HK1024480B - 3-thiocarbamoylpyrazole-derivatives as pesticides - Google Patents

Description

3-thiocarbamoylpyrazole derivatives as pesticides

The present invention relates to novel 3-thiocarbamoylpyrazole derivatives, to their various processes of preparation and to their use as pesticides.

Some substituted 1-arylpyrazoles which have been disclosed so far, such as 5-amino-1- [2, 6-dichloro-4- (trifluoromethyl) phenyl ] -3-cyano-4- [ (trifluoromethyl) sulfinyl ] -1H-pyrazole, exhibit good insecticidal activity (cf. for example EP-A-295117 and EP-A-352944).

Many other substituted 1-arylpyrazoles are disclosed which are also useful for controlling pests (cf. for example EP-A-201852, EP-A-418016, or EP-A-0659745).

However, the amounts and duration of the compounds of the prior art are not very satisfactory in all fields of application, especially for the control of specific insects or at low concentrations.

It has now been found that novel 3-thiocarbamoylpyrazole derivatives of the general formula (I)Wherein R is¹Represents H₂N-CS-，

R²Represents haloalkyl, haloalkenyl or haloalkynyl,

R³represents a hydrogen atom, an amino group or one of the following groups:or-NHR⁷

Wherein R is⁴Represents alkyl, haloalkyl, alkoxyalkyl or in each case optionally substituted phenyl or pyridyl,

R⁵represents a hydrogen atom or an alkyl group,

R⁶represents a hydrogen atom, an alkyl group, or a phenyl group or a pyridyl group each optionally substituted, and

R⁷represents alkyl, alkenyl, alkynyl, formyl, alkylcarbonyl, haloalkylcarbonyl, or alkoxycarbonyl;

ar represents phenyl or pyridyl, each of which is optionally substituted, and

n represents 0, 1 or 2.

It has additionally been found that novel 3-thiocarbamoylpyrazole derivatives having the general formula (I) can be obtained by the following process;

a) if appropriate in the presence of reaction auxiliaries and if appropriate in the presence of diluents, to give compounds of the formula (II)) The 3-cyanopyrazole derivative of (a) is reacted with hydrogen sulfide,

wherein, Ar, R²，R³As defined above;

or

b) Reacting a 3-thiocarbamoylpyrazole derivative having the general formula (III) with a thio halide having the general formula (IV), if appropriate in the presence of a diluent and if appropriate in the presence of a reaction auxiliary;

wherein Ar is as defined above

R^3-1Represents one of the following groups:or-NHR⁷

Wherein

R⁴，R⁵，R⁶And R⁷As defined above

Hal-S-R² (IV)

Wherein R is²As defined above, and

hal represents a halogen atom, especially chlorine or bromine;

or

c) The 2-thiocarbamoylpyrazole derivative having the general formula (Ia) obtained by process (a) or (b) is oxidized with an oxidizing agent, if appropriate in the presence of a diluent and if appropriate in the presence of a catalyst.

Wherein, Ar, R²，R³As aboveThe above definitions.

Finally, it has been found that novel 3-thiocarbamoylpyrazole derivatives of the general formula (I) have a remarkable biological activity and are particularly suitable for controlling animal pests, in particular insects, arachnids and nematodes, which occur in agriculture, in forestry, in the protection of stored products and materials and in the hygiene sector.

General formula (I) provides a general definition of the compounds of the present invention.

Preferred substituent groups or groups in the formulae given herein above and below are described below.

R¹Represents H₂N-CS-。

R²Preferably represents (C) having 1 to 12 halogen atoms₁-C₆) Haloalkyl, (C) having 1 to 8 halogen atoms₂-C₆) Haloalkenyl or (C) having 1 to 6 halogen atoms₂-C₆) -haloalkynyl.

R³Preferably represents a hydrogen atom, an amino group, or one of the following groups-:or-NHR⁷

Wherein R is⁴Is represented by (C)₁-C₆) Alkyl, (C) having 1 to 3 halogen atoms₁-C₆) -haloalkyl, (C)₁-C₆) -alkoxy- (C)₁-C₆) -alkyl, or represents phenyl or pyridyl optionally mono-to trisubstituted by identical or different substituents from the group consisting of: cyano, nitro, halogen atoms, C₁-C₆Alkyl radical, C₁-C₆-alkoxy, C₁-C₆Alkylthio radical, C₁-C₄-haloalkyl group, C₁-C₄Haloalkoxy, or C each having 1 to 5 halogen atoms₁-C₁-a haloalkylthio group,

R⁵represents a hydrogen atom or (C)₁-C₆) -alkanesThe base group is a group of a compound,

R⁶represents a hydrogen atom, (C)₁-C₆) -alkyl, phenyl optionally mono-to trisubstituted by identical or different substituents from the group consisting of: cyano, nitro, halogen atoms, C₁-C₆Alkyl radical, C₁-C₆-alkoxy, C₁-C₆Alkylthio radical, C₁-C₄-haloalkyl group, C₁-C₄Haloalkoxy, or C each having 1 to 5 halogen atoms₁-C₄-haloalkylthio, or hydroxy, or represents pyridyl substituted by the following substituents: cyano, nitro, halogen atoms, C₁-C₅Alkyl radical, C₁-C₆-alkoxy, C₁-C₆Alkylthio radical, C₁-C₄-haloalkyl group, C₁-C₄Haloalkoxy, or C each having 1 to 5 halogen atoms₁-C₄-haloalkylthio, and

R⁷is represented by (C)₁-C₆) Alkyl radicals, (C)₂-C₆) -alkenyl, (C)₂-C₆) -alkinyl, formyl, (C)₁-C₆) -alkylcarbonyl, (C) having 1 to 6 halogen atoms₁-C₆) A haloalkylcarbonyl group, or (C)₁-C₆) -an alkoxycarbonyl group.

Ar preferably represents phenyl or pyridyl optionally mono-to trisubstituted by identical or different substituents from the group consisting of: halo (C)₁-C₆) Alkyl, halo (C)₁-C₆) Alkylthio, halo (C)₁-C₆) -alkoxy, (C)₁-C₆) -alkoxy, methoxy, hydrazino, (C)₁-C₆) -dialkylhydrazino, amino, (C)₁-C₆) Alkylamino, di (C)₁-C₆) -alkylamino, (C)₁-C₆) -alkylimino, cyano, (C)₁-C₆) Alkylthio radicals or radicals

Wherein R is⁸And R⁹May be the same or different and represents a hydrogen atom or (C)₁-C₆) -an alkyl group.

n preferably represents 0, 1, or 2.

R¹Represents H₂N-CS-。

R²Particularly preferably represents (C) having 1 to 9 identical or different fluorine, chlorine, bromine halogen atoms₁-C₄) Haloalkyl, (C) having 1 to 5 identical or different fluorine, chlorine, bromine halogen atoms₂-C₄) Haloalkenyl, (C) having 1 to 5 identical or different fluorine, chlorine, bromine halogen atoms₂-C₄) -haloalkynyl.

R³Particularly preferably represents a hydrogen atom, an amino group, or one of the following groups:or-NHR⁷

Wherein R is⁴Is represented by (C)₁-C₄) Alkyl, (C) having 1 to 3 halogen atoms₁-C₄) -haloalkyl, (C)₁-C₄) -alkoxy- (C)₁-C₂) -alkyl, or phenyl optionally mono-to trisubstituted by identical or different substituents from the group consisting of: cyano, nitro, halogen atoms, C₁-C₄Alkyl radical, C₁-C₄-alkoxy, C₁-C₂-haloalkyl group, C₁-C₂Haloalkoxy, or C each having 1 to 3 halogen atoms₁-C₂-a haloalkylthio group,

R⁵represents a hydrogen atom or (C)₁-C₄) -an alkyl group,

R⁶represents a hydrogen atom, (C)₁-C₄) -alkyl, or phenyl optionally mono-or disubstituted by the same or different substituents as follows: hydroxy, cyano, nitro, halogen atom, C₁-C₄-alkanesBase, C₁-C₄-alkoxy, C₁-C₂-haloalkyl group, C₁-C₂Haloalkoxy, or C each having 1 to 3 halogen atoms₁-C₂Haloalkylthio, especially 4-hydroxy-3-methoxy-phenyl, and

R⁷is represented by (C)₁-C₄) Alkyl radicals, (C)₂-C₄) -alkenyl, (C)₂-C₄) -alkinyl, formyl, (C)₁-C₄) -alkylcarbonyl, (C) having 1 to 5 identical or different fluorine, chlorine, bromine halogen atoms₁-C₄) A haloalkylcarbonyl group, or (C)₁-C₄) -an alkoxycarbonyl group.

Ar particularly preferably represents phenyl or pyridyl which are optionally mono-to trisubstituted by identical or different substituents from the group consisting of: oxygen, chlorine, trifluoromethyl, trifluoromethylthio, trifluoromethoxy, methoxy, hydrazino, dimethylhydrazino, amino, methylamino, dimethylamino, iminomethyl, cyano, methylthio, or a group

Wherein R is⁸And R⁹May be the same or different and represents a hydrogen atom or (C)₁-C₄) -an alkyl group.

n particularly preferably represents 0, 1 or 2.

R¹Represents H₂N-CS-。

R²Most preferred is one of the following groups:

-CF₃，-CHF₂，

-CF₂-CH₃-CF₃-CHF₂，-CF₂-CHFCl，

-CH₂-CF₃，-CH₂-CF₂Cl，

-CH₂-CF₂-CHF₂，

-CF₂-CFCl-CF₃，

-C(Cl)(CF₃)-CF₂Cl，-C(Cl)(CF₃)-CHCl-CF₃，

-C(CF₃)＝CCl₂。

R³most preferably represents a hydrogen atom, an amino group, or one of the following groups:

-NH-CO-CH₃，-NH-CO-C₂H₅，

-N＝CH-NH₂，-N＝C(CH₃)-NH₂，

-N＝CH-N(CH₃)₂，-N＝C(CH₃)-N(CH₃)₂，

-N-HC₂H₅or-NH-CH₂-CH＝CH₂

Ar most preferably represents:

(1) phenyl which is disubstituted or trisubstituted by identical or different substituents, wherein on the phenyl ring fluorine or chlorine is in the 2-position, trifluoromethyl is in the 4-position, fluorine, chlorine, cyano, methoxy, methylthio, trifluoromethyl, trifluoromethoxy, trifluoromethylthio or hydrazino is in the 6-position; or

(2) 2-pyridyl substituted at the 4-position by trifluoromethyl and at the 6-position by fluorine or chlorine.

Most preferably, n represents one of the integers 0, 1, or 2.

The definitions or explanations of the radicals above or in the preferred ranges apply to the end products and analogously to the starting materials and intermediates. These definitions of radicals can be combined with one another as desired, that is to say combinations between the individual preferred ranges are also possible.

Preferred compounds of the general formula (I) according to the invention are those compounds which combine the abovementioned preferred embodiments (preferred meanings).

Particularly preferred compounds of the general formula (I) according to the invention are those which combine the abovementioned particularly preferred embodiments.

The most preferred compounds of the invention having the general formula (I) are those compounds which combine the above-mentioned most preferred embodiments.

In the definitions of the radicals mentioned above and given below, the hydrocarbon radicals, such as alkyl or alkenyl, and the compounds containing heteroatoms, such as alkoxy or alkylthio, are each, where possible, straight-chain or branched.

Preferred compounds are compounds having the general formula (IA):wherein, Ar and R²N is as defined above.

Examples of novel 3-thiocarbamoylpyrazole derivatives are shown in tables 1 to 60:TABLE 1

The compounds in table 1 correspond to general formula (IB) wherein:

ar is

R³Is NH₂

n is 0

R²Are listed in the following table:

R²

-CF₃

-CF₂-CH₃

-CF₃-CHF₂

-CF₂-CHFCl

-CH₂-CF₃

-CH₂-CF₂Cl

-CH₂-CF₂-CHF₂

-CF₂-CFCl-CF₃

-C(Cl)(CF₃)-CF₂Cl

-C(Cl)(CF₃)-CHCl-CF₃

-C(CF₃)＝CCl₂ TABLE 2

Table 2 contains compounds having the general formula (IB) wherein:

ar is

R²、R³And n is as listed in Table 1.TABLE 3

Table 3 contains compounds having the general formula (IB) wherein:

ar is

R²、R³And n is as listed in Table 1.TABLE 4

Table 4 comprises compounds having the general formula (IB) wherein:

ar is

R²、R³And n is as listed in Table 1.Tables 5 to 8

Tables 5-8 contain compounds having the general formula (IB) wherein:

R³is H

Ar、R²And n is as listed in tables 1-4.Tables 9 to 12

Tables 9-12 contain compounds having the general formula (IB) wherein:

R³is composed of

Ar、R²And n is as listed in tables 1-4.Tables 13 to 16

Tables 13-16 contain compounds having the general formula (IB) wherein:

R³is composed of

Ar、R²And n is as listed in tables 1-4.Tables 17 to 20

Tables 17-20 contain compounds having the general formula (IB) wherein:

R³is composed of

Ar、R²And n is as listed in tables 1-4.Tables 21 to 40

Tables 21-40 contain compounds having the general formula (IB) wherein:

n is 1

Ar、R²And R³As listed in tables 1-20.Tables 41-60

Tables 41-60 contain compounds having the general formula (IB) wherein:

n is 2

Ar、R²And R³As listed in tables 1-20.

For example, if 5-amino-3-cyano-4- (1, 1-difluoroethylthio) -1- (2, 6-dichloro-4-trifluoromethylphenyl) pyrazole and hydrogen sulfide are used as starting materials, the reaction sequence of the preparation process (a) in the present invention can be represented by the following formula:

for example, if 1- (2, 6-dichloro-4-trifluoromethylphenyl) -3-thiocarbamoyl-5- (pyrrol-1-yl) pyrazole and 1, 1-difluoroethylsulfinyl chloride are used as starting materials, the course of the reaction for preparation of process (b) according to the invention can be represented by the following formula:

for example, if 5- (pyrrol-1-yl) -3-thiocarbamoyl-4- (1, 1-difluoroethylthio) -1- (2, 6-dichloro-4-trifluoromethylphenyl) pyrazole and hydrogen sulfide are used as starting materials, the reaction sequence of preparation process (c) in the present invention can be represented by the following formula:

the starting materials for the preparation process (ｃA) according to the invention, i.e.the 3-cyanopyrazole derivatives having the general formulｃA (II), have been disclosed (e.g.EP-A-0295117 and EP-A-0659745) and/or can be prepared analogously using known methods.

The starting materials for the preparation process (b) according to the invention, i.e. the 3-thiocarbamoylpyrazole derivatives having the general formula (III), are novel compounds and are also an object of the present invention.

Preparation of the compounds of the general formula (III) according to the invention by the preparation process (a) in the presence, if appropriate, of reaction auxiliaries and, if appropriate, in the presence of diluentsReacting the 2-cyanopyrazole of formula (V) with hydrogen sulfide.

Wherein: ar and R^3-1As defined above.

The 2-cyanopyrazoles of the formulｃA (V) are known and/or can be prepared by known methods, for example by transamination of the corresponding 5-amino-3-cyanopyrazoles of the formulｃA (VI) by customary methods (cf. for example EP-A-0659745).

Wherein: ar is as defined above.

On the other hand, the compounds of the formulｃA (III) can be obtained by converting the amino group on 5-amino-3-thiocarbamoylpyrazole of the formulｃA (VII) by conventional methods (cf., for example, EP-A-0659745).

Wherein: ar is as defined above.

5-amino-3-thiocarbamoylpyrazoles of the general formula (VII) are novel compounds and are also an object of the present invention.

Preparation of the compounds of the general formula (VII), according to the preparation process (a) according to the invention, 5-amino-3-cyanopyrazoles of the general formula (VI) are reacted with hydrogen sulfide, if appropriate in the presence of a diluent (see also the preparation examples).

Another starting material for preparation process (b) according to the invention: the thio halides of the general formula (IV) are compounds known in the art of organic chemistry.

The raw materials for the preparation process (c) of the present invention: 3-Thiocarbamoylpyrazole derivatives of general formula (Ia) are compounds of the invention of the present application.

The preparation process (a) of the present invention is preferably carried out using a diluent. Suitable diluents are virtually any of a variety of inert organic solvents, preferably including: optionally halogenated aliphatic and aromatic hydrocarbons such as pentane, hexane, heptane, cyclohexane, petroleum ether, gasoline, petroleum benzine, benzene, toluene, xylene, methylene chloride, dichloroethane, chloroform, carbon tetrachloride, chlorobenzene and o-dichlorobenzene; ethers such as diethyl ether and dibutyl ether, ethylene glycol dimethyl ether and diethylene glycol dimethyl ether, tetrahydrofuran and dioxane; ketones such as acetone, methyl ethyl ketone, methyl isopropyl ketone, and methyl isobutyl ketone; esters such as methyl acetate and ethyl acetate; nitriles such as acetonitrile and propionitrile; amides such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone, as well as dimethyl sulfoxide, sulfolane and hexamethylene phosphoric triamide.

Reaction auxiliaries which can be used in the preparation process (a) are the various bases conventionally used in reactions of this type. Preferred reaction auxiliaries are the following: basic nitrides such as trimethylamine, triethylamine, tripropylamine, tributylamine, diisobutylamine, dicyclohexylamine, ethyldiisopropylamine, ethyldicyclohexylamine, N-dimethylbenzylamine, N-dimethylaniline, pyridine, 2-methyl, 3-methyl, 4-methyl, 2, 4-dimethyl, 2, 6-methyl, 2-ethyl, 4-ethyl and 5-ethyl-2-methylpyridine, 1, 5-diazabicyclo [4, 3, 0] -non-5-ene (DBN), 1, 8-diazabicyclo [5, 4, 0] -undec-7-ene (DBU) or 1, 4-diazabicyclo [2, 2, 2] -octane (DABCO). It is also possible to use an excess of the reaction auxiliary as a diluent.

In the preparation process (a) according to the invention, the reaction temperature can be varied within a relatively wide range. The reaction is generally carried out at a temperature of from 0 ℃ to 100 ℃, preferably from 10 ℃ to 80 ℃.

The preparation process (a) of the present invention is usually carried out under atmospheric pressure, however, it may be carried out under elevated pressure or reduced pressure.

For carrying out the preparation process (a) according to the invention, an excess of hydrogen sulfide is generally used. Typically, the reaction is carried out in the presence of a basic nitride in a suitable diluent. The treatment is carried out by conventional methods (cf. preparation examples).

Suitable diluents for the preparation process (b) according to the invention are inert organic solvents, preferably comprising: optionally halogenated aliphatic and aromatic hydrocarbons such as gasoline, benzene, toluene, xylene, chlorobenzene, petroleum ether, hexane, cyclohexane, dichloromethane, chloroform, carbon tetrachloride; ethers such as diethyl ether, dioxane, tetrahydrofuran, ethylene glycol dimethyl ether and ethylene glycol diethyl ether; ketones such as acetone and butanone; nitriles such as acetonitrile and propionitrile; amides such as dimethylformamide, dimethylacetamide, N-methylformanilide, N-methylpyrrolidone or hexamethylenephosphoric triamide; esters such as ethyl acetate; sulfoxides such as dimethyl sulfoxide; or acids such as acetic acid.

If appropriate, the preparation process (b) according to the invention can be carried out in the presence of reaction auxiliaries. Suitable reaction auxiliaries are various conventional inorganic or organic bases, including, for example: alkali metal hydroxides such as sodium hydroxide or potassium hydroxide; alkali metal carbonates or bicarbonates such as sodium carbonate, potassium carbonate or potassium bicarbonate; tertiary amines such as triethylamine, N-dimethylaniline, pyridine, N-dimethylaminopyridine, Diazabicyclooctane (DABCO), Diazabicyclononene (DBN) or Diazabicycloundecene (DBU).

In the preparation process (b) according to the invention, the reaction temperature can be varied within a relatively wide range. The reaction is generally carried out at a temperature of from-20 ℃ to 120 ℃, preferably from 0 ℃ to +50 ℃.

For carrying out the process (b) according to the invention, the thiohalide of the formula (IV) is generally added in an amount of from 1.0 to 2.5 mol, preferably from 1.0 to 1.5 mol, and also from 1.0 to 2.5 mol, preferably from 1.0 to 1.5 mol, of reaction auxiliary per mole of 1-arylpyrazole substituted in the 4-position of the formula (III). The reaction and the treatment of the reaction product are carried out according to conventional methods.

Suitable oxidizing agents for carrying out the process (c) according to the invention are the customary oxidizing agents which oxidize sulfur, particularly suitably hydrogen peroxide; organic peracids such as peracetic acid, m-chloroperbenzoic acid, p-nitroperbenzoic acid or atmospheric oxygen.

Suitable diluents in carrying out the process (c) according to the invention are also inert organic solvents. Preferably used are: hydrocarbons such as gasoline, benzene, toluene, hexane or petroleum ether; chlorinated hydrocarbons such as dichloromethane, 1, 2-dichloroethane, chloroform, carbon tetrachloride or chlorobenzene; ethers such as diethyl ether, dioxane or tetrahydrofuran; carboxylic acids such as acetic acid or propionic acid; or a dipolar aprotic solvent such as acetonitrile, acetone, ethyl acetate or dimethylformamide.

If appropriate, the process (c) according to the invention can be carried out in the presence of an acid binder. Suitable acid binders are various conventionally used organic or inorganic acid binders, preferably: alkaline earth metal hydroxides, alkaline earth metal acetates, alkaline earth metal carbonates, alkali metal hydroxides, alkali metal acetates or alkali metal carbonates, such as calcium hydroxide, sodium acetate or sodium carbonate.

If appropriate, the preparation process (c) according to the invention can be carried out in the presence of suitable catalysts. Suitable catalysts are the various catalysts conventionally used for such sulfur oxidation, and ammonium molybdate and sodium tungstate may be mentioned as examples.

In the preparation process (c) according to the invention, the reaction temperature can be varied within a relatively wide range. The reaction is generally carried out at a temperature of from-20 ℃ to +70 ℃, preferably from 0 ℃ to +50 ℃.

To carry out the preparation process (c) according to the invention, the compound of the formula (Ia) is generally reacted with from 0.8 to 1.2 mol, preferably an equimolar amount, of oxidizing agent per mole of sulfur oxidized to sulfoxide. If sulfur is oxidized to sulfones, the compound of the formula (Ia) is generally reacted with from 1.8 to 3.0 mol, preferably twice the molar amount, of oxidizing agent per mole of compound. The reaction and the end product are worked up and isolated in a conventional manner.

The active compounds according to the invention have good plant tolerance and low toxicity to warm-blooded animals and are therefore suitable for controlling animal pests, in particular insects, arachnids and nematodes, which occur in agriculture, in forestry, in the protection of stored products and materials and in the hygiene sector. They are active against normally sensitive and tolerant species and against all or some developmental stages. The pests include:

the eyes are equivalent: for example, Oniscus purpureus and Armadillidium vulgare.

Order of the bipedae class: for example, zebra finland.

Order of the phylum cheilopoda: for example, Geophilus carpophagus and Scutigera spp.

Purpose of the comprehensive outline: for example, Scutigerella immaculata.

From the Thysanura order: such as chlamydomonas occidentalis.

The order of the bullet tails: for example, a thorny springtail.

Straight wing order: for example, blattaria orientalis, blattaria americana, blattaria maderana, blattaria germanica, cricket domestica, gryllotalpa, locusta migratoria, and locusta migratoria.

From the order of the dermaptera: for example, Forficula auricularia.

From the order of the Isoptera: for example, the genus rhinoceros.

And (3) pediculizing: for example, body lice, blood lice and jawberries.

Food for the malcule: for example, the genera rodentia and pediculus oracioides.

From the order of thysanoptera: for example, greenhouse thrips tabaci and thrips gossypii.

Heteroptera sub-order: for example, brown plant bug, cotton plant bug, beet coriaria, temperate bed bug, long plant bug and trypanosoma spp.

From the order of homoptera: for example, whitefly sweet potato, whitefly green house, cotton aphid, cabbage aphid, Cryptozus phaeomyzus, beet aphid, apple aphid, woolly apple aphid, gall aphid, sitobion avenae, Oenomyzus nodorum, Homopyrum obulvus, Sinorum pomorum, Microleafhopper, leaf hopper, Nephotetter melanogaster, Lecanicillin, Nilaparvata lugens, Lecanicillin, and Triphaea.

Lepidoptera: for example, pink bollworm, looper, hornworm, codling moth, plutella xylostella, tenella, fusca, moth, cotton leaf miner, cutworm, noctuid, cotton spotted moth, bollworm, beet armyworm, cabbage looper, eyeworm, prodenia litura, armyworm, cabbage looper, codling moth, pieris, standing grain borer, corn borer, mediterranean pink borer, pyralid moth, bagatelle moth, netowfly, cabbage looper, moth, tea leaf looper, and oak green leaf looper.

Coleoptera order: for example, Easter punctatus, ips, Bruchiius obetus, Douglas fir, Alnus japonica, Buxi-purple beetle, Coleoptera tuberosa, Horseradish ape, Arctochilus striatus, Bytalidium rapae, Hippodamia variegata, Cryptomeria, Gothistle, Micerus, Gordonia, Tremella, Banana root weevil, Colubella, Lucerne leaf weevil, Dermatopteris nephrolepis, Pectenopharyngodon, Dermatopteris, Cercosphaera, Agnus, Pseudocercosphaera, Triplophysalis, Panonycis, Tortoise, and Chinema neozeae.

Hymenoptera: for example, the genera Melissa, Termite, Coprinus, and Vespa.

The order of Diptera: for example, Aedes, Anopheles, Culex, chimpanzee Drosophila, Musca, Dactylis, Red-headed blowfly, Drosophila, Chrysomyzidae, Scomberous, Gastrodia, Philips, Drosophila, Bisca, Drosophila, Pisca, Tabanus, a smaller kind of cicada cicada, Garden Mourella, Swedish fly, Mylabris, beet leaf fly, Mediterranean fly, Olive fly and Martiana moschata.

Siphonaptera: for example, Xenopsylla and Ceratophyllus.

Order of the arachnids: for example, scorpion and spidrox theivora and black widow corchoroid.

From the order Acarina: for example, aleyrodids, Cryptoryptoryptoryptoryptoryptoryptoryptoryptoryptoryptoryptoryptoryptoryptoryptoryptoryptoryptoryptoryptoryptoryptoryptoryptoryptoryptoryptoryptoryptoryptoryptoryptoryptoryptoryptoryptoryptoryptoryptoryptoryptoryptoryptoryptoryptoryptoryptoryptoryptoryptoryptoryptoryptoryptoryptoryptoryptoryptoryptoryptoryptoryptory.

Plant parasitic nematodes include: for example, Meloidogyne spp, Peroidogyne bicolor, Dioscorea batatas, Tylenchulus semipenetrans, Heterodera spp, Meloidogyne spp, Globodera spp, Ostertagia spp and Trichinella spp.

The compounds of the general formula (I) according to the invention are distinguished by their effective insecticidal activity, in particular in certain combinations by systemic activity in the roots.

They can be used particularly successfully for controlling insects which damage plants, for example, larvae of the mustard beetle (Phaedon cochliae), larvae of the diamondback moth (Plutella maculipennis), larvae of the Nephotettix cincticeps (Nephotettix cincticeps), larvae of the meadow armyworm (Spodoptera frugiperda), larvae of the Myzus persicae (Mycus persicae) or larvae of the Diabrotica beetle (Diabrotica bauata).

The active compounds can be converted into the customary formulations, such as solutions, emulsions, wettable powders, suspensions, powders, pastes, soluble powders, granules, suspoemulsions, natural and synthetic materials impregnated with active compound and microcapsules encapsulated with polymeric substances.

These formulations are produced in a known manner, for example by mixing the active compounds with extenders, that is, liquid solvents and/or solid carriers, in which formulations surfactants, that is, emulsifiers and/or dispersants and/or foam formers, may be used. In the case of using water as the filler, for example, an organic solvent may also be used as a co-solvent. Suitable liquid solvents are mainly: aromatic hydrocarbons such as xylene, toluene, or alkylnaphthalene, chlorinated aromatic hydrocarbons or chlorinated aliphatic hydrocarbons such as chlorobenzene, dichloroethane, or dichloromethane; aliphatic hydrocarbons such as cyclohexane, or paraffins (e.g., mineral oil fractions, mineral oils, and vegetable oils); alcohols such as butanol or ethylene glycol and their ethers and esters; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, or cyclohexanone; strongly polar solvents such as dimethylformamide and dimethylsulfoxide; and water.

Suitable solid carriers are: for example, ammonium salts and natural mineral powders such as kaolin, clay, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and synthetic mineral powders such as highly dispersed silica, alumina and silicates; suitable solid carriers for granules are: for example, crushed and fractionated natural rocks such as calcite, marble, pumice, sepiolite, dolomite and synthetic particles of inorganic or organic powders and particles of organic materials such as sawdust, coconut shells, corn ear stems and tobacco stems; suitable emulsifiers and/or foam formers are: for example, nonionic and anionic emulsifiers such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers (e.g., alkylaryl polyglycol ethers), alkylsulfonates, alkyl sulfates, arylsulfonates and protein hydrolysates; suitable dispersants are: such as lignosulfonate waste liquor and methyl cellulose.

Tackifiers such as carboxymethylcellulose and powders, particulate or latex-like synthetic polymers such as polyvinyl alcohol, polyvinyl acetate, natural phospholipids such as cephalins and lecithins, and synthetic phospholipids may also be used in the formulations. Other binders may be mineral and vegetable oils.

Possible colorants used are: for example, inorganic pigments such as iron oxide, titanium oxide, and prussian blue; organic dyes such as alizarin dyes, azo dyes, and metal phthalocyanine dyes; and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.

The formulations generally contain from 0.1% to 95%, preferably from 0.5% to 90%, by weight of active compound.

In their commercial formulations and the use forms for the preparation of their formulations, the active compounds according to the invention can be present in a mixture with other active compounds, such as insecticides, attractants, sterilants, bactericides, acaricides, nematicides, fungicides, growth regulators or herbicides. Pesticides include, for example, phosphates, carbamates, carboxylates, chlorinated hydrocarbons, phenylureas, microbially produced materials, and the like.

Examples of particularly advantageous ingredients in the mixture are as follows:fungicidal agents：

2-aminobutane, 2-anilino-4-methyl-6-cyclopropyl-pyrimidine, 2 ', 6' -dibromo-2-methyl-4 '-trifluoromethoxy-4' -trifluoromethyl-1, 3-thiazole-5-carboxanilide, 2, 6-dichloro-N- (4-trifluoromethylbenzyl) benzamide, (E) -2-methoxyimino-N-methyl-2- (2-phenoxyphenyl) acetamide, 8-hydroxyquinoline sulfate, (E) -2- {2- [6- (2-cyano-phenoxy) pyrimidin-4 yl-oxy-benzamide]Phenyl } -3-methoxyacrylate methyl ester, (E) -methoxyimino [ alpha- (o-tolyloxy) -o-tolyl]Methyl acetate, 2-phenylphenol (OPP), aldimorph, alanine, benomyl, penconazole, benalaxyl, iodocarboxin, benomyl, binapacryl, biphenyl, bitertanol, blasticidin, bromuconazole, butyrimidyl sulfonate, butrit, lime-sulfur, captafol, captan, carbendazim, carboxin, metconazole, chloroneb, chloropicrin, chlorothalonil, ethephon, thiabendazole, cymoxanil, cyproconazole, ethaboxam, antifungal, benzchlorotriazole, dichlofluanid, diclofluanid, nicamide, diethofencarb, difenoconazole, metrafloxil, dimethomorph, diniconazole, meprobamate, diphenylamine, pyrithion, triticonazole, dodecene, clofenbutazone, carboxanone, epoxyconazole, epoxolone, ethirimol, chlorpropham, diclofen, diclofenarimol, fenthizole, fenflurazone, fenpropiconazole, fenbutachlor, fenpropiconazole, fenpropi, Triphenytoin, ferbamate, azozone, fluazinam, fludioxonil, fluocinolone, fluquinconazole, flusilazole, flusulfamide, flutolanil, flutriafol, folpet, fosetyl-aluminum, tetrachlorophthalide, fuberidazole, furalaxyl, fenvinamine, dicapryguanamine, hexachlorobenzene, hexaconazole, mefenoxaprop, imazalil, imibenconazole, iminoctadine acetate, Iprobenfos (IBP), iprodione, isoprothiolane, kasugamycin, copper agents such as copper hydroxide, copper naphthenate, basic copper chloride, copper sulfate, copper oxide, mixture of oxine-copper and boldo, mancozeb, mancozeb, maneb, mepanipyrim, mefenoxam, metalaxyl, metconaole, sulbencarb, furametpyr, metiram, tiadinil, myclobutanil, flumiclone, iprodione, flufenarimol, meturamide, oxadixyl, oxamocarb, oxycarboxin, pefurazoate, penconazole, pencycuron, isoprothiolane, pimaricin, piperidinine, fop-zinc, polyoxin, probenazole, prochloraz, procymidone, propamocarb, propiconazole, metrazol, fenamiphos, pyrimethanil, pyroquilon, quintozene (PCNB), sulfur and thionic preparations, tebuconazole, phyllophytin, tetraconazole, thiabendazole, thiophanate-methyl, thiram, tolfenpyrad, tolbutamol, triadimefon, triadimenol, triazoxide, propiconazole, trifloxystrobin, fenpyrazone, trifloxystrobin, pyrazone, trifloxystrobin, trimethoprim, pyrazone, trimethoprim, trimet, Zineb, ziram.Bactericides：

Bronopol, antifungal phenol, chlorhexidine, nickel thiram, kasugamycin, isothiazolone, furancarboxylic acid, oxytetracycline, probenazole, streptomycin, phyllo-cumylphthalein, copper sulfate, and other copper preparations.Insecticide/acaricide/nematicide：

Abamectin, AC303630, acephate, fluthrin, gossypol, aldicarb, alphamethrin, amitraz, abamectin, AZ60541, azadirachtin, ethoprophos, valthion, azocyclotin, Bacillus thuringiensis, bendiocarb, benfuracarb, monosulfuron, cyfluthrin, bifenthrin, fenobucarb, brofenprox (brofenprox), bromophos, pirimicarb, buprofezin, butocarbofuran, butfenthion, carbaryl, carbofuran, trithion, carbosulfan, cartap, CGA 157419, CGA 184699, oxamyl, chlorenoxyfos, chlorpyrifos, chlorfenpyr, chlorfluazuron, chlorthion, chlorpyrifos-methyl, cis-benzothrin, cyhalothrin, clofentezine, fenvalerate, etofenprox, cyfluthrin, cyhalothrin, fenprox, fenpropathrin, metocloprid, metoclopramide, monocrotophos, metoclopramide, Isophorate II, acarbon, dinotefuran, clomiphos, dichlorvos, dicliphos, chlorothalofop, ethion, teflubenzuron, dimethoate, methoprene, dioxathion, disulfoton, edifenphos, emamectin, esfenvalerate, dichlorcarb, ethion, ethofenprox, ethoprophos, etrimfos, fenamiphos, fenoxycarb, fenpropathrin, fenamiphos, fenpropathrin, fenpyroximate, fenpropathrin, fluazinam, fluazuron, flucycloxuron, flucythrinate, flufenoxuron, flumethrin, flufenpropathrin, isofenthion, isofenpyrazofos, isofenthion, fenthion, lufenuon, malathion, thiothion, metoclopramide, fenthion, thiothion, metaldehyde, methomyl, metoclopramide, milbemectin, monocrotophos, moxidectin, naled, NC184, NI25, nitenpyram, omethoate, oxamyl, SULPHUN, ISOPHON, parathion, methyl parathion, permethrin, phenthoate, phorate, phosmet, phosphamidon, phoxim, pirimicarb, pirimiphos, profenofos, propamocarb, propapho, propoxur, phos, pomade, pymetrozin, pyrachlophos, pyrazophos, pyridaphenthrin, pyrethrin, pyridaben, pyrimiden, pyriproxfen, quinalphos, RH5992, fenthion, thion, silathion, fenthion, fenpropaphos, fenthion, fenbutazone, fenthion, fenbutazone, fen, Terbufos, chlorfenvinphos, thiafenox, thiodicarb, ketoxime, fosetyl methyl, triazophos, thuringiensis, tetrabromthrin, phenytoin, triazophos, triazuron, trichlorfon, chlorfluazuron, trimethacarb, thiofenthion, dimethylcarb, xylylcarb, YI5301/5302, zetamethrin.

Mixtures with other known active compounds, such as herbicides, or with fertilizers and growth regulators are also possible.

Furthermore, the active compounds according to the invention can be present in a mixture with synergists in their commercially available formulations and in the use forms in which they are prepared. Synergists increase the activity of the active compound, but the added synergist itself need not be an active compound.

The content of active compound in the use forms prepared from the commercially available preparations can vary within wide limits. The active compound concentration in the use forms is from 0.0000001% to 95% by weight, preferably from 0.0001% to 1% by weight.

The present compounds are used in a conventional manner in a form suitable for use.

When used for controlling hygiene pests and pests of stored products, the active compounds have excellent residual activity on wood and clay and good stability to alkaline lime substrates.

The active compounds according to the invention are active not only against pests of plants, hygiene and stored products, but also in the veterinary medicine sector against animal parasites (ectoparasites), such as hard ticks, soft ticks, mange mites, sand mites, flies (biting and sucking), parasitic fly larvae, lice, hair lice, bird lice and fleas. These parasites include:

and (3) pediculizing: for example, the genera Haemophilus, Pediculus, pediculus, Phtirus, and Anoplophora.

Trichomes, obtuse and fine sub-orders: for example, the genera Phthirius, Aleurites, Werneckiella, Lepikentron, Phthirius, Rodentia, and Phthirius.

Diptera, longhorn sub-order and brachhorn sub-order: for example, Aedes, Anopheles, Culex, gnat, Arachnocampa, Chrysomyelia, Lutzomyia, Culicoides, Tabanus, Philiplomyia, Drosophila, Musca, Hydrotaea, Drosophila, Hemophaga, Morellia, Daphtis, Liriomyza, Drosophila, Chrysomyzidae, Musca, Pisca, Gastrodia, Philippine, Lipoptena, tick.

Siphonaptera: for example, the genera Siphonaptera, Ctenocephalides, and Ceratophyllus.

Hemiptera: for example, the genera of bed bugs, rhynchophorus, and lygus.

Order of Blattaria: for example, Blatta orientalis, Blatta americana, Blattella germanica, Supella genus.

Acarina, prothoraciba and mesothoracia: for example, Iridium, Dermacentor, Pedicephalus, Rhipicephalus, hard tick, Blastomya, Ornithodium, Dermacentor, Haematococcus, Perophthora, Rhipicephalus, Dermatophagoides, Raillieria, Tyrophora, varroa.

Front valve sub-mesh and no valve sub-mesh: for example, the genus Acarina, Hyphelcosis, Dermatophagoides, sheep scabies, Demodex, tsutsugamushi, perverse mite, Dermatophagoides, Tyrophagus, Hypodects, Pothidae, Pruritus, Dermatophagoides, Euglena, Dermatophagoides, and.

For example, they have good control activity against flies (house flies), development inhibitory action against larvae of lucilia cuprina, good control effect against cockroaches (periplaneta americana) and ticks (Boophilus microplus), and also as oviposition inhibitors.

The active compounds of the general formula (I) according to the invention are also suitable for controlling arthropods which harm agricultural domestic animals, such as cattle, sheep, goats, horses, pigs, donkeys, camels, buffalo, rabbits, chickens, turkeys, ducks, geese, bees, and other domestic animals, such as dogs, cats, caged birds, aquarium fish, and so-called laboratory animals, such as hamsters, guinea pigs, rats and mice. By controlling these arthropods, it is intended to reduce animal death and to control yield losses (meat, milk, wool, skins, eggs, honey, etc.). The use of the active compounds according to the invention therefore makes it possible to achieve a more economical and simpler animal husbandry.

In the veterinary sector, the compounds of the invention can be administered by known methods. Enteral administration: for example, in the form of tablets, capsules, drinks, enemas, granules, pastes, boluses, feeding methods, suppositories, and the like; parenteral administration: such as injection (intramuscular injection, subcutaneous injection, intravenous injection, intraperitoneal injection, etc.), implantation; administration through nose; transdermal administration: for example by soaking or bathing, spraying, pouring or wiping, washing and dusting, and also with the aid of shaped articles containing the active compound, such as collars, ear ornaments, tail ornaments, limb loops, halters, decorative articles, etc.

When used in livestock, poultry and domestic animals, the active compounds of the formula (I) can be used in the form of preparations (e.g.powders, emulsions, flowables) with an active compound content of 1 to 80% by weight, either directly or after dilution by a factor of 100-10000, or as chemical soaking agents.

Furthermore, it has now been found that the compounds of the general formula (I) according to the invention have outstanding insecticidal activity against insects which are harmful to industrial articles.

The following insects may be mentioned and are preferred, but are not limited to:

beetles: for example, Hovenia, Tiger beetle, furniture beetle, red hair beetle, ptilinuspecticings, Dendrobium pertinenex, pine bark beetle, Priobium carpini, brown powder beetle, African powder beetle, flat neck powder beetle, raft powder beetle, Lyctus pubescens, Trognylone aque, Lepidopodium powder beetle, species of the genus Spatholobus, species of the genus Tryptodendron, coffee black beetle, oak long beetle, Heterobotrys brunneus, species of the genus Sinoxylon, bamboo long beetle.

From the order of the dermaptera: for example, young Meretrix meretrix, Meretrix giganteus, Oncorhynchus aethiopicus, Urocerus augur.

Termites: for example, wood termites, cryptomerite, aspermous termites, Scopolia sinensis, Reticulitermes santonensis, Reticulitermes lucifugus, Australian termites, Zootermopsis nevadensis, Coptotermes domestica.

Coating the fish: such as chlamydomonas occidentalis.

Industrial material in this context means non-living material, preferably for example: polymers, adhesives, tacky materials, paper and board, leather, wood products, and paints.

Materials protected from insect damage are most preferably wood and wood products thereof.

Wood and wood products which can be protected with the agent according to the invention or with a mixture containing the agent have the meaning: for example, construction timber, timber beams, railroad ties, bridge components, jetties, wooden cars, boxes, containers, utility poles, wooden mine roof timber, wooden windows and doors, plywood, particle board, woodworking articles, or wood products commonly used in home construction or in joinery.

The active compounds according to the invention can be used in the form of their concentrates or in the usual customary formulations, such as powders, granules, solutions, suspensions, emulsions or pastes.

The above formulations can be prepared in a manner known per se, for example by mixing the active compounds with at least one solvent or diluent, emulsifier, dispersant and/or binder or fixative, water repellent, also with dehydrating agents and UV stabilizers, also with dyes and pigments and other processing auxiliaries.

The concentration of the insecticidal compositions or concentrates for the protection of wood and wood products is from 0.0001 to 95% by weight, preferably from 0.001 to 60% by weight, of active compound.

The amount of the agent or concentrate used depends on the type and density of the insect, and the medium. The optimum dosage can be determined in each case by a series of tests. In general, however, it is sufficient to employ from 0.0001 to 20%, preferably from 0.001 to 10%, by weight of active compound, based on the material to be protected.

The solvent and/or diluent is organic chemical solvent or solvent mixture and/or low volatile oily or oil-like organic chemical solvent or solvent mixture and polar organic chemical solvent or solvent mixture and/or water, and may also be emulsifier and/or wetting agent.

Preferred organic chemical solvents used are oily or oil-like solvents having a volatility greater than 35 and a flash point greater than 30 ℃, preferably greater than 45 ℃. Such water-insoluble, low-volatility, oily or oily-like solvents are suitable mineral oils or aromatic fractions thereof or solvent mixtures containing mineral oils, preferably white spirit, petroleum and/or alkylbenzenes.

Preferably, mineral oil having a boiling range of 170-220 ℃, petroleum solvent having a boiling range of 170-220 ℃, spindle oil having a boiling range of 250-350 ℃, petroleum or aromatic compounds having a boiling range of 160-280 ℃, turpentine, and the like are used.

In a preferred embodiment, the substances used are liquid aliphatic hydrocarbons having a boiling range of 180-210 ℃ or high-boiling mixtures of aromatic and aliphatic hydrocarbons having a boiling range of 180-220 ℃ and/or spindle oil and/or monochloronaphthalene, preferably α -monochloronaphthalene.

The low volatility organic oily or oily-like solvent having a volatility greater than 35 and a flash point greater than 30 ℃, preferably greater than 45 ℃, may be partially replaced by a high or medium volatility organic chemical solvent, provided that the solvent mixture also has a volatility greater than 35 and a flash point greater than 30 ℃, preferably greater than 45 ℃, and the pesticide/fungicide mixture is soluble or emulsifiable in this solvent mixture.

In a preferred embodiment, part of the organic chemical solvent or solvent mixture or the aliphatic polar organic chemical solvent or solvent mixture may be replaced. Preferred alternatives are aliphatic organic chemical solvents containing hydroxyl and/or ester and/or ether groups, such as glycol ethers, esters, etc.

The organic chemical binders used in the present invention are binding drying oils and/or synthetic resins known per se, which can be diluted with water and/or are soluble, dispersible or emulsifiable in the organic chemical solvent employed, in particular those consisting of, or containing: acrylic resin; vinyl resins such as polyvinyl acetate; a polyester resin; a polycondensation or polyaddition resin; a polyurethane resin; alkyd resins or modified alkyd resins; a phenol resin; hydrocarbon resins such as indene-coumarone resins, silicone resins, drying vegetable oils and/or physically drying binders based on natural and/or synthetic resins.

The synthetic resin used as the binder may be used in the form of an emulsion, dispersion or solution. Bitumen or bituminous substances may also be used as binder substances in amounts of up to 10% by weight. In addition, colorants, pigments, water-proofing agents, odor masking agents and inhibitors or preservatives and the like known per se may be used in addition.

According to the invention, the composition or concentrate preferably contains at least one alkyd resin or modified alkyd resin and/or a drying vegetable oil as organic chemical binder. Substances which are preferably used according to the invention are alkyd resins having an oil content of more than 45% by weight, preferably from 50 to 68% by weight.

All or part of the above-mentioned binders may be replaced by fixatives (mixtures) or plasticizers (mixtures), which are intended to prevent volatilization and crystallization or precipitation of the active compounds. They preferably replace 0.01 to 30% of the binder (based on 100% of the binder used).

Plasticizers come from substances belonging to the following chemical classes: phthalic acid esters such as dibutyl phthalate, dioctyl phthalate or benzylbutyl phthalate; phosphoric acid esters such as tributyl phosphate; adipates such as di (2-ethylhexyl) adipate; stearates such as butyl stearate or amyl stearate; oleic acid esters such as butyl oleate; glycerol ethers or high molecular weight glycol ethers, glycerol esters and p-toluenesulphonic acid esters.

The fixing agents are chemically based on polyvinyl alkyl ethers, such as polyvinyl methyl ether, or ketones, such as benzophenone or vinylbenzophenone.

Another suitable solvent or diluent is (preferably) water, which may be a mixture of water with one or more of the above-mentioned organic chemical solvents or diluents, emulsifiers and dispersants.

Particularly effective wood protection is obtained by means of impregnation processes on an industrial scale, for example vacuum, double vacuum or pressure processes.

The directly usable composition may comprise other insecticides and may also comprise one or more fungicides.

Further components which may be incorporated therein are preferably insecticides and fungicides as mentioned in WO 94/29268. The compounds mentioned in the above-mentioned documents are specifically part of the present application.

The most preferred components which may be mentioned are: insecticides such as chlorpyrifos, phoxim, silafluofin, cyfluthrin, alphamethrin, cypermethrin, deltamethrin, permethrin, imidacloprid, flufenoxuron, hexaflumuron and chlorsulfuron; and fungicides such as epoxiconazole, hexaconazole, azaconazole, propiconazole, azaconazole, cyproconazole, metconazole (metconazole), imazalil, benfluanid, tolylfluanid, 3-iodo-2-propynyl butylcarbamate, N-octyl-isothiazolin-3-one and 4, 5-dichloro-N-octyl-isothiazolin-3-one.

The preparation and use of the active compounds according to the invention are described in the examples below.Preparation examples Example 1

11 g (0.024 mol) of 5-amino-3-cyano-4- (1, 1-difluoroethanesulfonyl) -1- (2, 6-dichloro-4-trifluoromethylphenyl) pyrazole were dissolved in 80 ml of pyridine and 10 ml of triethylamine, and then hydrogen sulfide was introduced thereinto at room temperature for about 3 hours. Next, the reaction solution was treated with water, and repeatedly extracted with dichloromethane. After drying over magnesium sulfate, the mixture was concentrated by vacuum distillation to remove the solvent, and the oily residue was stirred with diethyl ether and filtered through a suction filter.

This gives 8 g (68% of theory) of 5-amino-4- (1, 1-difluoroethanesulfonyl) -1- (2, 6-dichloro-4-trifluoromethylphenyl) -3-thiocarbamoylpyrazole having a melting point of 288-and 229 ℃.

The compounds of the general formula (I) listed in table a can be prepared analogously to example 1 or according to the customary preparation instructions. TABLE APreparation of novel starting materials of the general formula (VII) Example (VII-1)

3.8 g (0.012 mol) of 5-amino-3-cyano-1- (2, 6-dichloro-4-trifluoromethylphenyl) pyrazole was dissolved in 50 ml of pyridine and 5 ml of triethylamine, followed by hydrogen sulfide introduction at room temperature for about 2 hours, followed by further stirring at 50 ℃ for 10 minutes. The reaction solution was concentrated in vacuo and the residue was treated with water and dichloromethane. The mixture was extracted repeatedly with dichloromethane, the dichloromethane phase containing the product was dried over magnesium sulfate and concentrated in vacuo.

This gives 3.4 g (81% of theory) of 5-amino-1- (2, 6-dichloro-4-trifluoromethylphenyl) -3-thiocarbamoylpyrazole.

¹H-NMR (internal standard of tetramethylsilane-containing dimethyl sulfoxide; delta units: ppm):

9.49(1H)；9.08(1H)；8.21(2H)；5.96(1H)；5.69(2H)。preparation of novel starting materials of the general formula (III) Example (III-1)

The compound of example (III-1) was prepared analogously to 3-cyano-1- (2, 6-dichloro-4-trifluoromethylphenyl) -5- (pyrrol-1-yl) -pyrazole according to example (VII-1).

¹H-NMR (internal standard of tetramethylsilane-containing dimethyl sulfoxide; delta units: ppm):

9.95(1H)；9.58(1H)；8.30(2H)；7.19(1H)；6.20(2H)；6.13(2H)。application examples

In the following application examples, the following exemplified compounds were used as comparison substances:

(these compounds are disclosed in EP-A-0659745)Example A

Horseradish ape larva assay

Solvent: 7 parts by weight of dimethylformamide

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount of solvent and the stated amount of emulsifier, and the concentrate is diluted with water to the desired concentration.

After treatment by immersing cabbage leaves (Brassica oleracea) in the preparation of the active compound at the desired concentration, larvae of the mustard beetle (Phaedon cochleariae) are deposited while the leaves are still moist.

After the desired time, the lethality (%) was determined. 100% means that all larvae were killed; 0% means that no larvae were killed.

In this test, the lethality of the compounds of preparation examples 1 and 2 was 100% after 3 days at the tested concentration of the active compound of 0.00001%, while the lethality of the compound (a) was known to be only 25%.Example B

Cabbage moth assay

Solvent: 7 parts by weight of dimethylformamide

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount of solvent and the stated amount of emulsifier, and the concentrate is diluted with water to the desired concentration.

Cabbage leaves (Brassica oleracea) are treated by being dipped into the preparation of active compound at the desired concentration and, while the leaves are still moist, are populated with larvae of the diamondback moth (Plutella xylostella).

After the desired time, the lethality (%) was determined. 100% means that all larvae were killed; 0% means that no larvae were killed.

In this test, at a test concentration of 0.0001% of active compound, the mortality rate after 3 days for the compound of preparation example 1 was 75%, the mortality rate for the compound of preparation example 2 was 100%, whereas the mortality rate for compound (a) was only 15%.Example C

Grass armyworm test

Solvent: 7 parts by weight of dimethylformamide

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount of solvent and the stated amount of emulsifier, and the concentrate is diluted with water to the desired concentration.

Cabbage leaves (Brassica oleracea) are treated by being dipped into the preparation of active compound at the desired concentration and, while the leaves are still moist, are populated with caterpillars of the armyworm (Spodoptera frugiperda) species.

After the desired time, the lethality (%) was determined. 100% means that all larvae were killed; 0% means that no larvae were killed.

In this test, at a test concentration of 0.01% of active compound, the lethality of the compounds of preparation examples 1, 2 and 4 was 100% after 7 days, while the lethality of compounds (B) and (C) was known to be only 15% and 0%, respectively.Example D

Black tail hopper test

Solvent: 7 parts by weight of dimethylformamide

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount of solvent and the stated amount of emulsifier, and the concentrate is diluted with water to the desired concentration.

After treatment of rice seedlings (Oryza sativa) by immersion in a preparation of the active compound at the desired concentration, they were placed on leafhopper (Nephotettix cincticeps) while the seedlings were still moist.

After the desired time, the lethality (%) was determined. 100% means that all leafhoppers were killed; 0% means that no leafhoppers were killed.

In this test, at a test concentration of 0.1% of active compound, after 6 days, the lethality of the compounds of preparation examples 2 and 4 was 100%, the lethality of the compound of preparation example 5 was 80%, while the lethality of the compounds (a) and (D) was known to be only 10% and 0%, respectively.Example E

Oncorhynchus test

Solvent: 7 parts by weight of dimethylformamide

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount of solvent and the stated amount of emulsifier, and the concentrate is diluted with water to the desired concentration.

Cabbage leaves (Brassica oleracea) which are severely endangered by the green peach aphid (Myzus persicae) are treated by impregnation with a preparation of the active compound in the desired concentration.

After the desired time, the lethality (%) was determined. 100% means that all aphids were killed; 0% means that no aphids were killed.

In this test, the lethality of the compounds of the preparation examples at the tested concentration of active compound of 0.1% is as follows after 6 days: example 1 was 80%, example 2 was 98%, and example 4 was 100%, whereas the lethality of the known compound (C) was only 50%, and that of the known compound (B) was only 0%.Example F

Limit concentration test/soil-dwelling insects

Testing insects: larva of Diabrotica batatas (Diabrotica balteata) in soil

Solvent: 4 parts by weight of acetone

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To prepare a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount of solvent, the stated amount of emulsifier is added, and the concentrate is diluted with water to the desired concentration. The concentration of the active compound in the preparation is essentially immaterial, only the weight content of active compound per unit volume of soil is decisive, in ppm (mg/l). The soil was filled into a tank having a volume of 0.5 liter, and the tank was placed at 20 ℃.

The test was carried out by placing 5 germination treated corn cobs in each pot, placing the test insects in the treated soil after 1 day, and after 7 days, counting the number of dead and alive test insects and determining the efficacy (%) of the active compound. 100% indicates that all test insects were killed, 0% indicates that the number of test insects surviving was the same as the number of test insects surviving in the untreated control group.

In this testThe lethality of the compounds of preparation examples 2, 4 and 5 was 100% at the tested concentration of 0.002% of active compound.Example G

Limiting concentration test/systemic activity in roots

Testing insects: larva of Phaedon cochleariae

Solvent: 4 parts by weight of acetone

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To prepare a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount of solvent, the stated amount of emulsifier is added, and the concentrate is diluted with water to the desired concentration.

The active compound preparation is mixed beforehand with the soil. The concentration of the active compound in the preparation is essentially immaterial, only the weight content of active compound per unit volume of soil is decisive, in ppm (mg/l). The treated soil was filled into pots, and cabbage (Brassica oleracea) was planted in the pots. In this way, the active compound can be taken up by the plant from the soil via the roots and conducted to the leaves.

To determine the effect of systemic uptake in the roots, the above test insects were placed on the leaves 7 days later. After another 2 days, the number of dead insects was counted and estimated to evaluate the effect of the test. From the lethal data, the systemic effect in the roots of the active compounds is deduced. 100% means that all test insects were killed, 0% means that the number of surviving test insects was the same as the number of surviving test insects in the untreated control group.

In this test, the lethality of the compounds of preparation examples 1, 4 and 5 was 100% at the tested concentration of 0.002% of active compound.Example H

Fly test

Test animals: housefly (Musca domestica) adults, the Reichwald strain,

(OP, SP, carbamate resistant)

Solvent: 35 parts by weight of ethylene glycol monomethyl ether

35 parts by weight of nonylphenyl polyglycol ether

To prepare a suitable preparation of active compound, 3 parts by weight of active compound are mixed with 7 parts by weight of the abovementioned solvent/emulsifier mixture and the resulting emulsion concentrate is diluted with water to the desired concentration.

2 ml of the active compound preparation are pipetted onto a filter paper sheet (diameter 9.5cm) of suitable size which is placed in a petri dish. After the filter paper sheet was dried, 25 test animals were placed in a petri dish and the lid was closed.

1. After 3, 5, 24 hours, the efficacy of the active compound preparation is determined. 100% means that all flies were killed, 0% means that no flies were killed.

In this test, the compounds of preparation examples 1, 2, 4 and 5 all have a drug effect of 100% at the test concentration of active compound of 100 ppm.Example I

Green fly larva assay/development inhibitory Activity

Test animals: green fly (Lucilia cuprina) larva of various ages (resistant OP)

(pupae and adults do not come into contact with the active compound)

Solvent: 35 parts by weight of ethylene glycol monomethyl ether

35 parts by weight of nonylphenyl polyglycol ether

To prepare a suitable preparation of active compound, 3 parts by weight of active compound are mixed with 7 parts by weight of the abovementioned solvent/emulsifier mixture and the resulting emulsion concentrate is diluted with water to the desired concentration.

For each concentration, 30-50 larvae were placed in horse meat (1 cm) placed in a glass tube³) Then, 500. mu.l of the diluted solution of the drug was pipetted onto horse meat. The glass tube was placed in a plastic beaker, a layer of silica sand was spread on the bottom of the beaker, and placed in a thermostat (26 ℃. + -. 1.5 ℃, relative humidity 70%. + -. 10%). After 24 hours and 48 hours, the results (larvicidal activity) were measured. After the larvae left the glass tube (about 72 hours), the glass tube was removed and the beaker covered with a gas permeable plastic lid. After 1.5 times the development time (incubation of the control group of green flies), the number of incubated green flies and pupa/pupa shells was counted.

Evaluation criteria for the effects were: after 48 hours (larvicidal effect), the mortality of the treated larvae, or the inhibition of pupae hatching into adults, or the inhibition of pupation. The evaluation criteria for the substances outside the glass tube were: inhibition of flea development, or failure to develop before the adult stage. A larvicidal effect of 100% indicates that all larvae have died after 48 hours, and a growth inhibitory effect of 100% indicates that no adults have hatched.

In this test, the activity of the compounds of preparation examples 1, 2, 4 and 5 is 100% at the test concentration of active compound of 100 ppm.Example J

Resistant Boophilus microplus test/SP-resistant, Parkhurst strain

Test animals: adult female with blood-sucking function

Solvent: 35 parts by weight of ethylene glycol monomethyl ether

35 parts by weight of nonylphenyl polyglycol ether

To prepare a suitable preparation of active compound, 3 parts by weight of active compound are mixed with 7 parts by weight of the abovementioned solvent/emulsifier mixture and the resulting emulsion concentrate is diluted with water to the desired concentration.

10 resistant adult Boophilus microplus were immersed for 1 minute in the active compound preparation tested, transferred into plastic beakers and placed in an incubator and the degree of lethality determined. 100% means that all ticks have died, 0% means that none of the ticks have died.

In this test, the pharmacodynamic activity of the compounds of preparation examples 2, 4 and 5 is 100% at the test concentration of active compound of 100 ppm.Example K

Resistant Boophilus microplus test/SP-resistant, Parkhurst strain

Test animals: adult female with blood-sucking function

Solvent: dimethyl sulfoxide

Low-concentration preparations can be prepared by dissolving 20 mg of active compound in 1 ml of dimethyl sulfoxide and diluting with the same solvent.

The experiment was set up in 5 replicates. 1 microliter of the solution was spotted on the abdomen of the insects, and then the insects were transferred into a petri dish and placed in an incubator. The activity is expressed by oviposition inhibition rate. 100% means no tick has laid eggs.

In this test, the pharmacodynamic activity of the compounds of preparation examples 1, 3, 4 and 5 was all 100% at the tested concentration of active compound of 20. mu.g/insect.Example L

Cockroach test

Test animals: periplaneta americana (Periplaneta americana)

Solvent: 35 parts by weight of ethylene glycol monomethyl ether

35 parts by weight of nonylphenyl polyglycol ether

To prepare a suitable preparation of active compound, 3 parts by weight of active compound are mixed with 7 parts by weight of the abovementioned solvent/emulsifier mixture and the resulting emulsion concentrate is diluted with water to the desired concentration.

2 ml of the active compound preparation are pipetted onto a filter paper sheet (diameter 9.5cm) of suitable size which is placed in a petri dish. After the filter paper sheets were dried, 5 test animals of Periplaneta americana (Periplaneta americana) were placed in the petri dish and the lid was closed.

After 3 days, the efficacy of the active compound preparation is determined. 100% means that all cockroaches were killed, 0% means that none of the cockroaches were killed.

In this test, the pharmacodynamic activity of the compounds of preparation examples 1 and 2 is 100% at the test concentration of active compound of 100 ppm.

Claims (9)

1. Compounds having the general formula (I)

Wherein R is¹Represents H₂N-CS-，

R²Represents haloalkyl, haloalkenyl or haloalkynyl,

R³represents amino

Ar represents phenyl or pyridyl optionally mono-to trisubstituted by identical or different substituents from the group consisting of: halo (C)₁-C₆) Alkyl, halo (C)₁-C₆) Alkylthio, halo (C)₁-C₆) -alkoxy, (C)₁-C₆) -alkoxy, methoxy, hydrazino, (C)₁-C₆) -dialkylhydrazino, amino, (C)₁-C₆) Alkylamino, di (C)₁-C₆) -alkylamino, (C)₁-C₆) -alkylimino, cyano, (C)₁-C₆) Alkylthio radicals or radicals

Wherein R is⁸And R⁹May be the same or different and represents a hydrogen atom or (C)₁-C₆) -an alkyl group.

n represents 0, 1, or 2.

2. The compound of claim 1, wherein

R²Represents (C) having 1 to 12 halogen atoms₁-C₆) Haloalkyl, (C) having 1 to 8 halogen atoms₂-C₆) Haloalkenyl or (C) having 1 to 6 halogen atoms₂-C₆) -haloalkynyl.

3. The compound of claim 1, wherein R²Represents (C) having 1 to 9 identical or different fluorine, chlorine, bromine halogen atoms₁-C₄) Haloalkyl, (C) having 1 to 5 identical or different fluorine, chlorine, bromine halogen atoms₂-C₄) Haloalkenyl, (C) having 1 to 5 identical or different fluorine, chlorine, bromine halogen atoms₂-C₄) -haloalkynyl.

4. The compound of claim 1, wherein

R²Represents one of the following groups:

-CF₃，-CHF₂，

-CF₂-CH₃，-CF₃-CHF₂，-CF₂-CHFCl，

-CH₂-CF₃，-CH₂-CF₂Cl，

-CH₂-CF₂-CHF₂，

-CF₂-CFCl-CF₃，

-C(Cl)(CF₃)-CF₂Cl，-C(Cl)(CF₃)-CHCl-CF₃，

-C(CF₃)＝CCl₂。

5. the compound of any one of claims 1-4, wherein

Ar represents phenyl or pyridyl optionally mono-to trisubstituted by identical or different substituents from the group consisting of: fluoro, chloro, trifluoromethyl, trifluoromethylthio, trifluoromethoxy, methoxy, hydrazino, dimethylhydrazino, amino, methylamino, dimethylamino, iminomethyl, cyano, methylthio, or a group

Wherein R is⁸And R⁹May be the same or different and represents a hydrogen atom or (C)₁-C₄) -an alkyl group.

6. The compound of any one of claims 1-4, wherein

Ar represents:

(1) phenyl which is disubstituted or trisubstituted by identical or different substituents, wherein on the phenyl ring fluorine or chlorine is in the 2-position, trifluoromethyl is in the 4-position, fluorine, chlorine, cyano, methoxy, methylthio, trifluoromethyl, trifluoromethoxy, trifluoromethylthio or hydrazino is in the 6-position; or

(2) 2-pyridyl substituted at the 4-position by trifluoromethyl and at the 6-position by fluorine or chlorine.

7. A process for the preparation of a compound according to any one of claims 1 to 6, characterized in that:

a) if appropriate in the presence of reaction auxiliariesAnd if appropriate in the presence of a diluent, with hydrogen sulphide,

wherein, Ar, R²，R³As defined in any one of claims 1 to 6; or

b) Oxidizing the 2-thiocarbamoylpyrazole derivative having the general formula (Ia) obtained by process (a) with an oxidizing agent, if appropriate in the presence of a diluent and if appropriate in the presence of a catalyst,

wherein, Ar, R²，R³As defined above.

8. Insecticides, characterized in that they comprise at least one compound according to any one of claims 1 to 6 and a carrier.

9. Use of a compound according to any one of claims 1 to 6 for controlling pests.