HU180915B - Substituted insecticide preparation consists of pyrazoline agent and method for producing 1,3,4-disubstituted pyrazoline derivatives - Google Patents

Abstract

Compounds of the formula I <IMAGE> in which R1, R2, R3, R4 and X have the meaning defined in Patent Claim 1, are potent insecticides. They form the active substances of the novel insecticide preparations. They are prepared by reacting a compound of the formula II <IMAGE> with a compound of the formula III R1-N=C=X or with a compound of the formula <IMAGE> and, if appropriate, further reacting the resulting compound, in which R4 equals H, with an R4-halide.

Description

FIELD OF THE INVENTION The present invention relates to insecticidal compositions containing a substituted pyrazoline compound and to a process for the preparation of 1,3,4-substituted pyrazoline derivatives.

It is known from German Patent Publication No. 2,304,584 that pyrazoline compounds substituted at positions 1, 3 or 1, 3, 5 of the pyrazoline ring have a biocidal effect on arthropods, in particular mites and insects.

It has now been found that the novel pyrazoline derivatives of the formula I and having substituents at the 1-, 3- and 4-positions of the pyrazoline ring have very strong insecticidal activity.

1,3,4-substituted pyrazoline derivatives of formula (I)

X is halogen, C 1-4 alkyl, C 1-4 alkoxy, C 1-4 alkylthio or cyano in the alkyl moiety,

Y is halogen or (1-4C) alkoxy,

R 1 is C 1 -C 6, cyano, piperidino, or alkyldiamino, wherein the alkyl moieties are

They contain from 1 to 4 carbon atoms and represent a substituted alkyl group, together with carriers and / or additives.

The preparation of structurally related 1,3, 4-substituted pyrazoline derivatives is the subject of Dutch Patent Application No. 74 09433. The compounds described in the said Dutch application also have good insecticidal properties.

It has now been found that the compounds of the present invention have good biological insecticidal activity at low doses and are thus suitable for use in, for example, beetles, beetle larvae. as an active ingredient in mosquito larvae and preparations for killing caterpillars.

Surprisingly, it has been found that the compounds of the invention have a much better insecticidal activity than the known 1,3- and 1,3,5-substituted pyrazoline compounds. It has further been found that, in some cases, compositions containing the compounds of the invention kill the yellow fever mosquitoes and exhibit excellent activity against both the colorado beetle and the caterpillar. In the case of preparations containing the 1,3,5-substituted pyrazoline derivatives and the derivatives containing the 1,3-substituted compounds, it has been found that, in addition to having good activity against caterpillars, the colorado beetle has a weaker action against white cabbage larvae and generally has little or no effect. against mosquito larvae causing yellow fever.

For example, many of the agents used in the compositions of the present invention are active at concentrations ranging from 0.3 to 3 ppm against colorado beetle larvae and from 1 to 30 ppm.

-1180915 shows very good activity against its caterpillars, and at the concentration of 0.03-0.3 ppm it has the highest activity against yellow fever mosquito larvae. Examples of pyrazoline compounds of the present invention which exhibit biological activity include:

1) 1- (4-cyanophenylcarbamoyl) -3- (4-chlorophenyl) 4- (2-piperidinethyl) -2-pyrazoline, mp 148 ° C;

2) 1- (4-Isopropoxyphenylcarbamoyl) -3- (4-chlorophenyl) -4- (2-piperidinoethyl) -2-pyrazoline. Mp 113 ° C;

3) 1- (4-ethylphenylcarbamoyl) -3- (4-chlorophenyl) -4 (2-piperidinoethyl) -2-pyrazoline, m.p.

4) 1- (4-chlorophenylcarbamoyl) -3- (4-chlorophenyl) -4 (2-piperidinoethyl) -2-pyrazoline, m.p.

5) 1- (4-chlorophenylcarbamoyl) -3- (4-chlorophenyl) -4- (2-diethylaminoethyl) -2-pyrazoline, m.p.

6) 1- (4-ethylphenylcarbamoyl) -3- (4-chlorophenyl) -4- (2-diethylaminoethyl) -2-pyrazoline;

7) 1- (4-isopropoxyphenylcarbamoyl) -3- (4-chloro [nim] -4- (2-diethylaminoethyl) -2-pyrazoline;

3) 1- (4-cyanophenylcarbamoyl) -3- (4-chlorophenyl) 4- (2-diethylaminoethyl) -2-pyrazoline;

9) 1- (4-chlorophenylcarbamoyl) -3- (4-isopropoxyphenyl) -4H-diethylaminoethyl-2-pyrazoline;

10) 1- (4-isopropoxyphenylcarbamoyl) -3- (4-isopropoxyphenyl) -4 H -dicylaminoethyl-2-pyrazoline;

11) 1- (4-isopropylphenylcarbamoyl) -3- (4-isopropoxyphenyl) -4 H -diethylaminoethyl-2-pyrazoline;

12) 1- (4-chlorophenylcarbamoyl) -3- (4-chlorophenyl) 4- (3-piperidinopropyl) -2-pyrazoline,

Mp 107 ° C;

13) 1- (4-Cyanophenylcarbamoyl) -3- (4-chlorophenyl) 4- (3-piperidinopropyl) -2-pyrazoline, m.p.

120 ° C;

14) 1- (4-chlorophenylcarbamoyl) -3- (4-chlorophenyl) 4-cyanomethyl-2-pyrazoline, m.p.

15) 1- (4-Cyanophenylcarbamoyl) -3- (4-chlorophenyl) 4-cyanophenyl-2-pyrazoline. Mp 205 ° C;

16) 1- (4-Chloro-phenylcarbamoyl) -3- (4-chloro-phenyl) -4- (N-dimethylamino-ethyl) -2-pyrazoline, m.p.

131 ° C;

17) 1- (4-Cyanophenylcarbamoyl) -3- (4-chlorophenyl) -4- (R-dimethylaminoethyl) -2-pyrazoline, m.p.

175 ° C;

18) 1- (4-methylthiophenylcarbamoyl) -3- (4-chlorophenyl) -4 - ((5-dimethylaminoethyl) -2-pyrazoline, m.p. 117 DEG C .;

19) 1- (4-methoxyphenylcarbamoyl) -3- (4-chlorophenyl) -4- (R-dimethylaminoethyl) -2-pyrazoline, m.p.

103 ° C;

20) 1- (4-isopropylphenylcarbamoyl) -3- (4-chlorophenyl) -4- (R-dimethylaminoethyl) -2-pyrazoline, m.p.

21) 1- (4-methoxyphenylcarbamoyl) -3- (4-chlorophenyl) -4- (3-cyanopropyl) -2-pyrazoline, m.p.

126 ° C;

22) 1- (4-methylthio-phenyl-carbamoyl) -3- (4-chloro-phenyl) -4- (3-cyanopropyl) -2-pyrazoline, m.p.

109 ° C;

23) 1- (4-Chloro-phenylcarbamoyl) -3- (chloro-phenyl) -4 (3-cyano-propyl) -2-pyrazoline, m.p.

24) 1- (4-Isopropyl-phenyl-carbamoyl) -3- (4-chloro-phenyl) -4- (3-cyano-propyl) -2-pyrazoline, m.p. 154 σ.

In particular, compositions containing compounds of formula I exhibit very strong insecticidal properties in which R is a C 1-6 alkyl group substituted by a dialkylamino group whose alkyl groups are attached to the nitrogen atom to which they are attached, they form a heterocyclic ring.

In addition, it has been found that the compounds of formula (I) used as active ingredients of the composition of the present invention exhibit fungicidal properties in addition to strong insecticidal activity.

Due to their potent insecticidal activity, the active compounds of the compositions of the invention are suitable for insect control even in small doses. The size of the doses depends on various factors such as the material used, the type of insect, the formulation, the condition of the insect infested area and the prevailing weather conditions. In general, in agriculture and horticulture, a good insecticidal effect per hectare can be achieved with 0.05 to 1 kg of active ingredient.

For practical use, the compounds of the present invention are formulated into compositions. In these formulations, the active ingredient is mixed with a solid carrier or dissolved or dispersed in a liquid carrier, optionally in combination with excipients such as surfactants and stabilizers.

Exemplary compositions of the present invention include solvent solutions and dispersions, oily solutions and oily dispersions, pastes, spray powders, wettable powders, mixable oils, granules, reverse emulsions, aerosol compositions, and incense candles.

Wettable powders, pastes and mixable oils are concentrated preparations that can be diluted with water before or during use.

Inverted emulsions are used mainly in air when treating a relatively large air space with a relatively small amount of formulation. The reverse emulsions are prepared shortly before or during the spraying process by emulsifying water in an oily solution of the active ingredient in an oily dispersion. Many types of formulations are described in more detail later in the Examples.

Particulates are prepared by, for example, dissolving the active ingredient in a solvent and impregnating the resulting solution, optionally in the presence of a binder, with a granular carrier. Examples of such granular carriers are porous granules (e.g., pumice and attaclay), mineral non-porous granules (sand or ground marl), cellular granular materials (e.g., dried coffee grounds and cut tobacco stalks).

Granular compositions can also be prepared by compressing the active ingredient with powdered minerals, lubricants and binders, then crushing and granulating the compressed product to the desired grain size.

Spray powders, for example, are prepared by intimately mixing the vehicle with an inert solid such as 1 to 50% by weight, such as talc, kaolin, chalk, diatomaceous earth, dolomite, gypsum, limestone, bentonite, attapulgite, and the like. or mixtures of these and similar materials. Organic carriers include nutshell varieties.

Wettable powders are prepared by:

1 to 80 parts by weight of a solid carrier, such as any of the aforementioned inert carriers, are admixed with 10 to 80 parts by weight of active ingredient, 1 to 5 parts by weight of a dispersant such as lignin sulfonates or alkylnaphthalenesulfonates known for this purpose; for example, aliphatic alcohol sulfates, alkylarylsulfonates or fatty acid condensation products.

For preparing a miscible oil, the active ingredient is dissolved or finely divided in a suitable solvent, which is preferably a solvent which is poorly miscible with water, and an emulsifier is added to the solution. Suitable solvents are, for example, xylene, toluene, petroleum distillates containing large amounts of aromatic moieties, for example, solvents of petroleum, distilled tar oil and mixtures of such liquids. Emulsifying agents include, for example, alkylphenoxy polyglycol ethers, polyoxyethylene sorbitan fatty acid esters or polyoxyethylene sorbitol fatty acid esters. The concentration of this miscible oily active ingredient is not limited to narrow limits such as 2% to 50% by weight.

In addition to miscible oils, liquid and highly concentrated basic formulations of the active compounds in water-miscible liquids such as acetic acid, to which a dispersant and, if appropriate, a wetting agent, are added. Aqueous dispersions of the active ingredient are prepared from these by diluting them with water shortly before or during spraying.

An aerosol delay formulation of the present invention is also obtained in a similar manner. During the preparation, the active ingredient is optionally dissolved in a solvent, in a volatile liquid which can be used as a propellant, such as chlorofluoro derivatives of methane and ethane.

Incense candles and smoking powders, which are formulations that produce pesticidal smoke during combustion, are obtained by incorporating the active ingredient into a combustible mixture containing, for example, fuel, sugar or wood, preferably in a ground state, and a combustion medium such as ammonium nitrate or ammonium nitrate. and further includes, for example, kaolin, bentonite and / or colloidal silica for delaying combustion.

In addition to the substances mentioned above, the compositions of the invention may also contain other substances conventionally used in the preparation of such compositions, for example a lubricant such as calcium stearate or magnesium stearate, may be added to the wettable powder or the mixture to be granulated. "Adhesive" substances such as polyvinyl alcohol and cellulose derivatives or other colloidal substances such as glue may also be added to the compositions to increase adhesion of the pest control agent to the surface to be protected.

The compositions of the invention may also contain known pesticides. In this way, the spectrum of action of the formulations is broadened and the synergistic effect is increased.

The following known insecticidal, fungicidal and acaricidal compounds can be used in combination with the compositions of the present invention:

Insecticides. active compounds:

1. chlorinated hydrocarbons such as 2,2-bis (p-chlorophenyl) -1,1,1-trichloroethane and hexachlorepoxy-octahydro-dimethanonaphthalene;

2. carbamates, such as N-methyl-1-naphthylcarbamate;

.?. dinitrogenols such as 2-methyl-4,6-dinitrophenol and 2- (2-butyl) -4,6-dinitrophenyl) -3,3-dimethylacrylate;

4. Organophosphorus compounds such as dimethyl 2-methoxycarbonyl-2-methylvinylphosphate, 0,0-diethylO-p-nitrophenylphosphorothioate, 0,0-dimethylthiophosphate, oryl acetic acid-N- monomethyl-amide;

Acaricidal compounds:

5. diphenyl sulfates such as p-chlorobenzyl p-chlorophenyl sulfide and 2,4,4 ', 5'-tetrachlorodiphenyl sulfide;

6. diphenylsulfonates, such as p-chlorophenylbenzenesulfonate,

7. methylcarbinols such as 4,4-dichloro-a-trichloromethylbenzhydrol;

8. quinoxaline compounds such as methylquinoxalindithiocarbonate.

Fungicidal compounds:

9. organic mercury compounds such as phenylmercuric acid and methylmercuricyanoguanidine;

10. organotin compounds such as triphenyltin hydroxide and triphenyltin acetate;

11. alkylene bis dithiocarbamates, such as zinc ethylene bis dithiocarbamate and magnesium ethylene bis dithiocarbamate, and

12. Other compounds such as 2,4-dinitro-6- (2-octylphenyl) -crotonate, 1-bis (dimethylamino) phosphoryl-3-phenyl-5-amino-1,2,4-triazole-6-methyl -quinoxaline-2,3-dithiocarbonate, 1,4-dithio-anthraquinone-

2,3-dicarbonitrile, N-trichloromethylthiophthalimide N = trichloromethylthiothetrahydrophthalimide, N- (1,1 -

1,2,2-Tetrachloroethylthio) tetrahydrophthalimide, N-dichlorofluorophenylthio-N-phenyl-N '-dimethylsulfonylamide and tetrachlorophthalonitrile.

As mentioned above, the compounds of the general formula (I) are novel substances which can be prepared by analogous processes for the preparation of similar compounds.

, 3

-3180915

The 1,3,4-substituted pyrazoline derivatives of formula (Ϊ) are prepared according to the invention by reacting a compound of formula (II) wherein Y and R are as defined above with a compound of formula (III): X is as defined above.

The reaction is carried out at room temperature in the presence of a solvent such as an ether such as diethyl ether or petroleum ether.

The invention will be explained in more detail in the following examples.

Example 1 1- (4-Chloro-phenylcarbamoyl) -3- (4-chloro-phenyl) -4- (3-cyano-propyl) -2-pyrazoline;

(a) Dissolve 10.6 g of dimethylaminohydrochloride, 4.2 g of paraformaldehyde and 22.1 g of 4'-chloro-5-cyano-valerophenone in 30 ml of dioxane. The reaction mixture was heated at reflux for 30 hours and then cooled to room temperature. Most of the dioxane is evaporated under reduced pressure. Water and ether were added to the residue, the ether layer was separated, washed with water, dried over sodium sulfate and evaporated. 22.5 g

2- (p-chlorobenzoyl) -5-cyclopenten-1 is obtained.

b) 22.5 g of 2- (p-chlorobenzoyl) -5-cyclopenten-1 and

A solution of 3.5 ml of hydrazine hydrate in 50 ml of ethanol is refluxed for 5 hours. Removal of the solvent gave 23.8 g of 3- (p-chlorophenyl) -4- (3-cyanopropyl) -2-pyrazoline.

c) 3.1 g of p-chlorophenyl isocyanate are added to 4.95 g

Of a solution of 3- (p-chlorophenyl) -4- (3-cyanopropyl) -2-pyrazoline in 30 ml of anhydrous ether. After stirring for one hour, the ether was distilled off and replaced with 50 ml of light petroleum. Stirring is continued for another 5 hours and the petroleum ether is filtered off with suction. 4.9 g of the title compound are obtained, m.p. 120 ° C.

In a similar manner, the following compounds were prepared:

1- (4-chlorophenylcarbamoyl) -3- (4-chlorophenyl) -4-cyanomethyl-2-pyrazoline, m.p.

1- (4-cyanophenylcarbamoyl) -3- (4-chlorophenyl) -4-cyanomethyl-2-pyrazoline, m.p.

1- (4-methoxyphenylcarbamoyl) -3- (4-chlorophenyl) -4 (3-cyanopropyl) -2-pyrazoline, mp 126 ° C;

1- (4-methylthiophenylcarbamoyl) -3- (4-chlorophenyl) -

4- (3-cyanopropyl) -2-pyrazoline, m.p. 109 ° C;

1- (4-isopropylphenylcarbamoyl) -3- (4-chlorophenyl) 4- (3-cyanopropyl) -2-pyrazoline, m.p.

Example 2

1- (p-chlorophenylcarbamoyl) -3- (p-chlorophenyl) -4 (2-piperidinoethyl) -2-pyrazoline,

a) A suspension of 26.6 g of 4'-chloro-4-piperidinobutyrophenone, 4 g of paraformaldehyde and 10.6 g of dimethylamine hydrochloride in 40 ml of dioxane is refluxed for 24 hours. The mixture was evaporated, water was added and the reaction mixture was made basic with 50% sodium hydroxide solution and then extracted with ether. The extract was washed with water, dried and evaporated to give 26.7 g of 1- (dimethylamino) -2 (p-chlorobenzoyl) -4-piperidinobutane.

b) A solution of 26.7 g of compound (a) and 10 ml of hydrazine hydrate in 35 ml of ethanol is refluxed for 7 hours and then distilled. 18.1 g of 3- (p-chlorophenyl) -4- (2-piperidinoethyl) -2-pyrazoline are obtained. Boiling point (0.4-0.5 mmHg) 200-208 ° C.

c) 15.4 g of p-chlorophenyl isocyanate are added

29.2 g of a solution of 3- (p-chlorophenyl) -4- (2-piperidinoethyl) -2-pyrazoine in 500 ml of petroleum ether. The mixture was stirred for 12 hours and drained to give 36.4 g of the title compound. Mp 134 ° C.

In a similar manner, the following compounds were prepared:

1- (p-cyanophenylcarbamoyl) -3- (p-chlorophenyl) -4- (2-piperidinoethyl-2-pyrazoline, m.p. 148 DEG C .;

1- (p-isopropoxyphenylcarbamoyl) -3- (p-chlorophenyl) 4- (2-piperidinethyl) -2-pyrazoline, m.p. 113 DEG C .;

1- (p-ethylphenyl, arbamoyl) -3- (p-chlorophenyl) -4- (2-piperodimethyl) -2-pyrazoline, m.p.

1- (p-chlorophenylcarbamoyl) -3- (p-chlorophenyl) -4- (2-diethylaminoethyl) -2-pyrazoline, m.p.

1- (p-ethylphenylcarbamoyl) -3- (p-chlorophenyl) -4- (2-diethylaminoethyl) -2-pyrazoline;

1- (p-isopropoxyphenylcarbamoyl) -3- (p-chlorophenyl) 4- (2-diethylaminoethyl) -2-pyrazoline;

1- (p-cyanophenylcarbamoyl) -3- (p-chlorophenyl) -4- (2-diethylaminoethyl) -2-pyrazoline;

1- (4-chlorophenylcarbamoyl) -3- (4-isopropoxyphenyl) -4β-ethylamino-ethyl-2-pyrazoline;

1- (4-isopropoxyphenylcarbamoyl) -3- (4-isopropoxyphenyl) -4 H -diethylaminoethyl-2-pyrazoline;

1- (4-isopropylphenylcarbamoyl) -3- (4-isopropoxyphenyl) -4- [7-diethylaminoethyl-2-pyrazoline;

1- (4-chlorophenylcarbamoyl) -3- (4-chlorophenyl) -4- (3-piperidinopropyl) -2-pyrazoline; Mp 107 ° C;

- (4-cyanophenylcarbamoyl) -3- (4-chlorophenyl) -4- (3-piperidinopropyl) -2-pyrazoline; 120 ° C;

1- (4-chlorophenylcarbamoyl) -3- (4-chlorophenyl) -4- (R-dimethylaminoethyl) -2-pyrazoline; Mp 175 ° C;

- (4-methylthiophenylcarbamoyl) -3- (4-chlorophenyl) -4 - ((dimethylaminoethyl) -2-pyrazoline; Mp 117 ° C;

1- (4-methoxyphenylcarbamoyl) -3- (4-chlorophenyl) -4 - ((dimethylaminoethyl) -2-pyrazoline; Mp 103 ° C;

1- (4-Isopropylphenylcarbamoyl) -3- (-4-chlorophenyl) -4 (R) -dimethylaminoethyl) -2-pyrazoline; 157 ° C;

Example 3

The compounds of the invention are dispersed in water to form aqueous dispersions of the active ingredient in concentrations of 300, 100, 30, 10, 3, 1 and 0.3 mg / liter.

The insecticidal activity of these dispersions was determined on common moths against Leptinotersa decemlineata (Colorado beetle) and Pieris brassicae (cabbage moth).

The results are summarized in the following table. The symbols in the table mean:

+ = 90-100% mortality + - 50-90% mortality - = <50% mortality

Spreadsheet

Biocidal action against larvae of Leptinotarsa decemlineate and Pieris brassicae

Biocidal effect

Concentration: mg of active ingredient per liter of Leptinotarsa decemlineata (PPM) Pieris brassicae

300 100 30 10 3 1 0.3 300 100 30 10 3 1 0.3 1 + + ± + - + + 4 ~ + - 2 + + + + - + + + + + - 3 + + + + + - + + d- + ± - 4 + + + + ± - + + + + + + - 5 + + + + ± - d- + + + + - 6 + + + ± - + + + + + - 7 + + + - + + + + + - 8 + + + + - + + d- + - 9 + + ± - + + + + + - 10 + d- + - * 1 " + + "L · ± - 11 + + ± ± - + + + + + ± -

Spreadsheet

Biocidal activity against Cola L. and Picns brassicae

Biocidal effect

Compound as listed numbering concentration: mg of active ingredient Cola L.

per liter (PPM) Pieris brassicae

300 100 30 10 3 1 0.3 300 100 30 10 3 1 0.3 12 + + + + - + d- + + + - 13 + + + + - + + d- i - 14 + + + + + ± - + + + + - 15 d- + + + + - + + - 16 d- + + d- 4- + - + + + + i - 17 + d- + + - + + + - 18 + + + + + - + + + + - 19 d- + + ± - + + + + - 20 4- + + + ± - + + + + + ± - 21 + + + ± - + + - 22 + + + + ± - + + + - 23 + + + + d- + + + + + + + - 24 + + + ± - + + + + -

The process of the present invention and

The effect of the 1,3- and 1,3,5-substituted pyrazolines was investigated as in Example 3. The results are shown in the following table:

Spreadsheet

Results of comparative studies, activity against Piersis brassicae

Compound _v Y z R the) b) c) song - CN cl C ₆ H ₄ Cl-4 - (minus - (minus) 1 CN cl piperidinoethyl 4 1/2 + 8 CN cl (CH ₂ ) ₂ -N (C ₂ H ₅ ) ₂ 4 + 13 CN cl piperidino 3 1/2 + 15 CN cl CH ₂ CN 2 + 17 CN cl (CH ₂ ) ₂ -N (CH ₃ ) ₂ 3 + - cl cl c ₍₍ h ₅ 2+ 3+ - cl cl 4 1/2 + 4 cl cl piperidinoethyl 6 + 5 cl cl (CH ₂ ) ₂ N (C ₂ H ₅ ) ₂ 5 + 12 cl cl piperidino 5 + 14 cl cl CH ₂ CN 4 + 16 cl cl (CH ₂ ) ₂ -N) CH ₃ ) -> 4 1/2 + 23 cl cl (CH ₂ ) ₃ CN 6 +

In the table above, "-" means no activity at 300 ppm, eg "4 1/2 +" means: 300 100 30 10 3.1; etc

d! + + ~ "± -. "

The compositions of the present invention are described below as follows:

(a) A stable suspension is prepared by adding 25 parts by weight of 1- (4-chlorophenylcarbamoyl) -3- (4-chlorophenyl) -4- (3-cyanopropyl) -1-pyrazoline as the active ingredient and 5 parts by weight of lignin as a dispersant. sulfonate, 2 parts by weight of dibutyl naphthalene sulfonate as wetting agent and enough water to make up to 100 parts.

(b) 25 parts by weight of active ingredient 1- (4-chlorophenylcarbamoyl) -3- (4-chlorophenyl) -4- (3-cyanopropyl) -2-pyrazoline per wetting powder composition, 5 parts by weight of lignin sulfonate as a dispersant, 2 parts by weight as a wetting agent. parts by weight of dibutylnaphthalenylsulfonate and 68 parts by weight of kaolin are used.

(c) A wettable powder formulation of 80 parts by weight of 1- (4-chlorophenylcarbamoyl) -3- (4-chlorophenyl) -4- (3-cyanopropyl) -2-pyrazoline and 5 parts by weight of lignin sulfonate, 2 parts by weight of dibutyl naphthalene. sulfonate, 5 parts by weight of colloidal silicon dioxide and 6 parts by weight of kaolin.

(d) A clear solution of 20 parts by weight of 1- (4-chlorophenylcarbamoyl) -3- (4-chlorophenyl) -4- (3-cyanopropyl) -2-pyrazoline as an active ingredient, 20 parts by weight of calcium dodecylbenzene sulphonate and a mixture of an alkylaryl poly oxyethylene and the amount of cyclohexanone needed to make up to 100 parts.

PATENT CLAIMS

Claims (2)

PATENT CLAIMS CLAIMS 1. An insecticidal composition comprising a substituted pyrazoline active ingredient, wherein the active ingredient is in the range of from 1% to 80% by weight of a substituted pyrazoline derivative of the formula (I). - where X is halogen, C 1-4 alkyl, C 1-4 alkoxy, C 1-4 alkylthio or cyano, Y is halogen or C 1-4 alkoxy, R Represents a C 1-6 -alkyl substituted with cyano-piperidino or C 1-4 -alkyldiamino and at least one of the following carriers and / or additives: a solid carrier or a solvent, preferably cyclohexanone or kaolinite ; a dispersant, preferably lignin sulfonate; a wetting agent, preferably dibutyl naphthalene sulfonate; an emulsifier, preferably calcium dodecylbenzenesulfonate, and an alkylaryl polyoxyethylene. 2. A process for the preparation of a 1,3,4-substituted pyrazoline derivative of the Formula I wherein X is halogen, C 1-4 alkyl, C 1-4 alkoxy, C 1-4 alkylthio. Y is halogen or (C1-C4) -alkoxy, R1 (C1-C6), cyano, piperidino, or alkyldiamino substituted alkyl - characterized in that one of the following general formula (II): a 3,4-substituted pyrazoline wherein Y and R are as defined above, in the presence of an inert organic solvent, preferably an ether, with a substituted phenyl isocyanate of formula III wherein X is as defined above. at room temperature or at the reflux temperature of the solvent. Responsible for publishing: Director of Economic and Legal Publishing Zalai Nyomda 84 613 - Chief Executive Officer: Director József Gállá