Derivatives of 1-aryl-5-(substituted methylidene)pyrazole, method of combating harmful insects and insecticidal composition

 

(57) Abstract:

Usage: in agriculture. The essence of the invention: derivatives of 1-aryl-5-(substituted methylidene) pyrazole of the General formula (I), where R is cyano or chloro; R1- nitro, trifluoromethyl or a group R5S(O)nwhere R5- C1- C4-alkyl or trihalogen1- C4-alkyl, n=0-2; R2is unsubstituted phenyl or phenyl substituted by 1 to 4 identical or different groups selected from a range that contains hydroxy, halogen, cyano, nitro, C1- C4-alkyl, trifluoromethyl, C1- C10-alkoxy, C2- C8-alkanoyloxy, benzyloxy, C1- C4-alkylthio, NR6R7where R6and R7is independently hydrogen, C1- C4-alkyl or acetyl, or R2-4-pyridyl, 4-pyridyl-N-oxide, 2-thienyl, 2-furanyl, 2-imidazolyl, 6-benzo-[1,3-dioxole]; R3-halogen; R4-halogen, trifluoromethyl or triptoreline; X is nitrogen or a group of CCl or CH; a method of combating harmful insects by treating the source of infection an effective dose of a compound of formula (I) and insecticidal composition comprising of 0.1 to 50.0 wt.% the compounds of formula as an active ingredient in a mixture with a solid or liquid carrier and/or the .

The invention relates to new 1-aryl-5-(substituted)alkylidene the pyrazoles, methods for their preparation, to compositions containing these compounds, to methods of their use for combating arthropods, nematodes, helminths or protozoa pests. In particular, the present invention relates to the use of such compounds or compositions in agriculture as pesticides for the control of arthropods, such as insects, using methods involving the ingestion of harmful insects these pesticides, or contacting these insects with these pesticides.

A variety of 1-(substituted phenyl or pyridyl)-5-(substituted amino)pyrazoles are known as compounds with pesticidal activity, for example, as herbicides, plant growth regulators, insecticides and nematicides.

Of these compounds have been described following connections:

in U.S. patent No. 4 863 937 as insecticides, acaricides and nematicides disclosed 1-aryl-5-(substituted alkylidene)pyrazoles, which are unsubstituted or alkyl - or halogenated-substituted at the 3-position of the pyrazol ring;

in Europatent N 301 339 and with the s (S. 3, 6, 10 and 16 links), which are used as intermediates to obtain insecticidal compounds. These compounds are unsubstituted or alkyl - or galogenzameshchennye in the 3-position of the pyrazol ring;

in the work of Hennig L., and others J. Prakt. Chem. 332 3, 351-8, and the corresponding reference CAS 113(25): 231264g (this work is devoted entirely to chemistry) discloses 1-phenyl-5-(substituted phenylethylenediamine)pyrazoles that are either methyl - or phenyl-substituted in the 3-position of the pyrazol ring. Relative to the pesticidal activity of these compounds in this work, no guidance is available;

in the United Kingdom patent N 923734 disclosed 1-aryl-5-(substituted phenylethylenediamine)pyrazoles as dyes, which are only a cyano-substituted at the 3-position of the pyrazol ring;

in U.S. patent No. 4 685 957 disclosed as herbicides and plant growth regulators 1-aryl-5-(substituted imino-amino)pyrazoles, which are unsubstituted or alkyl-substituted in the 3-position of the pyrazol ring;

in EP N 295 117; WO 87/03781 (similar EP N 234119); EP N 295118 and EP N 350311 disclosed 1-phenyl-5-(substituted amino)pyrazolone compounds that are used to control arthropods, Nemat the herbicides 1-(substituted-2-pyridyl)-5-(substituted amino)-4-cyanopyridine, which are unsubstituted in the 3-position of the pyrazol ring;

in U.S. patent No. 4 772 312 are disclosed as herbicides 1-(substituted-2-pyridyl)-5-(substituted amino)pyrazoles, which are unsubstituted or alkyl-substituted in the 3-position of the pyrazol ring;

in U.S. patent No. 4 804 675 disclosed as insecticides, acaricides and nematicides 1-(substituted-2-pyridyl)-5-(substituted amino)pyrazoles, which are unsubstituted or alkyl - or halogen-substituted at the 3-position of the pyrazol ring;

in U.S. patent No. 4 740 232 disclosed as herbicides 1-(substituted phenyl)-5-(substituted amino)pyrazoles, which are unsubstituted in the 3-position of the pyrazol ring;

in EP N 398 499 disclosed as insecticides and acaricides phenyl-substituted heterocyclic compounds, including 1-(substituted phenyl)-5-(substituted amino)pyrazoles;

in U.S. patent No. 4 822 810 disclosed 1-aryl-4-cyano-3-(sulfur-substituted)-5-(alkoxyalkane)pyrazoles used for combating arthropod pests;

in U.S. patent N 3 686 171 disclosed N'-[(4-hydroxymethyl or formyl)-5-pyrazolyl]amidine, used as intermediates or anti-inflammatory drugs;

in periodstop to proteins;

in the work Simay T. et al. Acta Chemica Academiae Scintiezum Hungaricae, so 105(2), 127-139 (1980) describes the chemical synthesis and physical properties of various 5-(substituted amino)pyrazoles (e.g., compounds 2, 4, 7, 8 and 15-18).

From the above examples it is obvious that the nature and position of the groups of substituents on pyrazol ring vary widely, and accordingly they report pyrazolones compounds of different biological activity, the type and level of which are not easily definable.

The invention relates to new 1-aryl-5-(substituted alkylidene)the pyrazoles, which unexpectedly showed excellent properties as pesticides, particularly as insecticides when used to combat insects the method comprising the ingestion of insects such compounds or their contact with these compounds.

These compounds, including their isomers, for example, GeoStereo and optical isomers, can be represented by the General formula

(I)

where R1cyano, nitro, halogen, formyl, alkylsulphonyl or cycloalkylcarbonyl; and where the alkyl part is a straight or branched chains of 1-4 carbon atoms, and cycloalkyl portion contains 3 to 7 atoms ugley mono - or dialkyl-substituted sulfamoyl; unsubstituted or mono - or dialkyl-substituted aminocarbonyl; alkoxycarbonyl; or unsubstituted or substituted R9S(O)nwhere n=0, 1, or 2, and R9is alkyl, halogenation, cycloalkyl, halogencyclization, cycloalkylation or halogencyclization; and where the alkyl part is a straight or branched chains of 1-4 carbon atoms; cycloalkyl portion contains 3 to 7 carbon atoms, and halogen-substitution consists of one or more halogen atoms, which may be the same or different, up to full substitution of the alkyl or cycloalkyl parts;

R3is hydrogen, C1-4-alkyl, C1-4-alkoxy, C1-4-alkylthio or di-C1-4-alkylamino; and where the alkyl portion is straight or branched chain;

R4unsubstituted or substituted phenyl, or unsubstituted or substituted heteroaryl having 5 or 6 members on the monocyclic ring containing one or more identical or different heteroatoms of oxygen, sulfur or nitrogen; where the phenyl or heteroaryl substitution is one or more combinations of: hydroxy or inorganic or organic salts; sulphydryl or reorga the l-O-; halogenoalkane; alkanoyloxy; phenoxy; trialkylsilyl; phenyl; alkyl-S(O)nor halogenated-S(O)nwhere n=0, 1, or 2; NR10R11where each of R10and R11is hydrogen, alkyl, alkanoyl or halogenoalkanes; COR12where R12is NR10R11, alkoxy, alkylthio, hydroxy or inorganic or organic salt, hydrogen alkyl, or halogenation; or SO2R13where R13is NR10R11, alkoxy, alkylthio, or hydroxy or inorganic or organic salt; and where the alkyl and alkoxy part is a straight or branched chains of 1-4 carbon atoms, and halogen-substitution consists of one or more halogen atoms, which may be the same or different, up to full substitution of the alkyl or alkoxy-parts;

R5hydrogen, halogen or straight or branched C1-4-alkyl;

R6and R8are independently hydrogen or fluorine;

R7halogen, alkyl, halogenated, alkoxy, halogenoalkane, cyano, nitro, alkylsulphonyl, halogenoalkanes, alkyl-S(O)nor halogenated-S(O)nin which n=0, 1, or 2; and where the alkyl or alkoxy-part presented the channels at the atoms of halogen, which may be the same or different, up to full substitution of the alkyl or alkoxy-parts;

X is a nitrogen atom (N) or C-R14where R14is hydrogen, halogen, cyano, nitro, C1-4-alkyl, C1-4-alkylthio or C1-4-alkoxy, where the alkyl portion is straight or branched chain.

In the compounds of formula (I) defined above, in the case when R4is heteroaryl so heteroaryl are preferably (but not limited to): unsubstituted or substituted pyridyl, pyridyl, N-oxetanyl, furanyl, pyrrolyl, imidazole, triazole, or etc.

More preferred compounds of formula (I) are compounds in which:

R1represents a cyano, nitro, or halogen;

R2represents an unsubstituted or substituted R9S(O)nwhere n=0, 1, or 2, and R9is alkyl, or halogenation defined above;

R3represents hydrogen;

R4represents unsubstituted or substituted phenyl, or unsubstituted or substituted heteroaryl, which is pyridium, pyridyl N-oxide, teinila, TuranAlem, peradilan, imidazolium or triazolium;
oredom or fluorine;

R7represents halogen, alkyl, halogenated or halogenoalkane;

X represents a nitrogen atom (N) or C-R14where R14is hydrogen, halogen, cyano, alkyl, alkylthio or alkoxy.

Especially preferred compounds of formula (I) are compounds of the formula

(Ia)

where R2is an R9S(O)nwhere n=0, 1, or 2, and R9is an alkyl, preferably a stands; or halogenation, preferably by trihalomethyl or dehalogenation; and where halogen is F, C1 or Br or combinations thereof, and more preferably CF3, CCl3, CF2Cl, CFCl2, CF2Br, CHF2, CHClF or CHCl2;

R4represents unsubstituted or substituted phenyl, where the substituents are one or more hydroxy; halogen; preferably F, Cl, or Br; alkoxy, preferably methoxy or ethoxy; alkylthio, preferably methylthio; cyano; or alkyl, preferably methyl or ethyl; or combinations thereof; or R4is a 4-pyridium or 4-pyridyl N-oxide, optionally substituted by the substituents mentioned for phenyl;

R5represents alkyl, preferably methyl, or halogen, prepost is methyl; halogenated, preferably trihalomethyl, and more preferably trifluoromethyl; or halogenoalkane, preferably trihalomethane, and more preferably, triptoreline; where halogen is F, Cl or Br or combinations thereof;

X represents a nitrogen atom or C-R14where R14is hydrogen; halogen, preferably F, Cl or Br, cyano; alkyl, preferably the stands or ethyl; alkylthio, preferably methylthio or ethylthio; or alkoxy, preferably methoxy or ethoxy.

For the described preferred compounds of formula (I), in particular of formula (Ia), there are optimal combinations of the groups of substituents that optimize and maximize pesticide activity based on the optimal combination of chemical, physical and biological properties for each of the connection. In particular, from the above groups increased or unexpected emergence of pesticide activity contribute to the following groups:

In the case of R4preferred groups, for example, are:

1. 4-hydroxy-3-methoxyphenyl;

2. 4-hydroxyphenyl;

3. 3-hydroxy-4-methoxyphenyl;

4. 3,5-dimethyl-4-hydroxyphenyl;

5. 3,5-dimethoxy-4-hydroxyethoxyphenyl;

10. 3,4,5-trimethoxyphenyl;

11. phenyl

12. 2-hydroxyphenyl;

13. 3,4-dihydroxyphenyl;

14. 2,4-dimetilfenil;

15. 4-cyanophenyl;

16. 4-pyridyl;

17. 4-pyridyl N-oxide;

18. 3-chloro-4-hydroxyphenyl;

19. 2-chloro-4-hydroxyphenyl;

20. 5-bromo-4-hydroxy-3-methoxyphenyl;

21. 3-hydroxyphenyl;

22. 5-chloro-4-hydroxy-3-methoxyphenyl;

23. 2,4,5-trihydroxyphenyl;

24. 5-bromo-3,4-dihydroxyphenyl;

25. 4,5-dihydroxy-3-methoxyphenyl.

Of these groups for R4most preferred are taken separately group, N:

(A) 1-10, 12-15 or 18-25; or

In) 1-5, 7-9, 13 or 18-25; or

(C) 1-4, 18 or 19.

In the case of 1-phenyl - or 1-(2-pyridyl)-group having substituents R5, R6, R7, R8and R14preferred groups, for example, are:

1. 2,6-sodium dichloro-4-triptoreline;

2. 2,6-sodium dichloro-4-trifloromethyl;

3. 2-chloro-4-trifloromethyl;

4. 2-chloro-4-triptoreline;

5. 2,4,6-trichlorophenyl;

6. 2,6-sodium dichloro-4-forefeel;

7. 4-bromo-2,6-dichlorophenyl;

8. 2-chloro-6-methyl-4-trifluromethyl;

9. 2-chloro-6-methylthio-4-trifluromethyl;

10. 2,4-dichlorophenyl;

11. 2-chloro-4-forefeel;

12. 2 chloromethoxy-2-pyridyl;

16. 3-chloro-5-fluorescent-2-pyridyl;

17. 3,5-sodium dichloro-2-pyridyl;

18. 2-bromo-4-trifloromethyl;

19. 2-bromo-4-triptoreline;

20. 2-chloro-6-fluorescent-4-trifloromethyl;

21. 2-chloro-6-fluorescent-4-trifluromethyl;

22. 2-chloro-6-cyano-4-trifloromethyl.

Of these 1-phenyl or 1-(2-pyridyl)-groups, more preferred are groups N 1 8, 14 and 21 or 22. And the most preferred are group N 1 5, 7, 8, 14, 21 or 22.

Of the compounds of formula (I), more preferably formula (Ia), preferred are the following compounds with particularly good activity against larval insects using their method, involving the ingestion or contact, namely:

Connection N:

2. 1-(2,6-sodium dichloro-4-trifloromethyl)-3-cyano-4-trifloromethyl-5-[(4-hydroxy-3 - methoxyphenyl)methylidene]pyrazole;

3. 1-(2,6-sodium dichloro-4-trifloromethyl)-3-cyano-4-trifloromethyl-5-[(4-hydroxy-3 - methoxyphenyl)methylidene]pyrazole;

4. 1- (2,6-sodium dichloro-4-trifloromethyl)-3-cyano-4-trifloromethyl-5-[(4-hydroxyphenyl)methylidene]-pyrazole;

6. 1-(2,6-sodium dichloro-4-trifloromethyl)-3-cyano-4-dichlorophenolindophenol-5-[(4-hydroxy-3 is lpanel-5-[(4-hydroxy-3-methoxyphenyl) methylidene]pyrazole;

10. 1(2,6-sodium dichloro-4-trifloromethyl)-3-cyano-4-trifloromethyl-5-[(4-hydroxy-3 - methoxyphenyl)methylidene]pyrazole;

13. 1-(2,6-sodium dichloro-4-trifloromethyl)-3-cyano-4-trifloromethyl-5-[(3,5-dimethoxy-4-hydroxyphenyl) methylidene]pyrazole;

15. 1-(2,6-sodium dichloro-4-trifloromethyl)-3-cyano-4-trifloromethyl-5-[(3-hydroxy-4 - methoxyphenyl)methylidene]pyrazole;

16. 1-(2,6-sodium dichloro-4-trifloromethyl)-3-cyano-4-trifloromethyl-5-[(4-pyridyl)-methylidene]pyrazole;

17. 1-(2,6-sodium dichloro-4-trifloromethyl)-3-cyano-4-trifloromethyl-5-[(2,4-dihydroxyphenyl)-methylidene]pyrazole;

18. 1-(2,6-sodium dichloro-4-trifloromethyl)-3-cyano-4-trifloromethyl-5-[(4-pyridyl-N-oxide)methylidene]pyrazole;

19. 1-(2,6-sodium dichloro-4-trifloromethyl)-3-cyano-4-trifloromethyl-5-[(4-hydroxy-3 - were)methylidene]pyrazole;

22. 1-(2,6-sodium dichloro-4-trifloromethyl)-3-cyano-4-trifloromethyl-5-[(4-methylthiophenyl)-methylidene]-pyrazole;

23. 1-(2,6-sodium dichloro-4-trifloromethyl)-3-cyano-4-trifloromethyl-5-[(4-hydroxy-3 - were)methylidene]pyrazole;

24. 1-(2,6-sodium dichloro-4-trifloromethyl)-3-cyano-4-trifloromethyl-5-[(3,5-dimethyl-4 - hydroxyphenyl)IU the C-4-hydroxyphenyl)methylidene]pyrazole;

29. 1-(2,6-sodium dichloro-4-trifloromethyl)-3-cyano-4-trifloromethyl-5-[(3-ethoxy-4 - hydroxyphenyl)methylidene]pyrazole;

30. 1-(2,6-sodium dichloro-4-trifloromethyl)-3-cyano-4-trifloromethyl-5-[(3,4,5-trifloromethyl)- methylidene]pyrazole;

37. 1-(2,6-sodium dichloro-4-trifloromethyl)-3-cyano-4-trifloromethyl-5-[(2-chloro-4 - hydroxyphenyl)methylidene]pyrazole;

38. 1-(2,6-sodium dichloro-4-trifloromethyl)-3-cyano-4-trifloromethyl-5-[(3-chloro-4 - hydroxyphenyl)methylidene]pyrazole; or

76. 1-(2,3-sodium dichloro-4-trifloromethyl)-3-cyano-4-dichlorophenolindophenol-5-[(4-hydroxyphenyl)-methylidene]pyrazole.

Of these compounds, more preferred are compounds N 2 4, 6, 9, 10, 13, 15, 17, 19, 23, 24, 26, 29, 37, 38 or 76, and particularly preferred are compounds N 2, 3, 10, 15, 24, 37, 38 or 76.

In addition to these compounds, there are other more specific categories of compounds of the present invention, which is particularly preferred compounds of formula (I) or (Ia) where R4represents a phenyl radical which is at least substituted 3-hydroxy or 4-hydroxy, and the other substituents of the phenyl radical are takacsi - or 4-hydroxycodone form a separate and distinct subclasses within each of the groups already mentioned preferred compounds, and more preferred compounds independently from each other (further guidance also refers to independent). In addition, a separate R4part, a separate 1-phenyl - or 1-(2-pyridyl)-part of, or separate connections in the following preferred embodiments, C-L are separate and independent variants of the present invention:

A) the compounds of formula (I);

C) Compounds of formula (Ia);

C) Preferred groups R41-25;

D) Preferred groups R41-10, 12-15 or 18-25;

E) Preferred groups R41-5, 7-9, 13 or 18-25;

F) Preferred groups R41-4, 18 or 19;

G) 1-phenyl - or 1-(2-pyridyl)-groups 1-22;

H) 1-phenyl - or 1-(2-pyridyl)-groups 1-8 or 14-22;

I) 1-phenyl - or 1-(2-pyridyl)-groups 1-5, 7, 8, 14, 21, or 22;

J) Compounds N 2, 3, 4, 6, 9, 10, 13, 15 19, 22, 23, 24, 26, 29, 30, 37, 38 or 76;

K) Connection N 2 4, 6, 9, 10, 13, 15, 17, 19, 23, 24, 26, 29, 37, 38 or 76; or

L) Connection N 2, 3, 10, 15, 24, 37, 38 or 76.

The purpose of the present invention, the obtaining of new pesticidal compounds of the family of 1-aryl-5-(substituted alkyl-amino)pyrazoles of the known and/or readily available and inexpensive intermediate and raw materials.

The pesticide composition according to the invention are used against arthropods, in particular insects, plant nematode, helminth or protozoan LASS="ptx2">

Compounds according to the invention have a broad spectrum pesticidal activity, as well as selective specific activity, for example, officenow, acaricide, listlevel insecticide, soil insecticide and nematocide activity, as well as systemic, antifatigue or pesticide activity in grain processing.

The compounds are particularly active against insects, in particular in the larval stage of development, when the contact effect on pests.

In addition, the new compounds possess a high degree of user safety and the environment, can be obtained by optimization of chemical, physical and biological properties such as solubility, melting point, stability, electronic and steric parameters, etc.

Compounds of General formula (I) can be obtained using known or adaptation of known methods: for example, the intermediate 5-aminopyrazole compound of formula (II) (first obtained by known procedures, and then condense the standard ways: 1) with an appropriately substituted aldehyde or ketone with obtaining the compounds where R3is hydrogen or alkylic treated alkylthiol or dialkylamino in the presence of a base, for example, NaH, K2CO3and Na2CO3forming compounds in which R3is alkylthio or dialkylamino.

The intermediate 5-amino-1-phenylpyrazoles of the formula (II) are known compounds and can be obtained by methods described in EP 295117, published. 14.12.88; EP 295118, published. 14.12.88; EP 234119, published. 02.09.87 (similar WO 87/03781, published. 02.07.87); EP 350311, published. 10.12.90; all these works are introduced in the present description by reference.

Similar methods can be obtained 5-amino-1-phenylpyrazole and 5-amino-1-(2-pyridyl)pyrazolone intermediate compounds. According to a preferred method of synthesis of these compounds can be obtained from intermediate 1-(substituted-2-pyridyl)-3-alkoxycarbonyl-5-aminopyrazole connection with the subsequent substitution or derivatization using procedures similar to those described for 5-amino-1-phenylpyrazole compounds. The intermediate 5-amino-1-(2-pyridyl)pyrazolone connection is first obtained by cyclization in the presence of a base alkyl 2-oxo-3-cyanopropionic obtained by acid neutralization its corresponding enolates metal salt with an appropriately substituted 2-pyridylamino which can be obtained by standard methods, described in the chemical literature.

Aldehydes, ketones, orthoepy, alkylthio and dialkylamino also are generally known compounds of organic chemistry and either commercially available or can be derived from available compounds by standard methods.

The compounds of formula (I) described in chemistry as chiffony base, obtained by the condensation reaction, for example, aldehyde or ketone of the formula (II) with aminopyrazoles formula (III), in accordance with the following reaction:

< / BR>
where the substituents R1-R8defined above.

In the shown reaction of the aldehyde or ketone may be substituted for those described above orthoevra, R4C(O-C1-4-alkyl)3and the resulting alcohol is removed, resulting in a compound, where R3is alkoxy, which may be but need not be, converted into the compound, where R3is alkylthio or dialkylamino.

Conditions suitable for the formation of Schiff bases, depend on the nature of the source material and the desired properties of the formed product, i.e., solubility, reactivity, stability, etc., Although these conditions require individual selection, but ch J. Advanced Organic Chenuistsy, Mcbrav-Hill, 1985, S. 1165 and in the works cited in the present description.

Typical compounds of the present invention

In table. 1 illustrates some of the preferred compounds, or subgroups of compounds which can be represented by the General formula (I), and obtained as described in this application by standard methods with a suitable choice of reagents, conditions and procedures, well known to experts.

Detailed description of examples of synthesis of compounds

The following examples 1-5 illustrate in detail the methods of synthesis and physical properties of typical pesticide compounds of formula (I) and their chemical intermediates) of the present invention. In table. 2, 2A and 2B presents the compounds obtained in the examples and other compounds obtained in accordance with the same procedures described in the examples. Above the melting temperature for the compounds in the examples and table. 2, 2A and 2B represent the average values of the melting points obtained from the temperature range of melting defined for each connection, and, in addition, the average values obtained for individual determinations of melting points. Moreover, to identify and har the x analyses (IR, H1or F19NMR, MS and so on).

The condensation is preferably carried out in the presence of additional substances. Such substances may be organic or inorganic acid, e.g. sulfuric, hydrochloric, phosphoric, toluensulfonate or methansulfonate acid; catalysts in the form of ion-exchange resins; and/or additives that promote the removal of water, for example, sodium sulfate (or magnesium) or molecular sieves. To facilitate the reaction of the reaction water from the reaction mixture can also (but not necessarily) be removed by azeotropic distillation.

Particularly preferred reactive additives are resins supplied by the Dow Chemical Company trademark DOWEXor Bio-Rad Chemical Division trademarks AG, BIO-REXor CHELEX. Resin Bio-Rad, their properties and use are described in detail in "Bio-Rad guide to ion Exchange catalog N 140-997 (and the links), Bio-Rad Chemical Division 1414 Hasbour Way South, Richmond, California 94804. The resin of the specified type are also described in The Chemist's Copanion", Gorden A. J. and Ford, R. A. S. 386, John Wiley Sons of.

Especially preferred are acidic cation-exchange resin:

1. Phenol-aldehyde resin based on a strong sulfonic acid (RCH2SO3H) "BIO-REXUP>" 50 W (xSeries) "DOWEX" 50 (xSeries)

3. Polystyrene resin based intermediate phosphonic acid (froh3Na) "BIO-REX" 63

4. Acrylic resin on the basis of a weak acid (RCOONa) "BIO-REX" 70

5. Polystyrene resin based chelat forming a weak acid (fat2N(CH2COOH)2100

These commercial resins may be in the form of a proton acid or as a salt. If they are salts, they must be converted to the corresponding acid to best catalyze the condensation reaction.

The use of catalytic ion exchange resins are particularly preferred because they:

a) can be easily removed, for example by simple filtration;

b) avoid water main leaching the reaction product with the use of catalysts based on organic or inorganic acid;

c) to avoid hydrolysis of the target product;

d) allow to obtain higher yields, higher purity and accelerate the reaction;

e) can be used from very small to large particle sizes, which improves the reaction products and control;

f) allow to obtain the th reproducibility of results;

h) are economically advantageous because it can be used again/repeatedly;

i) are more flexible in their use in periodic, semi-continuous or continuous reaction processes.

When carrying out the condensation reaction, the reaction temperature can vary within relatively wide limits. Mostly the reaction is carried out at temperatures from about 70 to about 160oC and preferably at temperatures of from about 100 to about 130oC.

In accordance with the present invention for implementing the above-mentioned process is mainly used 1.0 to 5.0 equivalents, preferably 1.0 to 1.5 equivalents of an aldehyde or ketone of formula (III); and 0.01 to 2.0 equivalents, preferably 0.01 to 0.5 equivalents of reactive additives. If such additives are catalytic ion exchange resins, they can be used both in lower and in higher equivalent quantities. After the implementation of the reaction, the reaction products can be processed and allocated in accordance with standard methods.

To implement the above reaction used diluents for use in some EP, such as aliphatic, alicyclic, or aromatic, or optional halogenoalkane hydrocarbons, such as benzene, chlorobenzol, toluene or xylene.

Example 1. Obtain 1-(2,6-dichloro-4-trifloromethyl)-3-cyano-4-trifloromethyl-5-[(4-hydroxy-3 - methoxyphenyl)methylidene] pyrazole; connection N 2.

A mixture of 5-amino-1-(2,6-sodium dichloro-4-trifloromethyl)-3-cyano-4-trifluromethanesulfonate (2.5 g, 5,9 mm), 4-hydroxy-3 - methoxybenzaldehyde (1.1 g, 1.3 equivalents), n-toluensulfonate acid (0.15 g, 0.13 EQ) and toluene (750 ml) is heated under reflux using traps Dean-stark removal of water for 40 hours, the Toluene is removed in vacuo. The residue is dissolved with ethyl acetate. The organic solution once washed with saturated aqueous Na2CO, then with water, dried with a solution of MgSO4, filtered and concentrated in vacuo. The result is the target product (2.8 g, 85% of theory.) in the form of a yellowish solid substance, so pl. 132,5oC. H1and F19NMR analysis showed obtain the pure product.

Example 2. Obtain 1-(2,6-sodium dichloro-4-trifloromethyl)-3-cyano-4-trifloromethyl-5-[(4-nitrophenyl)methylidene] -pyrazole; the ash (2.0 g, 4,7 mm), 4-nitrobenzaldehyde (0.87 g, 1.25 EQ), p-toluensulfonate acid (0.02 g, 0.02 EQ) and toluene (200 ml) is heated under reflux using traps Dean-stark removal of water within 36 hours After cooling at room temperature, the toluene solution is vigorously stirred with an aqueous solution of NaHSO3in an ice bath for 5 minutes, the Two phases are separated. This procedure is repeated one more time. The organic layer is then washed with water, dried MgSO4, filtered and concentrated in vacuo. The crude product is recrystallized from tert.-butyl methyl ether and hexane, the result is the target product (1.42 g, 54.4% of output) in the form of a yellow solid, so pl. 167,5oC.

Example 3. Obtain 1-(2,6-sodium dichloro-4-trifloromethyl)-3-cyano-4-trifloromethyl-5-[(3,5-dimethoxy-4 - hydroxyphenyl)methylidene] pyrazole; connection N 26.

A mixture of 5-amino-1-(2,6-sodium dichloro-4 - triptoreline)-3-cyano-4-trifluromethanesulfonate (2.0 g, 4,58 mm), 3,5-dimethoxy-4-hydroxybenzaldehyde (1.0 g, 1.2 EQ), p-toluensulfonate acid (0.08 g, 0.1 EQ) and toluene (800 ml) is heated under reflux using traps Dean-stark removal of water for 8 days. The reaction Rasim solution of Na2CO3, dried MgSO4, filtered and concentrated in vacuo. The residue is subjected to column chromatography on silica gel, elwira with ethyl acetate and hexane. The result is the target product (1.2 g) as a yellow solid (yield 44%), so pl. 175oC.

Example 4. Obtain 1-(2,6-sodium dichloro-4-trifloromethyl)-3-cyano-4-trifloromethyl-5-[(3-methoxy-4-hydroxyphenyl)- methylidene] pyrazole; connection N 10.

A mixture of 5-amino-1-(2,6-sodium dichloro-4 - trifloromethyl)-3-cyano-4-trifluromethanesulfonate (60 g, 0,137 M), 3-methoxy-4-hydroxybenzaldehyde (25.6 g, 1.2 EQ) "DOWEX" (trademark), 50 x 8-400 resin (140 g) and toluene (1.5 l) is heated under reflux using traps Dean-stark removal of water for 4 days. After cooling at room temperature the reaction mixture is filtered. The toluene filtrate was concentrated in vacuo. The solid residue is crushed, then heated under reflux with heptane (600 ml). Solid yellow substance mixture is filtered in hot condition. The result is the target product as a solid (66.5 g), so pl. 155oC.

Example 5. Obtain 1-(2,6-sodium dichloro-4-trifloromethyl)-3-cyano-4-triflora is 1-(2,6-sodium dichloro-4-trifloromethyl)-3-cyano-4-trifluromethanesulfonate (5 g, 11.8 mm), 3-methoxy-4 - hydroxybenzaldehyde (2 g, 1.1 EQ), "DOWEX" (trademark), 50 x 8-100 resin (2 g) and toluene (400 ml) is heated under reflux using traps Dean-stark within 30 hours After cooling at room temperature the mixture is filtered through a thin layer of silica gel and celite. The filtrate is concentrated, the result is the target product as a white solid (6.85 g), so pl. 132,5oC.

Using procedures similar to those described in examples 1-5 were obtained with other compounds presented in table. 2, 2A and 2B

Example 6. The use of acaricides, insecticides, avicides and nematicides

The following tests using the compounds of the present invention was conducted in order to determine pesticidal activity of these compounds against ticks, some insects, including aphids, two species of caterpillars, flies, and three species of grubs (one leaf and two Korneev) and nematodes. In the tests used the following types:

The genus. species Common name Abbreviation

Tetranychus urtical Mite bimaculated spider TSM

Apliis nasturtii Aphid Kruchina BA

Spodoptera eridania South scoop SAW

Epilachna varivestis ladybug MW

Musca donestica R> Meloidogyne incognita Javanese root-knot nematode SRKN

Apliis Aphid gossypii cotton SA

Zchizapliis graniinum cereal Aphids of obuknov. GB

Heliotliis virescens Scoop-Packed TBW

Songs

To implement the testing of the methods described below for each procedure were made corresponding to the composition of the tested compounds.

For use against ticks, South worms, ladybugs and worms-Packed prepared solution or suspension by adding 10 mg of the test compound to the solution containing 160 mg of dimethylformamide, 838 mg of acetone, 2 mg of a mixture of Triton X-172: Triton X-152=3:1 (respectively, which mainly anionic or non-ionic nishinoshima emulsifiers, each of which represents a mixture of anhydrous alkilammonievymi alcohols with organic sulfonates), and 98,99 g of water. The final concentration of the test compound was 100 ppm.

For use against flies bedroom has received composition in a manner analogous to the above, but in 16.3 g of water with appropriate adjustments to other components, the result has been a concentration of 200 ppm. After final dilution with equal volumes of 20 wt. an aqueous solution of sucrose was given concentration of COI is travelcom.

For tests against West flea and South of a flea produced a solution or suspension in a manner analogous to that described for the test against flies bedroom with an initial concentration of 200 ppm. Aliquots of this preparation with a concentration of 200 ppm is then used in the tests was diluted with water to the desired concentration.

For use against root-knot nematodes and system tests against South Cutworm, cotton aphid, Cutworm-Packed and cereal aphids to prepare the mother solution or suspension by adding 15 mg of the test compound to 250 mg of dimethylformamide, 1250 mg of acetone and 3 mg of the mixture of the emulsifier described above. Then add water to obtain the concentration of the test compound to 150 ppm. If necessary, to ensure complete dispersion was performed sonication.

For contact test against scoops of pocked mother solution prepared by dissolving the test compound in acetone, followed by serial dilution to obtain the required concentrations.

Test procedures

The above preparations containing compound, was evaluated on pesticide activity at specific concentrations (in ppm parts per million, the major bimaculated spider mite, located in a Mature and nymph stage, and obtained from a pure culture, were placed on the primary leaves of dicotyledonous plants grown in 6-cm pot. Then after 24 h in fresh plant produced a sufficient number of ticks (150-200). The plants in pots (per connection per pot) were placed on a rotating table and sprayed with 100 ml containing 100 ppm of the test compound to the plant abundantly spacewalks until dripping with moisture, using sprinklers Divilbiss when the air pressure 40 ft/sq. inch (275,76 kPa). As infected control plants were sprayed with 100 ml of a solution containing water, acetone, DMF and emulsifier and containing no test compound. As the standard used control processing commercial connection (or dicofol or hexythiazox), prepared in the same way that compound. The treated plants were kept in six days, and then estimated the number of dead mites by counting motile animals.

Mite bimaculated spider (ovicidal test). Eggs were obtained from Mature dvukhmernogo Paulinho mite grown from a pure culture. Heavily infected leaves is neither about 24 hours, then the leaves of the plant were immersed into the solution TEPP (tetraethyllead) for the destruction of mobile forms and warnings for more egg laying. This procedure dive, which was repeated after drying of the plants had no effect, however, on the viability of eggs. Potted seedlings (one pot per compound) were placed on a rotating table and sprayed with 100 ml containing 100 ppm of the test compounds to plants abundantly spacewalks until dripping with moisture, using a Devilbiss spray (when the air pressure of 40 pounds per square inch (275,76 kPa)). As untreated control plants used infected plants sprayed with 100 ml of a solution containing water, acetone, DMF and emulsifier and containing no test compound. As treated control plants used plants treated with commercial connection (mainly Deltona prepared in the same manner as compound) and accepted for evaluation. The treated plants are kept for seven days, and then estimated the number of dead eggs by determining the residual activity to their hatching.

Aphids Kruchina or aphid x is AI or cotton to Mature and nymph stages. Potted seedlings (one pot per compound) were infected 100-150 aphids were placed on a rotating table and sprayed with 100 ml of a solution containing 100 ppm of the test compounds, using sprinklers Divilbiss at a pressure of 40 pounds per square inch (275,76 kPa). As untreated control plants used infected plants sprayed with 100 ml of a solution containing water, acetone, DMF and the emulsifier, but not containing the test compound. As treated control plants used plants, sprayed with a commercial compound (Malathion or cyhalothrin prepared in the same manner as compound) and take the test for the standard. After spraying kept for 1 day for kruchininoj aphids and 3 days for the cotton aphid, and then counted the number of dead individuals.

South scoop. Potted seedlings of leguminous plants were placed on a rotating table and sprayed with 100 ml containing 100 ppm of the test compounds, using sprinklers Divilbiss when the air pressure of 40 pounds per square inch (275,76 kPa). As untreated control plants used infected plants sprayed with 100 ml of a solution containing water, Aceto which the objects of study were plants, sprayed with a commercial connection (or cypermethrin or sulprofos prepared in the same manner as the test connection) and take the test for the standard. After drying, the leaves were placed in plastic cups, festilandia moistened filter paper. In each Cup was introduced five randomly selected larvae South scoops on the second age, then the Cup was closed and kept for five days. Larvae, unable to move along the entire length of his body even after stimulating their choice by any subject was considered dead.

Scoop-Packed. Potted cotton plants were placed on a rotating table and sprayed with 100 ml of a solution containing 100 ppm of the test compounds, using a Devilbiss spray when the air pressure of 40 pounds per square inch (275,76 kPa). As untreated control plants used infected plants sprayed with 100 ml of water, acetone, DMF and emulsifier that does not contain the test compound. Control plants were treated commercial connection (or cypermethrin or sulprofos prepared in the same manner as compound and has been in testing for the standards of the dental wick. In each Cup was then introduced one randomly selected larvae scoops of Packed, after which the Cup was closed and kept for five days. The larvae are unable to move the length of the body even after stimulating their choice by any subject was considered dead.

Ladybug. Potted bean plants were placed on a rotating table and sprayed with 100 ml of a solution containing 100 ppm of the test compounds to plants abundantly spacewalks until dripping with moisture, using a Devilbiss spray when the air pressure of 40 pounds per square inch (275,75 kPa). As untreated control plants used infected plants sprayed with 100 ml of a solution containing water, acetone, DMF and the emulsifier, but not containing the test compound. As treated control plants used plants, sprayed with a commercial connection (or cypermethrin or sulprofos prepared in the same manner as compound) and take the test for the standard. After drying, the leaves were placed in plastic cups, lined with moistened filter paper. Then in each Cup was introduced 5 randomly selected larvae of ladybirds on freedigits along the length of his body even after stimulating their choice in any subject, it was considered dead.

The fly room. According to the description of the Chemical Specialties Manufacturing Association (Blue Book, Mevair-Dorland Co., N. J. 1954; S. 243-244, 261) were grown in controlled conditions Mature of houseflies aged 4 days. Then these flies immobilizerpower by anaesthesia using carbon dioxide and 25 immobilized individuals, males and females were placed in a cage consisting of a standard mesh filter and the surface covered with wrapping paper. In Cup type souffle containing absorbent cotton swab, was added 10 ml of a preparation containing 100 ppm of the test compounds. As untreated control was used 10 ml of a solution containing water, acetone, DMF, emulsifier and sucrose but not containing the test compound. Treated control, which used a commercial connection Malathion prepared in the same way that you test the connection, took the test for the standard. Before making anastasiosandy flies from the inside of a strainer on the supply put the Cup with the bait. After 24 h analyses and those flies that did not move even after stimulation, believed dead.

South or West root of a flea. In a vessel containing 60 g of piccaninnie, diluted with water to obtain the appropriate concentration of the test compounds in the soil; 3.2 ml of water and 5 sprouted grains. The vessel was vigorously shaken to obtain a homogeneous distribution of the tested compositions. After this is done soil furrows made 20 eggs of the root of a flea (or in the case of WCRW (but not necessarily) 10 larvae in the first stage of development). Then, these grooves were added vermiculite (1 ml), optional used in the case of WCRW-tests, and water (1.7 ml). Untreated control was obtained in a similar manner using similar aliquots of a solution of water, acetone, DMF and emulsifier, which did not contain the test compound. In addition, the treated control was obtained using similarly prepared commercial connections (usually selected from terbufos, fonofos, porata, chlorpyrifos, carbofuran, isazofos or ethoprop) and accepted as a standard. After 7 days were counting the number of live larvae of the root of a flea, using the known method of extraction using a separating funnel Berlese.

Javanese root-knot nematode. Infected roots of tomatoes, containing a large mass of eggs of root-knot nematodes were removed from pure culture, ocimene and washed with water. Samples of the suspension of eggs was placed on a fine sieve over a vessel in which the water level was brought to contact with the surface of the sieve. From this vessel juvenile specimens were collected on a fine sieve. The conical bottom of the container was covered with vermiculite coarse, and then filled up to a level of 1.5 cm from the top of pasteurized soil in a volume of 200 ml. and Then into the recess made in the center of the soil, filling the cone, pietravalle an aliquot of the preparation containing 150 ppm of the test compounds. Treated control was obtained with the use of a solution containing water, acetone, DMF and the emulsifier, but not containing the test compound. Treated control was obtained with the use of commercial compounds fenamiphos and tested as standard. Immediately after soil treatment test compound cone-shaped vessel filled to the top 1000 juvenile individuals of root-knot nematodes in the second age. After 3 days in this cone-shaped vessel landed one healthy seedling of tomato. The specified vessel containing charged soil and seedlings of tomato, was kept in the greenhouse for 3 weeks. After the test is completed, the roots of seedlings of tomato were removed from the vessel and were evaluated on haloorange scale otnositel the resultant control;

3 small haloorange;

4 very small haloorange;

5 haloorange is absent, i.e., the complete destruction of larvae.

These results were then converted into values ED3or ED5(effective dose to get results 3 or 5 on the rating scale).

South scoop on the tomato system evaluation. This test was performed in conjunction with the evaluation test of Gallic nematode (see below). Tomatoes grown on the soil (at the initial level of screening of 6.6 ppm concentration of the soil or about 150 ppm solution concentration) for assessment test for nematodes, then used to assess the absorption of compounds by roots with subsequent systemic transfer them to the leaves of tomato plants. After completion of the test on nematodes, i.e. 21 days after treatment, the leaves of the tomato cut, placed in a plastic vessel and infected larvae South scoops on the second return under development. After 5 days was determined by the percentage of dead individuals.

Aphid cotton and scoop-pocket (cotton) and aphids cereal and a scoop-Packed (sorghum) system evaluation. Poured 7,0 ml aliquot of 150 ppm of the test solution for nematodes (calculated on an equivalent dose of the cotton aphid, two days before processing and cereal aphids in one day before treatment. After keeping these plants for about 3 days they were assessed on alidou activity. After 6 days the plants were again evaluated on alidou activity and counted the number of dead aphids cotton and cereal aphids. Then some leaves of cotton and sorghum were cut, placed in separate plastic containers and infected larvae scoops of pocked in the second stage of development. Potted seedlings were immersed in sulfotepp to destroy the remaining aphids and returned to their rearing. 13 days after treatment, the remaining leaves were cut and gave up showcam. Six days after infestation was estimated percentage of mortality.

Aphid cotton scoop and South (cotton) and cereal aphid and southern scoop (sorghum) system evaluation. The mother solution or suspension was obtained at a rate of 5 ml per dose concentration of 20 ppm soil with subsequent breeding and was poured into 6-cm pots containing cotton and sorghum. Cotton pre-infected cotton aphids two days before processing and cereal aphids in one day before treatment. After keeping these plants for about 3 days they were assessed on alidou activity. After 6 days the plants were again evaluated on alidou activity and genuine leather, were placed in separate plastic containers and were infected with larvae of the southern scoops in the second stage of development. Potted seedlings were immersed in sulfotepp to destroy the remaining aphids and returned to the greenhouse at Piglet. 13 days after treatment, the remaining leaves were cut and fed South showcam. Six days after infestation was estimated percentage of mortality.

Aphid cotton scoop and South (cotton and oats) seed treatment evaluation. Technical material was applied to grain oats, and cotton by making connections and seeds in a vessel of appropriate size and rotation of the vessel in a ball mill. Evaluation deposited on the seed material was performed by weighing. Then the grain was sown. After germination and sprouting plants at certain intervals of time was invasively insect hosts. And then estimated the percentage of mortality.

Scoop-Packed contact test. In accordance with the method of local application conducted an assessment of the contact toxicity of the test compounds against Cutworm larvae of Packed. The solution of the test compounds at concentrations followed a two breeding from 10 to 0.16 µg/µl was applied in duplicate then 500 8 µg/g of body weight. As control was used processing acetone without the use of any of the test compounds. As the standard used also treated control with the use of commercial compounds (cypermethrin or thiodicarb in acetone). The treated larvae were placed in individual plastic Petri dishes containing raw cotton sheets and wet dental wick. Treated larvae kept at a temperature of about 27oC and humidity of 50% After 1 and 4 days after treatment was estimated percentage of mortality.

Results. The results of the test acaricidal, insecticidal and nematocidal activity of some characteristics of the compounds of the present invention are discussed below, and the results for some of the compounds are presented in table. 3, which shows the relevant insect species (BA/CA, SAW, MBB, HF, TBW, SCRW/ WCRW values (abbreviations see above) and used doses. In table. 3 shows the compounds that showed 70-100% mortality for these species (this percentage specified X).

Some of the compounds of the present invention are also acaricides, for example, the compounds N 40, 47 and 57, which show the effectiveness of 30-70% against ticks at 100 ppm in the tests, the IU, system action against insect larvae and aphids in the processing of roots using the appropriate concentrations of the soil in accordance with the above procedures. For example, some compounds showed the following results: effectiveness against South scoops on tomatoes 50-100% (N 10, 11 and 12); effectiveness against South scoops on cotton in 6 days 30-100% (N 69, 89, 113 and 120) and 13 days 30-100% (N 64, 65, 67, 68 and 110); effectiveness against South scoops on sorghum in 6 days 30-100% (N 2, 10, 69, 72, 90, 100, 115 and 121) and 13 days 70-100% (N 65, 66, 110 and 117); effectiveness against scoops of pocked on sorghum in 6 days 100% (N 16 20); efficacy against cotton aphid in cotton after 6 days 30-100% (N 13, 16 19, 107, 110, 111, 112 and 126); effectiveness against cereal aphids on sorghum in 6 days 30-100% (N 4, 16 21, 74, 87, 90, 93, 107, 110 112 and 126).

Some compounds were found active during seed processing, for example, the compound N 2, applied at a concentration of 1.0 wt. on grain oats, showed 100% efficacy against South scoops in 6 days after treatment.

Compounds of the present invention also unexpectedly discovered excellent activity against scoops of Packed (TBW) in contact tests or for local application; for example, the effectiveness coed body was 50-100%

In addition, the compounds of the present invention was found nematocidal activity, for example, compounds No. 7, 10 and 89 given the magnitude of the ED3larvae SRKN (about 21 kg/ha), and compound No. 7, 9 and 11 and they gave the value of the ED3against eggs SRKN (approx 14-21 kg/ha).

In addition, the compounds of the present invention have antifatigue properties in relation to certain types of pests leaves such as South scoop and ladybug.

Compounds of the present invention can be used against various pests even at lower concentrations, for example, for application to the leaves can be used in concentrations in the range of about 50,0 is 0.5 ppm or less; for administration in the form of bait within approximately 50,0 is 0.05 ppm or less; for the soil is approximately in the range from 1.0 to 0.01 ppm.

In the above discussion and the results presented in table.3, the compounds were used in various concentrations. The dose of 1 ppm (the concentration of the compounds in the parts per million of the test solution to be applied on the wheels or suspension, or emulsion) was used in the calculation of approximately 1 g/ha of active ingredient, based on the volume to be processed by sputtering will bring what I 6,25-500 ppm corresponds to approximately 6-500 g/ha, for soil, the soil concentration of 1 ppm, based soil depth of 7.5 cm, corresponding to approximately 1000 g/ha for widespread field application. Or alternative soil concentration of 1 ppm, as described above, but when the tape making approximately 18 cm, corresponding to about 166 g/ha To contact a test dose of 10 µg/ml of body weight when applied to the larvae in a solution of 0.2 µg/ml (200 ppm) corresponds to using the fields for widespread introduction approximately 50-100 g/ha

Methods and compositions

As was shown above, the compounds of the present invention possess pesticidal activity and can be used to fight against some pests such as arthropods, in particular insects or mites; plant nematodes; helminths; protozoa. So, for example, the compounds of the present invention can be used in agriculture, horticulture, forestry, veterinary science or animal husbandry, as well as in health care.

The present invention also relates to a method of pest control, which is that the target lesions treated (for example, by application or administration) with an effective amount of compounds of General formula (I), and balaraman, themselves of the pests or their food, or their habitats such as plant, animal, man, field, buildings, houses with adjacent areas, forest, orchards, water sources, soil, plant or animal products, etc.

Compounds of the present invention preferably can be used for combating soil insects such as root flea beetle, termites (for example, to protect buildings), root maggots, wireworms, root weevils, svalilsya, shovels, root aphids or cerubidine larvae. These compounds can also be used against plant pathogenic nematodes such as hookworms, causing gallogermanate, cyst, tissue damage, stems or bulbs; scoops; mites. To fight against soil pests, for example, root flea beetles, the compounds of the present invention is mainly applied or administered in an effective amount in the soil, which is planted with cultivated plants or seeds, or roots of plants.

In addition, the compounds of the present invention can be used for pest control, for example, some arthropods, in particular insects or mites feeding on aboveground part of plants, which it may, in addition, be carried out by processing the roots of plants or seeds with subsequent systemic translocation to aboveground parts of plants.

Health compounds of the present invention can be used to fight against many insects, in particular, dung flies or other dockrillia insects such as fly room, gigalo autumn, liminka, gigalo small cow, deer gadfly, the gadfly of nasopharyngeal horses, Midge, lice, aphids, black or mosquitoes.

Compounds of the present invention can be used and pests such as arthropods, in particular insects or mites, nematodes, helminths or protozoa, and for the purposes specified below, namely:

to protect products stored, for example, beans, including seeds or flour; groundnuts; feed; isometrically or industrial goods, e.g. carpets and textiles, etc., i.e. goods that are susceptible to infection arthropods, in particular beetles, for example, weevils, moths or mites such as Ephestia spp. (Ognevka mill), Anthrenus spp. (Museum beetle), Eribolium spp. (khruschak flour), Sitophilus spp. (granary weevil) or Acarus spp. (ticks);

against cockroaches, ants, or to fight against mosquito larvae in waterways, wells, reservoirs or other running or standing water;

for the processing of foundations, buildings or soil to prevent infestation by termites, such as Reticulitermes spp. Heterotermes spp. Coptotermes spp.

in agriculture against adult butterflies and their larvae and eggs, for example, Heliotlus spp. such as Heliotlus virescens (scoop), Heliotlus armigera and Heliotlus zea, Spodoptera spp. such as S. exempta, S. frugiperda, S. exiga, S. littoralis (cotton bollworm), S. eridania (southern scoop) and Mamestra configurata (cabbage borer); Sarias spp. for example, E. insulana (prickly worm), Pectinophora spp. for example, Pectinophora gossypiella (pink box worm), Ostrinia spp. such as O. nubilalis (corn borer), Trichoplusia ni (scoop); Artogeia spp. (cabbage caterpillar), Laphygma spp. (scoops), Agrotis and Amathes spp. (scoop podgryzayuschie), Wiseana spp. (mol); Chilo spp. (borers), Tryporysa spp. Diatraea spp. (Ognevka sugar cane and rice borers stem), Sparganothis pilleriana (grape moth), Cydia pomonella (Apple moth), Archips spp. (tortrix net fruit), Plutilla xylostilla (cabbage moth), Bupalus riniarius, Cheimatolia brumota, Lithocollitis blancardilla, Hyponomeuta padilla, Plutella maculipennis, Malacosoma neustria, Euproctis chrysorrhoca, Lymantria spp. Bacculatrix thurberulla, Phyllocnistis citrella, Euxoa spp. Feltia brassical, Panolis flamnua, Prodenia litura, Carpocapsa pomonella, Pygausta nubilalis, Ephestia kuehuella, Galleria mullonella, Tineola bisselliella, Tinea pellionella, Hobmannophila pseudosp is Ilych and their larvae (beetles), for example, Hypothenemus hampei (borer), Hylisinus spp. (beetles), Authonomus spp. for example, Grandis (weevil cotton Acalynema spp. (leaf), Lema spp. Psylliodes spp. Leptinotarsa decemlineata (Colorado potato beetle), Diabrotica spp. (root blaska), Gonocephalum spp. (wireworms), Agriotes spp. Limonius spp. (the larva of the Nutcracker Columbia), Dermolepidas spp. Popillia spp. Heteronyclus spp. (white cerubidine larvae), Phaedon cochleariae (leaf shitty), Epitrix spp. (excavation of a flea), Lissorhoptrus oryzophilus (rice weevil water), Miligittus spp. (the rape pollen beetle), Ceutorhyncleus spp. Phyndchophorus and Cosmopolitis spp. (root weevils), Anobium punstatum, Rhizopertha dominica, Bruchidius obtectus, Acanthoscelides abtectus, Hylotrupes bajulus, Agelastica alni, Phylliodes chrysocephala, Epilachna varivestis, Atomaria spp. Oryzaephilus surnamensis, Sitophilus spp. Otirrhynclues sulcatus, Cosmoplites sordidus, Ceuthorrhynchus assimilis, Hypera postica, Dermestes spp. Trogoderma spp. Anthrenus spp. Attagenus spp. Lyctus spp. Maligethes aeneus, Pinus spp. Niptus hololencrus, Gibbium psylloides, Eribolium spp. Tenebrio moletor, Conoderus spp. Melolantha melolontha, Amplimallon solstitialis and Costelytra zealandica;

to combat raznokryloe (Heteroptera and ranonline robotname), for example, Psylla spp. Bemisia spp. Trialeurodes spp. Aphis spp. Myzus spp. Megoura vicial, Phylloxera spp. Adilges spp. Phoroden humuli (hop aphid), Aeneolamia spp. Nephotellix spp. (rice of cycatki), Empoasca spp. Nilaparvata spp. Perkinsiella spp. Pyrilla spp. Aonidiella spp. (San Jose scale red orange), Coccus spp. Pseudococcus spp. Helopeltis spp. (bug), Lygus spp. Dysdercus spp. Oxycaremes spp. Nezara spp. Eurygaster spp. Riesma quadrata, Cimex cectularius, Rhum avenae, Phordon humuli, Phopalosiphum padi, Euscedis bilobatus, Neplotettix cinticeps, Lecanium cormi, Saissetia oleal Laodilphax Striatellus;

to fight against the Hymenoptera, for example, Athalia spp. and Cephus spp. (slitter bread), Atta spp. (ant of paper), Dipron spp. Hopolocampa spp. Lasius spp. Mononearium spp. Polistes spp. Vespa spp. Hot spp. and Solenopsis spp.

to fight against dockrillia such as Delia spp. (root larvae), Atherigona spp. Chlorops spp. Sarcophaga spp. Musca spp. Phormia spp. Aldes spp. Anopheles spp. Simulium spp. (creeping Midge), Phytomuza spp. (fly cabbage), Cerattis spp. (fruit fly), Culex spp. Drosophila melanogaster, Ceratitis capitala, Dacusoleal, Tipula paludosa, Calliphora crythrocephala, Zurilia spp. Chrysomyia spp. Cuterebra spp. Gastrophilus spp. Hyppobosca spp. Slomoxys spp. Oestrus spp. Hypoclerma spp. Tabanus spp. Fannia spp. Bibio hortalanus, Oscinella fret, Phorbia spp. Pegomyia hyoscani;

to fight against thrips such as Ehrips tabaci, Hercinoithrips femoralis and Frankliniella spp.

to fight against Orthoptera such as Locusta and Schitocerca spp. (cicadas and crickets), for example, Gryllus spp. Acheta spp. for example, Blatta crientalis, Periplaneta americana, Leucorhaea maderal, Blatilla germanica, Acheta domesticus, Gryllotalpa spp. Locusta migratoria migratoricus, Melonoplus diffentiallis and Schistocerca gregaria;

to fight against springtails such as Smintluerus spp. and Onychiurus spp. (springtails); Periplaneta spp. and Blattela spp. (cockroaches);

to fight against termites such as Oclontotermes spp. Reticuletermes spp. Coptotermes spp. (termites);

to fight against earwigs, for example, Forticula spp. (earwig);

to fight against smithwork, for example, Lepisma saccharia;

to fight against lice, for example, Phylloxera vastatrix Penephigus spp. Pediculus hemiames corporis, Hacmatopinus spp. and Linognathus spp.

for leading wrestling fight against Phaedo, for example, Erichedectis spp. and Damalinea spp.

to fight against fleas, for example, Xenlpsylla shelpis and Ceratophullus spp.

to fight against other arthropods such as Blaniulus spp. (CISAC spotted), Scutigerella spp. (scutigerella), Oniscus spp. (millipedes-armadillos), Triops spp. (raki);

to fight against the centipedes, for example, Oniseus asellus, Armadillidium vulgare (woodlouse-battleship), Porcellio scaber;

to fight against Gubanova, for example, Geophilus carpophagus and Scutigera spex;

to fight against nematodes affecting plants or trees with high economic value, for example, in agriculture, forestry or horticulture, directly or by spreading bacterial, viral, Mycoplasma or fungal diseases of plants, e.g. nematodes, as Javanese root-knot nematode, in particular Meloidogune spp. (e.g. M. incognita); tuberous cyst nematodes such as Globodera spp. (for example, G. rostorhiensis); Heterodera spp. (for example, H. avenal ); Padopholus spculus spp. (for example, R. reniformis); Rotylenchus spp. (R. rubustus); Hilicotylenchus spp. (for example, H. nuclticinctus); Hemicycliophora spp. (for example, H. gracilis); Criconemoides spp. (for example, C. simils); Trichodorus spp. (for example, T. Primitivus); scoops such as Xiphinema spp. (for example, X. diversicaudatum), Longidorus spp. (for example, L. elongatus); Hopololaimus spp. (for example, H. coronatus); Aphelenchoidus spp. (for example, A. ritzemabosi, A. besseyi); stem nematode such as Dityleknchus spp. (e.g. D. dipsaci);

in the field of veterinary animal husbandry and health of the compounds of the present invention can be used against arthropods, helminths or protozoa, parasites inside or outside on vertebrates, particularly warm-blooded vertebrates, for example, in humans or domestic animals such as cattle, sheep, goats, horses, pigs, poultry, dogs, cats, etc., for example, against such parasites as Acarina, including ticks, for example, Ixodes spp. Boophilus spp. for example, Boophilus microplus, Anebluomma spp. Hyalomma spp. Rhipicephalus spp. for example, Rhipicephalus appendiculatus, Haemaphysalis spp. Dermacentor spp. Amithodorus spp. (e.g., Ornithodorus soubata) and ticks (for example, Damalinia spp. Dermahyssus gallinal, Sarcoptes spp. for example, Sarcoptes scabili, Psoroptes spp. Chorioptes spp. Demodex spp. Eutrombicula spp.); Diptera (e.g., edes spp. Anopheles spp. Musca spp. Hypoderma spp. Gasteropilus spp. Simulium spp. Hemiptera (e.g., Eriatoma spp.); Phthirapter (for example, Damalinica spp. Linognothus s is otiv infections of the gastrointestinal tract, caused by parasites nematodes, for example, family members Erichostrongylidae, Nippostrongylus brasiliensci, Trichinella spiralis, At contortus, Trichostrongyles colubriformis, Nematodirus batus, Ostertagus circumacincta, Trichostrongylus axei, Cooperia spp. and Hymenoleris nana; and for treatment of diseases caused by protozoa, for example, Eimeria spp. for example, Eimeria tenella, Eimeria acervulina, Eimeria brunetti, Eimeria maxima and Eimeria necatrix, Trypanosones cruzi, Leishaminia spp. Plasmodium spp. Babesis spp. Trichomonadidal spp. Histomanas spp. Giardia spp. Toxoplasma spp. Eutamaba kistolytica and Theileria spp.

As indicated above, the present invention relates to a method of combating pests by application or administration of an effective amount of compounds of formula (I) or (Ia) in the target foci of infection.

A practical way of combating arthropods, in particular insects or mites, and nematodes, is in the handling of plants or the environment of their habitat an effective amount of the compounds of the present invention. Typically, the active compound is introduced into the pockets of infected arthropods or nematodes as an effective dose of approximately 0.005 to 15 kg of active compound per hectare of cultivated land. In ideal conditions, depending on the target pest is possible to achieve an adequate effect by using the lower dose. However, bad weather proviincrement. The optimal dose depends on many factors, such as the type of destroying pest species or stage of growth of the infected plants, spacing, and method of application. The preferred effective dose of active compound is from about 0.01 kg/ha to about 2.0 kg/ha.

If pest infestations are transmitted through the soil, the active compound is usually in the form of the composition is uniformly spread over the treated soil (i.e., for example, randomly or tape making) any standard method. Optionally, such processing may be carried out in the fields, plots of cultivated plants, or the plants or seeds, or in close proximity to them. The active ingredient may be incorporated into the soil in the form of a diluted water preparation by spraying, or in undiluted form, based on his action after the rain. While making or after the composition of the active compounds, if necessary, can be mechanically distributed over the soil, for example, by plowing, disking or by using a chain loop. The treatment can be conducted before planting, during planting or after planting, but before emergence, or after and the relevant control after sowing.

Methods of pest control also include processing plant leaves to fight with arthropods, in particular insects or mites or nematodes affecting above-ground parts of plants. In addition, methods of pest control using the compounds of the present invention provide for the destruction of pests by feeding them parts of plants, remote from the center of processing, for example, feed on leaves pests are destroyed through systemic action of the active compounds, which were treated roots or seeds fed to the plants prior to planting. In addition, the compounds of the present invention can reduce the probability of infection of plants by pests due to its antifatigue or repellent action.

Compounds of the present invention and methods for their use in pest control is especially preferred for processing fields, fodder for livestock, plantations, greenhouses, fruit trees or losovyj crops, ornamental plants or forest trees, cereal crops (such as corn, wheat, rice, or sorghum), cotton, tobacco plants, vegetable crops (such as lettuce, legumes, cabbage, pumpkin, is or rape culture); sugar cane, pasture or forage crops (such as corn, sorghum or Lucerne), plantation crops (such as tea, coffee, cocoa, banana, oil palm, coconuts, rubber trees or spices, fruit or horticultural crops (such as stone or sarnicovia fruit trees, citrus, kiwifruit, avocado, mango, olive or nut trees), losovyj crops, ornamental plants, flowers, vegetables or greenhouse shrub plants, Park or flattering trees (deciduous and evergreen), growing in forests, plantations or in the reserves.

Compounds of the present invention can be also successfully used for the protection of timber (standing timber, felled forests, sawn timber, folding wood and construction timber) from damage by pests, such as sawflies, beetles or termites.

Compounds of the present invention can also be used to protect storage products such as grains, fruits, nuts, spices or tobacco products stored whole, shredded or in the form of compounds, from moths, beetles, mites or granary weevil. These compounds can be also natural form or in the form of products of processing (for example, carpets or fabrics from moths or beetles, as well as for protection of products of animal origin, for example, stored meat and fish from the beetles, mites or flies.

In addition, the compounds of the present invention and methods of use are especially valuable against arthropods, helminths or protozoa which are pathogens or vectors of diseases of man or animals mentioned above. Particularly preferable to use compounds of the present invention against mites, ticks, Phaedo, flies of Gallic, or stinging, annoying, or masywnych flies. Compounds of the present invention are particularly valuable in the fight against cinetology, helminth or protozoan parasites of domestic animals, in particular that live on the skin of the animal, or blood-sucking insects and can be administered orally, parenterally, percutaneously or locally.

In addition, the compounds of the present invention can be used for the treatment of coccidiosis, caused by the protozoan parasites of the genus Eimeria. It is a disease of domestic animals and poultry under intensive care and feeding, prinosima or rabbits, however, especially dangerous this disease is for poultry, in particular chickens. The introduction of small amounts of compounds of the present invention preferably together with food can prevent or significantly reduce the incidence of coccidiosis. The considered compounds is particularly effective in the forms of the disease, affecting blind gut or intestinal tract. Moreover, the compounds of the present invention may also have an inhibitory effect on oocyte by a significant reduction needs of sporulation. This disease of chickens is mainly spread through Slavyane bird of infectious organisms in the waste, contaminated litter, soil, feed and water for drinking. The disease is manifested by hemorrhage, accumulation of blood in the caecum, contact with blood in the faeces, weakness and digestive disorders. This disease often ends in death of the animal, however, the surviving bird has a much lower commercial value.

Described compositions can be applied to plants or to the growth of these plants, or they can be used for seed treatment, or alternative processing celali areas of natural landscapes.

The main target areas of application of the compounds of the present invention are:

growing plants, such as leaves, processed spray solutions, bustami, granules or foams, or their roots and the soil, the treated suspensions of finely dispersed or encapsulated compositions in the form of liquid solutions for irrigation, Farrukh Dustov, granules, smoke fumigation or pins, or seeds of cultivated plants, the treated liquid suspensions or bustami;

person or animal infected arthropods, helminths or protozoa, which in a certain period of time administered orally, parenterally or locally compositions containing the active ingredient with rapid or prolonged action on these pests. These compositions can be introduced, for example, with food, or as an oral pharmaceutical preparation, edible baits, salt lick, solutions for irrigation, solutions, sprays, baths, impregnations, showers or deposited by a stream or Farrukh Dustov, greases, shampoos, creams, ointments, or systems for Samoobrona animals;

environment, or mainly specific habitats of pests, raptoria can be treated using solutions for spraying, fine sediment Farrukh Dustov, smoky, checkers, ointments, paints, pellets and groundbaits or by digging into the waterways, wells, reservoirs or other sources of flowing or standing water;

Pets, which these compounds are added to food in order to kill the larvae of flies in their faeces.

As a rule, the compounds of the present invention includes compositions. These compositions can be used to fight against arthropods, in particular insects or mites, nematode, helminth or protozoan pests. These compositions can be of any shape, usually used to control the desired pests indoors or outdoors, either by introducing inside or outside application vertebrate. Consider the compositions contain at least one compound of the present invention described above, as an active ingredient in combination with one or more other joint components such as solid or liquid carriers or diluents, adjuvants, surfactants (surfactants), which are agronomically or therapeutically acceptable. These compositions, which can be obtained standat also contain other ingredients such as protective colloids, adhesives, thickeners, thixotropic additives, impregnating substance, sprayable oil (especially for acaricide use), stabilizers, preservatives (such as preservatives), passivator, etc. as well as other active ingredients, known for its pesticide properties (for example, insecticides, acaricides, nematicides and fungicides) or properties that regulate the growth of plants. In particular, the compounds can be combined with all the solid or liquid additives in accordance with the standard technique of compositing.

Compositions intended for use in agriculture, horticulture, etc. can be made in the form, for example, solutions for spraying, Farrukh Dustov, granules, fine powders, foaming solutions, emulsions, etc.

Compositions intended for insertion vertebrate or human, can be made in the form of drugs for oral, parenteral, transcutaneous (for example, in the form of lotions) injection, or topical application.

Compositions for oral administration can contain one or more compounds of General formula (I) in combination with a pharmaceutically acceptable the th, drug feeding, drinking water with the addition of medicines, dietary supplements with added medicines, boles slow release medicines or other preparations with prolonged action. Any of these drugs can include the active ingredient contained in microcapsules or coated cyclotourism, or deletelabel, or other pharmaceutically acceptable intersolubility coating. Feed premixes or concentrates, containing compounds of the present invention, can be used by adding it to food, water or other nutrients consumed by animals.

Compositions for parenteral administration can be made in the form of solutions, emulsions or suspensions in any suitable pharmaceutically acceptable carrier, or in the form of a solid or semi-solid subcutaneous implant, or in the form of tablets, designed to implement the prolonged release of the active ingredient. While these drugs are sterile and can be made by any suitable known methods.

Compositions for crescono impregnation, showers, lubricating greases, shampoos, creams, ointments, solutions for water, or devices for autobrake animal (for example, ear-rings, suspended animals for local or systemic treatment against arthropods).

Solid or liquid bait, designed to fight against arthropods, may contain one or more compounds of General formula (I) and a carrier or diluent, which may include food or other substances commonly consumed by arthropods.

The effective dose used compounds of the present invention can vary widely depending on the form of destroying pests and extent of contamination, for example, crop plants of these pests. According to the present invention these compositions typically contain about 0.05 to about 95,0 wt. one or more active ingredients; from about 1 to 95 wt. one or more solid or liquid carriers; and optionally from about 0.1 to about 50.0, wt. one or more other compatible components, such as surfactants, or etc.

In the description of the present invention, the term "carrier" denotes an organic or Neorganicheskie order to facilitate its application to processing plants, seed or soil. Therefore, the specified media is usually inert and necessarily agronomically or pharmaceutically acceptable.

The specified media may be solid, for example, clays, natural or synthetic silicates, krasnozem, resins, waxes, solid fertilizers (e.g. ammonium salts), ground natural minerals such as kaolin, clay, talc, loose limestone, quartz, attapulgite, montmorillonite, bentonite or diatomaceous earth, or ground synthetic minerals such as silica, alumina or silicates, such as aluminum silicate or magnesium. As solid carriers can be used pellets, for example, crushed or powdered natural rocks such as calcite, marble, pumice, thick and dolomite; synthetic granules of organic or inorganic flour; granules of organic material such as sawdust, coconut shell, rods corn cob, leaf wrap corn cob or shoots of tobacco plants; kieselguhr, tricalcium phosphate, powdered cork, or activated carbon; water-soluble polymers, resins, waxes; and solid fertilizers. These solid compositions may, optionally, contain one or NESC also serve as diluents.

Used carrier may be a liquid, such as alcohols, in particular butanol or glycol and also their simple or esters, in particular etilenglikolya; ketones, such as acetone, cyclohexanone, methyl ethyl ketone, methyl isobutyl ketone or isophorone; petroleum fractions such as paraffinic or aromatic hydrocarbons, particularly xylenes or alkylnaphthalene; mineral or vegetable oils; aliphatic chlorinated hydrocarbons, particularly trichloroethane or methylene chloride; aromatic chlorinated hydrocarbons, particularly trichloroethane or methylene chloride; aromatic chlorinated hydrocarbons, in particular, chlorobenzene; water-soluble or strongly polar solvents such as dimethylformamide, dimethylsulfoxide or N-organic; liquefied gases; etc., or mixtures thereof.

As surfactants can be used emulsifying agents, dispersing agents or wetting agents such as ionic and non-ionic type or a mixture thereof. Examples of surfactants can serve as salts of polyacrylic acids, salts of lingocellulosic acids, salts phenolsulfonate or naphthalenesulfonate acids, polycondensate of ethylenoxide with fatty alcohols, or simiarities), salts of esters sulfonterol acid derivative taurine (in particular alliterate), esters of alcohol and phosphoric acid or polycondensate of ethylene oxide with phenols, esters of fatty acids with polyols, or sulphate, sulphonate or phosphate functional derivatives of the above compounds. If the active ingredient and/or the inert carrier are water-insoluble or slightly water-soluble, and the diluent composition is water, the presence of at least one surfactant is required.

In addition, the compositions of the present invention may contain other additives such as adhesives or dyes. Examples of suitable adhesives are the carboxymethyl cellulose or natural or synthetic polymers in the form of powders, granules or latexes, such as the Arabian gum, polyvinyl alcohol or polyvinyl acetate, natural phospholipids such as capalini or lecithins, and synthetic phospholipids. As dyes can be used inorganic pigments, for example iron oxide, titanium dioxide or Prussian blue; organic dyes, for example, alizarin dyes, azo-dyes or metal phthalocyanine or zinc.

Compositions containing compounds of General formula (I) and used to fight against arthropod, plant nematode, helminth or protozoan pests, may also contain synergistic substances (for example, piperonylbutoxide or sesamex), stabilizing substances, other insecticides, acaricides, plant nematicides, anthelminthic or protivotsestodoznye tools, fungicides (agronomy or veterinary acceptable, for example, benomyl and iprodione), bactericides, attractants or repellents for arthropods or vertebrates, or pheromones, deodorants, perfumes tools, dyes, therapeutic supplements, such as tracking the number of elements. These additional components may contribute to the increased activity, stability, reliability, the change in the spectrum of destroying pests, if necessary, and to inspire other useful features of these compositions when they are applied to the same animal or the same space.

Examples of other pesticide-active compounds, which can be used in combination with the compositions of the present invention are acetat, chlorpyrifos, demeton-S-methyl, disulfoton, pirimiphosmethyl, terbufos, triazophos, cyfluthrin, cypermethrin, deltamethrin, fenpropathrin, fenvalerate, tefluthrin, aldicarb, carbosulfan, methomyl, oxamyl, pirimicarb, bendiocarb, teflubenzuron, dicofol, endosulfan, lindane, benoxinate, cartap, cyhexatin, tetradifon, avermectin, ivermectin, milbemycin, tiopinac, trichlorfon, dichlorvos, diaveridine or dimetridazole.

For agronomic purposes the compounds of formula (I) are mainly used in the form of compositions, which can have a variety of solid or liquid forms.

Solid forms of compositions used are fine powders (with a content of compounds of formula (I) up to 80%), wettable powders or granules (including water dispersible granules), in particular pellets obtained by extrusion, compacting, impregnation of a granulated carrier, or granulation of the original powder (the content of the compounds of formula (I) in these wettable powders or granules is from about 0.5 to about 80,0%). Solid homogeneous or heterogeneous compositions containing one or more compounds of General formula (I), for example, granules, tablets, pellets or capsules, can be used for the treatment of flowing or standing water in them is periodic irrigation water dispersible concentrates, above.

As liquid compositions can be used in aqueous or anhydrous solution or suspension (for example, emulsifiable concentrates, emulsions, liquid dispersions or solutions), or aerosols. Liquid compositions can also be emulsifiable concentrates, dispersions, emulsions, flowable materials, aerosols, wettable powders (or powders for spraying), the dry bulk material or paste, i.e., such compositions that take the liquid form, or you can take a liquid form, for example, aqueous solutions (including low and ultra-low volume), or suspensions, or aerosols in their use.

Liquid compositions, for example, in the form of emulsifiable or soluble concentrates usually contain from about 5 to about 80 wt. the active ingredient, and emulsions or solutions ready to use from about 0.01 to about 20.0 wt. the active ingredient. In addition to the solvent emulsifiable or soluble concentrates can contain, if necessary, from about 2 to about 50 wt. appropriate additives such as stabilizers, surfactants, penetrating agents, corrosion inhibitors, dyes or adhesives. From these concentrates by dilution with water can be obtained obrabotki plants. Compositions which can be used for the purposes of the present invention, also includes in its scope. The emulsion can be in the form of "water in oil" or "oil-in-water and have a thick, viscous consistency.

In addition to their normal agronomic application of the liquid composition of the present invention can also be used for processing substrates or specific lesions that are infected or likely to be infected arthropod or other pests, destroying the means of the present invention, including buildings and adjacent areas, warehouses, industrial space, containers, as well as sources of flowing or standing water.

All these aqueous dispersions or emulsions or compositions for spraying can be used for the treatment of cultivated plants by any appropriate means, mainly by spraying at a flow rate of from about 100 to about 1200 liters of the mixture to spray 1 ha, however, this dose may be higher or lower (e.g., low or ultra-low volume) depending on the purpose or application techniques. The compounds or compositions of the present invention can be successfully used for the treatment of vegetable crops, cha is altoadige of the invention is to Heihachi, i.e. adding a composition containing an active ingredient for irrigation water. Such irrigation may be the sprinkler for processing leaves, either irrigation or surface irrigation soil for tillage or system processing.

Concentrated suspensions, which can be used by spraying, are prepared so as to obtain a stable fluid product which does not Deposit (fine grinding) and which contains from about 10 to about 75 wt. the active ingredient, from about 0.5 to about 30.0 wt. Surfactant, from about 0.1 to about 10.0 wt. thixotropic agents, from about 0 to about 30 wt. suitable additives such as protivovspenivayushchie agents, corrosion inhibitors, stabilizers, sealing agents, adhesives, and as carrier, water or an organic liquid in which the active ingredient is poorly soluble or insoluble. Certain organic solids or inorganic salts may be dissolved in the carrier to prevent deposition or for lowering the freezing temperature of water.

Wettable powders (or powders for spraying) are usually contain from about 10 to about 80 wt. the active ingredient, from about 20 to about 90 wt. solid Odimo, from about 0 to about 80 wt. one or more stabilizers and/or other additives such as penetrating agents, adhesives, anti-caking, dyes, etc. To get these wettable powders, the active ingredient (or active ingredients) carefully stir in the corresponding mixer with additional substances that can be impregnated on the porous filter, and then pulverized in an appropriate mill. Using this procedure, obtain wettable powders with good wettability and suspenderbelt. They can be suspended in water to obtain any desired concentration and these suspensions can be advantageously used for coating on the leaves of the plant.

"Water-dispersible granules" (WG)(which are easily dispersed in water) have a composition, mainly close to the composition specified above for wettable powders. They can be obtained by granulating compositions described above for wettable powders or wet method (mixing finely ground active ingredient with an inert filler and a small amount of water, for example, 1-20 wt. or with the aqueous solution of dispersing agent or binder with the consequences of the LASS="ptx2">

Used dose (effective dose) of the active ingredient as composed of the composition is typically from about 0.005-about 15,0 kg/ha and preferably from about 0.01 to about 2.0 kg/ha it follows that the norms and concentration of the used compositions may vary depending on application method, composition or use. Basically compositions for use against arthropod, plant nematode, helminth or protozoan pests contain from about 0,00001 to about 95,0 wt. and, in particular, from about 0.0005 to about 50 wt. one or more compounds of General formula (I) or of all active ingredients (i.e. compounds of General formula (I) together with other substances with toxicity to arthropods, plant nematodes or worms, and also has anticoccidial and a synergistic effect; trace amounts of elements or stabilizers). The specific composition and dose of their use can be selected to achieve the desired effect by specialists, for example, a farmer, farmer, doctor, veterinarian or operator of pest control.

Solid or liquid composition for the local treatment of animals, timber products, is respectfully from about 0.001 to about 10.0 wt. one or more compounds of General formula (I). Compositions intended for oral or parenteral, and intradermal injection, which can be both solid and liquid, usually contain from about 0.1 to about to 90.0 wt. one or more compounds of General formula (I). Feed, including medicines typically contain from about 0.001 to about 3.0 wt. one or more compounds of General formula (I). Concentrates or feed additives for mixing with feeds usually contain from about 5 to about 90 wt. and preferably from about 5 to 50 wt. one or more compounds of General formula (I). Salt lick typically contains from about 0.1 to about 10.0 wt. one or more compounds of General formula (I).

Dusty or liquid compositions for use in animal husbandry, as well as for treatment of the person, goods, buildings and open spaces can contain from about 0.0001 to about 15 wt. and preferably from about 0,005 to about 2.0 wt. one or more compounds of General formula (I). Acceptable concentrations in the treated water concentrations are approximately of 0.001 to 5.0 ppm of one or more compounds of General formula (I), which can be therapeutically COI is ü from about 0.01 to about 5.0 wt. and preferably from about 0.01 to 1.0 wt. one or more compounds of the formula (I).

With the introduction of parenteral, oral, transcutaneous, or in other ways vertebrate dose of the compounds of General formula (I) will depend on the species, age or General condition of the spine, as well as from the nature, the extent of actual or potential contamination of arthropods, helminths or protozoa pests. For prolonged maintenance treatment with oral or parenteral single dose of about 0.1-100.0 mg, preferably about 2.0 to 20.0 mg per 1 kg of body weight of the animal, or dose for extended release is about 0.001 to 20.0 mg, preferably about 0.1 to 5.0 mg per 1 kg of weight of animal per day. When using drugs or devices for the sustained release of drugs daily dose, which must be within 1 month, can be combined and put the animal at once.

The following examples 7A-7L illustrate the use of compositions of the present invention against arthropods, especially mites or insects, plant nematode, helminth or protozoan pests that have Cutesy in the preparative examples. The compositions described in examples 7A 7F, can be diluted with water to form a sprayable composition in concentrations that are required for use on the fields. Here are descriptions of the basic chemical ingredients used in the compositions of examples 7A 7L, wt.

Brand Chemical composition

Atilan BCP Condensate of nonylphenolethoxylate

Suprior BSU Condensate of tristellateia

Arylan CA 70 wt. solution dodecylbenzenesulfonate calcium

Solvesso 150 Easy C10-aromatic solvent

Arylan S Dodecylbenzenesulfonate sodium

Darvon N 2 Lignosulfonate sodium

Celite PF (Synthetic magicality media

Suprofen T36 Sodium salt of polycarboxylic acids

Redigel 23 Polysaccharide xanthan gum

Concrete 38 Organic derivative of magnesium montmorillonite

Aerosil Fine silicon dioxide

Example 7A

Got a water-soluble concentrate having the following composition (%):

The active ingredient 7

Atilan BCP 10

N-organic 83

To a solution of atilano BCP dissolved in part of the N-methylpyrrolidone added active ingredient, heating and stirring until then, until he n the

Received emulsifiable concentrate (EC) with the following composition:

The active ingredient 7

Suprior BSU 4

Arylan CA 4

N-organic 50

Solvesso 150 35

The first three components were dissolved in N-organic, then to this solution was added solvesso 150 by the end of the volume.

Example 7C

Received wettable powder (WP) with the following composition:

The active ingredient 40

Arylan S 2

Darwin N2 5

Celite PF 53

The above ingredients were mixed and crushed in a hammer mill, resulting in the obtained powder with particle sizes less than 50 microns.

Example 7D

Aqueous fluid composition was obtained with the following composition:

The active ingredient 40,00

Atilan BCP 1,00

Apropos T360 0,20

The glycol 5,00

Redigel 230 0,15

Water 53,65

The ingredients are thoroughly mixed and grinded in a bead mill until then, until he had particles with a size less than 3 microns.

Example 7E

Received concentrate emulsifiable suspension with the following composition (%):

The active ingredient 30,0

Atilan BCP 10,0

Benton 38 0,5

Solvesso 150 59,5

These ingredients are thoroughly mixed and smallcaliber dispersible granules with the composition, (%):

The active ingredient 30

Darwin N2 15

Arylan S 8

Celite PF 47

The ingredients were mixed, crushed in a jet mill and then granulated in a rotary granulator by spraying water (up to 10%). The obtained granules were dried in the dryer fluidized bed to remove excess water.

Example 7G

A fine powder was obtained with the following composition (%):

Active ingredient 1 10

Ultrafine talc powder 99 90

The ingredients are thoroughly mixed, and then crushed to obtain the desired fine powder. This powder can be applied on the places infected arthropods, for example, landfills with waste products in storage, household items, infected animals or on the specified objects to the risk of infection arthropods, to combat these pests through ingestion, they described the funds. Appropriate means of applying the described dust to infect arthropods are mechanical fan sprayer, hand-held vibrator or device for Samoobrona cattle.

Example 7H

Received an edible bait with the following composition (%):

Active ingredient the desired shape. This lure can be distributed in certain areas subject to contamination, for example, in homes or industrial plants, namely, kitchens, hospitals, warehouses, open spaces affected arthropods such as ants, grasshoppers, cockroaches and flies, to combat these pests through ingestion or described pesticide baits.

Example 7I

Got the solution with the following composition (%):

The active ingredient 15

Dimethyl sulfoxide 85

The active ingredient was dissolved in dimethyl sulfoxide, stirring and/or heating as needed. This solution can be introduced domestic animal infected arthropods, transcutaneous introduction or topical application, in the case of parenteral use of this solution is injected after sterilization by filtration through a PTFE membrane (pore size 0.22 μm) at a dose of 1.2 to 12.0 ml per 100 kg of weight of animal.

Example 7J

Received wettable powder with the following composition:

The active ingredient 50

Atilan BCP 5

Aerosil 5

Celite PF 40

Atilan BCP absorbed on aerosole, which is then mixed with other ingredients and edit the to a concentration of 0.001 to 2.0 wt. the active ingredient, after that applied on the lesions of infected arthropods such as Diptera larvae or plant nematodes by spraying or introduced domestic animals that are infected or at risk of Contracting arthropods, helminths or protozoa, by spraying, impregnation or by oral administration by adding drinking water.

Example 7K

Bolus composition with a slow release received from granules containing depending on the purpose of use of the following components, with different percentages (similar to the above described compositions): an active ingredient; a thickening agent; an agent that slows the release; binder.

The ingredients are thoroughly mixed, formed into granules and compressed into a bolus with a specific gravity of 2 or more. This bolus may be administered orally ruminants pet, because staying in the rumen and reticulum (first and second stomach of some animal, respectively), it causes prolonged release of the active ingredient over a long enough period of time, thereby contributing to the effective impact of pesticide remedies against yovanny release of the active ingredient in the form of granules, briquettes, tablets, etc., having the following composition (%):

The active ingredient 0,5 25,0

Polyvinyl chloride 75,0 99,5

The dioctylphthalate (plasticizer) a Catalytic amount

The components were mixed and formed into the appropriate shape by extrusion from the melt or injection molding. These compositions can be used, for example, to add in standing water or for the manufacture of collars or earrings (i.e., ear tags) to attach the pet to control pests by means of these devices with slow release.

The invention is described in preferred examples of its implementation, but it can be made various changes, not beyond it being formulated in the following claims.

1. Derivatives of 1-aryl-5-(substituted methylidene)pyrazole of the General formula I

< / BR>
where R is cyano or chloro;

R1nitro, trifluoromethyl, or R5S(O)nwhere R5WITH1C4-alkyl or trihalogen1- C4-alkyl, n 0 2;

R2unsubstituted phenyl or phenyl substituted by 1 to 4 identical or different groups selected from a range that contains Hydra>C8- alkanoyloxy, benzyloxy, C1C4-alkylthio, NR6R7where R6and R7independently hydrogen, C1C4-alkyl or acetyl, or R2- 4-pyridyl, 4-pyridyl-N-oxide, 2-thienyl, 2-furanyl, 2-imidazolyl, 6-benzo-[1,3-dioxole]

R3halogen;

R4halogen, trifluoromethyl or triptoreline;

X is nitrogen or a group of CCL or CH.

2. Derivatives of 1-aryl-5-(substituted methylidene) pyrazole under item 1 of General formula I, where R is cyano, R2the group R5S(O)nwhere R5WITH1C4- alkyl or trihalogen-C1- C4-alkyl, n 0 2, R2unsubstituted phenyl or phenyl substituted by 1 to 4 identical or different groups selected from a range that contains hydroxy, halogen, cyano, C1C4-alkyl, C1- C4-alkoxy, C1WITH4-alkylthio, or R24-pyridyl, 4-pyridyl-N-oxide;

R3halogen;

R4halogen, trifluoromethyl or triptoreline;

X is nitrogen or a group of CCL or CH.

3. A method of combating harmful insects by treating the source of contamination derivatives of 1-aryl-5-(substituted methylidene) pyrazole, characterized in that as a function of 1-aryl-5-(substituted methylidene) pyrazole is, is that the treatment is carried out by applying the compounds of General formula I on the plants or their environment of origin.

5. The method according to PP. 3 and 4, characterized in that the specified soil insects are insects belonging to the order Lepidoptera, or leaf insects belonging to the order Coleoptera, or ranarridh.

6. Insecticidal composition containing as an active ingredient 0.1 to 50 wt. derivative of 1-aryl-5-(substituted methylidene) of pyrazole in a mixture with a solid or liquid carrier and/or auxiliary components, including diluents, adjuvants or surfactants, characterized in that as a function of 1-aryl-5-(substituted methylidene) pyrazole composition comprises the compounds of General formula I on p. 1.

 

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(I)

where R1represents hydrogen, lower alkyl, lower alkenyl, lower quinil, aryl lower alkyl, cycloalkyl lower alkyl, lower alkoxy lower alkyl, hydroxy lower alkyl, amino lower alkyl, mono - or di-lower alkyl, amino lower alkyl, formyl, lower alkylsulphonyl, amino lower alkylsulphonyl, lower alkoxycarbonyl, mono - or di-aryl-substituted lower alkyl, arylcarbamoyl lower alkyl, aryloxy lower alkyl, or lower alkylene

< / BR>
X represents O or S;

W represents hydrogen, halogen, hydroxy, lower alkoxy, aryl lower alkoxy, nitro, trifluoromethyl or

< / BR>
where R3represents hydrogen, lower alkyl or aryl lower alkyl, and R4represents lower alkyl or aryl lower alkyl; or alternatively the groupas a whole represents the

< / BR>
R5is hydrogen, lower alkyl, aryl or aryl lower alkyl; and

Z predepression

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< / BR>
< / BR>
ALK is a lower alkyl

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