GB1591280A - Phenylcarbamoyl-pyrazolines and their use as insecticides - Google Patents

Description

(54) NOVEL PHENYLCARBAMOYL-PYRAZOLINES AND THEIR USE AS INSECTICIDES (71) We, BAYER AKTIENGESELLSCHAFT, a Body Corporate, organised under the laws of Germany, of Leverkusen, Federal Republic of Germany, do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particuçarly described in and by the following statement:- The present invention relates to certain phenylcarbamoyl-pyrazolines, to a process for their preparation and to their use as arthropodicides, especially insecticides.

It is already known that phenylcarbamoyl-monophenyl- and -diphenylpyrazolines, for example 1 - (4 - chlorophenylcarbamoyl) - 3 - (4 - chlorophenylS, I - (4 - chiorophenylcarbamoyl) - (3 - chlorophenyl) - 4 - methyl - and 1 (4 - chiorophenylcarbamoyl) - 3,5 - bis - (4 - chlorophenyl) - 2 - pyrazoline, are distinguished by an insecticidal activity (see, for example, German Offenlegungsschriften (German Published Specifications) 2,304,584 and 2,529,689).

Reference is also made to U.K. Patent No. 1,398,196, which claims compounds of the general formula

where the symbols have the following meanings: A is a phenyl group, a phenyl group substituted by I or 2 substituents selected from a halogen atom, a cyano group, an alkyl group which contains from 1 to 4 carbon atoms and may be substituted by halogen, a cycloalkyl group, an alkoxy group containing from 1 to 4 carbon atoms, an alkylthio group containing from 1 to 4 carbon atoms and an amino group substituted by 1 or 2 alkyl groups which contain from I to 4 carbon atoms and which together with the nitrogen atom of the amino group can form a closed ring which may contain a second hetero atom selected from a sulphur atom, an oxygen atom and a nitrogen atom, or A is a thienyl or pyridyl group which may be substituted by a halogen atom or a lower alkyl group containing from 1 to 4 carbon atoms, B is a hydrogen atom, a phenyl group, a phenyl group substituted by from 1 to 3 substituents selected from a halogen atom, an alkoxy group containing from 1 to 4 carbon atoms, an alkyl group which contains from 1 to 4 carbon atoms and may be substituted by halogen, a cycloalkyl group, an alkylthio group containing from I to 4 carbon atoms, an alkylsulfonyl group containing from 1 to 4 carbon atoms, a dioxyalkylene group containing from 1 to 4 carbon atoms and an amino group substituted by 1 or 2 alkyl groups which each contain from 1 to 4 carbon atoms and which together with the nitrogen atom of the amino group can form a closed ring which may contain a second hetero atom or B is a furyl, pyrryl, thienyl or pyridyl group which may be substituted by a halogen atom or a lower alkyl group containing from 1 to 4 carbon atoms, R, is a halogen atom, an alkoxy group containing from 1 to 4 carbon atoms, an alkyl group which contains from 1 to 4 carbon atoms and may be substituted by halogen, a cycloalkyl group, an alkylthio group containing from 1 to 4 carbon atoms, an alkylsulpfonyl group containing from 1 to 4 carbon atoms, a cyano group, a nitro group or an amino group substituted by 1 or 2 alkyl groups which together with the nitrogen atom of the amino group can form a ring which may contain a second hetero atom, n is 0, 1 or 2, with the understanding that when A represents a phenyl group containing two substituents these substituents do not occupy the 2,6-positions of the phenyl group and that (R1)n must not be a 2,6-di-substitution.

The present invention now provides, as new compounds, the phenylcarbamoyl-pyrazolines of the general formula

in which R represents halogen, and R3 represents halogenoalkyl.

In Formula (I), R preferably represents chlorine or bromine and R3 preferably represents monochlorodifluoromethyl, dichloromonofluoromethyl, monofluoromethyl or difluoromethyl.

The invention also provides a process for the preparation of a pyrazoline of the formula (I), in which a 3 - halogenophenyl - 2 - pyrazoline of the general formula

in which R has the above-mentioned meaning, is reacted with a phenyl isocyanate of the general formula

in which R3 has the above-mentioned meaning, if appropriate in the presence of a solvent or diluent.

Surprisingly, the phenylcarbamoyl-pyrazolines according to the invention exhibit a better insecticidal action than the corresponding phenylcarbamoylmonophenyl- and -diphenyl-pyrazolines disclosed in the above-mentioned prior art, which are of analogous structure and of the same type of action. The products according to the present invention thus represent a genuine enrichment of the art.

The 3 - halogenophenyl - 2 - pyrazolines (II) to be used as starting materials are known or can be prepared in accordance with processes known from the literature (see, for example, German Offenlegungsschrift (German Published Specification) 2,529,689).

The following may be mentioned individually as examples of suitable 3 halogenophenyl - 2 - pyrazolines (II): 3 - (4 - chlorophenyl) - 2 - pyrazoline and 3 - (4 - bromophenyl) - 2 - pyrazoline.

The phenyl isocyanates (Ill) to be used as starting materials are in some cases known; they can be prepared in accordance with processes known from the literature (see, for example, German Offenlegungsschrift (German Published Specification) 2,529,689).

The following may be mentioned individually as examples of suitable phenyl isocyanates (III): 4-monofluoromethyl-phenyl isocyanate, 4-difluoromethyl-phenyl isocyanate, 4-monochlorodifluoromethylphenyl isocyanate and 4dichloromonofluoromethyl-phenyl isocyanate.

The process for the preparation of the compounds according to the invention is preferably carried out in the presence of a suitable solvent or diluent. Virtually all inert organic solvents can be used for this purpose, especially aliphatic and aromatic, optionally chlorinated, hydrocarbons, such as benzene, toluene, xylene, benzine, methylene chloride, chloroform, carbon tetrachloride and chlorobenzene; ethers, for example diethyl ether, dibutyl ether and dioxan; ketones, for example acetone, methyl ethyl ketone, methyl isopropyl ketone and methyl isobutyl ketone; and nitriles, such as acetonitrile and propionitrile.

The reaction temperature can be varied within a substantial range. In general, the reaction is carried out at a temperature of from 20 to 1200C, preferably at from 50 to 900 C.

In general, the reaction is allowed to take place under normal pressure.

To carry out the process, the starting materials are preferably employed in stoichiometric amounts. An excess of one or other component produces no significant advantages. The reaction is preferably carried out in one of the stated solvents or diluents, at an elevated temperature. After completion of the reaction, the mixture is cooled, whereupon the compounds crystallise out.

The new compounds (I) are obtained in the crystalline form, and are characterised by their melting point.

As already mentioned, the carbamoyl-pyrazolines according to the invention are distinguished by an excellent insecticidal activity. They are active against insects which damage plants and, in the veterinary medicine field, against ectoparasites, such as parasitic fly larvae.

The active compounds are well tolerated by plants, have a favourable level of toxicity to warm-blooded animals, and can be used for combating arthropod pests, especially insects which are encountered in agriculture, in forestry, in the protection of stored products and of materials, and in the hygiene field. They are active against normally sensitive and resistant species and against all or some stages of development. The abovementioned pests include: from the class of the Isopoda, for example Oniscus asellus, Armadillidium vulgare and Porcellio scaber; from the class of the Diplopoda, for example Blaniulus guttulatus; from the class of the Chilopoda, for example Geophilus carpophagus and Scutigera spec.; from the class of the Symphyla, for example Scutigerella immaculata; from the order of the Thysanurn, for example Lepisma saccharina; from the order of the Collembola, for example Onychiurus armatus; from the order of the Orthoptera, for example Blatta orientalis, Periplaneta americana, Leucophaea maderae, Blattella germanica, Acheta domesticus, Gryllotalpa spp., Locusta mizratoria migratorioides, Melanoplus differentialis and Schistocerca xregaria; from the order of the Dermaptera, for example Forficula auricularia; from the order of the Isoptera, for example Reticulitermes spp.; from the border of the Anoplura, for example Phylloxera vastatrix, Pemphigus spp., Pediculus humanus corporis, Haematopinus spp. and Linognathus spp.; from the order of the Mallophaga, for example Trichodectes spp. and Damalinea spp.; from the order of the Thysanoptera, for example Hercinothrips femoralis and Thrips tabaci; from the order of the Heteroptera, for example Eurygaster spp., Dysdercus in term edius, Piesma quadrata, Cimex lectularius, Rhodnius prolixus and Triatoma spp.; from the order of the Homoptera, for example Aleurodes brassicae, Bemisia tabaci, Trialeurodes vaporariorum, Aphis gossypii, Brevicoryne brassicae, Cryptomyzus rib is, Doralis fabae, Doralis pomi, Eriosoma lanigerum, Hyalopterus arundinis, Macrosiphum avenae, Myzus spp., Phorodon humili, Rhopalosiphum padi, Empoasca spp., Euscelis bilobatus, Nephotettix cincticeps, Lecanium corni, Saissetia oleae, Laodelphax striatellus, Nilaparvata lugens, Aonidiella aurantii, Aspidiotus hederae, Pseudococcus spp. and Psylla spp.; from the order of the Lepidoptera, for example Pectinophora gossypiella, Bupalus piniarius, Cheimatobia brumata, Lithocolletis blancardella, Hyponomeuta padella, Plutella maculipennis, Malacosoma neustria, Euproctis chrysorrhoea, Lymantria spp., Bucculatrix thurberiella, Phyllocnistis citrella, Agrotis spp., Euxoa spp., Feltia spp., Earias insulana, Heliothis spp., Laphygma exigua, Mamestra brassicae, Panolis flammea, Prodenia litura, Spodoptera spp., Trichoplusia ni, Carpocapsa pomonella, Pieris spp., Chilo spp., Pyrausta nubilalis, Ephestia kuehniella, Galleria mellonella, Cacoecia podana, Capua reticulana, Choristoneura fumiferana, Clysia ambiguella, Homona maRnanima and Tortrix viridana; from the order of the Coleoptera, for example Anobium punctatum, Rhizopertha dominica, Bruchidius obtectus, A canthoscelides obtectus, Hylotrupes bajulus, Agela*tica alni, Leptinotarsa decemlineata, Phaedon cochleariae, Diahrotica spp., Psylliodes chrysocephala, Epilachna varivestis, Atomaria spp., Oryzaephilus surinamensis, Anthonomus spp., Sitophilus spp., Otiorrhynchus sulcatus, Cosmopolites sordidus, Ceuthorrhynchus assimilis, Hypera postica, Dermestes spp., Trogoderma spp., Anthrenus spp., Attagenus spp., Lyctus spp., Meligethes aeneus, Ptinus spp., Niptus hololeucus, Gibbium psylloides, Tribolium spp., Tenebrio molitor, Agriotes spp., Conoderus spp., Melolontha melolontha, Amphimallon solstitialis and Costelytra zealandica; from the order of the Hymenoptera, for example Diprion spp., Hoplocampa spp., Lasius spp., Monomorium pharaonis and Vespa spp.; from the order of the Diptera, for example Aedes spp., Anopheles spp., Culex spp., Drosophila melanogaster, Musca spp., Fannia spp., Calliphora erythrocephala, Lucilia spp., Chrysomyia spp., Cuterebra spp., Gastrophilus spp., Hyppobosca spp., Stomoxys spp., Oestrus spp., Hypoderma spp., Tabanus spp., Tannia spp., Bihio hortulanus. Oscinella frit, Phorbia spp., Pegomyia-hyosc-vami, Ceratitis capitata, Dacus oleae and Tipula paludosa; from the order of the Siphonaptera, for example Xenopsylla cheopis and Ceratophyllus spp.

The active compounds can be converted to the cusiomary formulations, such as solutions, emulsions, wettable powders, suspensions, powders, dusting agents, foams, pastes, soluble powders, granules, aerosols, suspension-emulsion concentrates, seed-treatment powders, natural and synthetic materials impregnated with active compound, very fine capsules in polymeric substances and in coating compositions for use on seed, and formulations used with burning equipment, such as fumigating cartridges, fumigating cans and fumigating coils, as well as ULV (ultra-low-volume) cold mist and warm mist formulations.

These formulations may be produced in known manner, for example by mixing the active compounds with extenders, that is to say, liquid or solid or liquefied gaseous diluents or carriers, optionally with the use of surface-active agents, that is to say, emulsifying agents and/or dispersing agents, and/or foaming 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, especially solvents, there are suitable in the main, aromatic hydrocarbons, such as xylene, toluene, benzene or alkyl naphthalenes, chlorinated aromatic or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic or alicyclic hydrocarbons, such as cyclohexane or paraffins, for example mineral oil fractions, alcohols, such as butanol or glycol as well as their ethers and esters, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, or strongly polar solvents, such as dimethylformamide and dimethylsulphoxide, as well as water.

By liquefied gaseous diluents or carriers are meant liquids which would be gaseous at normal temperature and under normal pressure, for example aerosol propellants, such as dichlorodifluoromethane or trichlorofluoromethane.

As solid carriers there are preferably used ground natural minerals, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and ground synthetic minerals, such as highly dispersed silicic acid, alumina and silicates.

Preferred examples of emulsifying and foam-forming agents include nonionic and anionic emulsifiers, such as polyoxyethylene-fatty acid esters, polyoxyethylene-fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkyl sulphonates, alkyl sulphates and aryl sulphonates as well as albumin, hydrolysis products; and preferred examples of dispersing agents include lignin sulphide waste liquors and methylcellulose.

Adhesives such as carboxymethylcellulose and natural and synthetic polymers in the form of powders, granules or latices, such as gum arabic, polyvinyl alcohol and polyvinyl acetate, can be used in the formulations.

It is possible to use colorants such as inorganic pigments, for example iron oxide, titanium oxide and Prussian Blue, and organic dyestuffs, such as alizarin dyestuffs, azo dyestuffs or metal phthalocyanine dyestuffs, and trace nutrients, such as salts, of iron, manganese, boron, copper, cobalt, molybdenum and zinc.

The formulations in general contain from 0.1 to 95 per cent by weight of active compound, preferably from 0.5 to 90 per cent by weight.

The active compounds according to the invention may be used in the form of their formulations of the types that are commercially available or in the use forms prepared from these formulations.

The active compound content of the use forms prepared from the formulations of the types that are commercially available can vary within wide ranges. The active compound concentration of the use forms can be from 0.0000001 to 100% by weight of active compound, preferably from 0.01 to 10% by weight.

The compounds may be employed in a customary manner appropriate for the particular use forms.

In the veterinary field, the active compounds according to the invention may be used in a known manner, such as orally in the form of, for example, tablets, capsules, drenches and granules; dermally by means of, for example, dipping, spraying, pouring-on, spotting-on and powdering; and parenterally, for example by means of injections.

The present invention also provides an arthropodicidal composition containing as active ingredient a compound of the present invention in admixture with a solid or liquefied gaseous diluent or carrier or in admixture with a liquid diluent or carrier containing a surface-active agent.

The present invention also provides a method of combating arthropods (especially insects) which comprises applying to the arthropods, or to a habitat thereof, 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 also provides a method of freeing or protecting domesticated animals from ectoparasitical insects which comprises applying to said animals a compound according to the present invention, in admixture with a diluent or carrier.

The present invention further provides crops protected from damage by arthropods 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 present invention further provides domesticated animals whenever freed or protected from ectoparasitical insects by the application to said animals of a compound according to the present invention, in admixture with a diluent or carrier.

The insecticidal activity of the compounds of this invention is illustrated by the following biotest Example.

In this Example, the compound according to the present invention is identified by the number (given in brackets) of the corresponding preparative Example, which will be found later in this specification.

The known comparison compounds are identified as follows:

Example A Phaedon Larvae Test Solvent: 3 parts by weight of dimethylformamide.

Emulsifier: I part by weight of alkylaryl polyglycol ether.

To produce a suitable preparation of active compound, I part by weight of the active compound was mixed with the stated amount of solvent containing the stated amount of emulsifier and the concentrate was diluted with water to the desired concentration.

Cabbage leaves (Brassica oleracea) were sprayed with the preparation of the active compound until dripping wet and were then infested with mustard beetle larvae (Phaedon cochleariae).

After the specified periods of time, the degree of destruction was determined in %: 100% meant that all of the beetle larvae had been killed whereas 0% meant that none of the beetle larvae had been killed.

The active compounds, the concentrations of the active compounds, the evaluation times and the results can be seen from the following table: TABLE A (Insects Which Damage Plants) Phaedon Larvae Test Active compound Degree of de Active concentration struction in compounds in % after 4 days (A) 0.01 100 0.001 50 0.0001 0 (B) 0.01 100 0.001 20 0.0001 0 (C) 0.01 100 0.001 0 (1) 0.01 100 0.001 85 0.0001 50 The process of the present invention is illustrated by the following preparative Example.

Example 1

0.05 mol of 4-difluoromethyl-phenyl isocyanate in 20 ml of toluene were added, at 600 C, to a solution of 0.05 mol of 3 - (4 - chlorophenyl) - 2 - pyrazoline in 60 ml of toluene. The batch was stirred for 2 hours at 800C. After the reaction solution had cooled, the desired compound crystallised out, and after filtering it off, 1 - [(4 - difluoromethyl - phenyl) - carbamoyl] - 3 - (4 - chlorophenyl) - 2 pyrazoline having a melting point of 1700C was obtained.

WHAT WE CLAIM IS:- 1. Phenylcarbamoyl-pyrazolines of the general formula

in which R represents halogen, and R3 represents halogenoalkyl.

2. Compounds according to Claim 1, in which R represents chlorine or bromine and R3 represents monochlorodifluoromethyl, dichloromonofluoromethyl, monofluoromethyl or difluoromethyl.

3. The compound according to Claim 1 that is disclosed in Example 1.

**WARNING** end of DESC field may overlap start of CLMS **.

Claims (20)

**WARNING** start of CLMS field may overlap end of DESC **. Example A Phaedon Larvae Test Solvent: 3 parts by weight of dimethylformamide. Emulsifier: I part by weight of alkylaryl polyglycol ether. To produce a suitable preparation of active compound, I part by weight of the active compound was mixed with the stated amount of solvent containing the stated amount of emulsifier and the concentrate was diluted with water to the desired concentration. Cabbage leaves (Brassica oleracea) were sprayed with the preparation of the active compound until dripping wet and were then infested with mustard beetle larvae (Phaedon cochleariae). After the specified periods of time, the degree of destruction was determined in %: 100% meant that all of the beetle larvae had been killed whereas 0% meant that none of the beetle larvae had been killed. The active compounds, the concentrations of the active compounds, the evaluation times and the results can be seen from the following table: TABLE A (Insects Which Damage Plants) Phaedon Larvae Test Active compound Degree of de Active concentration struction in compounds in % after 4 days (A) 0.01 100 0.001 50 0.0001 0 (B) 0.01 100 0.001 20 0.0001 0 (C) 0.01 100 0.001 0 (1) 0.01 100 0.001 85 0.0001 50 The process of the present invention is illustrated by the following preparative Example. Example 1 0.05 mol of 4-difluoromethyl-phenyl isocyanate in 20 ml of toluene were added, at 600 C, to a solution of 0.05 mol of 3 - (4 - chlorophenyl) - 2 - pyrazoline in 60 ml of toluene. The batch was stirred for 2 hours at 800C. After the reaction solution had cooled, the desired compound crystallised out, and after filtering it off, 1 - [(4 - difluoromethyl - phenyl) - carbamoyl] - 3 - (4 - chlorophenyl) - 2 pyrazoline having a melting point of 1700C was obtained. WHAT WE CLAIM IS:-

1. Phenylcarbamoyl-pyrazolines of the general formula

in which R represents halogen, and R3 represents halogenoalkyl.

2. Compounds according to Claim 1, in which R represents chlorine or bromine and R3 represents monochlorodifluoromethyl, dichloromonofluoromethyl, monofluoromethyl or difluoromethyl.

3. The compound according to Claim 1 that is disclosed in Example 1.

4. A process for the preparation of a phenylcarbamoyl-pyrazoline according to Claim 1, in which a 3 - halogenophenyl - 2 - pyrazoline of the general formula

in which R has the meaning stated in Claim 1, is reacted with a phenyl isocyanate of the general formula

in which R3 has the meaning stated in Claim 1, if appropriate in the presence of a solvent or diluent.

5. A process according to Claim 4, in which the reaction is effected in an inert organic solvent.

6. A process according to Claim 4 or 5, in which the reaction is effected at from 20 to 1200C.

7. A process according to Claim 6, in which the reaction is effected at from 50 to 900C.

8. A process according to any of Claims 4 to 7, in which the reactants are employed in stoichiometric amounts.

9. A process according to any of Claims 4 to 8, in which the reactants are each as hereinbefore specifically mentioned.

10. A process for the preparation of a compound according to Claim 1, substantially as described in Example 1.

11. Compounds according to Claim 1 whenever prepared by a process according to any of Claims 4 to 10.

12. An arthropodicidal composition containing as active ingredient a compound according to any of Claims 1 to 3 and 11 in admixture with a solid or liquefied gaseous diluent or carrier or in admixture with a liquid diluent or carrier containing a surface-active agent.

13. A composition according to Claim 12 containing from 0.1 to 95 /a of the active compound, by weight.

14. A method of combating arthropods which comprises applying to the arthropods, or to a habitat thereof, a compound according to any of Claims 1 to 3 and 11 alone or in the form of a composition containing as active ingredient a compound according to any of Claims 1 to 3 and 11, in admixture with a diluent or carrier.

15. A method of freeing or protecting domesticated animals from ectoparasitical insects, which comprises applying to the said animals a compound according to any of Claims 1 to 3 and 11, in admixture with a diluent or carrier.

16. A method according to Claim 14 in which a composition is used containing from 0.0000001 to 100% of the active compound, by weight.

17. A method according to Claim 16 in which a composition is used containing from 9.01 to 10% of the active compound, by weight.

18. A method according to Claim 14, 16 or 17, in which the arthropods are insects.

19. Crops protected from damage by arthropods by being grown in areas in which immediately prior to and/or during the time of the growing a compound according to any of Claims 1 to 3 and 11 was applied alone or in admixture with a diluent or carrier.

20. Domesticated animals whenever freed or protected from ectoparasitical insects by the application to said animals of a compound according to any of Claims I to 3 and 11, in admixture with a diluent or carrier.