DE19532066A1 - Substituted 5-aminopyrazoles - Google Patents

Abstract

New substituted 5-aminopyrazols have the formula (I), in which Ar stands for optionally substituted phenyl, nitro being excluded from the possible substituents, or for optionally substituted pyridyl; A stands for a direct bond or for optionally substituted alkylene; R<1> stands for optionally substituted cycloalkyl or cycloalkenyl; and R<2>, R<3> and R<4> have the meanings given in the description. Also disclosed are processes for preparing these compounds and their use for controlling animal pests.

Description

The present invention relates to new substituted 5-aminopyrazoles, several Process for their preparation and their use in combating animal pests, especially insects, arachnids and nematodes, those in agriculture, in forests, in the protection of stocks and materials, and on occur in the hygiene sector.

It is known that certain N-heteroaryl-2-nitro-anilines, such as N- [1,3-Dimethylpyrazol-5-yl] -2,6-dinitro-4-trifluoromethylaniline, fungicidal and insect have ticidal properties (cf. EP-A 0 478 974, WO 93/19 054). The effect However, these connections are, under certain circumstances, especially not always with low concentrations of active ingredients and application rates quite satisfactory.

New substituted 5-aminopyrazoles of the formula (I)

found,
in which
Ar represents optionally substituted phenyl, where nitro is excluded as a substituent, or represents optionally substituted pyridyl,
A represents a direct bond or optionally substituted alkylene,
R¹ stands for optionally substituted cycloalkyl or cycloalkenyl,
R² and R³ independently of one another represent hydrogen, halogen, cyano, nitro, in each case optionally substituted alkyl, aryl or hetaryl or one of the radicals CO₂R⁵, CXNR⁶R⁷ or S (O) _n R⁵ and
R⁴ represents hydrogen, in each case optionally substituted alkyl, alkenyl, alkynyl, aralkyl, aryloxy or aralkyloxy or one of the radicals SO₂NR⁶R⁷, SO₂R⁹, COR¹⁰, CH₂N (R⁹) CO₂R⁵ or CH₂N (R⁹) SO₂R⁵, where
R⁵ represents alkyl,
R⁶ and R⁷ independently of one another represent hydrogen or alkyl or together with the N atom to which they are attached form a ring which optionally contains one or more further heteroatoms,
R⁸ represents alkyl or haloalkyl,
R⁹ represents alkyl or optionally substituted aryl,
R¹ ° represents alkyl, alkoxy or optionally substituted aryl or aryloxy,
X represents oxygen or sulfur and
n stands for 0, 1 or 2.

It was also found that one

• a) the substituted 5-aminopyrazoles of the formula (I) are obtained if 5-aminopyrazoles of the formula (II) in which
  A, R¹, R² and R³ have the meaning given above,
  with compounds of the formula (III) Hal-Ar (III) in which
  Ar has the meaning given above and
  Hal stands for halogen,
  in the presence of an acid acceptor and in the presence of a diluent
  and optionally the compounds of formula (Ia) thus obtained in which
  A, Ar, R¹, R² and R³ have the meaning given above,
  with compounds of the formula (IV) ER ^4-1 (IV) in which
  R ^{4-1 has} the meaning given above for R mit with the exception of hydrogen and
  E represents an anionic leaving group,
  in the presence of an acid acceptor and optionally in the presence of a diluent;
  or
• b) substituted 5-aminopyrazoles of the formula (Ib) in which
  A, Ar, R¹, R², R³ and R ^{4-1 have} the meaning given above,
  obtained when 5-aminopyrazoles of the formula (II) in which
  A, R¹, R² and R³ have the meaning given above,
  with compounds of the formula (IV) ER ^4-1 (IV) in which
  E and R ^{4-1 have} the meaning given above,
  in the presence of an acid acceptor and in the presence of a diluent, and the compounds of the formula (V) thus obtained in which
  A, R¹, R², R³ and R ^{4-1 have} the meaning given above,
  then with compounds of the formula (III) Hal-Ar (III) in which
  Ar and Hal have the meaning given above,
  in the presence of an acid acceptor and in the presence of a diluent.

Finally it was found that the new substituted 5-aminopyrazoles of Formula (I) have strong biological properties and especially for Control of animal pests, especially insects, arachnids and nematodes, which are used in agriculture, in the forest, in the reserve and Material protection as well as in the hygiene sector are suitable.  

The substituted 5-aminopyrazoles according to the invention are represented by the formula (I) generally defined.

Preferred substituents or ranges of those mentioned in the above and below The radicals listed in formulas are explained below:

Ar preferably represents optionally up to five times, equal to or different from halogen, cyano, C₁-C₄-alkyl, C₁-C₆-haloalkyl, C₁- C₄-alkoxy, C₁-C₆-haloalkoxy, C₁-C₄-alkylthio, C₁-C₆-haloalkyl thio, C₁-C₆-haloalkylsulfinyl or C₁-C₆-haloalkylsulfonyl substituted ized phenyl or for optionally up to three times the same or differentiated by halogen, cyano, nitro, C₁-C₄-alkyl, C₁-C₆-halo genalkyl, C₁-C₄-alkoxy, C₁-C₆-haloalkoxy, C₁-C₄-alkylthio, C₁-C₆- Haloalkylthio, C₁-C₆-haloalkylsulfinyl or C₁-C₆-haloalkylsul fonyl substituted pyridyl.

A preferably stands for a direct bond or for straight-chain or branched C₁-C₄ alkylene, optionally by halogen or by optionally single to triple, identical or different by halogen, Cyano, nitro, C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy, C₁-C₄- Halogenalkoxy, C₁-C₄-alkylthio or C₁-C₄-haloalkylthio substituted Phenyl is substituted.

R¹ preferably represents in each case optionally up to five times, the same or different from C₁-C₈-alkyl, halogen, C₁-C₈-haloalkyl, C₁-C₄- Alkoxy-C₁-C₈-alkyl or optionally single to triple, the same or different from halogen, C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alk oxy, C₁-C₄-haloalkoxy, C₁-C₄-haloalkylthio, cyano or nitro sub substituted phenyl substituted C₃-C₇-cycloalkyl or C₄-C₇-cycloalkenyl.

R² and R³ independently of one another preferably represent hydrogen, halogen, cyano, nitro, C₁-C₈-alkyl, C₁-C₈-haloalkyl, C₁-C₈-hydroxyalkyl, each in each case optionally up to three times, identically or differently by halogen, C₁-C₄- Alkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkyl or C₁-C₄-Ha logenalkylthio substituted phenyl or thienyl or for one of the residues CO₂R⁵, CXNR⁶R⁷ or S (O) _n R⁸.

R⁴ preferably represents hydrogen, C₁-C₈-alkyl, C₁-C₈-haloalkyl, C₁-C₈- Hydroxyalkyl, C₁-C₄-alkoxy-C₁-C₈-alkyl, C₃-C₈-alkenyl, C₃-C₅-halogen alkenyl, C₃-C₈-hydroxyalkenyl, C₁-C₄-alkoxy-C₃-C₅-alkenyl, C₃-C₅-Al kinyl, C₃-C₈-haloalkynyl, C₃-C₈-hydroxyalkynyl, C₁-C₄-alkoxy-C₃-C₈ alkynyl, each optionally up to triple, the same or ver distinguished by halogen, C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkyl or C₁-C₄ haloalkoxy substituted phenoxy, benzyl or benzyloxy or for one of the radicals SO₂NR⁶R⁷, SO₂R⁹, COR¹⁰, CH₂N (R⁹) CO₂R⁵ or CH₂N (R⁹) SO₂R⁵.

R⁵ is preferably C₁-C₈ alkyl.

R⁶ and R⁷ independently of one another preferably represent hydrogen C₁-C₈-alkyl or together with the N atom to which they are attached for a 5- to 7-membered ring, which may contain up to two additional hetero contains atoms from the series N, O and S.

R⁸ is preferably C₁-C₈-alkyl or C₁-C₈-haloalkyl.

R⁹ is preferably C₁-C₈ alkyl or optionally up to three fold, the same or different by halogen, C₁-C₄-alkyl or C₁-C₄-alk oxy substituted phenyl.

R¹⁰ preferably represents C₁-C₈-alkyl, C₁-C₈-alkoxy or any given if single to triple, identical or different by halogen, C₁-C₄- Alkyl or C₁-C₄ alkoxy substituted phenyl or phenoxy.

X preferably represents oxygen or sulfur.

n is preferably 0, 1 or 2.

Ar particularly preferably represents the same, if appropriate single to five times or different from fluorine, chlorine, bromine, cyano, C₁-C₂-alkyl, C₁-C₂- Alkoxy, C₁-C₂-alkylthio or C₁-C₄-haloalkyl, C₁-C₄-haloalkoxy, C₁-C₄ haloalkylthio, C₁-C₄ haloalkylsulfinyl or C₁ -C₄ halo kylsulfonyl, each with 1 to 7 identical or different halogen atoms from the series fluorine, chlorine and bromine substituted phenyl or for gege  if necessary, up to three times, the same or different from fluorine, chlorine, Bromine, cyano, nitro, C₁-C₂-alkyl, C₁-C₂-alkoxy, C₁-C₂-alkylthio or C₁- C₄-haloalkyl, C₁-C₄-haloalkoxy, C₁-C₄-haloalkylthio, C₁-C₄- Haloalkylsulfinyl or C₁-C₄-haloalkylsulfonyl, each with 1 to 7 same or different halogen atoms from the series fluorine, chlorine and bromine substituted pyridyl.

A particularly preferably stands for a direct bond or for straight-chain or branched C₁-C₄ alkylene, optionally by chlorine, bromine or by optionally single or double, the same or different by fluorine, chlorine, bromine, cyano, nitro, C₁-C₂-alkyl, C₁-C₂-alkoxy, C₁- C₂-alkylthio or C₁-C₂-haloalkyl, C₁-C₂-haloalkoxy or C₁-C₂- Haloalkylthio each with 1 to 5 identical or different halo Phenyl genomic atoms from the series fluorine, chlorine and bromine is substituted.

R¹ particularly preferably represents in each case optionally up to triple, identical or different by C₁-C₆-alkyl, fluorine, chlorine, bromine, cyano, Nitro, C₁-C₆ haloalkyl with one to three identical or different Halogen atoms from the series fluorine, chlorine and bromine, C₁-C₂-alkoxy-C₁- C₆-alkyl or optionally single to triple, the same or different by fluorine, chlorine, bromine, C₁-C₃-alkyl, C₁-C₃-alkoxy or C₁-C₃-halo genalkyl, C₁-C₃-haloalkoxy or C₁-C₃-haloalkylthio, each with one to three identical or different halogen atoms from the series Fluorine, chlorine and bromine substituted phenyl substituted C₃-C₇- Cycloalkyl or C₅-C₇-cycloalkenyl.

R² and R³ independently of one another particularly preferably represent hydrogen, fluorine, chlorine, bromine, cyano, C₁-C₆-haloalkyl having one to six identical or different halogen atoms from the series fluorine, chlorine and bromine, each optionally one to three times identical or different phenyl or thienyl substituted by fluorine, chlorine, bromine, C₁-C₃-alkyl or C₁-C₃-alkoxy or for one of the residues CO₂R⁵, CXNR⁶R⁷ or S (O) _n R⁸.

R⁴ particularly preferably represents hydrogen, each optionally by one to three halogen atoms from the series fluorine, chlorine, bromine substituted  C₁-C₆-alkyl, C₃-C₆-alkenyl or C₃-C₆-alkynyl, for C₁-C₄-alkoxymethyl, for each, if necessary, single or double, the same or different benzyl or benzyloxy substituted by fluorine, chlorine or bromine or for one of the radicals SO₂R⁹, COR¹⁰ or CH₂N (R⁹) CO₂R⁵.

R⁵ is particularly preferably C₁-C₄ alkyl.

R⁶ and R⁷ independently of one another are particularly preferably hydrogen Methyl or ethyl.

R⁸ is particularly preferably a C₁-C₄-alkyl or C₁-C₄-haloalkyl up to three halogen atoms from the fluorine and chlorine series.

R⁹ particularly preferably represents C₁-C₄-alkyl or optionally simple up to three times the same or different by fluorine, chlorine or bromine substi tuated phenyl.

R¹⁰ particularly preferably represents C₁-C₄ alkyl or optionally simple up to three times the same or different by fluorine, chlorine or bromine substi tuated phenyl.

X particularly preferably represents oxygen or sulfur.

n particularly preferably represents 0, 1 or 2.

Ar very particularly preferably stands for one to five times, the same or different from fluorine, chlorine, bromine, cyano, trifluoromethyl, trifluor methoxy, trifluoromethylthio or trifluoromethylsulfonyl substituted Phe nyl or for single or double, identical or different by fluorine, Chlorine, bromine, cyano, nitro, trifluoromethyl, trifluoromethoxy, trifluorme thylthio or trifluoromethylsulfonyl substituted pyridyl.

A very particularly preferably represents a direct bond or one of the Groupings -CH₂-, -CH (CH₃) -, -C (CH₃) ₂-, -CH (C₂H₅) - or -CH (CH₂Cl) -.  

R¹ very particularly preferably represents in each case simple or twice, identical or different by methyl) ethyl, n- or i-propyl, n-, i-, s- or t-butyl substituted cyclopropyl, cyclobutyl, cyclopentyl, Cyclohexyl, cyclopentenyl or cyclohexenyl.

R² and R³ independently of one another very particularly preferably represent chlorine, bromine, cyano, trifluoromethyl and pentafluoroethyl, optionally phenyl which is monosubstituted to trisubstituted by fluorine, chlorine, bromine, methyl or methoxy or one of the radicals CO₂R⁵, CXNR⁶R⁷ or S (O) _n R⁸.

R⁴ very particularly preferably represents hydrogen methyl, ethyl, 2-propenyl, 2-propynyl, methoxymethyl, ethoxymethyl, propoxymethyl, i-propoxy methyl, n-butoxymethyl.

R⁵ very particularly preferably represents methyl or ethyl.

R⁶ and R⁷ very particularly preferably represent hydrogen.

R⁸ very particularly preferably represents methyl, ethyl, trifluoromethyl, 1,1- Difluoroethyl, 2,2,2-trifluoroethyl.

X very particularly preferably represents oxygen or sulfur.

n very particularly preferably represents 0, 1 or 2.

The residue definitions listed above or in preferred areas or explanations apply to the end products and to the initial and Intermediates accordingly. These residual definitions can be thus also be combined as desired between the respective preferred areas.

According to the invention, preference is given to the compounds of the formula (I) in which a combination of the Be listed as preferred (preferred) interpretations are available.  

According to the invention, particular preference is given to the compounds of the formula (I), in which are a combination of those listed as particularly preferred above Meanings exist.

The compounds of the formula are very particularly preferred according to the invention (I) in which a combination of the above is particularly preferred listed meanings is present.

In the residue definitions listed above and below are hydrocarbons residues such as alkyl or alkenyl - also in compounds with heteroatoms such as Alkoxy or alkylthio - if possible straight or branched.

In addition to the production examples, the individual ones are those in the following table 1 compounds listed:  

Table 1

For example, if 5-amino-1-cyclohexyl-3,4-dicyano-pyrazole, 1- Fluorine-2,6-dichloro-4-trifluoromethylbenzene and chloromethylethyl ether as starting substances, the course of the reaction of process (a) according to the invention can be carried out the following formula scheme can be reproduced:

For example, 5-amino-1-cyclohexyl-4-cyano-3-trifluoromethyl is used pyrazole, iodomethane and 1-fluoro-2,6-dichloro-4-trifluoromethylbenzene as starting substances, the course of the reaction of process (b) according to the invention can be carried out the following formula scheme can be reproduced:

The to carry out the processes (a) and (b) as 5-Aminopyrazoles to be used as starting materials are represented by the formula (II) generally defined.

Some of the 5-amino-pyrazoles of the formula (II) are known. You can in Analogy to known methods can be produced (see, for example, Chem. Het. Comp. 17 (1981), 1; J. Org. Chem. 21 (1956), 1240; EP 0 201 852; EP 0 392 241; Chem. Ber. 95: 2871 (1962); J. Org. Chem. 29 (1964) 1915; Isv. Attad. Nauk SSR, Ser. Khim 11 (1990) 2583; J. Chem. Research (5) 1993, 76 and US 5,294,612).

Novel and also the subject of this invention are 5-aminopyrazoles of the formula (IIa)

in which
R ^{2-1 represents} chlorine, cyano, trifluoromethyl or pentafluoroethyl and
R¹ and A have the meaning given above,
being connected with
R ^2-1 = CF₃ and
A = direct bond and

is excluded.  

The 5-aminopyrazoles of formula (IIa) are obtained by using compounds of the formula (VI)

in which
R ^{2-1 has} the meaning given above and
L represents chlorine or cyano,
with hydrazines of the formula (VII)

R¹-A-NHNH₂ (VII)

in which
R¹ and A have the meaning given above,
or with their acid addition salts in the presence of a diluent and, if appropriate, in the presence of a reaction auxiliary.

The compounds of formula (VI) are known and / or can be in general known way can be obtained (see, for example, Zh. Org. Khim. 1981, 17, 268-272 and J. Org. Chem. 1967, 32, 1941-1944).

The hydrazines of formula (VII) and their acid addition salts, such as wise hydrochloride are generally known compounds of the organic Che mie.

As a diluent for the preparation of the 5-aminopyrazoles of the formula (IIa) inert organic solvents are suitable. Are preferably usable aliphatic, alicyclic or aromatic, optionally halogenated carbons Hydrogen, 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 or diethyl ether, nitriles, such as acetonitrile or propionitrile, amides, such as dimethyl formamide, dimethylacetamide, N-methylformanilide, N-methylpyrrolidone or Hexamethylphosphoric acid amide, esters, such as ethyl acetate or sulfoxides, such as dimethyl sulfoxide, alcohols such as methanol or ethanol or basic Lö solvents such as pyridine or triethylamine.

The process for the preparation of the 5-aminopyrazoles of formula (IIa) is preferably carried out in the presence of a suitable reaction auxiliary. As such, all commonly used inorganic and organic bases in question. Alkali metal hydrides are preferably used, hydroxides, alcoholates, acetates, carbonates or bicarbonates, for example wise sodium hydroxide, sodium methylate, sodium ethylate, potassium t-butoxide, Na trium acetate, potassium acetate, sodium carbonate, potassium carbonate or sodium hydro gene carbonate or tertiary amines, for example triethylamine, N, N-dimethylaniline, Pyridine, N, N-dimethylaminopyridine, diazabicyclooctane (DABCO), diazabicyclo nonen (DBN) or diazabicycloundecene (DBU). Also acidic reaction aids such as p-toluenesulfonic acid may be advantageous.

The reaction temperatures in the preparation of the 5-aminopyrazoles Formula (IIa) can be varied over a wide range. Generally works one at temperatures between 0 ° C and + 130 ° C, preferably at temperatures between 20 ° C and 80 ° C.

To carry out the process for the preparation of the 5-aminopyrazoles of For mel (IIa) is generally 1 to 1 per mole of compound of the formula (VI) 4 moles, preferably 1 to 2 moles of hydrazine of the formula (VII) and given if 1 to 3 mol, preferably 1 to 2 mol, of reaction auxiliary.

Carrying out the reaction, working up and isolating the reaction products takes place according to generally accepted methods (see also the production examples).

The also in the process (a) and (b) according to the invention as a starting point Compounds to be used are generally de finishes.  

Hal preferably represents fluorine, chlorine or bromine, particularly preferably fluorine or chlorine.

The compounds of formula (III) are known and / or can be analogous to known processes can be prepared (see, for example, EP 0 398 499, J. Org. Chem. 47 (1982) 2856; U.S. 3,888,932; US 3,928,416).

The starting point in process (a) and (b) according to the invention Compounds to be used are generally de by the formula (IV) finishes.

E preferably represents chlorine, bromine, iodine, acetoxy, tosyl or mesyl.

The compounds of formula (IV) are generally known substances of the organization African chemistry.

The processes (a) and (b) according to the invention are preferably used diluents. As a diluent come in handy table all inert organic solvents in question. These include preferential wise aliphatic and aromatic, optionally halogenated hydrocarbons substances such as pentane, hexane, heptane, cyclohexane, petroleum ether, gasoline, ligroin, Benzene, toluene, xylene, methylene chloride, ethylene chloride, chloroform, tetrachlor carbon chlorobenzene or o-dichlorobenzene, ethers such as diethyl, dibutyl ether, Glycol dimethyl ether, diglycol dimethyl ether, tetrahydrofuran or dioxane, ketones such as acetone, methyl ethyl, methyl isopropyl or methyl isobutyl ketone, esters such as methyl acetate or ethyl ester, nitriles such. B. acetonitrile or Propionitrile, amides such as e.g. B. dimethylformamide, dimethylacetamide or N-Me thylpyrrolidone and dimethyl sulfoxide, tetramethylene sulfone or hexamethylene phosphoric triamide.

All of them can be used as acid acceptors in processes (a) and (b) according to the invention Acid binder which can usually be used for such reactions be set. Alkali metal and alkaline earth metal are preferred hydrides, such as lithium, sodium, potassium or calcium hydride, alkali metal or Alkaline earth metal hydroxides, such as lithium, sodium, potassium or calcium hydroxide, Alkali metal or alkaline earth metal carbonates or bicarbonates, such as Na trium or potassium carbonate or hydrogen carbonate or calcium carbonate, alkali  metal acetates, such as sodium or potassium acetate, alkali metal alcoholates, such as Na trium or potassium tert-butoxide, also basic nitrogen compounds, such as Trimethylamine, triethylamine, tripropylamine, tributylamine, diisobutylamine, di cyclohexylamine, ethyldiisopropylamine, ethyldicyclohexylamine, N, N-dimethyl benzylamine, N, N-dimethyl-aniline, pyridine, 2-methyl, 3-methyl, 4-methyl, 2,4- Dimethyl, 2,6-dimethyl, 2-ethyl, 4-ethyl or 5-ethyl-2-methyl-pyridine, 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).

The reaction temperatures in process (a) and (b) can be varied over a wide range. Generally one works at Temperatures between 0 ° C and 100 ° C, preferably at temperatures between 10 ° C and 80 ° C.

Processes (a) and (b) according to the invention are generally described under Nor painting done. However, it is also possible to increase or decrease pressure to work.

To carry out processes (a) and (b) according to the invention, the respective because starting materials are generally required in approximately equimolar amounts gene used. However, it is also possible to use either of the two To use components in a larger excess. The reactions who generally in a suitable diluent in the presence of a Acid acceptor performed, and the reaction mixture is at several hours the required temperature is stirred. The processing takes place at the The methods according to the invention in each case by customary methods (cf. the manufacturer examples).

The compounds of the formula (Ia) can also be obtained by reacting 5- Halogenpyrazoles with appropriately substituted anilines. The necessary for this 5-halopyrazoles are, for example, from the pyrazoles of the formula (H) Diazotization and subsequent Sandmeyer reaction accessible, while sub Substituted anilines are known in large numbers and are often commercially available or easily available are to be delivered, for example by reducing the corresponding nitro compounds.

The active ingredients are suitable for good plant tolerance and inexpensive warmth blood toxicity to control animal pests, especially insects,  Arachnids and nematodes found in agriculture, in forests, in and material protection as well as in the hygiene sector. You can before are preferably used as pesticides. You are against normal sen sible and resistant species as well as against all or individual stages of development effective. The pests mentioned above include:

From the order of the Isopoda z. B. Oniscus asellus, Armadillidium vulgare, Por cellio scaber.

From the order of the Diplopoda z. B. Blaniulus guttulatus.

From the order of the Chilopoda z. B. Geophilus carpophagus, Scutigera spec.

From the order of the Symphyla z. B. Scutigerella immaculata.

From the order of the Thysanura z. B. Lepisma saccharina.

From the order of the Collembola z. B. Onychiums armatus.

From the order of Orthoptera z. B. Blatta orientalis, Periplaneta americana, Leucophaea maderae, Blattella germanica, Acheta domesticus, Gryllotalpa spp., Locusta migratoria migratorioides, Melanoplus differentialis, Schistocerca gregaria.

From the order of the Dermaptera z. B. Auricular Forficula.

From the order of the Isoptera z. B. Reticulitermes spp.

From the order of the Anoplura z. B. Pediculus humanus corporis, Haematopinus spp., Linognathus spp.

From the order of the Mallophaga z. B. Trichodectes spp., Damalinea spp.

From the order of the Thysanoptera z. B. Hercinothrips femoralis, Thrips tabaci.

From the order of Heteroptera z. B. Eurygaster spp., Dysdercus interrnedius, Piesma quadrata, Cimex lectularius, Rhodnius prolixus, Triatoma spp.  

From the order of Homoptera z. B. Aleurodes brassicae, Bemisia tabaci, Trialeurodes vaporariorum, Aphis gossypii, Brevicoryne brassicae, Cryptomyzus ribis, Aphis fabae, Aphis pomi, Eriosoma lanigemm, Hyaloptems arundinis, Phylloxera vastatrix, Pemphigns spp., Macrosiphum avenae, Myzus spp., Phorodon humuli, Rhopalosiphum padi, Empoasca spp., Euscelis bilobatus, Nephotettix cincticeps, Lecanium comi, Saissetia oleae, Laodelphax striatellus, Nilaparvata lugens, Aonidiella aurantii, Aspidiotus hederae, Pseudococcus spp., Psylla spp.

From the order of the Lepidoptera z. B. Pectinophora gossypiella, Bupalus piniarius, Cheimatobia brnmata, 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., Spodoptera exigua, Mamestra brassicae, Panolis flammea, Spodoptera litura, Spodoptera spp., Trichoplusia ni, Carpocapsa pomonella, Pieris spp., Chilo spp., Pyrausta nubilalis, Ephestia kuehniella, Galleria mellonella, Tineola bisselliella, Tinea pellionella, Hofmannophila pseudospretella, Cacoecia podana, Capua reticulana, Choristoneura fumiferana, Clysia ambiguella, Homona magnanima, Tortrix viridana.

From the order of the Coleoptera z. B. Anobium punctatum, Rhizopertha dominica, Bruchidius obtectus, Acanthoscelides obtectus, Hylotrupes bajulus, Agelastica alni, Leptinotarsa decemlineata, Phaedon cochleariae, Diabrotica spp., Psylliodes chrysocephala, Epilachna varivestis, Atomaria spp., Oryzaephilus surinamensis, Ahthonomus 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, Costelytra zealandica.

From the order of the Hymenoptera z. B. Diprion spp., Hoplocampa spp., Lasius spp., Monomorium pharaonis, Vespa spp.

From the order of the Diptera z. B. 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., Bibio  hortulanus, Oscinella frit, Phorbia spp., Pegomyia hyoscyami, Ceraütis capitata, Dacus oleae, Tipula paludosa.

From the order of the Siphonaptera z. B. Xenopsylla cheopis, Ceratophyllus spp.

From the order of the Arachnida z. B. Scorpio maurus, Latrodectus mactans.

From the order of Acarina z. B. Acarus siro, Argas spp., Ormthodoros spp., Dermanyssus gallinae, Eriophyes ribis, Phyllocoptruta oleivora, Boophilus spp., Rhipicephalus spp., Amblyomma spp., Hyalomma spp., Ixodes spp., Psoroptes spp., Chorioptes spp., Sarcoptes spp., Tarsonemus spp., Bryobia praetiosa, Panonychus spp., Tetranychus spp.

The plant parasitic nematodes include z. B. Pratylenchus spp., Radopho lus similis, Ditylenchus dipsaci, Tylenchulus semipenetrans, Heterodera spp., Globodera spp., Meloidogyne spp., Aphelenchoides spp., Longidorus spp., xiphinema spp., Trichodorus spp.

The compounds of the formula (I) according to the invention are particularly noteworthy with a high level of insecticidal activity.

They can be used to control plants with particularly good success harmful insects, such as against the horseradish leaf beetle larvae (Phaedon cochlaeriae) or against the caterpillars caterpillars (Plutella xylostella) deploy.

The active ingredients can be converted into the usual formulations, such as Solutions, emulsions, wettable powders, suspensions, powders, dusts, pastes, soluble powders, granules, suspension emulsion concentrates, active ingredient-impregnated nated natural and synthetic substances as well as very fine encapsulation in polymers Fabrics.

These formulations are prepared in a known manner, e.g. B. by Ver mixing the active ingredients with extenders, i.e. liquid solvents and / or solid carriers, optionally using surface-active agents Agents, that is emulsifiers and / or dispersants and / or foam generators resources.  

In the case of the use of water as an extender, e.g. B. also organic Solvents are used as auxiliary solvents. As a liquid solvent essentially come into question: aromatics, such as xylene, toluene, or alkyl naphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chlorethylene or methylene chloride, aliphatic coal water serstoffe, such as cyclohexane or paraffins, e.g. B. petroleum fractions, mineral and vegetable oils, alcohols, such as butanol or 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 dimethyl sulfoxide, and Water.

The following are suitable as solid carriers:
e.g. B. ammonium salts and natural rock powders, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic rock powders, such as highly disperse silica, aluminum oxide and silicates; as solid carriers for granules come into question: z. B. broken and fractionated natural rocks such as calcite, marble, pumice, sepiolite, dolomite and synthetic granules from inorganic and organic flours as well as granules from organic material such as sawdust, coconut shells, corn cobs and tobacco stems; as emulsifying and / or foam-generating agents come into question: z. B. nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, e.g. B. alkylaryl polyglycol ethers, alkyl sulfonates, alkyl sulfates, aryl sulfonates and protein hydrolyzates; as dispersing agents come into question: z. B. lignin sulfite and methyl cellulose.

Adhesives such as carboxymethyl cellulose, natural, can be used in the formulations Liche and synthetic powdery, granular or latex-shaped polymers used such as gum arabic, polyvinyl alcohol, polyvinyl acetate, and natural Phospholipids such as cephalins and lecithins, and synthetic phospholipids. Other additives can be mineral and vegetable oils.

Dyes such as inorganic pigments, e.g. B. iron oxide, titanium oxide, Ferrocyan blue and organic dyes such as alizarin, azo and metal phthalalo cyanine dyes and trace nutrients such as salts of iron, manganese, boron, copper, Cobalt, molybdenum and zinc can be used.  

The formulations generally contain between 0.1 and 95 weight Percent active ingredient preferably between 0.5 and 90%.

The active ingredient according to the invention can be in its commercially available formulations as well as in the application forms prepared from these formulations in Mi with other active ingredients, such as insecticides, attractants, sterilants, Bak tericides, acaricides, nematicides, fungicides, growth regulators or herbicides. Insecticides include, for example, phosphorus acid esters, carbamates, carboxylic acid esters, chlorinated hydrocarbons, phenyl ureas, substances produced by microorganisms u. a.

Particularly cheap mixing partners are e.g. B. the following:

Fungicides

2-aminobutane; 2-anilino-4-methyl-6-cyclopropyl-pyrimidine; 2 ′, 6′-dibromo-2-methyl-4′-trifluoromethoxy-4′-trifluoromethyl-1,3-thiazole-5-carboxanide; 2,6-di chloro-N- (4-trifluoromethylbenzyl) benzamide; (E) 2-methoxyimino-N-methyl-2- (2-phenoxyphenyl) acetamide; 8-hydroxyquinoline sulfate; Methyl- (E) -2- {2- [6- (2-cyanophenoxy) pyrimidin-4-yloxy] phenyl} -3-methoxyacrylate; Methyl (E) methoximino [alpha- (o-tolyloxy) -o-tolyl] acetate; 2-phenylphenol (OPP), aldimorph, ampropylfos, anilazine, azaconazole,
Benalaxyl, Benodanil, Benomyl, Binapacryl, Biphenyl, Bitertanol, Blasticidin-S, Bromuconazole, Bupirimate, Buthiobate,
Calcium polysulfide, captafol, captan, carbendazim, carboxin, quinomethionate (quinomethionate), chloroneb, chloropicrin, chlorothalonil, chlozolinate, cufraneb, cymoxanil, cyproconazole, cyprofuram,
Dichlorophene, diclobutrazole, diclofluanid, diclomezin, dicloran, diethofencarb, difenoconazole, dimethirimol, dimethomorph, diniconazole, dinocap, diphenylamine, dipyrithione, ditalimfos, dithianon, dodine, drazoxolone,
Edifenphos, epoxyconazole, ethirimol, etridiazole,
Fenarimol, Fenbuconazole, Fenfuram, Fenitropan, Fenpiclonil, Fenpropidin, Fen propimorph, Fentinacetat, Fentinhydroxyd, Ferbam, Ferimzone, Fluazinam, Fludi oxonil, Fluoromide, Fluquinconazole, Flusilazole, Flusu1famide, Flutolanetol, Foli , Furalaxyl, Furmecyclox,
Guazatine,
Hexachlorobenzene, hexaconazole, hymexazole,
Imazalil, Imibenconazol, Iminoctadin, Iprobefos (IBP), Iprodione, Isoprothiolan,
Kasugamycin, copper preparations such as: copper hydroxide, copper naphthenate, copper oxychloride, copper sulfate, copper oxide, oxine copper and Bordeaux mixture,
Mancopper, Mancozeb, Maneb, Mepanipyrim, Mepronil, Metalaxyl, Metconazol, Methasulfocarb, Methfuroxam, Metiram, Metsulfovax, Myclobutanil,
Nickel dimethyldithiocarbamate, nitrothal isopropyl, Nuarimol,
Ofurace, oxadixyl, oxamocarb, oxycarboxin,
Pefurazoate, penconazole, pencycuron, phosdiphen, phthalide, pimaricin, piperalin, polycarbamate, polyoxin, probenazole, prochloraz, procymidon, propamocarb, propiconazole, propineb, pyrazophos, pyrifenox, pyrimethanil, pyroquilon,
Quintozen (PCNB),
Sulfur and sulfur preparations,
Tebuconazole, tecloftalam, tecnazene, tetraconazole, thiabendazole, Thicyofen, thiophanate-methyl, thiram, Tolclophos-methyl, tolylfluanid, triadimefon, Triadi menol, triazoxide, Trichlamid, tricyclazole, tridemorph, triflumizole, triforine, triticonazole,
Validamycin A, vinclozolin,
Zineb, ziram.

Bactericides

Bronopol, dichlorophene, nitrapyrin, nickel dimethyldithiocarbamate, Kasugamy cin, octhilinone, furan carboxylic acid, oxytetracycline, probenazole, streptomycin, Tecloftalam, copper sulfate and other copper preparations.

Insecticides / acaricides / nematicides

Abamectin, AC 303 630, Acephat, Acrinathrin, Alanycarb, Aldicarb, Alpha methrin, Amitraz, Avermectin, AZ 60541, Azadirachtin, Azinphos A, Azinphos M, Azocyclotin,
Bacillus thuringiensis, Bendiocarb, Benfuracarb, Bensultap) Betacyfluthrin, Bifen thrin, BPMC, Brofenprox, Bromophos A, Bufencarb, Buprofezin, Butocarboxin, Butylpyridaben,
Cadusafos, Carbaryl, Carbofuran, Carbophenothion, Carbosulfan, Cartap, CGA 157 419, CGA 184699, Chloethocarb, Chlorethoxyfos, Chlorfenvinphos, Chlor fluazuron, Chlormephos, Chlorpyrifos, Chlorpyrifos M, Cis-Resmethrin, Clocy thrin, Chrinophhrin, Clophin Cyhalothrin, cyhexatin, cypermethrin, cyromazine,
Deltamethrin, Demeton M, Demeton S, Demeton-S-methyl, Diafenthiuron, Di azinon, Dichlofenthion, Dichlorvos, Dicliphos, Dicrotophos, Diethion, Diflu benzuron, Dimethoat, Dimethylvinphos, Dioxathion, Disulfoton,
Edifenphos, Emamectin, Esfenvalerat, Ethiofencarb, Ethion, Ethofenprox, Etho prophos, Etrimphos,
Fenamiphos, Fenazaquin, Fenbutatinoxid, Fenitrothion, Fenobucarb, Fenothiocarb, Fenoxycarb, Fenpropathrin, Fenpyrad, Fenpyroximat, Fenthion, Fenvalerate, Fipronil, Fluazinam, Flucycloxuron, Flucythrinat, Flufenoxuron, Flufenothxinfox, Fufionophon, Fufionophon, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufon
HCH, heptenophos, hexaflumuron, hexythiazox,
Imidacloprid, Iprobefos, Isazophos, Isofenphos, Isoprocarb, Isoxathion, Iver mectin, Lambda-cyhalothrin, Lufenuron,
Malathion, Mecarbam, Mervinphos, Mesulfenphos, Metaldehyde, Methacrifos, Methamidophos, Methidathion, Methiocarb, Methomyl, Metolcarb, Milbemectin, Monocrotophos, Moxidectin,
Naled, NC 184, NI 25, Nitenpyram,
Omethoate, Oxamyl, Oxydemethon M, Oxydeprofos,
Parathion A, Parathion M, Permethrin, Phenthoat, Phorat, Phosalon, Phosmet, Phosphamidon, Phoxim, Pirimicarb, Pirimiphos M, Pirimiphos A, Profenofos, Promecarb, Propaphos, Propoxur, Prothiofos, Prothoat, Pymetrozin, Pyrachlophhine, Pyrachlophhion, Pyrachlophion, Pyrachlophin, Pyrachlophin, Pyrachlophin, Pyrachlophin, Pyrachlophin, Pyrachlophin, Pyrachlophion Pyridaben, pyrimidifen, pyriproxifen,
Quinalphos,
RH 5992,
Salithion, Sebufos, Silafluofen, Sulfotep, Sulprofos,
Tebufenozid, Tebufenpyrad, Tebupirimphos, Teflubenzuron, Tefluthrin, Temephos, Terbam, Terbufos, Tetrachlorvinphos, Thiafenox, Thiodicarb, Thiofanox, Thio methon, Thionazin, Thuringiensin, Tralomichonon, Triaromenontron, Triaromenontron, Triarathenlarbon, Triarathenltronium, Triarathenltronium, Triarathenltronium, Triarathenltronium, Triarathenltronium, Triarathenltronium, Triaromenontrin, Triarathenltronium, Triaromenontrin, Triarathenltron, Triaromenontron
Vamidothione, XMC, xylylcarb, YI 5301/5302, zetamethrin.

A mixture with other known active ingredients, such as herbicides or with Fertilizers and growth regulators are possible.

The active compounds according to the invention can also be used in their commercially available form formulations and in the application forms prepared from these formulations in a mixture with synergists. Synergists are connections through which the effect of the active ingredients is increased without the added synergist must be actively active itself.

The active ingredient content of the prepared from the commercially available formulations Application forms can vary widely. The drug concentration  the use forms can be from 0.0000001 to 95% by weight of active ingredient, preferably between 0.0001 and 1% by weight.

The application takes place in a customary manner adapted to the application forms Wise.

When used against hygiene and storage pests, the stands out Active ingredient through an excellent residual effect on wood and clay as well due to good stability to alkali on limed substrates.

It has also been found that the compounds of the formula 1 show a high insecticidal activity against insects, the technical materials to destroy.

The following are examples and preferably - but without limitation - Called insects:

Beetle like
Hylotrupes bajulus, Chlorophorus pilosis, Anobium punctatum, Xestobium rufovillosum, Ptilinus pecticornis, Dendrobium pertinex, Ernobius mollis, Priobium carpini, Lyctus brunneus, Lyctus africanus, Lyctus planicollis, Lyctus linearesces, Lyctus pubis linearis, Lyctus pubis linearis, speculum Tryptodendron spec. Apate monachus, Bostrychus capucins, Heterobostrychus brunneus, Sinoxylon spec. Dinoderus minutus.

Skin wings like
Sirex juvencus, Urocerus gigas, Urocerus gigas taignus, Urocerus augur.

Termites like
Kalotermes flavicollis, Cryptotermes brevis, Heterotermes indicola, Reticulitermes flavipes, Reticulitermes santonensis, Reticulitermes lucifugus, Mastotermes dar winiensis, Zootermopsis nevadensis, Coptotermes formosanus.

Bristle tails, such as Lepisma saccharina.  

In the present context, technical materials include non-living ones To understand materials, such as preferably plastics, adhesives, glues, Pa paper and cardboard, leather, wood and wood processing products and paints.

It is very particularly preferred to prevent insect attack protective material around wood and wood processing products.

Among wood and wood processing products, which by the invention Agents or mixtures containing them can be protected is exemplary to understand: timber, wooden beams, railway sleepers, bridge parts, jetties, Wooden vehicles, boxes, pallets, containers, telephone poles, wooden panels, Wooden windows and doors, plywood, chipboard, carpentry or wood pro products that are used in general in house construction or in joinery Find.

The active ingredients can be used as such, in the form of concentrates or in general usual formulations such as powders, granules, solutions, suspensions, emul sions or pastes.

The formulations mentioned can be prepared in a manner known per se be, e.g. B. by mixing the active ingredients with at least one solution or diluents, emulsifiers, dispersants and / or binders or fixatives, Water repellants, possibly desiccants and UV stabilizers and counter if necessary dyes and pigments and other processing aids.

The insecticidal agents used to protect wood and wood-based materials or concentrates contain the active ingredient according to the invention in a concentra tration from 0.0001 to 95 wt .-%, in particular 0.001 to 60 wt .-%.

The amount of agents or concentrates used depends on the type and type come from insects and depending on the medium. The optimal amount to use can be determined by test series in the application. Generally in my opinion, however, it is sufficient 0.0001 to 20% by weight, preferably 0.001 to 10 wt .-%, of the active ingredient, based on the material to be protected.

An organic chemical solvent serves as the solvent and / or diluent solvent or solvent mixture and / or an oily or oily heavy  volatile organic chemical solvent or solvent mixture and / or a polar organic chemical solvent or solvent combination mixed and / or water and optionally an emulsifier and / or wetting agent.

The organic chemical solvents used are preferably oily or oily ones Solvents with an evaporation number above 35 and a flash point above half 30 ° C, preferably above 45 ° C, used. As such smoldering, water-insoluble, oily and oily solvents become corresponding mine ralöle or their aromatic fractions or mineral oil-containing solvent mixtures cal, preferably white spirit, petroleum and / or alkylbenzene used.

Mineral oils with a boiling range of 170 to 220 ° C are advantageous, test petrol with a boiling range of 170 to 220 ° C, spindle oil with a boil range from 250 to 350 ° C, petroleum or aromatics with a boiling range of 160 up to 280 ° C, turpentine oil and the like.

In a preferred embodiment, liquid aliphatic hydrocarbons substances with a boiling range of 180 to 210 ° C or high-boiling mixtures of aromatic and aliphatic hydrocarbons with a boiling range from 180 to 220 ° C and / or locker oil and / or monochloronaphthalene, preferably two se α-monochloronaphthalene used.

The organic non-volatile oily or oily solvents with a Evaporation rate above 35 and a flash point above 30 ° C, preferably above 45 ° C, can be partly due to slightly or medium-volatile organic chemistry cal solvents are replaced, with the proviso that the solvent mix also an evaporation number above 35 and a flash point above 30 ° C, preferably above 45 ° C, and that the insecticide fungicide Mixture is soluble or emulsifiable in this solvent mixture.

According to a preferred embodiment, part of the organic chemical Solvent or solvent mixture or an aliphatic polar orga niche chemical solvent or solvent mixture replaced. Preferably come alipha containing hydroxyl and / or ester and / or ether groups organic chemical solvents such as glycol ether, esters or the like for use.  

As an organic chemical binder in the present Er finding the known water-dilutable and / or in the used organic chemical solvents soluble or dispersing or emul gable synthetic resins and / or binding drying oils, especially binders consisting of or containing an acrylic resin, a vinyl resin, e.g. B. polyvinyl acetate, Polyester resin, polycondensation or polyaddition resin, polyurethane resin, alkyd resin or modified alkyd resin, phenolic resin, hydrocarbon resin such as indene Coumarone resin, silicone resin, drying vegetable and / or drying oils and / or physically drying binders based on a natural and / or Resin used.

The synthetic resin used as a binder can be in the form of an emulsion, disper sion or solution. Bitumen or bituminous substances up to 10 wt .-%, are used. In addition, you can dyes, pigments, water-repellants, odor correctors known per se tien and inhibitors or corrosion protection agents and the like. Be used.

According to the invention, preference is given to organic chemical binders least an alkyd resin or modified alkyd resin and / or a drying one vegetable oil contained in the medium or in the concentrate. According to the invention alkyd resins with an oil content of more than 45 wt .-%, preferably as 50 to 68 wt .-%, used.

The binder mentioned can be wholly or partly by a fixation medium (mixture) or a plasticizer (mixture) can be replaced. These additions should volatilize the active ingredients and crystallize or from prevent falling. They preferably replace 0.01 to 30% of the binder (based on 100% of the binder used).

The plasticizers come from the chemical classes of phthalic acid esters such as Dibutyl, dioctyl or benzyl butyl phthalate, phosphoric acid esters such as tributyl phosphate, adipic acid esters such as di- (2-ethylhexyl) adipate, stearates such as butyl stearate or amyl stearate, oleates such as butyl oleate, glycerol ether or higher molecular weight Gly kolether, glycerol ester and p-toluenesulfonic acid ester.

Fixing agents are chemically based on polyvinyl alkyl ethers such as. B. Polyvinyl methyl ether or ketones such as benzophenone, ethylene benzophenone.  

Water is also particularly suitable as a solvent or diluent, optionally in a mixture with one or more of the above organic chemical solvents or diluents, emulsifiers and dispersers gators.

A particularly effective wood protection is provided by industrial impregnation drive, e.g. B. vacuum, double vacuum or printing process.

The ready-to-use agents can optionally also be other insecticides and optionally contain one or more fungicides.

The additional mixing partners are preferably those in WO 94/29 268 Insecticides and fungicides mentioned in question. The ones mentioned in this document Connections are an integral part of this application.

Insecticides such as chloropyriphos, phoxime, silafluofin, alphamethrin, cyfluthrin, cypermethrin, delta methrin, permethrin, intidacloprid, M-25, flufenoxuron, hexaflumuron and tri flumuron can be used as very particularly preferred mixing partners.
as well as fungicides such as epoxyconazole, hexaconazole, azaconazole, propiconazole, tebuconazole, cyproconazole, metconazole, imazalil, dichlorofluoride, tolylfluanid, 3-iodo-2-propynylbutylcarbamate, N-octyl-isothiazolin-3-one and 4,5-n octylisothiazolin-3-one,
be.

The manufacture and use of the active compounds according to the invention start out the following examples.

Manufacturing examples example 1 (Method (a))

To 0.45 g (0.0148 mol) sodium hydride (80% mineral oil dispersion) in 18 ml Dimethylformamide becomes a solution of 2 g (0.0074 mol) of 5-amino-1- Cyclohexyl-3,4-dicyano-pyrazole (Ex. IIa-1) added dropwise in 8 ml of dimethylformamide. The mixture is left to stir at 25 ° C. for 10 minutes and then added dropwise a solution of 3.45 g (0.0148 mol) of 1-fluoro-2,6-dichloro-4-trifluoromethylbenzene in 8 ml of dimethylformamide. The reaction mixture is at 60 ° C for one hour stirred and then poured onto ice water. The resulting solid is filtered off and chromatographed over silica gel with methylene chloride as a run medium cleaned.

1.95 g (56% of theory) of N- (1-cyclohexyl-3,4-dicyano-pyrazol-5-yl) are obtained. 2,6-dichloro-4-trifluoromethylaniline, melting point 163 ° C.  

Analogous to Example 1 or according to the general information on the preparation the compounds of formula (I) given in Table A below hold:

Table A

Preparation of the starting compounds of the formula (IIa) Example (IIa-1)

To a suspension of 6.50 g (0.043 mol) of cyclohexylhydrazine hydrochloride in 54 ml of absolute ethanol, 3.8 g (0.043 mol) of 45% sodium hydroxide solution are added dropwise and then a solution of 5.5 g (0.043 Mol) tetracyanoethylene in 70 ml ethanol. It is after 2 hours at 25 ° C stirred, the reaction solution concentrated to a third and stirred in water. The precipitated product is suctioned off and air-dried.

4.42 g (38% of theory) of 5-amino-1-cyclohexyl-3,4-dicyano-pyrazole are obtained melting point 189 ° C (decomposition).  

Analogous to example (IIa-1) or according to the general information on the preparation the compounds of the formula given in Table B below (IIa) received:

Table B

Examples of use

In the following application examples, the Ver binding used as reference substance:

Compound (A) known from WO 93/19054  

Example A Phaedon larval test

Solvent: 7 parts by weight of dimethylformamide
Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To prepare a suitable preparation of active compound, 1 Ge is mixed most of the active ingredient with the specified amount of solvent and the specified amount of emulsifier and dilute the concentrate with water to the wanted concentration.

Cabbage leaves (Brassica oleracea) are dipped into the active ingredient preparation the desired concentration and treated with horseradish leaf beetle larvae Phaedon cochleariae occupied while the leaves are still moist.

After the desired time, the kill is determined in%. Here means 100% that all beetle larvae have been killed; 0% means that no beetles Larvae were killed.

In this test, e.g. B. the connection according to Production Example 1 an exemplary active ingredient concentration of 0.1% a kill of 100% after 7 days, while the compound (A) known from the prior art caused no kill.  

Example B Plutella test

Solvent: 7 parts by weight of dimethylformamide
Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To prepare a suitable preparation of active compound, 1 Ge is mixed most of the active ingredient with the specified amount of solvent and the specified amount of emulsifier and dilute the concentrate with water to the wanted concentration.

Cabbage leaves (Brassica oleracea) are dipped into the active ingredient preparation the desired concentration and treated with caterpillars Plutella maculipennis occupied while the leaves are still moist.

After the desired time, the kill is determined in%. Here means 100% that all caterpillars have been killed; 0% means that no caterpillars were killed.

In this test, e.g. B. the connection according to Production Example 1 an exemplary active ingredient concentration of 0.1% a kill of 100% after 7 days, while the compound (A) known from the prior art caused no kill.

Claims (8)

1. Compounds of formula (I) in which
Ar represents optionally substituted phenyl, with nitro being excluded as a substituent, or represents optionally substituted pyridyl,
A represents a direct bond or optionally substituted alkylene,
R¹ stands for optionally substituted cycloalkyl or cyclo alkenyl,
R² and R³ independently of one another represent hydrogen, halogen, cyano, nitro, in each case optionally substituted alkyl, aryl or hetaryl or one of the radicals CO₂R⁵, CXNR⁶R⁷ or S (O) _n R⁸ and
R⁴ represents hydrogen, in each case optionally substituted alkyl, alkynyl, alkynyl, aralkyl, aryloxy or aralkyloxy or one of the radicals SO₂NR⁶R⁷, SO₂R⁹, COR¹⁰, CH₂N (R⁹) CO₂R⁵ or CH₂N (R⁹) SO₂R⁵, where
R⁵ represents alkyl,
R⁶ and R⁷ are independently hydrogen or alkyl or together with the N atom to which they are attached form a ring which may contain one or more further heteroatoms,
R⁸ represents alkyl or haloalkyl,
R⁹ represents alkyl or optionally substituted aryl,
R¹⁰ represents alkyl, alkoxy or optionally substituted aryl or aryloxy,
X represents oxygen or sulfur and
n stands for 0, 1 or 2. 2. Process for the preparation of compounds of formula (1) according to claim 1, characterized in that

• a) the compounds of the formula (I) are obtained if 5-aminopyrazoles of the formula (II) in which
  A, R¹, R² and R³ have the meaning given in claim 1,
  with compounds of the formula (III) Hal-Ar (III) in which
  Ar has the meaning given above and
  Hal stands for halogen,
  in the presence of an acid acceptor and in the presence of a diluent
  and optionally the compounds of formula (Ia) thus obtained in which
  A, Ar, R¹, R² and R³ have the meaning given above,
  with compounds of the formula (IV) ER ^4-1 (IV) in which
  R ^{4-1 has} the meaning given in claim 1 for R⁴ with the exception of hydrogen and
  E represents an anionic leaving group,
  in the presence of an acid acceptor and optionally in the presence of a diluent;
  or
• b) compounds of the formula (Ib) in which
  A, Ar, R¹, R², R³ and R ^{4-1 have} the meaning given above,
  obtained when 5-aminopyrazoles of the formula (II) in which
  A, R¹, R² and R³ have the meaning given above,
  with compounds of the formula (IV) ER ^4-1 (IV) in which
  E and R ^{4-1 have} the meaning given above,
  in the presence of an acid acceptor and in the presence of a diluent and the compounds of the formula (V) thus obtained in which
  A, R¹, R², R³ and R ^{4-1 have} the meaning given above,
  then with compounds of the formula (III) Hal-Ar (III) in which
  Ar and Hal have the meaning given above,
  in the presence of an acid acceptor and in the presence of a diluent.

3. Compounds of the formula (IIa) in which
R ^{2-1 represents} chlorine, cyano, trifluoromethyl or pentafluoroethyl and
R¹ and A have the meaning given above,
being connected with
R ^2-1 = CF₃ and
A = direct bond and is excluded. 4. pesticides, characterized by a content of min at least one compound of formula (I) according to claim 1. 5. Use of compounds of formula (I) according to claim 1 for Pest control. 6. A method for controlling pests, characterized in that compounds of formula (I) according to claim 1 on pests and / or let their living space take effect. 7. Process for the manufacture of pesticides, thereby characterized in that compounds of the formula (I) according to Claim 1 mixed with extenders and / or surfactants. 8. Use of compounds of formula (I) according to claim 1 for Manufacture of pesticides.