R ⁴ may contain 1 to 4 carbon atoms, the preferred alkyl group being the methyl group. The alkenyl group R ³ is usually 1-propenyl. The dialkylamino group R @ ³ is preferably dimethylamino. Particularly preferred R ³ radicals are methyl or trifluoromethyl.

A preferred group of compounds of the invention are those wherein p has a value of 3.

A particularly preferred group of compounds are those compounds of formula I wherein m is 1, nax have a value of 0, p is 3, R is halogen, R ³ represents an alkyl group having 1 to 4 carbon atoms optionally substituted by halogen and R ² is hydrogen.

⁶

Particularly preferred compounds of this group are those in which

R ³ represents a methyl or trifluoromethyl group and

R ⁴ is a radical of formula R ⁸ (Oj _q CO, wherein R ⁸ is C 1 -C 12 alkyl optionally substituted with C 1 -C 4 alkoxy, C 3 -C 6 cycloalkyl, halogen, phenoxy or as defined above substituted cycloalkyl, C3-C7 cycloalkyl, C2-C10 alkenyl, optionally substituted by phenyl or halo-substituted phenyl, C2-C6 alkynyl or phenyl, and q is 0 or 1, provided that when q is 0, R ⁸ can also be hydrogen.

The compounds of the invention are effective against a number of economically important insect pests causing serious and widespread damage to crop plants, such as Lepidoptera (butterflies), including, caterpillar (Plutella maculipennis), cabbage white (Pierls brassicaej, Spodoptera littoralis and Heliothis spec. Many of the compounds also show activity against other caterpillars, such as the caddisfly caterpillar (Laspeyresia pomonella). Some of the compounds of the invention show activity against other pests, such as the beetles of the order of the order. Coleoptera, such as the leaf beetle (Phaedon cochleariae j, pilus (Sitophilus granarius), the darkling beetle (Tribolium castaneumj and the darkling beetle (Tenebrio.molitorj), against cockroaches of the order Orthoptera (. Hemiptera, such as the vetch (Megoura viciae j.

Many of the compounds of the invention also show activity against a number of economically important mites and insect pests of animals, including cattle. For example, many of these compounds are effective against larval stages of insect pests of the order Diptera (diptera), such as the buzzard (Lucilia spec.) And mosquitoes such as Aedes aegypti. Some of the compounds of the invention, particularly those in which R ⁴ is a carbamoyl or thiocarbamoyl group, have systemic activity, i.e. the insecticidal effect is also present in the internal tissues of the animal treated with the compound. This property is important in the treatment of animals, such as cattle, infested with the developmental stages of insects found in the tissues, such as the respective developmental stages of the puncture (Hypoderma spec.) Some of the compounds are also effective against lice and sheep, and parasites from the family of the mites, in particular against ticks such as Bo213371 ophllus microplus and against mites such as Sarcoptes spec.

It has been found that some of the compounds of the invention also have fungicidal activity, herbicidal activity and function as regulators. plant growth.

The present invention provides an insecticidal composition comprising an inert diluent and a compound of formula I as active ingredient. These compositions may contain more than one compound of the invention and as a diluent a solid or liquid material, optionally together with a surfactant, for example dispersing, emulsifying or wetting agent. .

One or more other pesticides, such as compounds known to have acaricidal or insecticidal activity, may be added to the compositions of the invention to enhance their activity or broaden their spectrum of activity.

Such other pesticides include, for example: organophosphorus compounds such as tetrachlorvinphos, phenitrothion, demeton-S: -methyl, phosalone, dioxathione, chlorfenvin • phos, dichlorvos, bromophosethyl, diazinone, dimethoate, methyl parathion, Bolstar [0-ethyl-0- ( 4-methylthiophenyl) -S-propylphosphorodithioate] or chlorpyrifos, carbamates such as methomyl, carbaryl, pirimicarb or promecarb, diphenyl derivatives containing bridges such as tetradifon, tetrasul or DDT, chlorinated hydrocarbons such as hexachlorobenzene, endosulafene, endosulphan, endrinuline, endrin amitraz, chlordimeform, clenpyrin, chlormeithiuron or nimidane, synthetic pyrethroids such as permethrin, fenvalerate or cypermethrin, or tin-based pesticides such as cyhexatin or fenbutatin oxide.

The compositions of the invention may be in any form known in the art of processing pesticidal compounds, for example in the form of solutions, aqueous dispersions, aqueous emulsions, dusts, dispersible powders, emulsifiable concentrates and granules. These formulations include not only ready-to-use formulations, but also concentrated primary formulations which must be diluted with an appropriate amount of water or other diluent prior to administration.

Dispersion compositions consist of a compound of the invention dispersed in an aqueous medium. Often, it is expedient to deliver to the consumer primary concentrated compositions which can be diluted with water to dispersions of the desired concentration. The primary concentrates may be in any of the following forms:

Firstly, they are dispersible solutions which comprise a compound of the invention dissolved in a water-miscible solvent, with the addition of a dispersant. Alternatively, these concentrates may be prepared in the form of a dispersible powder comprising a compound of the invention and a dispersant. Another alternative concentrate is a paste or cream which is prepared by thoroughly mixing the compound of the invention in the form of a fine powder in combination with a dispersant with water to form the desired paste or cream. The paste or cream may optionally be added to an oil-in-water emulsion to form a dispersion of the active ingredient in the aqueous-oil emulsion.

Emulsion preparations comprise a compound of the invention in a water-immiscible solvent, which solution is converted into an emulsion by the addition of water in the presence of an emulsifier. Emulsions of the desired concentration may be prepared from primary concentrates containing a compound of the invention in combination with an emulsifier, water and a water-immiscible solvent. Alternatively, emulsifiable concentrates comprising a solution of a compound of the invention in a water-insoluble solvent containing an emulsifier can be delivered to the consumer.

Another form of the compositions of the invention is a dust containing the compound of the invention thoroughly ground and ground with a solid powdered diluent, for example kaolin.

The granular formulations consist of a compound of the invention in combination with similar diluents used to prepare dusts, but the difference is that the mixture is granulated in a known manner. Alternatively, the granulate may contain the active ingredient absorbed or adsorbed on a pre-treated granular carrier such as fuller's earth, attapulgite or crushed limestone.

When a single active ingredient is used, the concentration of the active ingredient in preparations intended for direct application to the crops is generally in the range from 0.001 to 10% by weight, in particular from 0.005 to 5% by weight, but in the case of aerial spraying, it may be desirable to use more concentrated formulations containing up to 20% active ingredient. In concentrated primary compositions, the concentration of the active ingredient can be varied within wide limits, for example from 5 to 95% by weight of the composition.

As mentioned above, the compounds of the present invention exhibit outstanding activity as insecticides, and the invention therefore includes a method for controlling insects by applying a compound of formula I to an insect area, i.e., to the insect itself or to an environment where lives. The compounds of the invention may be administered as such, but more preferably in the form of any of the above compositions.

The numerous insect species against which the compounds of the invention are effective, for example Lepidoptera and Diptera, attack insect plants and, in accordance with the invention, the plants are preferably protected against insect infestation by applying the compound of formula I to the plant growing site. Thus, for example, Plutella maculipennis (field bitch) and Pieris brassicae (white tip) attack various vegetables such as crucifers, and Spodoptera littoralis is a serious cotton pest.

Direct alpination is often preferred, for example by spraying or dusting plants affected by insects, but the active ingredient can also be applied to the soil in which the plants grow, in the form of granules or watering. In such cases, the active substance is taken up by the roots of the plants, which then protect the insect from over. The rates of application of the active ingredient may vary within wide limits, depending on the circumstances, but are usually from 0.01 to 20 kg / ha, in particular from 0.1 to 10 kg / ha.

It is also within the scope of the present invention to provide a method of protecting animals against pest infestation by treating an animal with a compound of formula I. Animals such as cattle are often irritated by parasites, many of which can be combated by external application of a compound of formula I. application to an animal or application to places where animals are kept, such as buildings, etc.

The compounds of the present invention can be prepared in a number of ways, such as:

1) reaction of a compound of formula II

IR

(SR * III) with a compound of the formula NH ² NR ² R ⁴

When R ^{@ 2} and R ^{@ 4} are both hydrogen atoms, the product obtained can be acylated by:

(a) an acyl halide or acid anhydride where R ² or R ⁴ is to be an acyl group;

b) chlormřavefičaliem chlorthiomravenčanem since in case R ² or R ⁴ is an ester residue, or '

c) an isocyanate when R ² or R ⁴ is intended to mean a carbamoyl group.

It should be noted that herein the term "acylating agent" means any ^one of these three types of compounds.

The reaction with hydrazine or the hydrazine derivative is usually carried out at a temperature of from 50 to 100 ° C, in the presence of acetic acid.

The acylation reaction is preferably carried out in the presence of an inert organic liquid as the reaction medium, which is also a solvent for the reactants, at a temperature of from 0 ° C to 100 ° C. The reaction is preferably carried out in the presence of a suitable acid binding agent, for example a tertiary alkylamine, pyridine or alkali metal carbonate. If a halide is used as the acylating agent, it is preferably the corresponding chloride.

Compounds of formula II wherein p is 3 are new and can be prepared by reaction of a sulfonyl halide of formula

R ³ SO ² X wherein X represents a halogen atom, preferably chlorine, with the corresponding 4'-hydroxy derivative of the general formula III

lili)

This reaction is preferably carried out in the presence of an inert organic solvent and an acid binding agent.

Compounds of formula II, wherein p is 0, can be prepared by Friedel-Crafts reaction of a compound of formula II

wherein Y is a halogen atom, usually chlorine, with a compound of formula

Compounds of formula (II) in which p has a value of 2 can be prepared by oxidation of the corresponding compound in which p has a value of 0, for example with hydrogen peroxide.

2) Compounds of the invention wherein p is 3 are prepared by reacting a compound of formula IV

wherein R ² and R ^{4 are} not both hydrogen and the compound of formula

RSO 2 Y wherein Y is a halogen atom, preferably chlorine.

This reaction is preferably carried out at a temperature of 0 to 100 ° C, usually in the presence of an acid binding agent.

Compounds of formula IV may be prepared by reaction of a suitable hydrazine derivative of formula

NH ² NR ² R ⁴ with a compound of formula III above. preferably in the presence of an inert organic solvent and optionally in the presence of acetic acid. Compounds of formula IV in which R ² and R ⁴ are not both simultaneously hydrogen are novel reactants and are also within the scope of the invention.

As is known in the art, most of the reactions described above result in products consisting of mixtures of E- and Z-isomers.

It should be noted that the general formula I of Scheme 1 illustrating the compounds of the invention encompasses both of these isomers. ¹ In all cases it is possible to separate the two isomers by conventional methods such as chromatography or fractional crystallization, but as a mixture of isomers having useful insecticidal activity, generally does not produce any separation of isomers advantages. The activity of the individual isomers of any of the compounds described above may be different, and in some cases, the activity of one of the isomers may be only marginal. Pure isomers lacking insecticidal activity do not fall within the scope of the invention.

The novel reactants of formula (IV) above also exist in isomeric forms and the structural formula of these compounds encompasses both of these isomers.

The invention is illustrated by the following non-limiting examples.

The compounds of the invention are prepared according to any of the following reaction schemes:

OSO /? ³ 4, ^wherein at least of R Jaden

R ² and R ⁴ .neznamená hydrogen.

^os ° ^íRi

Scheme 2.

^[R ^ - ^ ry ~ CO - <f] V ^0S0 ? ^R3

Myb) (R from Scheme i

Scheme 3

Scheme 4

NNH _Z

OSO? R acylating agent (? R? From Scheme Z, 2

(RX ^{R n} from Scheme i

NB ₂ NR ² R ^1f

r ³ $ o _l ci

-y

OSOf * from scheme 1

Scheme 5

acylating agent ->

Scheme 6

oxidation of * ^h from Scheme 4

Scheme 7

nh ^ nr ^

The term "acylating agent" includes acid halides, acid anhydrides and isocyanates.

Examples 1 to 7 represent typical examples of preparation according to the individual schemes.

The structures of all compounds prepared by the process of the invention were confirmed by IR spectroscopy.

Example 1

This example illustrates the procedure of Scheme X.

Friedel-Crafts reaction of phenol with p-chlorobenzoyl chloride in the presence of aluminum chloride affords 4-chloro-4‘-hydroxybenzophenone melting at 179-181 ° C (A). To a solution of 5 g of this material in 8 ml of pyridine was added 2.5 g of methanesulfonyl chloride at room temperature, the reaction mixture was heated on a steam bath for 1.5 hours and then poured into dilute hydrochloric acid. The precipitated solid is filtered off, air-dried and recrystallized from denatured alcohol. There was obtained 4-chloro-4'-methylsulfonyloxybenzophenone, m.p. 120 DEG-121 DEG C. (B).

A solution of 9.4 g of this product and 7.8 g of ethyl carbazate in 8 ml of glacial acetic acid and 200 ml of ethanol was heated at reflux for 48 hours and then evaporated to dryness in vacuo. The residue is extracted with 250 ml of methylene chloride, the extract is washed with water, 2.5N aqueous sodium hydroxide and again with water, dried and evaporated to dryness. 4-Chloro-4'-methylsulfonyloxybenzophenone ethoxycarbonylhydrazone, m.p. 132.5-140 ° C (C).

Example 2

This example illustrates the procedure of Scheme 2.

To a solution of 9.35 g of the product (B) of Example 1 in 200 ml of ethanol was added first 8 ml of hydrazine hydrate and then 1.5 ml of glacial acetic acid. The mixture was refluxed for 17 hours with stirring, then the solvent was evaporated under reduced pressure. The oily residue is extracted with chloroform, the extract is washed with water, aqueous sodium hydroxide solution and again with water and then dried over magnesium sulphate. The solvent was evaporated under reduced pressure. The oily residue crystallizes on standing. The hydrazone of 4-chloro-4'-methylsulfonyloxybenzophenone melting at 70-110 ° C (D) is obtained.

Example 3

This example illustrates the procedure of Scheme 3.

A solution of 2 g of propionyl chloride in 15 ml of ether was added dropwise with stirring to a solution of the compound of Example 2 (6.2 g) in 20 ml of pyridine at 0-5 ° C over 30 minutes with stirring. The mixture was stirred at room temperature for 1.5 hours, then poured into 1 liter of water, the solid material was filtered off, washed with dilute hydrochloric acid and water, and dried under vacuum at 60 ° C for 1.5 hours. There was obtained propionylhydrazone of 4-chloro-4'-methylsulfonyloxybenzophenone (G), m.p. 128-144 ° C.

Example 4

This example illustrates the procedure of Scheme 4.

A solution of 92.8 g of the compound (Aj from Example 1, 100 grams of ethyl carbazate and 100 ml of glacial acetic acid in 1 liter of ethanol is heated under reflux for 48 hours. The solvent is evaporated under reduced pressure and the resulting suspension is evaporated. The solid material was washed with a small amount of cold denatured alcohol and dried under vacuum at 50 ° C.

The filtrate was evaporated under reduced pressure, the oily residue was extracted with chloroform, ex213371

The tract was washed with aqueous sodium carbonate solution and water, then dried over magnesium sulfate and evaporated under reduced pressure to give a second crop of solid product.

Recrystallization of the combined solids from the denatured alcohol gave 4-chloro-4'-hydroxybenzophenone ethoxycarbonylhydrazone (E), m.p. 185-187 ° C.

To a solution of 95.55 g of (E) and 90 ml of triethylamine in 700 ml of tetrahydrofuran was added dropwise 44.7 g of methanesulfonyl chloride in 25 ml of tetrahydrofuran over 35 minutes, a fine precipitate being formed with heat release. The reaction mixture is allowed to react overnight with stirring, then poured into 500 ml of water and extracted with 500 ml of methylene dichloride. The extract was washed five times with 500 ml of water each time and dried over magnesium sulfate. Evaporation of the solvent under reduced pressure gave a semi-solid residue which was triturated with denatured alcohol. Filtration and washing with additional solvent gave a white solid which, after drying in vacuo at 75 ° C for 3 hours, afforded 4-chloro-1'-methylsulfonyloxybenzoophenone (C) ethoxycarbonylhydrazone (C), m.p. 132-142 ° C.

Example 5

This example illustrates the procedure of Scheme 5.

Friedel-Crafts reaction of isopropylphenyl sulfide with 4-chlorobenzoyl chloride in the presence of aluminum chloride affords 4-chloro-4‘-isopropylthiobenzophenone (F), m.p. 105-107 ° C. ·· ·

To a solution of 101 g of (F) in 650 ml of ethanol is added 67.5 ml of hydrazine hydrate. The mixture was refluxed for 24 hours, then the solvents were evaporated under reduced pressure. Water was added to the residue, the mixture was extracted with chloroform, the chloroform extract was washed with aqueous sodium hydroxide solution and water, then dried over magnesium sulfate and evaporated under reduced pressure. 4-Chloro-4'-isopropylthiobenzophenone (G) hydrazone, b.p.

This product was treated with ethyl chloroformate analogously to Example 3 to give 4-chloro-4'-isopropylthiobenzophenone (H) ethoxycarbonylhydrazone (H), m.p. 115-135 ° C.

and

Example 6

This example illustrates the procedure of Scheme 6.

The procedure described in Example 5 gave 4-chloro-16 using the FriedehCraits reaction

-4‘-propylthiobenzophenone (F), mp 94-95 ° C. 2.9 g of this material was dissolved in glacial acetic acid and added

3.5 ml 30.36% (volume%] of hydrogen peroxide. The mixture was heated for 5 hours with stirring at 60 ^Q C, then poured into water. The solid product was filtered, washed with water, dried and recrystallized from ethanol. To give with 4-chloro-4'-propylsulfonylbenzophenone (I), m.p. 140.5-142.5 ° C.

This material was treated with hydrazine hydrate as described in Example 5 to give 4-chloro-4'-propylsulfonylbenzophenone hydrazone (J), m.p. 110-120 ° C, which, by treatment with propionyl chloride analogously to Example 3, gave propionylhydrazone 4-chloro-4'-propylsulfonylbenzophenone (K), m.p. 155-170 ° C.

Example 7

This example illustrates the procedure of Scheme 7.

A solution of 14.52 g (FJ of Example 5) was treated with ethyl carbazate in an analogous manner to Example 1 to give 4-chloro-4-isopropylthiobenzophenone ethoxycarbonylhydrazone, m.p. 115-35 ° C.

In the previous and following examples, the resulting products generally result as mixtures of geometric isomers with different ratios of the two isomers.

Examples 8 to 267

Depending on any of the schemes above, the compounds summarized in the following table are prepared in an analogous manner to that described in any of the preceding examples.

Physical data (melting point in degrees Celsius, unless otherwise indicated) of the final products are given in column J, the starting materials in column K and the intermediates in column L.

In Scheme 3, the product of the previous example was used as the starting material.

In working according to Scheme 1, 2 or 4, the starting material (column-K) is of the type A (type A), when working according to Scheme 5 or 7, the starting material is of the type (FJ) type.

Using Scheme 1 or -2, the intermediate (column LJ is of the substance type (iBJ), using Scheme -4, the substance of type (-EJ and using Scheme 5, the substance of type (G)).

The column labeled A lists the types of acylating agents or hydrazine derivatives used, using abbreviations with the following meanings:

Acylating Reagents

M = acylhaiogenide N = acid anhydride

N * = mixed acetic anhydride and formic anhydride

O = methyl isocyanate P = phenyl isocyanate

MM = p-chlorophenyl isocyanate

NN = ethyl isocyanate = tert-butyl isocyanate

PP = butyl isocyanate

QQ = propyl isocyanate N '= phthalic anhydride RR = 2-chloroethyl isocyanate MA = n-butyrolactone MB = ethyl oxalyl chloride MC = ethyl fluoroacetate MD = isopropyl isocyanate ME = trichloroacetyl isocyanate MF = ethoxycarbonylmethyl isocyanate MG = tert-butylisocyanate Mis tert-butyl isocyanate MK = vinyl chloroformate

Hydrazine derivatives

S =

T =

U =

V =

W = x =

Y = z = ss =

TT = uu = vv = ww =

XX =

YY = zz = SA- SB = sc = SD = SE = SF = SG = SH = SJ = SK = SL = SN = sat = SP = SQ = ethyl carbazate methyl carbazate semicarbazide benzyl carbazate

N-aminomorpholine thiosemicarbazide

4,4-dimethylsemicarbazide

N-carbazoylmorpholine

2-carbazoyl-2-methoxypropane

2-carbazoylethanol

2i-carbazoylpropan-2-ol aminopiperidine

2.2.2- oxamoylhydrazine trichloroethyl carbazate

ΙΗ, ΙΗ-heptafluorobutyl carbazate

3-Amino-2-oxo-oxazolidine

2.2.2-trifluoroethyl carbazate

2-methylsemicarbazide

2-imidazolin-2-ylhydrazine hydrobromide 2,2,3,3-tetrafluoropropylcarbazate tert-butylcarbazate

2,4-dimethylsemicarbazide

3-Aminoperhydro-1,3-oxazin-2-one

2.4.4-trimethylsemylcarbazide propynyl carbazate

1,1-dimethylhydrazine

2-methylallylcarbazate

3-Amino-5-allyloxymethyloxazolidin-2-one

2,4-dimethylthiosemicarbazide 2 ', 4,4-trimethylthiosemicarbazide 2-methyl-4-tert-butyl semylcarbazide

The column labeled B shows the number of the scheme used.

In the column labeled C, there is an example number describing the preparation of the respective starting material.

In addition, the following symbols and abbreviations are used in the table:

NS = not determined x = starting material prepared by reaction of the product of Example 2 with methylhydrazine to give crude methylhydrazone 4-chloro-4'-methylsulfonyloxybenzophenone + = intermediate in column L was prepared by diazotizing 4-amino-4'-chlorobenzophenone and treatment with sulfur dioxide to give the sulfonyl chloride derivative (m.p. 113-114 ° C), which is then reacted with the appropriate dialkylamine

1) = the intermediate in column L was prepared as described in Example 6; methylthiohenzophenone has a melting point of 132-133.5 ° C

2) = intermediate in column L is obtained by reacting the substance of column K with hydrazine and treating the product with butyric anhydride.

Me = methyl Et = ethyl Pr = propyl Bu = butyl Ph = phenyl Pr ^f = isopropyl

Bu '= t-butyl Bu ^s = sec-butyl Bu * = isobutyl co cn co

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Example 312

The product of Example 4 is separated into high geometric liquid isomers into individual geometric isomers. The E-isomer melts at 160-161 ° C. The Z-isotaer has a melting point of 152-158 ° C.

Example 313

Neutralization of the product of Example 269 with sodium carbonate gave a free base melting at 188-190 ° C.

Example 314

The products of Example 312 were treated with dimethyl sulfate and sodium hydride to give the N-ethoxycarbonyl-N-methylhydrazone (E) -4-chloro-4'-methylsulfonyloxybenzophene, m.p. Mp 100-101 ° C.

Example 315

This example illustrates the efficacy of the compounds of the invention against larvae of the preform (Plutella maculipennis).

The larvae of the field lice are placed in a test tube together with a square cut of cabbage leaf (approx. 2.5 X 2.5 cm) which has been immersed in the testi! solution and allowed to dry. After 24 hours, untreated leaf was placed in the tube as feed and after 24 hours the mortality of the test insects was determined.

Solutions with different concentrations of the test compounds are used, and for each test compound the experiment is repeated twice so that the LD 50 value can be calculated from the results obtained.

The results obtained in the above test are summarized in the following summary:

Example compound no. LD50 (ppm) Example compound no. LD50 (ppm) 1 13 41 21 , 2 33 42 50 3 14 43 270 4 13 44 24 5 27 Mar: 45 13 6 190 46 18 7 27 Mar: 47 43 8 50 48 50 9 16 49 37 10 110 50 100 ALIGN! 11 27 Mar: 51 16 12 33 52 27 Mar: 13 91 53 18 14 11 54 37 15 Dec 33 55 33 16 190 56 14 17 <500 57 50 18 14 58 18 19 Dec 20 May 59 43 20 May 43 60 520 21 19 Dec 61 50 22nd 270 62 220 23 16 63 190 24 50 64 21 25 14 65 67 26 18 66 61 27 Mar: 33 67 50 28 510 68 58 29 33 69 67 30 12 70 220 31 43 71 27 Mar: 32 .33 72 10 33 27 Mar: 73 10 34 520 74 780 35 780 75 110 36 500 76 2000 37 100 ALIGN! 77 25 38 25 78 67 39 110 79 33 40 100 ALIGN! 80 33

LD50 (ppm) Example compound no. LD50 (ppm) 1900 146 50 1600 147 67 2.2 148 2200 33 149 37 19 Dec 150 13 500 151 25 650 152 67 25 153 190 27 Mar: 155 2200 50 156 2200 33 157 43 37 158 220 37 159 250 14 160 42 33 161 2000 820 162 100 ALIGN! 43 163 190 160 164 2500 59 165 27 Mar: 50 166 280 1600 167 140 9 168 59 50 169 78 50 170 140 710 171 77 18 17.2 50 16 173 110 50 174 190 25 175 220 37 176 220 2200 177 3000 29 178 83 43 179 160 220 180 220 220 181 160 50 182 no 25 183 590 16 184 59 21 185 50 190 186 50 570 187 58 220 188 500 320 189 59 18 190 190 42 191 > 2500 925 192 31 33 193 2500 25 194 650 280 195 50 220 196 710 29 197 550 520 198 700 1100 199 310 110 200 59 18 201 37 12 202 610 220 203 67 2200—5000 204 43 77 205 1600 120 206 780 20 May 207 1600 16 208 200 190 209 270 37 210 91 160 21.1 1600

213 371

Example compound no. LD50 (ppm) Example compound no. LD50 (ppm) 212 37 265 190 213 50 266 110 214 7l0 267 160 215 100 ALIGN! 268 7 216 2200 269 220 217 50 . 270 43 218 220 271 14 219 220 272 370 220 100 ALIGN! 273 58 221 16 274 16 222 <500 275 18 223 100 ALIGN! 276 23 224 2200 277 160 225 160 278 50 226 25 279 7 227 10 280 8 228 13 2.81 50 229 14 282 77 230 50 283 7 231 61 284 220 232 6 285 50 233 11 286 37 234 190 287 110 235 2 288 7 236 3 289 <100 237 2 290 5 238 1 291 27 Mar: 239 330 292 9 240 X 293 50 241 50 294 540 242 710 295 610 243 190 296 320 244 110 297 500 245 13 298 43 246 37 299 7 247 4 300 5 248 780 301 67 249 77 302 6 250 570 303 31 251 2200 304 <100 252 570 305 2 253 610 306 ~ 500 254 27 Mar: 307 11 255 43 308 160 256 33 309 37 257 67 310 <100 258 140 311 <100 259 50 312 12 (E-isomer) 260 33 16 (Z-isomer) 261 <100 313 67 26i2 25 314 50 (E-isomer) 263 42 33 (Z-isomer) 264 Legend: 190 the vast majority more efficient than of the compounds of the invention this known comparative

* LD 50 = 41 against claw buzz.

(Lucilla spec.)

Example 316

Under these conditions, the known commercial insecticide "methomyl", which is S-methyl-N-methylcarbamoyloxy) thloacetimldate, has an LD 50 value of 130 mg / kg, indicating that

This example describes the composition of various types of concentrates containing as active ingredients compounds of the invention:

Water Dispersible Concentrate Product of Example 4

15.0% (w / v)

Ethylan BV (ethoxylated nonylphenol)

15, ΰ% (w / v)

Ethylan C40 AH (ethoxylated castor oil)

15.0% (w / v) cyclohexanone

30.0% (w / v)

N-methylpyrrolidone

31.0% (w / v)

Aqueous liquid composition product of Example 4

33.0% (w / v)

Dyapol PT (sodium salt of cresolsufonic acid condensation product with formaldehyde)

5.0% (w / v)

Monolan PB (copolymer of ethylene oxide and propylene oxide)

0.25% (w / v)

Antifoam Μ3Ώ (silicone based emulsion)

0.5% (w / v)

Rhodopol (high molecular weight polysaccharide) - - ZO / o gel

0.1% (w / v) water up to · 100.0% v / v

Oil suspension product of Example 4

33.0% (w / v)

Dyapol PT 1.0% (w / v;)

Ethylan ENTX (ethoxylated alkylphenol)

15.0% (w / v)

Antimousse 411 (emulsion based on silicone)

0.5% (w / v) light liquid paraffin up to · 100.0% v / v

Dispersible Powder Product of Example 4

50.0% (w / v)

Dyapol PT 10.0% (w / v)

Aerosol OT-B (dioctyl ester of sodium salt of succinic acid)

0.5% (w / v) precipitated silica

10.0% (w / v)

Polyviol M13 / 140 (polyvinyl alcohol)

2.0% (w / v) kaolin 27.5% (w / v)

Claims (4)

Subject Insecticidal composition, characterized in that it contains an inert diluent or carrier and, as active ingredient, a compound of the formula I R ² - R ^ \ / N! ((O) _p SR ³ 4/3 = / I R \! R \ (!) In which either m has a value of 0 and n has a value of 0 or m has a value of lan has a value of 0 or 1, p has a value of 0, 2 or · 3, OF THE INVENTION x is 0 or 1, R @ ¹ , R @ ⁵ and R @ ^{7 each} independently represent an atom. halo, (C 1 -C 4) alkyl, (C 1 -C 4) haloalkyl or (C 1 -C 4) alkoxy, or R ¹ and adjacent R ⁵ together with the benzene ring to which they are attached form a naphthyl group, each of R ² and R ⁴ , which may be the same or different, each represents a hydrogen atom, a C 1 -C 4 alkyl group, an ester or a thioester radical of formula R ⁸ XCO, where X represents oxygen or sulfur and R ⁸ represents alkyl C 1 -C 12, optionally substituted C 1 -C 4 alkoxy, C 3 -C 6 cycloalkyl, halogen, cyano, hydroxyl, N-C 1 -C 4 -alkylcarbamoyloxy, phenoxy is itself optionally substituted by halogen or nitro, further by phenyl, which is itself optionally substituted by halogen, further by carboxy, carboxymethy or (C 1 -C 6) alkanoyloxy, or R ⁸ is C 2 -C 10 alkenyl, optionally substituted by phenyl, which is itself optionally substituted by halogen, or is C 2 -C 6 alkynyl. C 6 optionally substituted by halogen, C 3 -C 3 cycloalkyl 7 carbon atoms, morpholino, aryl in which the aromatic ring contains 6 to 10 carbon atoms or heteroaryl in which the aromatic ring contains 5 or 6 atoms and the heteroatoms are selected from the group consisting of oxygen, sulfur and nitrogen, or R ² and R ⁴ each represent an acyl group of formula R ⁹ CO wherein R ⁹ represents an ethoxycarbonyl group, a carbamoyl group, a hydrogen atom or a radical R ^8, or R ² and R ⁴ are each a carbamoyl radical of the formula -CONR ^{1 O} R ^u wherein R ¹⁰ and R ¹¹ they are the same or different and in each case represent a hydrogen atom, an alkyl group having from 1 to 4 carbon atoms or an alkyl group having from 1 to 4 carbon atoms; substituted haloethoxy or ethoxycarbonyl, C 1 -C 4 alkanoyl optionally substituted by halogen, or phenyl optionally substituted by halogen, or R ² and R ^{4 each} represent N-alkyl or N, N-dialkylthiocarbamoyl in which the alkyl moiety contains in each case 1 to 4 carbon atoms, or R ² and R ⁴ together with the nitrogen atom to which they are attached form a 5- to 7-membered ring, which may optionally contain oxygen or nitrogen as another heteroatom, and R ³ represents a C 1 -C 4 alkyl group optionally substituted by halogen, a C 2 -C 3 alkenyl group, a N, N-dialkylamino group having 1 to 2 carbon atoms in each alkyl moiety, or a phenyl group optionally substituted by a methyl group, or halogen, with the proviso that if p is 0, not both R ² and R ⁴ are hydrogen. 2. A composition according to claim 1, which comprises a compound selected from the group consisting of formylhydrazone 4-chloro-4'-methylsulfonyloxybenzophenone, pentanoylhydrazone 4-Chloro-4'-methylsulfonyloxybenzophenone, ethoxycarbonylhydrazone 4-chloro-4'-methylsulfonyloxybenzophenone 4-chloro-4'-methylsulfonyloxybenzophenone cyclopentylhydrazone, 2,2-dimethylpropanoylhydrazone-4-chloro-4 ' -methylsulfonyloxybenzophenone, heptafluorobutyrylhydrazone 4-chloro-4 &apos; -ethylsulfonyloxybenzophenone, 4-chlorobenzoylhydrazone 4-chloro-4'-methylsulfonyloxybenzophenone, 3-chlorobenzoylhydrazone 4-chloro-4'-methylsulfonyloxybenzophenone, benzoylhydrazone 4-chloro-4'-methylsulfonyloxybenzophenone, 4-chlorobenzoylhydrazone 4-Chloro-4´-methylsulfonyloxybenzophenone 3-fluorobenzoyl drazone 4-chloro-4'-methylsulfonyloxybenzophenone, 3,4-dichlorobenzoylhydrazone 4-chloro-4´-methylsulfonyloxybenzophenone, 4-Chloromethylbenzoylhydrazone 4-chloro-4 &apos; -methylsulfonyloxybenzophenone, ethoxycarbonylhydrazone. 4-chloro-4'-trifluoromethylsulfonyloxybenzophenone, 4-methylsemicarbazone 4-chloro-4'-methylsulfonyloxybenzophenone, semicarbazone 4-bromo-4'-methylsulfonyloxybenzophenone, semicarbazone 4-chloro-4'-methylsulfonyloxybenzophenone, isopropoxycarbonylhydrazone 4-chloro-4'-methylsulfonyloxybenzophenone and 4-chloro-4'-methylsulfonyloxybenzophenone methylsulfonyloxybenzophenone. Severography, n. P., Plant 7, Most