WO1999017613A1

WO1999017613A1 - Methode of insect control

Info

Publication number: WO1999017613A1
Application number: PCT/EP1998/006658
Authority: WO
Inventors: Tai-Teh Wu
Original assignee: Rhone-Poulenc Agro
Priority date: 1997-10-07
Filing date: 1998-10-05
Publication date: 1999-04-15
Also published as: AU1031199A

Abstract

A method of control of insects which comprises the delivery of a 3-cyanopyrazole of formula (II), to a locus by means of an application to the locus of a compound of formula (I), and then a conversion of the compound of formula (I) to the 3-cyanopyrazole of formula (II).

Description

Method of Insect Control

The present invention relates to a new method of control of insects at a locus.

In the field of insecticides, there are various references which describe 1 -arylpyrazoles as foliar insecticides and seed treatments. Among these references, WO 97/28126 provides hydroxyamidine and aminoamidine insecticides.

Insecticidally active compounds are used to destroy or control insects. The said insecticidally active compounds may be formulated in a number of different ways. The object of a particular formulation is to apply the insecticidal active ingredient to a locus where insect control is desired in a convenient, safe and effective way.

It is a constant problem in the field of insecticides to deliver lower doses of the active ingredient. In other words it is a constant problem to increase the bioavailability of the active ingredient and thus to lower its required dose rate.

It is an object of the present invention to provide a new method of the control of insects.

It is an object of the present invention to provide new insecticides that may be used in a manner by which a proinsecticide is readily converted to an insecticide.

It is an object of the present invention to increase the bioavailability of insecticidally active ingredients. These objects are met in whole or in part by means of the instant invention.

The present invention relates to a method of control of insects present or expected to be present at a locus which comprises the delivery of a 3-cyanopyrazole of formula (II):

[II] wherein:

W is a halogen or a group bonded through C, N, O, S or P; Ar is an optionally substituted aromatic hydrocarbon group or an optionally substituted aromatic heterocyclic group; and

R is H, a halogen or a group bonded through C. N, O, S or P to the locus by means of an application to the locus of an arylpyrazole of formula (I):

wherein Ar is an optionally substituted aromatic hydrocarbon group or an optionally- substituted aromatic heterocyclic group. R is H. a halogen or a group bonded through C. N, O, S or P, W is a halogen or a group bonded through C. N, O, S or P. X is a group bonded through N. O or S. Y is H or a group bonded through C. N, O, S or P, or X and Y being combined, a group of the formula

A N

is an optionally substituted nitrogen-containing heterocyclic group which may further have N. O. S and/or P as a ring-constituting atom or a salt or metal complex thereof; and wherein the locus is soil or a plant wherein the plant is planted in soil.

It is to be understood that the term "insect^"' (and terms derived from it) is used in its ordinary or everyday sense as meaning generally an arthropod pest, for example a small invertebrate segmented animal, usually an arthropod of the class Insereta.

The method of the invention permits the delivery of a 3-cyanopyrazole of formula (II) in an alternative form, as the compound of formula (I). The chosen compound of formula (I), as well as providing an alternative for application may also offer other advantages over the 3-cyanopyrazole itself. It may, for example, be less toxic to operators applying the material; easier or more convenient to formulate (or to apply); or its absorption into a plant or target insect either directly from topical application or systemically, e.g. from soil, may be improved.

The method of the present invention is generally effected wherein the rate of application of the compound of formula (I) is from about 10 g/Ha (grams per hectare) to about 200 g/Ha, preferably from about 25 g/Ha to about 1 OOg/Ha.

Most preferably, after application of the compound of formula (I) there is then a conversion of the compound of formula (I) to the 3-cyanopyrazole of formula (II).

The method of preparation of the arylpyrazoles of the present invention is found in WO 97/28126. The method of formulation is also found therein. All enolic tautomeric forms are embraced by the present invention. Furthermore in certain cases the various substituents may contribute to isomerism. for example, optical isomerism and/or stereoisomerism. All such forms are embraced by the present invention.

Preferably the method is used when the locus is a plant or a crop growing area. Most preferably the locus is a rice plant planted in soil, particularly the leaves of the rice plant. The locus may also be advantageously the soil where the plant is growing or the locus may be the seed from which the plant grows. The compound of formula (I) may be applied to the soil around the seed or as a seed dressing.

The compound of formula (I) must be converted into a compound of formula (II) for an insecticidal effect to take place. The conversion may take place in or on the soil or the plant.

By the term conversion is meant a biological transformation in the soil or on the plant by action of a combination of biological factors which may include light, contact with foliage, bacteria, micro-organisms in general and the like. When the plant is rice, the conditions are such that the plant is not grown up directly in water without soil. The conversion may take place before the plant absorbs the 3-cyanopyrazole.

Other modifications of groups may take place on the compound of formula (I). For example, when W comprises a sulfide or sulfoxide group, these may be converted to a sulfoxide or a sulfone respectively.

It has also been unexpectedly found that Termites may be controlled by delivery of a 3-cyanopyrazole of formula (II)

[II] wherein:

W is a halogen or a group bonded through C, N, O, S or P;

Ar is an optionally substituted aromatic hydrocarbon group or an optionally substituted aromatic heterocyclic group; and

R is H, a halogen or a group bonded through C, N, O, S or P to the termites by means of an application to a locus of an arylpyrazole of formula (I):

wherein Ar is an optionally substituted aromatic hydrocarbon group or an optionally substituted aromatic heterocyclic group, R is H, a halogen or a group bonded through C, N, O, S or P, W is a halogen or a group bonded through C, N, O, S or P, X is a group bonded through N, O or S, Y is H or a group bonded through C, N, O, S or P, or X and Y being combined, a group of the formula

is an optionally substituted nitrogen-containing heterocyclic group which may further have N, O, S and/or P as a ring-constituting atom or a salt or metal complex thereof; and then a conversion of the arylpyrazole of formula (I) to the 3-cyanopyrazole of formula (II).

The compound of formula (I) may be applied, for example, to the ground, in a bait, in a trap, in a termite mound, on the soil, on the termites themselves, around the structures of buildings and other such loci known to the skilled addressee. The composition of the bait may be a gel, granules and other forms known to the skilled addressee.

The present invention also relates to a method of control of cockroaches by delivery of a 3-cyanopyrazole of formula(II):

[II] wherein:

W is a halogen or a group bonded through C, N, O, S or P;

Ar is an optionally substituted aromatic hydrocarbon group or an optionally substituted aromatic heterocyclic group; and R is H, a halogen or a group bonded through C, N, O, S or P to the termites by means of an application to a locus of an arylpyrazole of formula (I):

wherein Ar is an optionally substituted aromatic hydrocarbon group or an optionally substituted aromatic heterocyclic group, R is H, a halogen or a group bonded through C, N, O, S or P, W is a halogen or a group bonded through C, N, O, S or P, X is a group bonded through N, O or S, Y is H or a group bonded through C, N, O, S or P, φ ^■■ . and Y being combined, a group of the formula

is an optionally substituted nitrogen-containing heterocyclic group which may further have N, O, S and or P as a ring-constituting atom or a salt or metal complex thereof; and then a conversion of the compound of formula (I) to the 3-cyanopyrazole of formula (II).

It will be understood that the optionally substituted nitrogen-containing heterocyclic group which may further have N, O, S and or P as a ring-constituting atom may also comprise further carbon atoms in the ring.

Generally the locus is an area where cockroaches are inhabiting or expected to inhabit. The said loci are preferably buildings or structures but may also include soil. Generally the compound of formula (I) or salt or metal complex thereof is applied to the locus in a bait, the contents of which are generally known by the skilled addressee. Most advantageously, the conversion of the method occurs in the cockroaches themselves.

In the above formulae, Ar is an optionally substituted aromatic hydrocarbon group or an optionally substituted aromatic heterocyclic group.

Examples of the aromatic hydrocarbon group in the optionally substituted aromatic hydrocarbon group for Ar include a Cβ.\_\. aromatic hydrocarbon group such as phenyl, naphthyl, biphenyl, anthryl, phenanthryl and the like.

Examples of the substituent on the aromatic hydrocarbon group include a .g alkyl group (e.g. methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert- butyl, n-pentyl, sec-pentyl, isopentyl, n-hexyl), which may optionally be substituted with 1 to 4 substituents selected from the group consisting of, for example, hydroxy, C _j.g alkoxy (e.g. methoxy, ethoxy, propoxy, isopropoxy, butoxy, pentyloxy, hexyloxy, etc.), halogen (e.g. fluorine, chlorine, bromine, iodine, etc.) and a ino which may optionally be mono- or di-substituted with C \. alkyl (e.g. methylamino, ethylamino, propylamino, dimethyla ino, diethylamino, etc.); an amino group which may optionally be mono- or di-substituted with C }.g alkyl or .g alkanoyl (e.g. methylamino, ethylamino, propylamino, dimethylamino, diethylamino, acetylamino, propionylamino. etc.); a hydro xyl group; a carboxyl group; a nitro group; SF5; a C\_β alkoxy group (the same as defined above); a C\.β alkanoyloxy group (e.g. formyloxy, acetyloxy, propionyloxy, n- butyryloxy. iso-butyryloxy, etc.); a cyano group; and a halogen atom (the same as defined above).

The number of substituents is from 1 to 6, preferably from 1 to 4, most preferably from 1 to 3, within the substitutable range. When the substituent is halogen atom, substitution may be performed within the maximum substitutable range. As the aromatic heterocyclic group in the optionally substituted aromatic heterocyclic group for Ar, for example. 5- to 8-membered aromatic heterocyclic groups having 1 to 4 hetero atoms selected from O, S, N. etc., in addition to carbon atom(s), which may be condensed with a C5.10 cyclic hydrocarbon ring (e.g. cyclopentane, cyclohexane. benzene, naphthalene, etc.) or 5- or 6-membered heterocyclic ring having 1 to 4 hetero atoms selected from N, 0 and S may be used.

Specifically, 5-membered aromatic heterocyclic group having 1 to 4 hetero atoms selected from O, S, N, etc.. in addition to carbon atom(s), (e.g. 2- or 3-thienyl, 2- or 3- furyl, 2-, 4- or 5-oxazolyl, 2-. 4- or 5-thiazolyl, 3-, 4- or 5-pyrazolyl, 2-, 4- or 5- imidazolyl. 3-, 4- or 5-isoxazolyl, 3-, 4- or 5-isothiazolyl, 1 ,2,5-thiadiazolyl, 1 ,2,3- triazolvl, 1 ,2.4-triazolyl, etc.); 6-membered aromatic heterocyclic group having 1 to 4 hetero atoms selected from O, S, N, etc., in addition to carbon atom(s), (e.g. 2-, 3- or 4- pyridyl or N-oxide thereof, 2-, 4- or 5-pyrimidinyl or N-oxide thereof, 3 or 4-pyridazinyl or N-oxide thereof, pyrazinyl, etc.); and dicyclic or tricyclic condensed aromatic heterocyclic group having 1 to 4 hetero atoms selected from O, S, N, etc., in addition to carbon atom(s), (e.g. benzofuryl, benzothiazolyl, benzoxazolyl, tetrazolo(l ,5- b]pyridazinyl, triazolo[4,5-b]pyridazinyl, imidazo(l,2-a]pyridinyl, benzoimidazolyl, quinolyl, isoquinolyl, cinnolinyl, phthalazinyl, quinazolinyl, quinoxalinyl, indolidinyl, quinolidinyl, 1 ,8-naphthylidinyl, purinyl, pteridinyl, dibenzofuranyl, carbazolyl, acridinyl, phenanthridinyl, chromanyl, benzoxazinyl, phenazinyl, phenothiazinyl, phenoxazinyl, etc.) are used. As the substituent on the aromatic heterocyclic group, for example, the same substituent as that of the aromatic hydrocarbon group for Ar are used. The number of substitutents is from 1 to 6, preferably from 1 to 4, most preferably from 1 to 3, within the substitutable range. As the halogen atom for W or R, for example, fluorine, chlorine, bromine, iodine, etc. are used. Among them, chlorine is preferred.

Examples of the group bonded through C for W, R, X or Y include all organic residues bonded through a carbon atom. For example, an optionally substituted hydrocarbon group, an optionally substituted acyl group, a cyano group, an optionally substituted carbamoyl group, an amidino group or an optionally substituted heterocyclic group having a chemical bond at a carbon atom is used.

As the hydrocarbon group, for example, alkyl group, alkenyl group, alkynyl group, cycloalkyl group, aryl group, aralkyl group, etc. are used. Among them, a C_j_24 hydrocarbon group is preferred. As the alkyl group, for example, a C1 5 alkyl group (e.g. methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, etc.) is used. Among them, a Ci .5 alkyl group such as methyl, ethyl, propyl, isopropyl, butyl, t-butyl, pentyl, hexyl, etc. is particularly preferred. As the alkenyl group, for example, a C2-io_> alkenyl group (e.g. vinyl, allyl, 2-methylallyl, 2-butenyl, 3-butenyl, 3-octenyl, etc.) is used. Among them, a C2-6 alkenyl group such as vinyl, butadienyl, hexatrienyl, etc. is preferred. As the alkynyl group, for example, a C2-10 alkynyl group (e.g. ethynyl, 2-propynyl, isopropynyl, butynyl, t-butynyl, 3-hexynyl, etc.) is used. Among them, a C2-6 alkynyl group is preferred. As the cycloalkyl, for example, a C3.6 cycloalkyl group such as cyclopropyl, cyclopentyl, cyclohexyl, etc. is preferred. As the aryl group, for example, a C6- 14 aryl group such as phenyl, naphthyl, anthracenyl, etc. is used. As the aralkyl group, for example, a C7.20 aralkyl group such as benzyl, phenylethyl, benzhydryl, trityl, etc. is used. Among them, a C7.15, aralkyl group is preferred.

These hydrocarbon groups may be substituted with the substituents as described hereinafter. As the substituted hydrocarbon group, for example, an alkoxyalkyl group (e.g. Cι_3 alkoxy-C^.g, alkyl group such as methoxymethyl, ethoxymethyl, ethoxybutyl, propoxymethyl, propoxyhexyl etc.), a hydroxyalkyl group (e.g. hydroxy Cj.g (, alkyl group such as hydroxymethyl, hydroxyethyl, hydroxybutyl, hydroxypropyl, etc.) and a halogenated alkyl group (e.g. mono-, di- or tri-halogenated Cj.g alkyl group such as chloromethyl, fluoromethyl, bromomethyl, chloroethyl, dichloromethyl. trichloromethyl, trifluoromethyl, etc.) are preferred.

As the acyl group in the optionally substituted acyl group, for example, an acyl group derived from a Cj_24 aliphatic carboxylic acid is used. Specifically, for example, a C\_ _y alkanoyl group such as formyl, acetyl, ethylcarbonyl, propylcarbonyl, tert- butylcarbonyl, etc.; a Cj.g alkoxy-carbonyl group such as methoxycarbonyl, ethoxycarbonyl, etc.; a C6_i4,. aryl-carbonyl group such as benzoyl, etc. ; a Cg_i 4 aryloxy-carbonyl group such as benzoxycarbonyl, etc.; a C7.15 aralkyl-carbonyl group such as benzylcarbonyl, etc.; and a C7.15 aralkyloxy-carbonyl group such as benzyloxycarbonyl, etc. are used. As the optionally substituted carbamoyl, for example, a carbamoyl group which may be substituted with an optionally substituted Cι _20 hydrocarbon group (e.g. Cj_ι 5 alkyl, C2-10 alkenyl, C2-10 alkynyl, C _\_ aryl or C7.20 aralkyl group, etc.) is used. Specifically, a mono- or di-Cj .15 alkyl-carbamoyl group (e.g. mono- or di-Cj.g alkyl- carbamoyl group such as methylcarbamoyl, ethylcarbamoyl, hexylcarbamoyl, dimethylcarbamoyl, methylethylcarbamoyl, etc.) is preferred.

As the heterocyclic group in the optionally substituted heterocyclic group having a chemical bond at a carbon atom, for example, a 3- to 8-membered heterocyclic group having 1 to 4 hetero atoms selected from N, O and S, etc., in addition to carbon atom(s), which may be condensed with a C5.1Q cyclic hydrocarbon ring (the same as defined above) or 5- or 6-membered heterocyclic ring having 1 to 4 hetero atoms selected from N, O and S are used.

Specifically, 5-membered cyclic group having 1 to 4 hetero atoms selected from O, S and N, in addition to carbon atom(s) (e.g. 2- or 3-thienyl, 2- or 3-furyl, 2- or 3- pyrrolyl, 2-, 3- or 4-pyridyl, 2-, 4- or 5-oxazolyl, 2-, 4- or 5-thiazolyl, 3-, 4- or 5- pyrazolyl, 2-, 4- or 5-imidazolyl, 3-, 4- or 5-isoxazolyl, 3-, 4- or 5-isothiazolyl, 3- or 5- (1,2,4-oxadiazolyl), 1,3,4-oxadiazolyl, 3- or 5-(l,2,4-thiadiazolyl), 1,3,4-thiadiazolyl, 4- or 5-(l,2,3-thiadiazolyl), 1,2,5-thiadiazolyl, 1,2,3-triazolyl, 1,2,4-triazolyl, lH- or 2H- tetrazolyl, etc.); 6-membered cyclic group having 1 to 4 hetero atoms selected from O, S and N, in addition to carbon atom(s) (e.g. N-oxide-2-, 3- or 4-pyridyl, 2-, 4- or 5- pyrimidinyl, N-oxide-2-, 4- or 5-pyrimidinyl, 2- or 3-thiomorpholinyl, 2- or 3- morpholinyl, oxotriazinyl, dioxotriazinyl, pyrrolidinyl, piperidinyl, pyranyl, thiopyranyl, 1 ,4-oxadinyl, 1 ,4-thiazinyl, 1,3-thiazinyl, 2- or 3-piperazinyl, triazinyl, oxotriazinyl, 3- or 4-pyridazinyl, pyrazinyl, N-oxide-3- or 4-pyridazinyl, etc); and dicyclic or tricyclic condensed aromatic heterocyclic group having 1 to 4 hetero atoms selected from O, S and N in addition to carbon atom (e.g. benzofuryl, benzothiazolyl, benzoxazolyl, tetrazolo[l,5-b]pyridazinyl, triazolo[4,5-b]pyridazinyl, imidazo[l,2-a]pyridinyl, benzoimidazolinyl, quinolyl, isoquinolyl, cinnolinyl, phthalazinyl, quinazolinyl, quinoxalinyl, indolidinyl, quinolidinyl, 1,8-naphthylidinyl; purinyl, pteridinyl, dibenzofuranyl, carbazolyl, acridinyl, phenanthridinyl, chromanyl, benzoxazinyl, phenazinyl, phenothiazinyl, phenoxazinyl, etc.) are used.

These hydrocarbon group, acyl group, carbamoyl group substituted with a Cι_20, hydrocarbon group and heterocyclic group having a chemical bond at carbon atom may have substituents. As the substituents, for example, a nitro group; a hydroxyl group; an oxo group; a thioxo group; a cyano group; a carbamoyl group; a carboxyl group; a C\.\_ζ acyl group (e.g- €_{. alkoxy-carbonyl (e.g methoxycarbonyl, ethoxy carbonyl, n-propoxycarbonyl, iso-propoxycarbonyl, n-butoxycarbonyl, iso-butoxycarbonyl, tert- butoxycarbonyl, etc.), \. alkanoyl (e.g. formyi, acetyl, propionyl, n-butyryl, iso-butyryl, etc., C .\_\ aryl-carbonyl (e. g. benzoyl, etc.)]; a sulfo group; a halogen atom (the same as defined above); a C1 4 hydrocarbon-oxy group [e.g. C\. alkoxy (the same as defined above), C .i 4 aryloxy (e.g. phenoxy, naphthyloxy, etc.)] which may optionally be mono- to tri-substituted with halogen (e.g. o-, m- or p-chlorophenoxy, o-, m- or p-bromophenoxy, etc.); -S(O)_n»R^ wherein n", is 0, 1 or 2, R^ is a C 1.14 hydrocarbon group such as C\. , alkyl, Cβ-H aryl (e.g. C g alkylthio (e.g. methylthio, ethylthio, propylthio, isopropylthio, n-butylthio, sec-butylthio, tert-butylthio, etc.), Cg._j4 arylthio (e.g. phenylthio, etc.), C j.g alkylsulfinyl (e.g. methylsulfinyl, ethylsulfinyl, propylsulfinyl, butylsulfinyl, etc.), C\_β alkylsulfonyl (e.g. methylsulfonyl, ethylsulfonyl, propylsulfonyl, butylsulfonyl, etc.)]; an amino group which may optionally be mono- to tri-substituted with \. alkyl-carbonyl or C\_ alkyl (e.g. acetylamino, propionylamino, etc.); an imino group which may optionally be substituted with C\_ alkyl, hydroxy or Cj.g alkoxy (e.g. methylimino, ethylimino, propylimino, butylimino, methoxyimino, eythoxyimino, n-propoxyimino, etc.); a hydrazono group which may optionally be substituted with mono- or di-substituted with C\__\ alkyl (e.g. methylhvdrazono. ethylhydrazono. dimethylhydrazono, etc.); and 5- or 6-membered heterocyclic group which may have 1 to 4 substituents selected from (a) halogen atom (the same as defined above), (b) C }_4 alkyl group (e.g. methyl, ethyl, propyl, isopropyl, etc.) and (c) mono- to tri-halogenated phenoxy group (e.g. o-, m- or p-chlorophenoxy, o-, m- or p-bromophenoxy. etc.) and has 1 to 4 hetero atoms selected from O, S and N, etc., in addition to carbon atom(s) (e.g. 2- or 3-thienyl, 2 or 3-furyl, 3-, 4- or 5-pyrazolyl, 2-, 4- or 5-thiazolyl, 3-, 4- or 5-isothiazolyl, 2-, 4- or 5-oxazolyl, 3-, 4- or 5-isoxazolyl, 2-, 4- or 5-imidazolyl. 1,2,3- or 1,2,4-triazolyl, 1H- or 2H-tetrazolyl, 2-, 3- or 4-pyridyl, 2- 4- or 5-pyrimidinyl, 3- or 4-pyridazinyl, quinolyl, isoquinolyl. indolyl. etc.). The number of substituents is from 1 to 5. preferably from 1 to 3, within the substitutable range. Examples of the group bonded through N for W, R, X or Y include all organic residues bonded through a nitrogen atom. For example, (1) a nitro group. (2) a group of the formula: -NR1 R2 wherein RI and R^ each are H, an optionally substituted hydrocarbon group, an optionally substituted acyl group, an optionally substituted carbamoyl group; an optionally substituted heterocyclic group, a hydroxyl group, an optionally substituted hydrocarbon-oxy group or a group of the formula: -SOpR^ (R^ is

H or an optionally substituted hydrocarbon group, and p is 1 or 2), (3) an optionally substituted heterocyclic group having a chemical bond at a nitrogen atom and (4) a group of the formula: -N=C(R3)R4 wherein R^ and R^ each are H, an optionally substituted hydrocarbon group, an optionally substituted hydrocarbon-oxy group or a group of the formula: -NR^RIO (R9 and RlO each are H, a hydroxyl group or an optionally substituted hydrocarbon group) are used.

As the optionally substituted hydrocarbon group for RI^", R^, R3, R _? R8_^ R9 _or RIO, the same one as the above optionally substituted hydrocarbon group defined in the group bonded through C is used.

As the optionally substituted hydrocarbon group of the optionally substituted hydrocarbon-oxy group for Rl, R^, R^or R^, the same one as the above optionally substituted hydrocarbon group defined in the group bonded through C is used.

As the optionally substituted acyl or optionally substituted carbamoyl group for Rl or R2, the same one as the above optionally substituted acyl or optionally substituted carbamoyl group defined in the group bonded through C is used.

As the heterocyclic group in the optionally substituted heterocyclic group for Rl or R2, the same one as the above heterocyclic group defined by the optionally substituted heterocyclic group having a chemical bond at a carbon atom is used. As the heterocyclic group having a chemical bond at a nitrogen atom defined in the group bonded through N for W, R, X or Y, for example, 3- to 8-membered heterocyclic groups having a chemical bond at a nitrogen atom and 1 to 4 hetero atoms selected from N, O and S in addition to carbon atom(s) and one nitrogen atom which may be condensed with a C5.1 Q cyclic hydrocarbon ring or 5- or 6-membered heterocyclic ring having 1 to 4 hetero atoms selected from N, O and S are used. Specifically, for example, lH-1-pyrτolyl, 1-imidazolyl, 1-triazolyl, 1-pyrazolyl, 1-indolyl, lH-indazolyl, 7-purinyl, 1-aziridinyl, 1-pyrrolidinyl, lpyrrolinyl, 1-imidazolidinyl, 2-isoxazolidinyl, pyrazolidinyl, piperazinyl, pyrazolinyl, 1-piperidinyl, 4-morpholinyl, 4-thiomorpholinyl, etc. are used. As the substituent on the heterocyclic group for Rl or R^ and the heterocyclic group having a chemical bond at a nitrogen atom, for example, a Cι_20 hydrocarbon group [e.g. C\. alkyl (the same as defined above), C2-6 alkenyl (the same as defined above), C2- alkynyl (the same as defined above), C3.6 cycloalkyl (the same as defined above), C5.7 cycloalkenyl (e.g. cyclopentenyl, cyclohexenyl, etc.), C7.20 aralkyl (the same as defined above), C6.14 aryl (the same as defined above)], which may optionally be mono- to tri-substituted with halogen; a Cι_i4 hydrocarbon-oxy group (e.g. Ci _g alkoxy (the same as defined above), C .\_ aryloxy (the same as defined above)]; a C^.

15 acyl group [e.g. Cj.g alkanoyl (the same as defined above), C .\_\ aryl-carbonyl (the same as defined above) Cj.g alkoxycarbonyl (the same as defined above)]; a C \_i_ζ acyloxy group [e.g. C\. alkanoyloxy (the same as defined above), _\_ aryl- carbonyloxy (e.g. benzoyloxy, etc.)]; a carboxyl group; a carbamoyl group which may optionally be mono- or di-substituted with C 1.4 alkyl (e.g. N-methylcarbamoyl,

N-ethylcarbamoyl, N-propylcarbamoyl, N-isopropylcarbamoyl, N-butylcarbamoyl. N.N-dimethylcarbamoyl. N,N-diethylcarbamoyl, N.N-dipropylcarbamoyl,

N.N-dibutylcarbamoyl, etc.); a cyclic aminocarbonyl group (e.g. 1-aziridinylcarbonyl, 1 -azetidinylcarbonyl, 1 -pyrrolidinylcarbonyl, 1 -piperidinylcarbonyl, N-methylpiperidinylcarbonyl. morpholinocarbonyl, etc.), a halogen atom (the same as defined above); an oxo group; an amidino group; an amino group which may optionally be substituted with C g alkyl group (the same as defined above); an amino group which may optionally be mono- or di-substituted with C\. alkyl, carbamoyl or N-mono- or

N,N-di-C_j_4 alkyl-carbamoyl (e.g. N-methylcarbamoylamino, N-ethylcarbamoylamino,

N-propylcarbamoylamino, N-isopropylcarbamoylamino, N-butylcarbamoylamino, N,N-dimethylcarbamoylamino, N-Ndiethylcarbamoylamino. etc.); a 3- to 6-membered cyclic amino group having carbon atom(s) and one nitrogen and optionally, 1 to 3 hetero atoms selected from O, S and N (e.g. aziridinyl, azetidinyl, pyrrolidinyl, pyrrolinyl, pyrrolyl, imidazolyl, triazolyl, pyrazolyi, imidazolidinyl, piperidino, morpholino, dihydropyridyl, pyridyl, N-methylpiperazinyl, N-ethylpiperazinyl, etc.); a C\. alkanoyl- amido group (e.g. formamido, acetamido, trifluoroacetamido, propionylamido, butylylamido, isobutylylamido, etc.); a benzamido group; a Cj_3 alkylenedioxy group

(e.g. methylenedioxy, ethylenedioxy, etc.); -B(OH)2; a hydroxyl group; a nitro group; a cyano group; -S(O)_n"Rb wherein n", is 0, 1 or 2 and R^ is H, hydroxyl or a Ci-14 hydrocarbon group (e.g. mercapto, sulfo, sulfino, _6 alkylthio (e.g. methylthio, - ethylthio, propylthio, isopropylthio, n-butylthio, sec-butylthio, tert-butylthio, etc.), C _\_ arylthio (e.g. phenylthio, etc.), _6 alkylsulfinyl (e.g. methylsulfinyl, ethylsulfinyl, propylsulfinyl, butylsulfinyl, etc.), C .\_ arylsulfinyl (e.g. phenylsulfinyl, etc.), C \. alkylsulfonyl (e.g. methylsulfonyl, ethylsulfonyl, propylsulfonyl, butylsulfonyl, etc.) and C5.14 arylsulfonyl (e.g. phenylsulfonyl, etc.), etc.]; a sulfamoyl group which may optionally be mono- or di-substituted with C\_β alkyl (e.g. N-methylsulfamoyl,

N-ethylsulfamoyl, N-propylsulfamoyl, N-isopropylsulfamoyl, N-butylsulfamoyl, N.N-dimethylsulfamoyl, N,N-diethylsulfamoyl, N,N-dipropylsulfamoyl, N.N-dibutylsulfamoyl, etc.), are used. The number of substituents is from 1 to 6, preferably from 1 to 3, within the substitutable range. Among the above groups bonded through N, for example. (1) a group of the formula: -NR^R^ wherein R ^a is H. an optionally substituted alkyl group, an optionally substituted aralkyl group, an optionally substituted acyl group, an optionally- substituted carbamoyl group, an optionally substituted cycloalkyl group, an optionally substituted aryl group, an optionally substituted alkoxy group, an optionally substituted aralkyloxy group, a hydroxy group, an optionally substituted heterocyclic group or

-SOpR^^a (p is 1 or 2, and R^^a is an optionally substituted alkyl group or an optionally substituted aryl group); and R^ is H, an optionally substituted aralkyl group or an optionally substituted alkyl group, (2) a heterocyclic group having a bond at nitrogen atom, such as IH-1 -pyrrolyl. 1 -imidazolyl. 1 -triazolyl, pyrazolyl. indolyl. lH-1-indazolyl, 7-purinyl, 1-aziridinyl, 1-pyrrolidinyl, 1-pyrrolinyl, 1-imidazolidinyl, 2-isoxazolidinyl, pyrazolidinyl. piperidinyl, pyrazolinyl, 1-piperidinyl, 4-morpholinyl, 4-thiomorpholinyl, etc. and (3) a group of the formula: -N=C(R3^a)R4a wherein R^^a and R^^a each are -H, an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted alkoxy group, a mono- or di-alkylamino group or a hydroxyamino group, are preferred.

As the alkyl group in the optionally substituted alkyl group for R^^a, R^^a, R3a_? R^ or R^^a. for example, a Cj.g alkyl group such as methyl, ethyl, propyl, isopropyl, butyl, t-butyl, pentyl, hexyl, etc. is used. As the aralkyl group in the optionally substituted aralkyl group for R^^a or R2a, for example, a C7..15 aralkyl group such as benzyl, phenylethyl, etc. is used.

As the cycloalkyl group in the optionally substituted cycloalkyl group for Rla for example, a C3.6 cycloalkyl group such as cyclopropyl, cyclopentyl, cyclohexyl, etc. is used.

As the aryl group in the optionally substituted aryl group for R^^a, R3a_? R4a _or

R°^a, for example, a Cβ_\_ aryl group such as phenyl, naphthyl, anthracenyl, etc. is used.

As the alkoxy group in the optionally substituted alkoxy group for Rl , R->a _or R^^a, for example, a C\. alkoxy group such as methoxy, ethoxy, propoxy, butoxy, etc. is used.

As the aralkyloxy group in the optionally 1 substituted aralkyloxy group for R^³, for example, a C7..14 aralkyloxy group such as benzyloxy, phenethyloxy, etc. is used.

As the acyl group in the optionally substituted acyl group for R^^a, for example, a C\-6 ^acyl g^rouP ^such as formyl, acetyl, propionyl, etc. is used.

As the carbamoyl group in the optionally substituted carbamoyl group for R ^a the same one as the above optionally substituted carbamoyl group defined in the group bonded through C is used.

As the mono- or di-alkylamino group in the optionally substituted mono- or di- alkylamino group for R^^a or R^^a. for example, a mono- or di-Cj_4 alkylamino group such as methylamino, ethylamino, dimethylamino, diethylamino, etc. is used.

As the substituent of these alkyl, aralkyl, cycloalkyl, aryl, alkoxy, aralkyloxy, acyl, carbamoyl and mono- or di-alkylamino, for example, the same substituent as that of the hydrocarbon group mentioned for the group bonded through C is used. As the optionally substituted heterocyclic group for Rla, f_or example, there can be used the same one as the optionally substituted heterocyclic group for R or R2.

Examples of the group bonded through O for W, R, X or Y include all organic residues bonded through an oxygen atom. For example, a group of the formula: -OR^ wherein R^ is (1) H, (2) an optionally substituted hydrocarbon group, (3) an optionally substituted heterocyclic group, (4) an optionally substituted acyl group, (5) an optionally substituted carbamoyl group, (6) a group of the formula: -NRl 1R12 (Rl 1 and Rl2 each are H, an optionally substituted hydrocarbon group or an optionally substituted heterocyclic group) or (7) a group of the formula: -SiRl , (Rl3 is an optionally substituted hydrocarbon group) is used.

As the optionally substituted hydrocarbon group for R^, Rl 1, Rl2 _OΓ R13_; f_or example, the same one as the above optionally substituted hydrocarbon group defined in the group bonded through C is used. As the optionally substituted heterocyclic group for R^, Rl 1 or Rl , for example, the same one as the above optionally substituted heterocyclic group for Rl or R2 is used. As the optionally substituted acyl group or the optionally substituted carbamoyl group for R^, for example, the same one as the above optionally substituted acyl group or the above optionally substituted carbamoyl group defined in the group bonded through C is used.

Among the groups bonded through O, for example, a group of the formula:

-OR^a wherein R^^a is H, an optionally substituted alkyl group, an optionally substituted acyl group, an optionally substituted cycloalkyl group, an optionally substituted aryl group, an optionally substituted heterocyclic group, an optionally substituted arylcarbonyl group, an optionally substituted alkoxycarbonyl group, an optionally substituted aryloxycarbonyl group, an optionally substituted carbamoyl group, a group of the formula: -NRl laRl2a (Rl la _ancj Rl2a _{are t}h_{e same as} defined for R*^a and R a) ₀r a group of the formula: -SiRl^^a3 (Rl a [_s an alkyl group) is preferred.

The optionally substituted alkyl, acyl, carbamoyl, cycloalkyl, aryl or heterocyclic group for R^^a i_s the same as those for Rl^a.

As the arylcarbonyl group in the optionally substituted arylcarbonyl group for R^^a, for example, a C .14 aryl-carbonyl group such as benzoyl, etc. is used. As the alkoxycarbonyl group in the optionally substituted alkoxycarbonyl group for R$^a, for example, a Cj.g alkoxy-carbonyl group such as methoxy carbonyl, ethoxycarbonyl, etc. is used.

As the aryloxycarbonyl group in the optionally substituted aryloxycarbonyl group for R^ for example, a C .14 aryloxy-carbonyl group such as phenoxycarbonyl, etc. is used.

As the substituent of these arylcarbonyl, alkoxycarbonyl and aryloxycarbonyl, for example, the ame substituent of the hydrocarbon group mentioned for the group bonded through C. Examples of the group bonded through S for W, R, X or Y include all organic residues bonded through a sulfur atom. For example, a group of the formula: -S(O)nR6 wherein R^ is an optionally substituted hydrocarbon group or an optionally substituted heterocyclic group, and n is an integer of 0 to 2 is used.

As the optionally substituted hydrocarbon group for R", for example, the same one as the above optionally substituted hydrocarbon group defined in the group bonded through C is used.

As the optionally substituted heterocyclic group for R", for example, the same one as the above optionally substituted heterocyclic group for Rl or R is used.

Among the groups bonded through S, for example, an optionally substituted alkylthio group, an optionally substituted cycloalkylthio group, an optionally substituted arylthio group, an optionally substituted aralkylthio group, an optionally substituted heterocyclic thio group, an optionally substituted alkylsulfinyl group, an optionally substituted alkylsulfonyl group and an optionally substituted arylsulfonyl group are preferred. As the optionally substituted alkyl, cycloalkyl, aryl, aralkyl or heterocyclic group in the optionally substituted alkylthio group, optionally substituted cycloalkylthio group, optionally substituted arylthio group, optionally substituted heterocyclic thio group, optionally substituted alkylsulfinyl group, optionally substituted alkylsulfanyl group or optionally substituted aryisulfonyl group, for example, the same one as that for Rl is used. As the aralkyl group in the optionally substituted aralkylthio group, for example, ^a 7-15 aralkyl group such as benzyl, phenylethyl, etc. is used. As the substituent of the aralkyl group, for example, the same substituent as that of the hydrocarbon group mentioned for group bonded through C. Examples of the group bonded through P for W, R or Y include all groups bonded through a phosphorous atom. For example, a group of the formula: -PO(OR7)2 wherein R^ is H or an alkyl group is used.

As the alkyl group for R^"7, for example, a

alkyl group such as methyl. ethyl, propyl. isopropyl. butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl. octyl, nonyl. decyl. undecyl, dodecyl, tridecyl. tetradecyl, pentadecyl. etc. is used.

Among the groups bonded through P, for example, a C2-12 dialkylphosphano group such as diethylphosphono, dimethylphosphono, etc. is preferred.

As the nitrogen-containing heterocyclic group of the optionally substituted nitrogen-containing heterocyclic group of the formula:

formed by combining X with Y, which may have N, O, S and/or P as a ring-constituting atom, for example. 5 to 8-membered nitrogen-containing heterocyclic groups which may have 1 to 3 hetero atoms selected from N, O, S and P, etc., in addition to one carbon atom are used. Specifically, a group of the formula:

wherein Rl4 is H or an optionally substituted hydrocarbon group; L is O or a Cj_3 alkylene group (e.g. methylene, ethylene, etc.); and Z is O or a group of the formula: - RIS (Rl 5 }_s H or an optionally substituted hydrocarbon group) is used. As the optionally substituted hydrocarbon group for Rl4 or R^, for example, the same one as the above optionally substituted hydrocarbon group defined in the group bonded through C. Among them, a C \_β alkyl group such as methyl, ethyl, propyl, etc. is preferred.

More specifically, as the nitrogen-containing heterocyclic group formed by combining X with Y, for example, a group of the formula:

wherein the symbols are as defined above is used.

In the above formulae, Ar is preferably an optionally substituted aromatic hydrocarbon group. The aromatic hydrocarbon group is preferably a Cβ.\_ aromatic hydrocarbon group (e.g. phenyl, naphthyl, anthryl. etc.) , more preferably a Cβ_\2 aromatic hydrocarbon group (e.g. phenyl, etc.). As the substituent. for example, a halogen atom, a C\__β alkyl group and a mono-, di- or tri-halogenated C j _g alkyl group are preferred. The number of the substituents is preferably 1 to 4. Particularly, 2,6-dihalogenophenyl group substituted with a C i _β alkyl group and/or a mono, di- or tri-halogenated Cj.g alkyl group is preferred. As Ar, 2,6-dichloro-4- trifluoromethylphenyl is most preferred.

R is preferably a group bonded through N. Among them, a group of the formula: - NRlbR2b wherein Rib and R b each are H, an optionally substituted Cj.20 hydrocarbon group (e.g. C\_\$ alkyl, Cg_i4 aryl, C7.20 aralkyl), an optionally substituted mono- or di- C [_4 alkyl-carbamoyl group, or an optionally substituted C 1.7 acyl group (e.g. Ci _g- alkanoyl, benzoyl), or a group of the formula: -N=C(R3b)R4b wherein R and R^b each are H; a C\.\ζ alkyl group; a Cβ.\_\ aryl group which may optionally be substituted with Cι_4 alkoxy and or hydroxyl; a Ci .^5 alkoxy group; a mono- or di-Cj.i 5 alkylamino group or a hydroxylamino group is preferred. As the substituent of the Cι_20 hydrocarbon group, mono- or di-Cμ4 alkylcarbamoyl group or C \_η acyl group, the same substituent as that of the hydrocarbon group mentioned for the group bonded through C is used. The number of substituents is from 1 to 3, preferably form 1 or 2. It is more preferred that Ri and R²b each are H, a C\.β alkyl group, a C7.15 aralkyl group, a mono- or di- _4 alkyl-carbamoyl group or a C 1.7 acyl group and R b is H or a C_j.g alkyl group and, further, and R⁴b _1S a C \._ alkoxy group, a Cg-14 aryl group, a mono- or di-Ci .4 alkylamino group or a hydroxyamino group. As R, an amino group, a mono- or di-Cι _4 alkylamino group, and a group of -N=CHOCH3 or -N=CHOCH2CH3 are particularly preferred.

W is preferably not a group of the formula:

wherein χl is an optionally substituted haloalkyl group; X² is H, or a group bonded through C, N, O, S or P; γl is a group bonded through N, O, S or P, an optionally substituted aryl group, an optionally substituted heterocyclic group bonded with a carbon atom, or an alkyl group substituted with a cyano, nitro, alkoxycarbonyl or optionally substituted carbamoyl group; and χ2 and γl may be combined to form a thioxo group, a hydroxyimino group or an oxirane ring, and R and γl may be combined to form an optionally substituted C2-4 alkylene or C2-4 alkenylene group whose constituent carbon atom is substituted with at least one hetero atom selected from O, N, S and P.

W is more preferably a halogen atom, or a group bonded through N, O, S or P. A group of the formula: -S(O)nR6 wherein R6 and n are as defined above is particularly preferred. As the hydrocarbon group represented by R⁶, for example, a C 1.24 hydrocarbon group is preferred. Among them, a Cι_ι 5 alkyl group is more preferred. More specifically, R is preferably a C\.β alkyl group which may optionally be substituted with 1 to 4 halogen atoms. As R^, trifluoromethyl is most preferred.

X is preferably a group bonded through N. Among them, a group of the formula -NR1°R2^C wherein Rl° and R4^C each are H, a hydroxyl group, an optionally substituted Ci _20 hydrocarbon group (e.g. Cι_i5 alkyl, Cβ.\_ aryl, C7.20 aralkyl) or an optionally substituted C\_\ζ acyl group is more preferred. As the substituent of the Cj_20 hydrocarbon group or C \ . \ 5 acyl group, the same substituent as that of the hydrocarbon group mentioned for the group bonded through C is used. The number of substituents is from 1 to 3, preferably from 1 or 2. R! ° and R2° each are preferably H, hydroxyl group, a C\_β alkyl group or a C\.β acyl group. Particularly, X is preferably amino, mono- or di-methylamino. acetylamino, N-hydroxy-N-methylamino, etc.

Y is preferably H or a group bonded through C, N or O. Among them, H, a hydroxyl group, an optionally substituted Cj_i5 acyloxy group, an optionally substituted mono- or di-Cι.4 alkyl-carbamoyloxy group, an optionally substituted C\_\$ alkoxy group, an optionally substituted C\_\$ acyl group or a group of the formula: -NRl°_ _2d wherein Rid and R d each are H, or an optionally substituted Cι_20 hydrocarbon (e.g.

Cl-15 alkyl, Cg_i4 aryl, C7.20 aralkyl) or Cι_ι 5 acyl group is preferred. As the substituent of the \_\^ acyloxy, mono- or di-Cj.4 alkyl-carbamoyloxy, C^_ι 5 alkoxy.

Cl-15 ^acyl ^or Ci-20 hydrocarbon group, the same substituent as that of the hydrocarbon group mentioned for the group bonded through C is used. The number of substituents is from 1 to 3, preferably from 1 or 2. More specifically, Y is preferably H; a group bonded through O such as a hydroxyl, Cι _i5 acyloxy (preferably C\.β alkanoyloxy which may be mono- to tri-substituted with halogen; mono- or di-Cι.4 alkyl-carbamoyloxy, C\.β alkoxy-carbonyloxy; Cβ.\_ aryl-carbonyloxy which may be substituted with Cj.g alkyl) ι_i5 alkoxy (preferably, C\.β alkoxy) which may be mono- or di-substituted with C\._ alkoxy; a group bonded through N such as a group of the formula: -NRl" R2d wherein Rid' and R2d' each are H, C\._β alkyl, Cj.g alkanoyl or C\_β alkoxy-carbonyl; a group bonded through C such as C\_\ζ alkyl (preferably, C\.β alkyl), etc. When W is a group bonded through S, a halogen atom or a nitro group and X is a hydroxyl group or a thiol group, Y is a group other than a hydrogen atom, i.e. preferably group bonded through C, N, O, S or P. In this case, as Y, a group bonded through C exclusive of an substituted alkyl group, a group bonded through N, a group bonded through O, a group bonded through S, or a group bonded through P.

Specifically, when W is a group bonded through S, a halogen atom or a nitro group, X is a group other than a hydroxyl group and a thiol group.

Specifically, as the optionally substituted nitrogen-containing heterocyclic group formed by combining X with Y, for example, a group of the formula:

wherein R^^a is H or a C \ _β alkyl group is preferred. As the group of the formula:

1.2,4-oxadiazol-3-yl is most preferred. Another group of preferred arylpyrazoles of formula (I) have one or more of the following features wherein: W is S(O)_n*R3 * or 4,5-dicyanoimidazol 2-yl or haloalkyl;

R3* is alkyl or haloalkyl;

R is selected from the group consisting of hydrogen, halogen, -NR5*Rg*, -C(O)OR7. , -S(O)_m*R₇*, alkyl, haloalkyl, -OR₈*, -N=C(R₉*)(R₁₀*) and -C(O)alkyl; R5* and Rg* are independently selected from a hydrogen atom, alkyl, haloalkyl,

-C(O)alkyl, -C(O)OR7*_; -S(O)_r*CF₃; or R₅ . and Rg* form together a divalent alkylene radical which may be interrupted by one or more heteroatoms, preferably selected from oxygen, nitrogen and sulfur; R7* is selected from alkyl and haloalkyl;

Rg* is selected from alkyl, haloalkyl and hydrogen;

R9* is selected from hydrogen and alkyl;

RlO* is selected from phenyl or heteroaryl each of which is unsubstituted or substituted by one or more hydroxy. halogen, -O-alkyl, -S-alkyl, cyano. or alkyl or combinations thereof:

Ar is

wherein:

X* is selected from nitrogen and -C-R12*; l 1 * and R12* are independently selected from halogen or hydrogen or CN or NO2; Rl3* is selected from halogen, haloalkyl, haloalkoxy, -S(0)q* CF3, -SF5; m*, n*, q*, r* are independently selected from 0, 1 , and 2; provided that when R2* is 4,5-dicyanoimidazol 2-yl, R4* is CI. Rj 1 * is CI, R13* is CF3, and X* is =C-C1.

The alkyl and alkoxy groups and moieties thereof of the formula (I) of this preferred group are preferably lower alkyl and alkoxy groups (that is, groups having one to six carbon atoms). The haloalkyl and haloalkoxy groups likewise preferably have one to four carbon atoms. The haloalkyl and haloalkoxy groups can bear one or more halogen atoms; preferred groups of this type include -CF3 and -OCF3. It shall be understood that the ring formed by the divalent alkylene radical represented by R5 * and Rg* and including the nitrogen atom to which R5* and Rg* are attached is generally a 5, 6, or 7-membered ring.

Specifically preferred arylpyrazoles of formula (I) are included in Tables 1-13.

Comp. No. R6 R X Y n

1-3 Me NH₂ NH₂ OMe 2

1-5 CF₃ NH₂ NH₂ NH₂ 1

1-6 CF₃ NH₂ NH₂ NHMe 1

1-7 CF₃ NH₂ NH₂ NMe2 1

1-9 CF₃ NH₂ NH₂ NMeCOMe 1

1-10 CF₃ NH₂ NH₂ NHCO₂Et 1

1-11 CF₃ NH₂ NH₂ OMe 1

1-13 CF₃ NH₂ NHCOMe OMe 1

1-14 CF₃ NHCOMe NHCOMe OMe 1

1-15 CF₃ NH₂ NHMe OMe 1

1-16 CF₃ NHMe NHMe OMe 1

Table 2

Comp. No. R6 R X Y n

1 -17 CF₃ NH₂ NH₂ NH₂ 2

1-18 CF₃ NH₂ NH₂ NHMe 2

1-19 CF₃ NH₂ NH₂ NMe2 2

1-20 CF₃ NH₂ NH₂ NHCOMe 2

1-21 CF₃ NH₂ NH₂ NMeCOMe 2

1-22 CF₃ NH₂ NH₂ NHCO₂Et 2

1-23 CF₃ NH₂ NH₂ OMe 2

1-24 CF₃ NH₂ NH OCOMe 2

1-25 CF₃ NH₂ NHCOMe OMe 2

1-26 CF₃ NHCOMe NHCOMe OMe 2

1 -27 CF₃ NH₂ NHMe OMe 2

1 -28 CF₃ NHMe NHMe OMe 2

1-31 CF₃ NH₂ NH₂ OCO₂Me 1

1-32 CF₃ NH₂ NH₂ ~0^

1-33 CF₃ NH₂ NH₂ Ni_ j

1-34 CF₃ NH₂ NH₂ OCH(OMe) ₂ 1

1-35 CF₃ NH₂ NH₂ Me 1 Table 3

Comp. No. R⁶ R X Y m.p. (°C)

1-38 CF₃ NHMe NH₂ OH 0

1-39 CF₃ NMe NH₂ OH 0

1-40 CF₃ NHEt NH₂ OH 0

1-41 CF₃ NEt₂ NH₂ OH 0

1-42 CF₃ NHPrⁿ NH₂ OH 0

1-43 CF₃ NPrⁿ ₂ NH OH 0

1-44 CF₃ NHPr¹ NH₂ OH 0

1-45 CF₃ NHCH₂Ph NH₂ OH 0

1-46 CF₃ N(CH Ph) 2 NH₂ OH 0

1-47 CF₃ NH₂ NH₂ OH

1-48 CF₃ NHMe NH₂ OH

1-49 CF₃ NMe2 NH₂ OH

1-50 CF₃ NHEt NH OH

1-51 CF₃ NEt2 NH₂ OH

1-52 CF₃ NHPr¹¹ NH₂ OH

1-53 CF₃ NPrⁿ2 NH₂ OH

1-54 CF₃ NHPr¹ NH₂ OH

1-55 CF₃ NHCH₂Ph NH₂ OH

1-56 CF₃ N(CH₂Ph)₂ NH₂ OH

1-57 CF₃ NH₂ NH₂ OH 2

1-58 CF₃ NHMe NH₂ OH 2

1-59 CF₃ NMe2 NH₂ OH 2

1-60 CF₃ NHEt NH₂ OH 2 181-182 Table 4

Comp. No. R6 R X Y n

1-61 CF₃ NEt₂ NH₂ OH 2

1-62 CF₃ NHPrⁿ NH₂ OH 2

1-63 CF₃ NPrⁿ ₂ NH₂ OH 2

1-64 CF₃ NHPr' NH₂ OH 2

1-65 CF₃ NHCH₂Ph NH₂ OH 2

1-66 CF₃ N(CH₂Ph) 2 NH₂ OH 2

1-67 CF₃ NH₂ N(OH)Me H 0

1-68 CF₃ NHMe N(OH)Me H 0

1-69 CF₃ NMe2 N(OH)Me H 0

1-70 CF₃ NHEt N(OH)Me H 0

1-71 CF₃ NEt₂ N(OH)Me H 0

1-72 CF₃ NHPr¹ N(OH)Me H 0

1-73 CF₃ NPrⁿ ₂ N(OH)Me H 0

1-74 CF₃ NHPri N(OH)Me H 0

1-75 CF₃ NHCH₂Ph N(OH)Me H 0

1-76 CF₃ N(CH₂Ph)₂ N(OH)Me H 0

1-77 CF₃ NHMe N(OH)Me H

1-78 CF₃ NMe2 N(OH)Me H

1-79 CF₃ NHEt N(OH)Me H

1-80 CF₃ NEt N(OH)Me H

1-81 CF₃ NHPr¹¹ N(OH)Me H

1-82 CF₃ NPrⁿ2 N(OH)Me H

1-83 CF₃ NHPr¹ N(OH)Me H Table 5

Comp. No. R⁶ R X Y

1-84 CF₃ NHCH₂Ph N(OH)Me H 1

1-85 CF₃ N(CH Ph)₂ N(OH)Me H 1

1-86 CF₃ NH₂ N(OH)Me H 2

1-87 CF₃ NHMe N(OH)Me H 2

1-88 CF₃ NMe2 N(OH)Me H 2

1-89 CF₃ NHEt N(OH)Me H 2

1-90 CF₃ NEt₂ N(OH)Me H 2

1-91 CF₃ NHPrⁿ N(OH)Me H 2

1-92 CF₃ NPrⁿ N(OH)Me H 2

1-93 CF₃ NHPr¹ N(OH)Me H 2

1-94 CF₃ NHCH₂Ph N(OH)Me H 2

1-95 CF₃ R(CH₂Ph)₂ N(OH)Me H 2

O

II

1-96 CF₃ OCNHEt

NH₂ NH₂ 1

O

II OCCH₂Cl

1-97 CF₃ NH₂ NH₂ 1

O

II OCNMe₂

1-98 CF₃ NH₂ NH₂ 1

1-99 CF₃ NHCONHEt NH₂ OH 1

1-100 CF₃ NHCOPh NH₂ OH 2

1-101 CF₃ NHCOPh NH2 OH 1 Table 6

Comp. No . R⁶ R Rl7

2-1 Me N=CH^OMe O H 0

2-2 CF₃ NH₂ O H

2-3 CF₃ NH₂ O Me

2-4 CF₃ NH₂ NH H

2-5 CF₃ NH₂ NH Me

2-6 CF₃ NH₂ NMe Me

2-7 CF₃ NH₂ O H 2

2-8 CF₃ NH₂ O Me 2

2-9 CF₃ NH₂ NH H 2

2-10 CF₃ NH₂ NH Me 2

2-1 1 CF₃ NH₂ NMe Me 2

2-12 CF₃ NH₂ O H 0

2-13 CF₃ N=CH-NHOH O H 0

2-14 N=CH^NHOH

CF₃ 0 H 1

2-15 CF₃ N=CH~OMe 0 H 1

2-16 CF₃ N=CH~OMe 0 H 2

2-17 CF₃ N=CH"^»OMe O H 0

2-18 CF₃ N=CH*~NHMe O H 1

N=CH-NMe₂

2-19 CF₃ O H 1

2-20 CF₃ NHCHO O H 0

2-21 CF₃ NHCHO O H 1 Table 7

Comp. No . R⁶ R Rl7 m.p. (°C)

2-22 CF₃ NHMe 0 H 0

2-23 CF₃ NMe2 0 H 0

2-24 CF₃ NHEt 0 H 0

2-25 CF₃ NEt₂ O H 0

2-26 CF₃ NHPrⁿ O H 0

2-27 CF₃ NPrⁿ2 O H 0

2-28 CF₃ NHPr¹ O H 0

2-29 CF₃ NHCH₂Ph O H 0

2-30 CF₃ N(CH Ph)₂ O H 0

2-31 CF₃ NHMe O H

2-32 CF₃ NHMe2 0 H

Z-JJ CF₃ NHEt 0 H

2-34 CF₃ NEt2 0 H

2-35 CF₃ NHPr¹¹ O H

2-36 CF₃ NPrⁿ O H

2-37 CF₃ NEPr¹ O H

2-38 CF₃ NHCH Ph O H

2-39 CF₃ N(CH₂Ph)₂ O H

2-40 CF₃ NHMe O H 2

2-41 CF₃ NMe2 O H 2

2-42 CF₃ NHEt O H 2

2-43 CF₃ NEt₂ O H 2

2-44 CF₃ NHPrⁿ O H 2

2-45 CF₃ NPrⁿ ₂ O H 2 Table 8

Comp. No . R⁶ R Rl7 m.p. (°C)

2-46 CF₃ NHPr¹ O H 2

2-47 CF₃ NHCH₂Ph 0 H 2

2-48 CF₃ N(CH₂Ph) 2 0 H 2

2-49 CF₃ NHAC O H 2

2-50 CF₃ NHAC O H 1

2-51 CF₃ NHCO₂Me O H 2

2-52 CF₃ N=CHOEt O H 1

2-53 CF₃ N=CH—OEt O H 2

2-54 CF₃ NHCO₂Me O H 1

2-57 CF₃ NHCONHEt O H 1

2-58 CF₃ NHCOPh O H 2

2-59 N=CH OEt

CF₃ O H 0

2-60 CF₃ NHAC O H . 0

2-61 CF₃ NHCOPh O H 1

Table 9

Comp. No. R⁶ R¹⁹ R L m.p. (°C)

3-1 CF₃ H NH₂ NH CH₂ 1

3-2 CF₃ H NH₂ NH CH₂CH₂ 1

3-3 CF H NH₂ NH CH₂ 2

3-4 CF₃ H NH₂ NH CH₂CH₂ 2

3-5 CF₃ H NH₂ NH O 1

3-6 CF₃ Me NH₂ NH O 1

3-7 CF₃ Et NH₂ NH 0 1

3-8 CF₃ H NH₂ NH O 0

3-9 CF₃ H NHMe NH 0 0

3-10 CF₃ H NMe2 NH 0 0

3-1 1 CF₃ H NHEt NH 0 0

3-12 CF₃ H NEt2 NH 0 0

3-13 CF₃ H NHPrⁿ NH 0 0

3-14 CF₃ H NPrⁿ ₂ NH 0 0

3-15 CF₃ H NHPr¹ NH O 0

3-16 CF₃ H NHCH₂Ph NH O 0

3-17 CF₃ H N(CH₂Ph)2 NH O 0 Table 10

Comp. No. R⁶ R¹⁹ R

3-18 CF₃ H NHMe NH 0

3-19 CF₃ H NHMe₂ NH 0

3-20 CF₃ H NHEt NH 0

3-21 CF₃ H NEt₂ NH 0

3-22 CF₃ H NHPrⁿ NH O

3-23 CF₃ H NPrⁿ ₂ NH 0

3-24 CF₃ H NHPr¹ NH 0

3-25 CF₃ H NHCH₂Ph NH 0

3-26 CF₃ H N(CH₂Ph) ₂ NH 0

3-27 CF₃ H NH₂ NH 0 2

3-28 CF₃ H NHMe NH 0 2

3-29 CF₃ H NMe2 NH 0 2

3-30 CF₃ H NHEt NH 0 2

3-31 CF₃ H NEt NH 0 2

3-32 CF₃ H NHPrⁿ NH 0 2

CF₃ H NPrⁿ ₂ NH 0 2

3-34 CF₃ H NHPr¹ NH 0 2

3-35 CF₃ H NHCH Ph NH 0 2

3-36 CF₃ H N(CH₂Ph)₂ NH O 2

3-37 CFT H N=CH—OMe NH O 1 Table 11

Comp. No. R⁶ R m.p. (°C)

4-1 CF₃ NH NH O

Table 12

Comp. No. R6 R m.p. (°C)

5-1 CF₃ NH₂ 0

5-2 CF₃ NHMe 0

5-3 CF₃ NMe2 0

5-4 CF₃ NHEt 0

5-5 CF₃ NEt₂ 0

5-6 CF₃ NHPrⁿ 0

5-7 CF₃ NPrⁿ2 0

5-8 CF₃ NHPr¹ 0 Table 13

Comp. No. R⁶ R m.p. (°C)

5-9 CF₃ NHCH₂Ph 0

5-10 CF₃ N(CH₂Ph) ₂ 0

5-1 1 CF₃ NH₂

5-12 CF₃ NHMe

5-13 CF₃ NMe2

5-14 CF₃ NHEt

5-15 CF₃ NEt

5-16 CF₃ NHPrⁿ

5-17 CF₃ NPrⁿ

5-18 CF₃ NHPr¹

5-19 CF₃ NHCH₂Ph

5-20 CF₃ N(CH₂Ph)₂

5-21 CF₃ NH₂ 2

5-22 CF₃ NHMe 2

5-23 CF₃ NMe2 2

5-24 CF₃ NHEt 2

5-25 CF₃ NEt2 2

5-26 CF₃ NHPrⁿ 2

5-27 CF₃ NPrⁿ ₂ 2

5-28 CF₃ NHPr¹ 2

5-29 CF₃ NHCH₂Ph 2

5-30 CF₃ N(CH₂Ph)₂ 2 The following named compounds are also preferred:

I ) 5-Amino- 1 -[2,6-dichloro-4-(trifluoromethyl)phenyl]-N-hydroxy-4-trifluoro- methylsulfinyl- 1 H-pyrazole-3-carboximidamide 2) 5-Amino- 1 -[2,6-dichloro-4-(trifluoromethyl)phenyl]-N-methoxy-4-trifluoro- methylsulfιnyl-lH-pyrazole-3-carboximidamide

3) 5-Amino- 1 -[2,6-dichloro-4-(trifluoromethyl)phenyl]-N-hydroxy-4-ethylsulfinyl- 1 H-pyrazole-3-carboximidamide

4) 5-Amino- 1 - [2.6-dichloro-4-(trifluoromethy l)phenyl]-N-hydroxy-4-ethylthio- 1 H- pyrazole-3-carboximidamide

5) 5-Amino-l-[2,6-dichloro-4-(trifluoromethyl)phenyl]-N-hydroxy-4-methyl- sulfiny 1- 1 H-pyrazole-3-carboximidamide

6) 5-Amino- 1 -[2,6-dichloro-4-(trifluoromethoxy)phenyl]-N-hydroxy-4-methyl- sulfmyl- 1 H-pyrazole-3-carboximidamide 7) 5-Amino-l-[2,6-dichloro-4-(trifluoromethyl)phenyl]-N-hydroxy-4-methyl- sulfonyl-lH-pyrazole-3-carboximidamide

8) 5-Amino-l-[2.6-dichloro-4-(trifluoromethyl)phenyl]-N-hydroxy-4-methyl- thio-lH-pyrazole-3-carboximidamide

9) 5-Amino- 1 -[2.6-dichloro-4-(trifluoromethyl)pheny l]-N-hydroxy-4-ethyl- sulfony I- 1 H-pyrazole-3-carboximidamide

10) 5-Amino-l-[2,6-dichloro-4-(trifluoromethyl)phenyl]-N-methoxy-4-methylsulfιnyl- 1 H-pyrazole-3-carboximidamide

I I) 5-Amino-l-[2,6-dichloro-4-(trifluoromethyl)phenyl]-N-methoxy-N'-methyl- 4-methylsulfιnyl- 1 H-pyrazole-3-carboximidamide 12) 5-Amino- 1 -[2.6-dichloro-4-(trifluoromethyl)phenyl]-N-hydroxy-4- (2-fluoroethylsulfιnyl)- 1 H-pyrazole-3-carboximidamide

13) 5-Amino-l-[2,6-dichloro-4-(trifluoromethyl)phenyl]-N-hydroxy-4- (2-fluoroethylsulfonyl)-lH-pyrazole-3-carboximidamide

14) 5-Amino-l-[3-chloro-5-(trifluoromethyl)-2-pyridinyl]-4-ethylsulfιnyl-N- hydroxy-lH-pyrazole-3-carboximidamide

15) 5-Amino- 1 -[3-chloro-5-(trifluoromethyl)-2-pyridinyl]-4-methylsulfιnyl-N- hydroxy- 1 H-pyrazole-3-carboximidamide

16) 1 -[2,6-Dichloro-4-(trifluoromethyl)phenyl]-N-hydroxy-5-methylamino-4- methylsulfinyl- 1 H-pyrazole-3 -carboximidamide

17) 1 -[2,6-Dichloro-4-(trifluoromethyl)phenyl]-5-ethylamino-N-hydroxy-4- methy lsulfiny 1- 1 H-pyrazole-3 -carboximidamide

18) 1 -[2,6-Dichloro-4-(trifluoromethyl)phenyl]-5-[2-(ethylsulfonyl)ethylamino]- N-hydroxy-4-methylsulfιnyl- 1 H-pyrazole-3 -carboximidamide

19) 5-[2-(Cyano)ethylamino]-l -[2,6-dichloro-4-(trifluoromethyl)phenyl]-N- hydroxy-4-methylsulfinyl- 1 H-pyrazole-3 -carboximidamide 20) 5-(Aminocarbonylmethylamino)- 1 -[2,6-dichloro-4-(trifluoromethyl)phenyl]-N- hydroxy-4-methy lsulfiny 1- 1 H-pyrazole-3 -carboximidamide

21) l-[2,6-Dichloro-4-(trifluoromethyl)phenyl]-4-methylsulfmyl-5-[ (phenylsulfonyl)ethylamino]-N-hydroxy-lH-pyrazole-3-carboximidamide

22) 5-Amino-l-[2,6-dibromo-4-(trifluoromethyl)phenyl]-4-methylsulfmyl-N- hydroxy- 1 H-pyrazole-3 -carboximidamide

23) l-[2-Bromo-6-chloro-4-(trifluoromethyl)phenyl]-5-ethylamino-4-methylsulfιnyl- N-hydroxy-lH-pyrazole-3 -carboximidamide

24) 5-Amino-l-[2-bromo-6-chloro-4-(trifluoromethyl)phenyl]-4-methylsulfιnyl-N- hydroxy-lH-pyrazole-3 -carboximidamide 25) 1 -[2,6-Dichloro-4-(tri_luoromethyl)phenyl]-4-ethylsulfmyl-5-[2-

(methylsulfmyl)ethylamino]-N-hydroxy-lH-pyrazole-3-carboximidamide

26) l-[2,6-Dichloro-4-(tri luoromethyl)phenyl]-4-methylsulfmyl-5-[2- (methylsulfmyl)ethylamino]-N-hydroxy-lH-pyrazole-3-carboximidamide

27) l-[2,6-Dichloro-4-(trifluoromethyl)phenyl]-4-ethylsulfιnyl-5-[2- (ethylsulfmyl)ethylamino]-N-hydroxy-lH-pyrazole-3-carboximidamide

28) l-[2,6-Dichloro-4-(trifluoromethyl)phenyl]-4-methylsulfιnyl-5-[(prop-2- yny l)amino] - N-hydroxy- 1 H-pyrazole-3 -carboximidamide

29) 5-Amino-l-[2-chloro-4-(trifluoromethyl)phenyl]-4-methylsulfιnyl-N-hydroxy- 1 H-pyrazole-3 -carboximidamide 30) 5-Amino- 1 -[2,6-dichloro-4-(trifluoromethyl)phenyl]-4-methylsulfιnyl-N-amino- 1 H-pyrazole-3 -carboximidamide; 31 ) 5-Amino- 1 -[2,6-dichloro-4-(trifluoromethyl)phenyl]-4-methylsulfιnyl-N- (isopropylcarbony l)amino- 1 H-pyrazole-3 -carboximidamide;

32) 5-Amino-l-[2,6-dichloro-4-(trifluoromethyl)phenyl]-4-methylsulfinyl-N-(n- heptylcarbonyl)amino- 1 H-pyrazole-3 -carboximidamide; 33) 5-Amino-l-[2,6-dichloro-4-(trifluoromethyl)phenyl]-4-methylsulfιnyl-N- (ethoxycarbonyl)amino- 1 H-pyrazole-3-carboximidamide;

34) 5-Amino- 1 -[2,6-dichloro-4-(trifluoromethyl)phenyl]-4-trifluoromethylsulfιnyl-N- amino- 1 H-pyrazole carboximidamide;

35) 5-Amino-l-[2,6-dichloro-4-(trifluoromethyl)phenyl]-4-ethylsulfιnyl-N-amino- 1 H-pyrazole carboximidamide:

36) 5-Amino-l -[2,6-dichloro-4-(trifluoromethyl)phenyl]-4-trifluoromethylsulfιnyl-N- acetylamino- 1 H-pyrazole carboximidamide:

37) 5-Amino-l-[2,6-dichloro-4-(trifluoromethyl)phenyl]-4-methylsulfmyl-N-(l- methylethenylcarbonylamino)- 1 H-pyrazole carboximidamide; 38) 5-Amino-l-[2,6-dichloro-4-(trifluoromethyl)phenyl]-4-methylsulfinyl-N-(tert- butylcarbonylamino)-l H-pyrazole carboximidamide;

39) 5-Amino-l-[2,6-dichloro-4-(trifluoromethyl)phenyl]-4-methylsulfιnyl-N-(2- methylethenylcarbonylamino)- 1 H-pyrazole carboximidamide;

40) 5-Amino-l-[2,6-dichloro-4-(trifluoromethyl)phenyl]-4-methylsulfinyl-N- (ethylcarbonylamino)-l H-pyrazole carboximidamide:

41 ) 5-Amino-l-[2,6-dichloro-4-(trifluoromethyl)phenyl]-4-methylsulfmyl-N- (propylcarbonylamino)- 1 H-pyrazole carboximidamide;

42) 5-Amino-l-[2,6-dichloro-4-(trifluoromethyl)phenyl]-4-methylsulfιnyl-N-(l- ethylpropylcarbonylamino)-l H-pyrazole carboximidamide; 43) 5-Amino-l-[2,6-dichloro-4-(trifluoromethyl)phenyl]-4-methylsulfιnyl-N- (butylcarbonylamino)- 1 H-pyrazole carboximidamide;

44) 5-Amino-l-[2,6-dichloro-4-(trifluoromethyl)phenyl]-4-methylsulfιnyl-N- (pentylcarbonylamino)- 1 H-pyrazole carboximidamide;

45) 5-Amino- 1 -[2,6-dichloro-4-(trifluoromethyl)phenyl]-4-methylsulfιnyl-N- (hexylcarbonylamino)-l H-pyrazole carboximidamide; 46) 5-Amino-l-[2,6-dichloro-4-(trifluoromethyl)phenyl]-4-ethylsulfιnyl-N- acety lamino- 1 H-pyrazole carboximidamide;

47) 5-Amino- 1 -[2,6-dichloro-4-(trifluoromethyl)phenyl]-4-methylsulfιnyl-N- chloroacetylamino- 1 H-pyrazole carboximidamide; 48) 5-Amino-l-[2,6-dichloro-4-(trifluoromethyl)phenyl]-4-methylsulfιnyl-N- (tridecy lcarbonylamino)- 1 H-pyrazole carboximidamide;

49) 5-Amino- 1 -[2,6-dichloro-4-(trifluoromethyl)phenyl]-4-methylsulfιnyl-N-(n- propoxycarbonylamino)- 1 H-pyrazole carboximidamide;

50) 5-Amino-l-[2,6-dichloro-4-(trifluoromethyl)phenyl]-4-methylsulfιnyl-N-(l .l- dimethylpropyloxycarbonylamino)- 1 H-pyrazole carboximidamide;

51) 5-Amino-l-[2,6-dichloro-4- trifluoromethyl)phenyI]-4-methylsulfinyl-N- (tertbutyloxycarbony lamino )-l H-pyrazole carboximidamide;

52) 5-Amino-l-[2,6-dichloro-4-(trifluoromethyl)phenyl]-4-methylsulfιnyl-N- (acetyloxy) -1 H-pyrazole carboximidamide; 53) 5-Amino-l -[2,6-dichloro-4-(trifluoromethyl)phenyl]-4-ethylsulfιnyl-N- (acetyloxy) -1 H-pyrazole carboximidamide;

54) 5-Amino- 1 -[2,6-dichloro-4-(trifluoromethyl)phenyl]-4-methylsulfinyl-N- (ethylcarbonyloxy) -1 H-pyrazole carboximidamide;

55) 5-Amino-l-[2,6-dichloro-4-(trifluoromethyl)phenyl]-4-methylsulfιnyl-N- (propylcarbonyloxy) -1 H-pyrazole carboximidamide:

56) 5-Amino- 1 -[2,6-dichloro-4-(trifluoromethyl)phenyl]-4-methylsulfιnyl-N-(2- methylethenylcarbonyloxy) -1 H-pyrazole carboximidamide;

57) 5-Amino-l-[2,6-dichloro-4-(trifluoromethyl)phenyl]-4-methylsulfιnyl-N- (benzoyloxy) -1 H-pyrazole carboximidamide; 58) 1 -[2,6-Dichloro-4-(trifluoromethyl)phenyl]-5-methylamino-4-methylsulfιnyl-N- (acetyloxy)- 1 H-pyrazole carboximidamide;

59) 5-Amino-l-[2,6-dichloro-4-(trifluoromethyl)phenyl]-4-methylsulfonyl-N- (acety loxy)- 1 H-pyrazole carboximidamide;

60) 5-Amino- 1 -[2,6-dichloro-4-(trifluoromethyl)pheny l]-4-methylsulfinyl-N- (heptylcarbonyloxy) -1 H-pyrazole carboximidamide; 61 ) 5-Amino- 1 -[2,6-dichloro-4-(trifluoromethyl)phenyl]-4-methylsulfonyl-N- (heptylcarbonyloxy) -1 H-pyrazole carboximidamide;

62) 5-Amino-l-[2,6-dichloro-4-(trifluoromethyl)phenyl]-4-methylsulfenyl-N- (acetyloxy)- 1 H-pyrazole carboximidamide; 63) 5-Amino-l-[2,6-dichloro-4-(tri luoromethyl)phenyl]-4-methylsulfenyl-N- (heptylcarbonyloxy) -1 H-pyrazole carboximidamide;

64) 5-Amino-l-[2,6-dichloro-4-(trifluoromethyl)phenyl]-4-trifluoromethylsulfinyl-N- (acetyloxy)- 1 H-pyrazole carboximidamide;

65) l-[2,6-Dichloro-4-(trifluoromethyl)phenyl]-5-formylamino-4-ethylsulfenyl-N- (acetyloxy)-l H-pyrazole carboximidamide;

66) 5-Amino- 1 -[2,6-dichloro-4-(trifluoromethyl)phenyl]-4-methylsulfinyl-N- (hexylcarbonyloxy) -1 H-pyrazole carboximidamide:

67) 5-Amino- 1 -[2,6-dichloro-4-(trifluoromethyl)phenyl]-4-methylsulfιnyl-N- (pentylcarbonyloxy) -1 H-pyrazole carboximidamide; 68) 5-Amino- 1 -[2,6-dichloro-4-(trifluoromethyl)pheny l]-4-methylsulfinyl-N- (butylcarbonyloxy) -1 H-pyrazole carboximidamide:

69) 5-Amino-l-[2,6-dichloro-4-(trifluoromethyl)phenyl]-4-methylsulfenyl-N- (cyclopentylcarbonyloxy) -1 H-pyrazole carboximidamide:

70) 5-Amino- 1 -[2.6-dichloro-4-(trifluoromethyl)phenyl]-4-methylsulfmyl-N- (cyclopentylcarbonyloxy) -1 H-pyrazole carboximidamide:

71 ) 5-Amino-l-[2,6-dichloro-4-(trifluoromethyl)phenyl]-4-methylsulfinyl-N-(tert- butylcarbonyloxy) -1 H-pyrazole carboximidamide;

72) 5-Amino- 1 -[2,6-dichloro-4-(trifluoromethyl)phenyl]-4-methylsulfιnyl-N-(iso- propylcarbonyloxy) -1 H-pyrazole carboximidamide; 73) 1 -[2.6-Dichloro-4-(trifluoromethyl)phenyl]-5-formylamino-4-ethylsulfinyl-N- (acetyloxy)-l H-pyrazole carboximidamide;

74) 5-Amino- 1 -[2,6-dichloro-4-(trifluoromethyl)phenyl]-4-methylsulfinyl-N- (chloroacetyloxy)- 1 H-pyrazole carboximidamide;

75) 5-Amino- 1 -[2,6-dichloro-4-(trifluoromethyl)phenyl]-4-methylsulfιnyl-N- (bromoacetyloxy)-l H-pyrazole carboximidamide; 76) 5-Amino-l-[2,6-dichloro-4-(trifluoromethyl)phenyl]-4-methylsulfιnyl-N-(l- ethylpropylcarbonyloxy)-l H-pyrazole carboximidamide; or

77) 5-Amino-l-[2,6-dichloro-4-(trifluoromethyl)phenyl]-4-methylsulfιnyl-N-[(3- acetyloxy)phenylcarbonyloxy]-l H-pyrazole carboximidamide. 78) 5-Amino-l-[2,6-dichloro-4-(trifluoromethyl)phenyl]-N-hydroxy-4-trifluoro methylsulfonyl- lH-pyrazole-3 -carboximidamide 79) 5-Amino-l-[2,6-dichloro-4-(trifluoromethyl)phenyl]-N-hydroxy-4-trifluoro methylsulfenyl-lH-pyrazole-3 -carboximidamide 80) 5-Amino-l-[2,6-dichloro-4-

(trifluoromethyl)phenyl]-4-methylsulfιnyl-N-hydroxy-N-methyl-l H-pyrazole carboximidamide or

81 ) 5-Amino-l-[2,6-dichloro-4-(trifluoromethyl)phenyl]-4-trifluoromethyIsulfinyl-N- hydroxy-N-methyl-1 H-pyrazole carboximidamide.

Wherein R₃ is NH₂; R4 is C-Cl, M is C-Cl, R₅= R6=H; R₆ is CF₃ and

82) With respect to the structure of Table 8, J is O, R is NH2, R6 is CH₃, R17 is CF₃ n is 1 ;

83) With respect to the structure of Table 8, J is O, R is NH2, R6 is CH₃, R17 is CCI3, n is 1 ;

84) With respect to the structure of Table 8, J is O, R is NH2, Rβ is Et, R17 is CF₃, n is

1 : 85) With respect to the structure of Table 8, J is O. R is NH2. Rβ is CF₃, R17 is CF3, n is 1;

86) With respect to the structure of Table 8, J is O, R is NH2, 6 is CH₃, R17 is CH , n is 1;

87) With respect to the structure of Table 8, J is NH, R is NH2, R6 is CF₃, R17 is CF₃, n is 1;;

88) With respect to the structure of Table 10, R₆ is CH3, R₁₉ is -C(CH₃)2CH OH, R is

NH₂, Z is NH, L is NH,

89) With respect to the structure of Table 10, Rg is CH3, R19 is CF3, R is NH2, Z is NH, L is NH; 90) With respect to the structure of Table 10, Rβ is CH3, R19 is 2-furanyl, R is NH2, Z is NH, L is NH, n is 1 ;

91) With respect to the structure of Table 10, Rg is CH3, R19 is (3-methyl)phenyl, R is

NH , Z is NH, L is NH, n is l; 92) With respect to the structure of Table 10, Rβ is CH3, R19 is COOH. R is NH2, Z is NH, L is NH, n is l;

93) With respect to the structure of Table 10, Rg is CH3, R19 is phenyl, R is NH2, Z is

NH, L is NH, n is l;

94) With respect to the structure of Table 10, Rg is CH3, R19 is methyl, R is NH2, Z is NH, L is O, n is i;

95) With respect to the structure of Table 10, Rg is CH3, R19 is phenyl. R is NH2, Z is

NH, L is O. n is l;

96) With respect to the structure of Table 11, Rg is CH3, R is NH2, Z is NH, L is NH, n is 1; 97) With respect to the structure of Table 11 , Rg is CH3 , R is NH2, Z is NiPr, L is NH, n is 1.

The following examples illustrate the invention.

Example 1 Compound 1 is sprayed on the leaves of rice plants growing in soil at rate of lOOg/Ha. After 2 days, fipronil is detected when the plant is analysed for residues. There is substantially no damage to the rice plants by rice leaffolder or rice stemborer.

Example 2 Compound 5 is applied to rice seeds of at rate of 500g/Quintal and the rice seed sown in soil. When the rice plants emerge, 5-Amino-3-cyano-l -[2,6-dichloro-4- (trifluoromethyl)phenyl]-4-methy lsulfiny 1-1 H-pyrazole and 5-Amino-3-cyano-l-[2,6- dichloro-4-(trifluoromethyl)phenyl]-4-methylsulfonyl-l H-pyrazole are detected when the plant is analysed for residues. There is substantially no insect damage to the rice plants. Example 3

Compound 5 is applied to the soil for control of Ondontotermes at 120 g/Ha of active ingredient. After 62 days, the control of termites is substantially better than commercial standards. When the dead termites are analysed, fipronil and the sulfone analog are found.

Example 4

Compound 5 is formulated as a 0.1% bait for cockroach control and placed in a closed container. One hundred (100) Blattella germanica are placed in the container and allowed to feed on the bait. After one day all the cockroaches are dead.

Claims

1. A method of control of insects present or expected to be present at a locus which comprises the delivery of a 3-cyanopyrazole of formula (II):

PI] wherein:

W is a halogen or a group bonded through C, N, O, S or P;

Ar is an optionally substituted aromatic hydrocarbon group or an optionally substituted aromatic heterocyclic group; and R is H, a halogen or a group bonded through C, N, O, S or P to the locus by means of an application to the locus of a compound of formula (I):

wherein Ar is an optionally substituted aromatic hydrocarbon group or an optionally substituted aromatic heterocyclic group, R is H, a halogen or a group bonded through C, N, O, S or P, W is a halogen or a group bonded through C, N, O, S or P. X is a group bonded through N, O or S, Y is H or a group bonded through C, N, O, S or P, or X and Y being combined, a group of the formula

is an optionally substituted nitrogen-containing heterocyclic group which may further have N, O, S and/or P as a ring-constituting atom or a salt or metal complex thereof; and wherein the locus is soil or a plant wherein the plant is planted in soil.

2. The method according to Claim 1 wherein the rate of application is from about lOg/Ha to about 200g/Ha.

3. The method according to Claim 1 or Claim 2 wherein there is a conversion of the compound of formula (I) to the 3-cyanopyrazole of formula (II).

4. The method according to any one of the foregoing claims wherein the locus is a rice plant planted in soil.

5. The method according to claim 1 wherein the conversion is in or on the plant or in or on the soil or both.

6. The method according to claim 1 wherein modification of another group on the compound of formula (I) or a salt or metal complex thereof may take place.

7. The method according to any one of the foregoing claims wherein W comprises a sulfide or sulfoxide that is converted to a sulfoxide or sulfone group.

8. The method according to any one of claims 1 to 7 wherein the conversion occurs before the compound of formula (II) or a salt or metal complex thereof is absorbed into a plant.

9. A method of control of Termites by delivery of a 3-cyanopyrazole of formula (II)

[II] wherein:

W is a halogen or a group bonded through C, N, O, S or P;

R is H. a halogen or a group bonded through C, N, O, S or P to the termites by means of an application to a locus of an arylpyrazole of formula (I):

wherein Ar is an optionally substituted aromatic hydrocarbon group or an optionally substituted aromatic heterocyclic group, R is H. a halogen or a group bonded through C. N, O, S or P. W is a halogen or a group bonded through C, N, O, S or P. X is a group bonded through N, O or S. Y is H or a group bonded through C, N, O, S or P, or X and Y being combined, a group of the formula

is an optionally substituted nitrogen-containing heterocyclic group which may further have N, O, S and/or P as a ring-constituting atom or a salt or metal complex thereof; and then a conversion of the compound of formula (I) to the 3-cyanopyrazole of formula (II).

10. The method according to Claim 9 wherein the compound of formula (I) or a salt or metal complex thereof is applied in a bait.

1 1. The method according to Claim 9 wherein the locus is tRe termites themselves or on or in the soil or both.

12. The method according to Claim 9 wherein the conversion occurs in or on the soil and the compound of formula (II) is absorbed by the termites.

13. The method according to Claim 9 wherein the conversion occurs in the termites.

14. A method of control of cockroaches by delivery of a 3-cyanopyrazole of formula (II):

[II] wherein:

W is a halogen or a group bonded through C, N, O, S or P;

Y

\

N

15. The method according to Claim 14 wherein the compound of formula (I) or a salt or metal complex thereof is applied in a bait.

16. The method according to Claim 14 wherein the locus is an area where cockroaches are inhabiting or expected to inhabit.

17. The method according to Claim 14 wherein the conversion occurs in the cockroaches.