Arylpyrazole insecticides

ES 2 187 751 T3

DESCRIPTION

Arylpyrazole insecticides.

Technique field

The present invention relates to novel 1-aryl-pyrazole derivatives or their salts, their production and agronomic compositions containing the same.

Previous technique

Although various synthesized compounds that have inhibitory actions against harmful pests have been used so far as insecticides, almost all of them belong to orgaonic phosphate osters, carbamic osesters, organic chlorine-containing compounds or pyrethroid compounds.

On the other hand, it has been reported that 1-aryl-pyrazole derivatives, in which position 3 of a pyrazole ring is a hydrogen atom, an alkyl group, a cycloalkyl group, a haloalkyl group, a cyano group, a nitro group, a halogen atom, a carbamoyl group or a thiocarbamoyl group have an insecticidal activity (USP 5,232,940 corresponding to JP-A-228065/1987, USP 4,771,066 corresponding to JP-A -207259/1987, USP 5,236,938 corresponding to JP-A-148240/1993, EP-A-386809, USP 5,306,694 and WO 93/06089).

These pyrazole derivatives have insecticidal actions, however, they have high toxicities for humans, domestic animals and fish. Sometimes pyrazole derivatives exhibit toxicity to natural enemies of pests, and high residual property in soils or the like. Therefore, a satisfactory effect is not actually obtained at the present time.

In order to solve the above problems, the present inventors have studied intensively over a long period of time in such a way that they have found an insecticide having a structure that is completely different from that of an insecticide that has been used so far. As a result, it has been unexpectedly found that a new pyrazole derivative or a salt thereof has a very strong insecticidal activity. The pyrazole derivative or a salt thereof has also been found to be safe because it gives little chemical damage to plants and its toxicity to humans, domestic animals, fish, natural enemies of pests, etc. is low. . Furthermore, the present inventors have conducted intensive studies based on these findings and developed the present invention.

Description of the invention

The present invention refers to:

(1) a compound of formula:

<img file="ES2187751T3_D0001.tif" />

where: Ar is

ES 2 187 751 T3 an aromatic hydrocarbon group C_6-14 which may be optionally substituted with 1 to 6 substituents selected from (1) C1-6 alkyl which may be optionally substituted with 1 to 4 substituents selected from hydroxy, C alkoxy_1-6, halogen and amino which may be optionally mono or di-substituted with C1-6 alkyl, (2) amino which may be mono- or di-substituted with C1-6 alkyl or C1-6 alkanoyl, (3) hydroxyl, (4) carboxyl, (5) nitro, (6) SF5, (7) C1-6 alkoxy, (8) C1-6 alkanoyloxy, (9) cyano and (10) halogen,

Res (i) a group of formula: -NR^{1 B}R^2b in which R^{1 B} and R^2b are each (a) H, (b) a C1-20 hydrocarbon group which may be optionally substituted with 1 to 3 substituents selected from the group (A) consisting of (1) nitro, (2) hydroxyl, (3) oxo (4) thioxo, (5) cyano, (6) carbamoyl, (7) carboxyl, (8) C1-15 acyl, (9) sulfo, (10) halogen, (11) C1-14 hydrocarbonoxy which may optionally be monoa tri-substituted with halogen, (12) -S (O)_nR^to where n "is 0, 1 or 2, and R^to is a C1-14 hydrocarbon group, (13) amino which may be optionally mono- or di-substituted with C1-6 alkyl or C1-6 alkylcarbonyl, (14) imino which may be optionally substituted with C1-6 alkyl, hydroxy or C 1-6 alkoxy, (15) hydrazone which may be optionally mono- or di-substituted with C 1-4 alkyl and (16) a 5- or 6-membered heterocyclic group having 1 to 4 heteroatoms selected from O, S and Besides the carbon atom (s), which may be optionally substituted with 1 to 4 substituents selected from halogen, C 1-4 alkyl and mono to tri-halogenated phenoxy, (c) a C 1-7 acyl group which may be optionally substituted with 1 to 3 substituents selected from group (A ) described above or (d) a mono or di-C1-4alkyl-carbamoyl group which may be optionally substituted with 1 to 3 substituents selected from group (A) described above or (ii) a group of the formula: -N = C (R^3b) R^4bin which R^3b yR^4b each are H; C1-15 alkyl; C6-14 aryl which may be optionally substituted with C1-4 alkyl and / or hydroxyl; C1-15 alkoxy; mono- or di-C1-15 alkyl-amino or hydroxyamino.

R⁶ is a C1-6 alkyl group which may be optionally mono to tetra-substituted with halogen, and n is an integer nuomer from 0 to 2,

X is a group of formula: -NR^{1 C}R^{2 C} in which R^{1 C} yR^{2 C} are each (a) H, (b) hydroxyl, or (c) a C1-20 hydrocarbon or C1-15 acyl group, each of which may be optionally substituted with 1 to 3 substituents selected from (1) nitro, ( 2) hydroxyl, (3) oxo (4) thioxo, (5) cyano, (6) carbamoyl, (7) carboxyl, (8) C1-15 acyl, (9) sulfo, (10) halogen, (11) hydrocarbonoxy C1-14 which may be optionally mono- to tri-substituted with halogen, (12) -S (O)_nR^to wherein n "is 0, 1 or 2, and Ra is a C1-14 hydrocarbon group, (13) amino which may be optionally mono- or di-substituted with C1-6 alkyl or C1-6 alkylcarbonyl, ( 14) imino which can be optionally substituted with C1-6 alkyl, hydroxyo C1-6 alkoxy, (15) hydrazone which can be optionally mono- or di-substituted with C1-4 alkyl and (16) a heterococlic group of 5 or 6 elements that have 1 to 4 heteroaotomes selected from O, S and N in addition to the carbon atom (s), which may be optionally substituted with 1 to 4 substituents selected from halogen, C1-4 alkyl and mono- to tri-halogenated phenoxy,

Yes (a) H, (b) hydroxyl, (c) a C1-15 alkoxy, mono- or di-C1-4 alkyl-carbamoyloxy, C1-15 acyloxy or C1-15 acyl group, each of which may be substituted with 1 to 3 substituents selected from the group (A) consisting of (1) nitro, (2) hydroxyl, (3) oxo, (4) thioxo, (5) cyano, (6) carbamoyl, (7) carboxyl, (8) C1-15 acyl, (9) sulfo, (10) halogen, (11) C1-14 hydrocarbonoxy which may be optionally mono- to tri-substituted with halogen, (12) -S (O)_n„R^to where n "is 0, 1 or 2, and R^to is a C1-14 hydrocarbon group, (13) amino which may be optionally mono- or di-substituted with C1-6 alkyl or C1-6 alkylcarbonyl, (14) imino which may be optionally substituted with C1-6 alkyl, hydroxy or C1-6 alkoxy, (15) hydrazone which may be optionally mono- or di-substituted with C1-4 alkyl and (16) a 5- or 6-membered heterocolic group having 1 to 4 heteroatoms selected from O, S and N in addition of the carbon atom (s), which may be optionally substituted with 1 to 4 substituents selected from halogen, C1-4 alkyl and mono- to tri-halogenated phenoxy or (d) a group of the formula: -NR^1dR^2d in which R^1d yR^2d each are H or a C1-20 hydrocarbon or C1-15 acyl group, each of which may be optionally substituted with 1 to 3 substituents selected from group (A) described above, X and Y combined being a group of the formula:

ES 2 187 751 T3

<img file="ES2187751T3_D0002.tif" />

which is a nitrogen-containing heterocyclic group, which may further have N, O, S and / or P as a constituent ring atom and which may be optionally substituted with 1 to 6 substituents selected from group (B) consisting of (1 ) a C1-20 hydrocarbon group which may be optionally mono- to tri-substituted with halogen, (2) C hydrocarbonoxy_1-14, (3) acyl C_1-15, (4) C1-14 acyloxy, (5) carbamoyl which may be optionally mono- or di-substituted with C1-4 alkyl, (6) cayclic aminocarbonyl, (7) halogen, (8) oxo, (9) amidino, (10) imino which may be optionally substituted with C1-6 alkyl, (11) amino which may be optionally mono- or di-substituted with C1-6 alkyl, carbamoyl or N, N-di-C1-4 alkyl-carbamoyl, (12) cayclic amino having 3 to 6 elements having carbon atom (s) and a nitrogen and optionally, 1 to 3 heteroatoms selected from O, S and N, (13) C1-6 alkanoyl-amido, (14) benzamido, (15) C1-3 alkylenedioxy, (16) -B (OH) 2, (17) hydroxyl, ( 18) nitro, (19) cyano, (20) -S (O)_n„R^b where n ”is 0, 1, á2, and R^b is H or a hydrocarbon group C_1- 14 and (21) sulfamoyl which may be optionally mono- or di-substituted with C1-6 alkyl, or a salt thereof, and / or P as a constituent atom of the ring, or a salt thereof, (2) a process for produce the compound as defined in (1) or a salt thereof comprising:

(i) reacting a phaormula compound:

<img file="ES2187751T3_D0003.tif" />

in which the symbols are as defined above, or a salt thereof with a compound of formula:

Q-NH2 in which Q is a group linked through C, N, O, S, a, or P, to produce a phaormula compound:

<img file="ES2187751T3_D0004.tif" />

in which the symbols are as defined above, or a salt thereof, or (ii) reacting a phaormula compound:

ES 2 187 751 T3

<img file="ES2187751T3_D0005.tif" />

in which Ar, R⁶ and n are as defined above, J is O or -NR¹⁶ (R¹⁶ is H or a group attached through C), or a salt thereof with a compound of the formula:

R¹⁷C (OR¹⁸)₃ in which R¹⁷ is H or a C1-6 alkyl group, and R¹⁸ is a C1-6 alkyl group, to produce a compound of formula:

<img file="ES2187751T3_D0006.tif" />

A r in which the symbols are as defined above, or a salt thereof, or (iii) oxidize a compound of the formula:

<img file="ES2187751T3_D0007.tif" />

in which Ar, R and Q are as defined above, R⁶ is an optionally substituted hydrocarbon group or an optionally substituted heterocolic group, or a salt thereof to produce a compound of the formula:

<img file="ES2187751T3_D0008.tif" />

ES 2 187 751 T3 in which n 'is 1 or 2, the other symbols are as defined above, or a salt thereof, or (iv) reacting a compound of formula:

<img file="ES2187751T3_D0009.tif" />

in which the symbols are as defined above, or a salt thereof with a compound of the formula:

Y-NH2 where Y is as defined above, or a salt thereof, to produce a compound of (1) or a salt thereof.

(3) an agrochemical composition comprising an effective amount of the compound as defined in (1) or a salt thereof, and (4) use of the compound of (1) or a salt thereof in the preparation of an insecticidal composition, etc

The above formula compound [I] or a salt thereof of the present invention sometimes have geoetric and / or stereoisoomers, and the present invention includes all such isoomers.

In the above formulas, Ar is an optionally substituted aromatic hydrocarbon group.

Examples of the aromatic hydrocarbon group in the optionally substituted aromatic hydrocarbon group for Ar include a C6-14 aromatic hydrocarbon group such as phenyl, naphthyl, biphenylyl, anthryl, phenanthryl and the like.

Examples of the substituent on the aromotic hydrocarbon group include a C1-6 alkyl group (eg, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, sec-pentyl , isopentyl, and n-hexyl), which may be optionally substituted with 1 to 4 substituents selected from the group consisting of, for example, hydroxy, C 1-6 alkoxy (for example methoxy, ethoxy, propoxy, isopropoxy, butoxy, pentyloxy , hexyloxy, etc.), halogen (for example, fluorine, chlorine, bromine, iodine, etc.) and amino which may be optionally mono- or di-substituted with C1-6 alkyl (for example methyl-amino, ethylamino, propylamino, dimethylamino, diethylamino, etc); an amino group which may be optionally mono- or di-substituted with C1-6 alkyl or C1-6 alkanoyl (for example, methyl amino, ethylamino, propylamino, dimethylamino, diethylamino, acetylamino , propionyl-amino, etc); a hydroxyl group; a carboxyl group; a nitro group; SF5; a C1-6 alkoxy group (the same as defined above); an alkanoyloxy group (eg, 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, and most preferably from 1 to 3, within the substitutable range. When the substituent is a halogen atom, the substitution can be effected within the maximum substitutable range.

As the halogen atom for R⁶ For example, fluorine, chlorine, bromine, iodine, etc. Among them, chlorine is preferred.

Examples of the group attached through C to Y include all orgaonic moieties attached 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 heterocolic group having a chemical bond on a carbon oatom 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 hydrocarbon group is preferred

ES 2 187 751 T3 ^C1-24^.

As the alkyl group, for example, a C1-15 alkyl group is used (for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, etc). Among them, a C1-6 alkyl group such as methyl, ethyl, propyl, isopropyl, butyl, t-butyl, pentyl, hexyl etc. is particularly preferred. As the alkenyl group, for example, a C 2-10 alkenyl group (eg vinyl, allyl, 2-methyl-allyl, 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 C 2-10 alkynyl group (eg ethynyl, 2-propynyl, isopropynyl, butynyl, t-butynyl, 3-hexynyl, etc.) is used. Among them, a C 2-6 alkynyl group is preferred. As the cycloalkyl group, for example, a C 3-6 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 can be substituted with the substituents as described hereinafter. As the substituted hydrocarbon group, for example, an alkoxyalkyl group (for example, C 1-3 alkoxy-C 1-6 alkyl group such as methoxy-methyl, ethoxy-methyl, ethoxy-butyl, propoxy-methyl, propoxy-hexyl etc. are preferred. ), a hydroxyalkyl group (for example a hydroxy-C1-6 alkyl group such as hydroxy-methyl, hydroxy-ethyl, hydroxy-butyl, hydroxy-propyl, etc.) and a halogenated alkyl group (for example, C1-6 alkyl group di- or tri-halogenated such as chloromethyl, fluoro-methyl, bromo-methyl, chloro-ethyl, dichloro-methyl, trichloro-methyl, thifluoro-methyl, etc).

As the acyl group in the optionally substituted acyl group, for example, an acyl group obtained from a C1-24 aliphaotic carboxylic acid is used. Specifically, for example, a C1-6 alkanoyl group such as formyl, acetyl, ethylcarbonyl, propylcarbonyl, tert-butylcarbonyl, etc are used; an alkoxycarbonyl group such as methoxycarbonyl, ethoxycarbonyl, etc); an aryl-carbonyl group such as benzoyl, etc; an aryloxycarbonyl group such as benzoxycarbonyl, etc; a C7-15 aralkylcarbonyl group such as benzylcarbonyl, etc; and an aralkyloxycarbonyl group such as benzyloxycarbonyl.

As the optionally substituted carbamoyl, for example, a carbamoyl group which may be substituted with an optionally substituted C1-20 hydrocarbon group (for example C1-15 alkyl, C2-10 alkenyl, C2-10 alkynyl, C7 aryl group is used -14 or C7-20 aralkyl). Specifically, a mono- or di-C1-15-alkylcarbamoyl group (for example, a mono- or di-C1-6alkyl-carbamoyl group such as methylcarbamoyl, ethylcarbamoyl, hexylcarbamoyl, dimethyl- carbamoyl, methylethylcarbamoyl, etc).

As the heterocolic group in the optionally substituted heterocolic group having a chemical bond in a carbon atom, for example, a 3- to 8-membered heterocolic group having 1 to 4 heteroaotoms selected from N, O, and S, etc., are used. In addition to the carbon atom (s) which may be fused with a C5-10 hydrocarbon hydrocarbon ring (the same as defined above) or a 5- or 6-membered heterocolic ring having 1 to 4 heteroatoms selected from N, O and S.

Specifically, 5-membered coclic groups are used having 1 to 4 heteroaotoms selected from O, S, and N, in addition to the carbon atom (s) (for example, 2- o or 3-thienyl, 2- o or 3-furyl, 2 - 3-pyrrolyl, 2-, 3- or 4-pyridyl, 2-, 4-, 5-oxazolyl, 2-, 4-, or 5-thiazolyl, 3-, 4- or 5-pyrazolyl, 2-, 4- oo 5imidazolyl, 3-, 4- oo 5-isoxazolyl, 3-, 4-, oo 5-isothiazolyl, 3- oo 5- (1,2,4-oxadiazolyl), 1,3,4-oxadiazolyl,

3- oo 5- (1,2,4-thiadiazolyl), 1,3,4-thiadiazolyl, 4- oo 5- (1,2,3-thiadiazolyl), 1,2,5-thiadiazolyl, 1,2, 3-triazolyl,

1,2,4-triazolyl, 1H- or 2H-tetrzolyl, etc); 6-membered coclic groups having 1 to 4 heteroatoms selected from O, S, and N, in addition to carbon atom (s) (e.g., N-oxide-2-, 3-, or 4-pyridyl, 2-,

4- oo 5-pyrimidinyl, N-ooxide-2-, 4- oo 5-pyrimidinyl, 2- oo 3-thiomorpholinyl, 2- oo 3-morpholinyl, oxotriazinyl, dioxotriazinyl, pyrrolidinyl, piperidinyl, pyranyl, thiopyranyl, 1,4 -oxadinyl, 1,4-thiazinyl, 1,3-thiazinyl, 2o or 3-piperazinyl, triazinyl, oxotriazinyl, 3-oo 4-pyridazinyl, pyrazinyl, N-ooxide-3-o or 4-pyridazinyl, etc); and dicoclic or trichoclic condensed aromatic heterococlic groups having 1 to 4 heteroaotoms selected from O, S, and N in addition to the carbon atom (for example, benzofuryl, benzothiazolyl, benzooxazolyl, tetrazolo [1,5-b] pyridazinyl, triazolo [4, 5-b) pyridazinyl, imidazo [1,2-a] pyridinyl, benzoimidazolinyl, quinolyl, isoquinolyl, cinnolinyl, phthalazinyl, quinazolinyl, quinoxalinyl, indolidinyl, quinolidinyl, 1,8naphthylidinyl, purinyl, phteridinyl, dibenzinyl carbazolyl, acridinyl, phenanthridinyl, chromanyl, benzoxazinyl, phenazinyl, phthenothiazinyl, phenoxazinyl, etc).

These hydrocarbon group, acyl group, carbamoyl group substituted with a C1-20 hydrocarbon group, and heterocolic group having a chemical bond on the carbon atom may have substitutes.

ES 2 187 751 T3 yentes. 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 C1-15 acyl group [for example C1-6 alkoxycarbonyl (methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, iso-propoxycarbonyl, n-butoxycarbonyl, iso-butoxycarbonyl, tert-butoxy carbonyl, etc.), C 1-6 alkanoyl (for example formyl, acetyl, propionyl, n-butyryl, iso-butyryl, etc.), C6-14 aryl-carbonyl (for example benzoyl, etc.)]; a sulfo group;

a halogen atom; (the same as defined above); a hydrocarbonoxy group C_1-14 [eg C alkoxy_1-6 (the same as defined above), aryloxy (eg phenoxy-naphthyloxy, etc)] which may be optionally mono- to tri-substituted with halogen (eg, o-, m- or p-chloro-phenoxy, o- , m- or p-bromo-phenoxy, etc); -SW)_n// R^to where n "is 0, 1 or 2, R^to is a hydrocarbon group C_1-14such as Ci_6 alkyl, C6_i4 aryl [for example Ci_6 alkyl-thio (eg methyl-thio, ethyl-thio, propylthio, isopropyl-thio, n-butyllithium, sec-butyllithium, tert-butyl-thio, etc. ), C6_14 aryl-thio (for example phenyl-thio, etc.), C1_6 alkyl-sulfinyl (for example methyl-sulfinyl, ethyl-sulfinyl, propyl-sulfinyl, butyl-sulfinyl, etc), C1_6-alkyl-sulfonyl (for example methyl -sulfonyl, ethylsulfonyl, propyl-sulfonyl, butylsulfonyl, etc.)]; an amino group which may be optionally mono- to tri-substituted with C1_6 alkylcarbonyl or C1_6 alkyl (eg acetylamino, propionyl amino, etc); an imino group which may be optionally substituted with C1_6 alkyl, hydroxy or C1_6 alkoxy (for example methyl imino, ethyl imino, propyl imino, butyl imino, methoxy imino, ethoxy imino, n-propoxy imino, etc. ); a hydrazone group which may be optionally substituted with mono- or di-substituted C1_4 alkyl (eg methyl hydrazone, ethyl hydrazone, dimethyl hydrazone, etc); and 5- or 6-membered heterocyclic group which may have 1 to 4 substituents selected from (a) or halogen atom (the same as defined above), (b) C1_4 alkyl group (for example methyl, ethyl, propyl, isopropyl) and (c) mono- to tri-substituted phenoxy group (for example o-, mo or p-chloro-phenoxy, o-, m- or p-bromo-phenoxy, etc.) and has 1 to 4 heteroatoms selected from O, S and N, etc in addition to carbon atom (s) (for example 2- oo 3-thienyl, 2- oo 3-furyl, 3-, 4- oo 5-pyrazolyl, 2-, 4- oo 5-thiazolyl, 3-, 4-oo 5-isothiazolyl, 2-, 4- oo 5-oxazolyl, 3-, 4- oo 5-isoxazolyl, 2-, 4- óo 5-imidazolyl, 1,2,3- óo

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 attached through N to R, X, or Y include all organic moieties attached through a nitrogen atom. For example, we use (1) a nitro group, (2) a group of formula: -NR¹R² in which R¹ yR² each are H, an optionally substituted hydrocarbon group, an optionally substituted acyl group, an optionally substituted carbamoyl group; an optionally substituted heterocolic group, a hydroxyl group, an optionally substituted hydrocarbonoxy group, or a group of the formula: -SOpR⁸ (R⁸ is H or an optionally substituted hydrocarbon group and p is 1 or 2), (3) an optionally substituted heterocolic group having a chemical bond on a nitrogen atom, and (4) a group of the formula: -N = C (R³) R⁴ in which R³ yR⁴ are H, an optionally substituted hydrocarbon group or a group of the formula: -NR⁹R¹⁰ (R⁹ yR¹⁰ are each H, a hydroxyl group or an optionally substituted hydrocarbon group).

As the optionally substituted hydrocarbon group for R¹, R², R³, R⁴, R⁸, R⁹ oR¹⁰, the same as the above optionally substituted hydrocarbon group defined is used in the group attached through C.

As the optionally substituted hydrocarbon group of the optionally substituted hydrocarbonoxy group for R¹, R², R³ oR⁴, the same as the above optionally substituted hydrocarbon group defined in the group attached through C is used.

As the optionally substituted acyl group or optionally substituted carbamoyl group for R¹oR², the same as the above optionally substituted acyl group or optionally substituted carbamoyl group defined in the group attached through C is used.

As the heterococlic group in the optionally substituted heterococlic group for R¹ oR² the same as the above heterococlic group defined by the optionally substituted heterococlic group having a chemical bond on a carbon atom is used.

As the heterococlic group having a chemical bond in a nitrogen atom defined in the group attached through N to W, R, X, or Y, for example, 3 to 8 membered heterococlic groups having a chemical bond in one nitrogen atom and 1 to 4 heteroatoms selected from N, O and S in addition to the carbon atom (s) and a nitrogen atom (s) that can be condensed with a C5_10 hydrocarbon hydrocarbon ring or a 5- or 6-membered heterocolic ring that has 1 to 4 heteroatoms selected from N, O, and S. Specifically , for example, 1H-1-pyrrolyl, 1-imidazolyl, 2-triazolyl, 1-pyrazolyl, 1-indolyl, 1H-indazolyl, 7-purinyl, 1-aziridinyl, 1-pyrrolidinyl, 1-pyrrolinyl, 1 -imidazolidinyl,

ES 2 187 751 T3

2-isoxazolidinyl, pyrazolidinyl, piperazinyl, pyrazolinyl, 1-piperidinyl, 4-morpholinyl, 4-thiomorpholinyl, etc.

As the substituent on the heterocyclic group for R¹ or R² and the heterocyclic group having a chemical bond on a nitrogen atom, for example, a C hydrocarbon group is used_1-20[for example C alkyl_1-6 (same as defined above), C alkenyl_2-6 (the same as defined above), C2-6 alkynyl (the same as defined above), C3-6 cycloalkyl (the same as defined above), C5-7 cycloalkenyl (for example cyclopentyl, cyclohexenyl, etc), aralkyl C7-20 (the same as defined above), C6-14 aryl (the same as defined above)], which may optionally be monoa tri-substituted with halogen; a C1-14 hydrocarbonoxy group [eg C1-6 alkoxy (the same as defined above), C6-14 aryloxy (the same as defined above)]; a C1-15 acyl group [for example C1-6 alkanoyl (the same as defined above), C6-14 aryl-carbonyl (the same as defined above), C1-6 alkoxy-carbonyl (the same as defined above )]; a C1-15 acyloxy group [eg C1-6 alkanoyloxy (the same as defined above), C6-14 aryl-carbonyloxy (eg benzoyloxy, etc)]; a carboxyl group; a carbamoyl group which may be optionally mono- or di-substituted with C1-4 alkyl (for example N-methyl-carbamoyl, N-ethyl-carbamoyl, N-propyl-carbamoyl, N-isopropyl-carbamoyl, N-butyl-carbamoyl , N, N-dimethyl-carbamoyl, N, N-diethyl-carbamoyl, N, N-dipropyl-carbamoyl, N, N-dibutyl-carbamoyl, etc); a cyclic aminocarbonyl group (for example 1-aziridinylcarbonyl, 1-azetidinylcarbonyl, 1-pyrrolidinylcarbonyl, 1-piperidinylcarbonyl, N-methylpiperadinylcarbonyl, morpholinocarbonyl, etc.), a halogen atom (the same as defined above); an oxo group; an amidino group; an imino group which may be optionally substituted with a C1-6 alkyl group (the same as defined above); an amino group which may be optionally mono- or di-substituted with C1-6 alkyl, carbamoyl or N-mono- or N, N-di-C1-4 alkylcarbamoyl (for example N-methylcarbamoyl-amino, N-ethylcarbamoyl-amino , N-propylcarbamoyl-amino, N-isopropylcarbamoyl-amino, N-butylcarbamoyl-amino, N, N-dimethylcarbamoylamino, N, N-diethylcarbamoyl-amino, etc); a cyclic amino group of 3 to 6 elements having carbon atom (s) and a nitrogen and optionally, 1 to 3 heteroatoms selected from O, S and N (for example aziridinyl, azetidinyl, pyrrolidinyl, pyrrolinyl, pyrrolyl, imidazolyl, triazolyl , pyrazolyl, imidazolidinyl, piperidino, morpholino, dihydropyridyl, pyridyl, N-methyl-piperazinyl, N-ethyl-piperazinyl, etc); a C 1-6 alkanoyl amido group (for example formamido, acetamido, trifluoro-acetamido, propionyl-amido, butylyl-amido, isobutyl-amido, etc); a benzamido group; a C1-3 alkylenedioxy group (for example methylenedioxy, ethylenedioxy, etc); -B (OH)₂; a hydroxyl group; a nitro group; a cyano group; -SW)_n// R^bwhere n "is 0, 1 or 2yR^b is H, hydroxyl or a C1-14 hydrocarbon group [for example mercapto, sulfo, sulfino, C1-6 alkylthio (for example methylthio, ethylthio, propylthio, isopropylthio, n-butylthio , sec-butyl-thio, tert-butyl-thio, etc.), C6-14 aryl-thio (for example phenyl-thio, etc.), C1-6 alkyl-sulfinyl (for example methyl-sulfinyl, ethyl-sulfinyl, propyl -sulfinyl, butyl-sulfinyl, etc), C6-14 aryl-sulfinyl (for example phenyl-sulfinyl, etc.), C1-6 alkyl-sulfonyl (for example methyl-sulfonyl, ethyl-sulfonyl, propyl sulfonyl, butyl sulfonyl, etc) and C5-14 aryl sulfonyl (eg phenyl sulfonyl, etc) etc]; a sulfamoyl group which may be optionally mono- or di-substituted with C1-6 alkyl (for example N-methyl-sulfamoyl, N-ethyl-sulfamoyl, N-propyl-sulfamoyl, N-isopropyl-sulfamoyl, N-butyl-sulfamoyl , N, N-dimethyl-sulfamoyl, N, N-diethyl-sulfamoyl, N, N-dipropyl-sulfamoyl, N, N-dibutyl-sulfamoyl, etc. The number of substituents is from 1 to 6, preferably from 1 to 3, within the substitutable range.

Among the above groups linked via N, for example, (1) a group of formula is preferred: -NR^1stR^2nd in which R^1st is H, an optionally substituted alkyl group, an optionally substituted aralkyl group, an optionally substituted aralkyl group, an optionally substituted acyl group, an optionally substituted carbamoyl group, an optionally substituted cycloalkyl 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 io -SOpR^8a (p is 1 or i 2, and R^8a is an optionally substituted alkyl group or an optionally substituted aryl group); and R^2nd is H, an optionally substituted aralkyl group or an optionally substituted alkyl group, (2) a heterocyclic group having a bond at the nitrogen atom, such as 1H-1-pyrrolyl, 1-imidazolyl, 1-triazolyl, pyrazolyl, indolyl , 1H-1indazolyl, 7-purinyl, 1-aziridinyl, 1-pyrrolidinyl, 1-pyrrolinyl, 1-imidazolidinyl, 2-isoxazolidinyl, pyrazolidinyl, piperadinyl, pyrazolinyl, 1-piperidinyl, 4-morpholinyl, 4-thiomorpholinyl, etc 3) a group of formula -N = C (R^3rd) R^4th in which R^3rd yR^4th They are each H, an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted alkoxy group, a mono- or di-alkyl-amino group, or a hydroxy-amino group.

As the alkyl group in the optionally substituted alkyl group for R^1st, R^2nd, R^3rd, R^4th oR^8aFor example, a C1-6 alkyl group such as methyl, ethyl, propyl, isopropyl, butyl, t-butyl, pentyl, hexyl, etc. is used.

ES 2 187 751 T3

As the aralkyl group in the optionally substituted aralkyl group for R^1st oR^2ndFor example, a C7-15 aralkyl group such as benzyl, phenylethyl, etc. is used.

As the cycloalkyl group in the optionally substituted cycloalkyl group for R^1stFor example, a C 3-6 cycloalkyl group such as cyclopropyl, cyclopentyl, cyclohexyl, etc. is used.

As the aryl group in the optionally substituted aryl group for R^1st, R^3rd, R^4th oR^8a , for example, a C6-14 aryl group such as phenyl, naphthyl, anthracenyl, etc. is used.

As the alkoxy group in the optionally substituted alkoxy group for R^1st, R^3rd oor R^4thFor example, a C1-6 alkoxy group such as methoxy, ethoxy, propoxy, butoxy, etc. is used.

As the aralkyloxy group in the optionally substituted aralkyloxy group for R^1stFor 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^1st For example, a C1-6 acyl group such as formyl, acetyl, propionyl, etc. is used.

As the carbamoyl group in the optionally substituted carbamoyl group for R^1st, the same as the above optionally substituted carbamoyl group defined in the group attached through C.

As the mono or di-alkyl amino group in the optionally substituted mono or di-alkyl amino group for R^3rd oor R^4thFor example, a mono- or di-alkylamino group such as methyl amino, 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 mentioned hydrocarbon group is used for the group attached through by C.

As the optionally substituted heterococlic group for R^1st, for example, the same as the optionally substituted heterocolic group for R can be used¹ oor R².

Examples of the group attached through O to Y include all organic moieties attached through an oxygen atom. For example, a group of formula -OR is used⁵ in which R⁵ is (1) H, (2) an optionally substituted hydrocarbon group, (3) an optionally substituted heterocolic group, (4) an optionally substituted acyl group, (5) an optionally substituted carbamoyl group, (6) a group of the formula: -NR¹¹R¹² (R¹¹ yR¹² are each H, an optionally substituted hydrocarbon group or an optionally substituted heterococlic group or (7) a group of the formula: -SiR¹³3 (R13 is an optionally substituted hydrocarbon group).

As the optionally substituted hydrocarbon group for R⁵, R¹¹, R¹² oor R¹³, for example, the same as the above optionally substituted hydrocarbon group defined in the group attached through C is used.

As the optionally substituted heterococlic group for R⁵, R¹¹ oor R¹², for example, the same as the above optionally substituted heterocolic group is used for R¹ oor R².

As the optionally substituted acyl group or the optionally substituted carbamoyl group for

R³, for example, the same as the above optionally substituted acyl group or the above optionally substituted carbamoyl group defined in the group attached through C.

Among the groups linked through O, for example, a group of formula is preferred: -OR^5th in which _R5a 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 heterocolic group, an optionally substituted aryl-carbonyl group, an optionally substituted alkoxycarbonyl group, an optionally substituted aryloxycarbonyl group, an optionally substituted carbamoyl group, a group of the formula: -NR^11aR^12a (R^11a yR^12a are the same as defined for R^1st yR^2nd) or a group of formula: -SiR^13a3 (R^13a is an alkyl group).

The optionally substituted alkyl, acyl, carbamoyl, cycloalkyl, aryl, or heterocolic group for _R5a is the same as those for R^1st.

ES 2 187 751 T3

As the aryl-carbonyl group in the optionally substituted aryl-carbonyl group for R^5th, for example, a C6-14 aryl-carbonyl group such as benzoyl, etc. is used.

As the alkoxycarbonyl group in the optionally substituted alkoxycarbonyl group for R^5thFor example, a C 1-6 alkoxycarbonyl group such as methoxycarbonyl, ethoxycarbonyl, etc. is used.

As the aryloxycarbonyl group in the optionally substituted aryloxycarbonyl group for R^5thFor example, a C6-14 aryloxycarbonyl group such as phenoxycarbonyl, etc. is used.

As the substituent of these arylcarbonyl, alkoxycarbonyl and aryloxycarbonyl, for example, the same substituent of the mentioned hydrocarbon group is used for the group attached through C.

As examples of the group attached through S use -S (O) nR⁶ in which R⁶ is an optionally substituted hydrocarbon group or an optionally substituted heterocyclic group, and n is an integer from 0 to 2.

As the optionally substituted hydrocarbon group for R⁶For example, the same as the above optionally substituted hydrocarbon group defined in the group attached through C is used.

As the optionally substituted heterokali group for R⁶, for example, the same as the above optionally substituted heterocyclic group is used for R¹ oR².

Among the groups linked via S, for example, an optionally substituted alkylthio group, an optionally substituted cycloalkylthio group, an optionally substituted arylthio group, an optionally substituted aralkylthio group, a heterokyl- optionally substituted thio, optionally substituted alkylsulfinyl group, optionally substituted alkylsulfonyl group, and optionally substituted arylsulfonyl group.

As the optionally substituted alkyl, cycloalkyl, aryl, aralkyl or heterokyl group in the optionally substituted alkyl-thio group, optionally substituted cycloalkyl-thio group, optionally substituted aryl-thio group, optionally substituted heterocyclic-thio group, optionally substituted alkyl-sulfinyl group , optionally substituted alkyl sulfonyl group or optionally substituted arylsulfonyl group, for example, the same as for R is used^1st.

As the aralkyl group in the optionally substituted aralkylthio group, for example, a C7-15 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 is used for the group attached through C.

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

Y

TO

X formed by combining X with Y, which can have N, O, S, and / or P as a constituent atom of the ring, for example, heterocayclic groups that contain nitrogen of 5 to 8 elements that can have 1 to 3 heteroatoms are used selected from N, O, S and P, etc, in addition to the carbon atom.

Specifically, a group of formula is used:

ES 2 187 751 T3

<img file="ES2187751T3_D0010.tif" />

in which R¹⁴ is an optionally substituted hydrocarbon group; L is 0 or a C1-3 alkylene group (eg methylene, ethylene, etc); and Z is O or a group of phaormula: -NR¹⁵ (R¹⁵ is H or an optionally substituted hydrocarbon group).

As the optionally substituted hydrocarbon group for R¹⁴ oá R¹⁵For example, the same as the above optionally substituted hydrocarbon group defined in the group attached through C is used. Among them, a C1-6 alkyl group such as methyl, ethyl, propyl, etc. is preferred.

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

<img file="ES2187751T3_D0011.tif" />

in which the symbols are as defined above.

In the above formulations, Ar is an optionally substituted aromatic hydrocarbon group. The aromatic hydrocarbon group is a C6-14 aromatic hydrocarbon group (eg phenyl, naphthyl, anthryl, etc.), more preferably a C6-12 aromatic hydrocarbon group (eg phenyl, etc.). As the substituent, for example, a halogen atom, a C1-6 alkyl group and a mono-, di-, or tri-halogenated C1-6 alkyl group are preferred. The number of substituents is preferably 1 to 4. Particularly preferred is a 2,6-di-halogeno-phenyl group substituted with a group with a C1-6 alkyl group and / or a mono-, di-, C1-6 alkyl group. oá tri-halogenated. As Ar, 2,6-dichloro-4-trifluoromethylphenyl is most preferred.

R is preferably a group attached through N. Among these, a group of formula: -NR is preferred^{1 B}R^2b in which R^{1 B} yR^2b each are H, an optionally substituted C1-20 hydrocarbon group (for example C1-15 alkyl, C6-14 aryl, C7-20 aralkyl), an optionally substituted mono- or di-C1-4 alkylcarbamoyl group, or a optionally substituted C1-7 acyl group (for example C1-6 alkanoyl, benzoyl), or a group of formula: -N = C (R^3b ) R^4b) in which R^3b yR^4b they are each H; a C1-15 alkyl group; a C6-14 aryl group which may be optionally substituted with C1-4 alkoxy and / or hydroxyl; a C1-15 alkoxy group; a mono- or di-C1-15-alkyl-amino group or a hydroxyl-amino group. As the substituent of the C1-20 hydrocarbon group, mono- or di-C1-4 alkylcarbamoyl group or C1-7 acyl group, the same substituent as that of the mentioned hydrocarbon group is used for the group attached through C. The number of substituents is from 1 to 3, preferably from 1 to 2. It is more preferred than R^{1 B} yR^2b be each H, an alkyl group C_1-6 , an aralkyl group C_7-15, a monoa di-C1-4 alkyl-carbamoyl group or a C1-7 acyl group and R^3b let H, or a C1-6 alkyl group and, furthermore, and R^4b be it a C1-4 alkoxy group, a C6-14 aryl group, a mono- or di-C1-4 alkyl-amino group or a hydroxy-amino group. As R, an amino group, a mono- or di-C1-4alkyl-amino group, and a -N = CHOCH3 or -N = CHOCH2 -CH3 group are particularly preferred.

In the phaormula group: -S (O) nR⁶ in which R⁶ and are still defined above, the hydrocarbon group represented by R⁶, for example, a C hydrocarbon group is preferred_1-24. Among them, a C1-15 alkyl group is more preferred. More specifically, R⁶ is preferably a group

ES 2 187 751 T3 C1-6 alkyl which may be optionally substituted with 1 to 4 halogen atoms. Like R⁶ , trifluoromethyl is the most preferred.

X is a group linked through N. Among these, a group of the formula -NR is most preferred.^{1 c} R^{2 C}in which R^{1 C} yR^{2 C} They are each H, a hydroxyl group, an optionally substituted C1-20 hydrocarbon group (eg, C1-15 alkyl, C6-14 aryl, C7-20 aralkyl) or an optionally substituted C1-15 acyl group. As the substituent of the C1-20 hydrocarbon group or C1-15 acyl group, the same substituent as that of the mentioned hydrocarbon group is used for the group attached through C. The number of substituents is from 1 to 3, preferably from 1 oor 2. R^{1 C} yR^{2 C} each are preferably H, hydroxyl group, a C1-6 alkyl group or a C1-6 acyl group. Particularly, X is preferably amino, mono- or di-methyl-amino, acetylamino, N-hydroxy-N-methyl-amino, etc.

Y is preferably H or a group attached through C, N or O. Among them, H, a hydroxyl group, an acyloxy group C_1-15 optionally substituted, a mono- or di-C alkyl group_1-4optionally substituted carbamoyloxy, an optionally substituted C1-15 alkoxy group, an optionally substituted C1-15 acyl group or a group of the formula: -NR^1dR^2d in which R^1d yR^2d each are H, or an optionally substituted C1-20 hydrocarbon group (eg C1-15 alkyl, C6-14 aryl, C7-20 aralkyl) or a C1-15 acyl group. As the substituent of the C1-15 acyloxy, mono- or di-C1-4 alkylcarbamoyloxy, C1-15 alkoxy, C1-15 acyl or C1-20 hydrocarbon group, the same substituent as that of the mentioned hydrocarbon group is used for the group attached through C. The number of substituents is from 1 to 3, preferably 1 or 2. Maos specifically, Y is preferably H; a group attached through O such as a hydroxyl, C1-15 acyloxy (preferably C1-6 alkanoyloxy which may be mono- to tri-substituted with halogen; monoo or di-C1-4 alkylcarbamoyloxy, C1-6 alkoxycarbonyloxy C6-14 aryl-carbonyloxy which may be substituted with C1-6 alkyl), C1-15 alkoxy (preferably C1-6 alkoxy) which may be mono- or di-substituted with C1-4 alkoxy; a group attached through N such as a group of the formula: -NR^1d R^2d in which R^1d yR^2d they are each H, C 1-6 alkyl, C 1-6 alkanoyl or C 1-6 alkoxycarbonyl; a group attached to C through C such as C1-15 alkyl (preferably C1-6 alkyl), etc.

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

<img file="ES2187751T3_D0012.tif" />

<img file="ES2187751T3_D0013.tif" />

<img file="ES2187751T3_D0014.tif" />

in which R^{14 to} is H or a C1-6 alkyl group.

As the formula group:

<img file="ES2187751T3_D0015.tif" />

1,2,4-oxadiazol-3-yl is the preferred maos.

ES 2 187 751 T3

The compound [I] or a salt thereof of the present invention can be produced by the following method.

When the compound [I] can be obtained as a free form or a salt by the following production method, it can be converted into the above-described salt or the free form by conventional methods, respectively. When a compound included in the compound [I] is used as a starting material to produce the other kind of compound [I], it can be used as is in the free form or used as the salt. When the other starting material can be the salt described above, it can also be used as is in the free form or used as the salt. Accordingly, the compounds and starting materials used for the following production method include their salts (eg salts with the acids described with respect to compound [I] above.

Reaction scheme (A)

<img file="ES2187751T3_D0016.tif" />

<img file="ES2187751T3_D0017.tif" />

ES 2 187 751 T3

Reaction scheme (C)

<img file="ES2187751T3_D0018.tif" />

ES 2 187 751 T3

Reaction scheme (D)

<img file="ES2187751T3_D0019.tif" />

ES 2 187 751 T3

Reaction scheme (E)

<img file="ES2187751T3_D0020.tif" />

Reaction scheme (F)

<img file="ES2187751T3_D0021.tif" />

Reaction scheme (G)

<img file="ES2187751T3_D0022.tif" />

<img file="ES2187751T3_D0023.tif" />

I

A r

CXXVII)

ES 2 187 751 T3

Reaction scheme (H)

<img file="ES2187751T3_D0024.tif" />

A r

<img file="ES2187751T3_D0025.tif" />

(Vlla) (; single or double bond)

Reaction scheme (I)

[XXYIII]

<img file="ES2187751T3_D0026.tif" />

(Vlla) [XXIX] &lt;: single or double bond)

Reaction scheme (J)

<img file="ES2187751T3_D0027.tif" />

ES 2 187 751 T3

Reaction scheme (K)

<img file="ES2187751T3_D0028.tif" />

Reaction scheme (L)

<img file="ES2187751T3_D0029.tif" />

ES 2 187 751 T3

Reaction scheme (M)

<img file="ES2187751T3_D0030.tif" />

Reaction scheme (N)

<img file="ES2187751T3_D0031.tif" />

Reaction scheme (O)

<img file="ES2187751T3_D0032.tif" />

ES 2 187 751 T3

Reaction scheme (P)

<img file="ES2187751T3_D0033.tif" />

Reaction scheme (Q)

<img file="ES2187751T3_D0034.tif" />

Reaction scheme (R)

<img file="ES2187751T3_D0035.tif" />

ES 2 187 751 T3

Reaction scheme (S)

<img file="ES2187751T3_D0036.tif" />

Reaction scheme (T)

<img file="ES2187751T3_D0037.tif" />

ES 2 187 751 T3

Reaction scheme (U)

-Ν

TO

ΪΊ ¡ΐ

N NH_;

-&gt;

oxidizing agent

J - N, A 'N, S (O) n' R f

A r CXLIV]

Reaction scheme (V) * n nh,

I

A r

CXLV)

<img file="ES2187751T3_D0038.tif" />

Reaction scheme (W)

<img file="ES2187751T3_D0039.tif" />

In schematic reactions (A) to (W), Ar, R, X, Y, R⁶, R¹⁷, R¹⁸, n ', QyJson as defined above.

In the schematic reactions (C), (D), and (T), X³, X⁴ yX⁵ they are each a halogen atom.

In schematic reactions (G), (H), (J), (K), (L), (P), and (W), R¹⁹, R²⁰, R²⁴ yR²⁶ they are each H or a C1-6 alkyl group.

In the schematic reactions (H), (K), (M), (V) and (W), R²¹ yR²⁵ are each a C1-6 alkyl group, and R²³ is a C1-6 alkyl group, a C1-6 alkoxy group, a C6-14 aryl group or a gungrupomono-o or di-C1-4 alkyl-amino.

ES 2 187 751 T3

In the schematic reactions (J) and (L), R²² is H, a C1-6 alkyl group or a hydroxyl group.

In the schematic reactions (D) and (R), M^{k +} is a positive metal ion of valence k. Like M^{k +} , for example, Na⁺ , K⁺ , Mg²⁺, etc.

In reaction schemes (G), (T) and (U), Rf is a perfluoro C1-6alkyl group.

In reaction scheme A, the starting compound [II] can be produced according to a known method described in the literature (for example Japanese Unexamined Patent Publication No.

316771/1988) or modified methods. Compound [IV] can be produced by reacting compound [II] with amines represented by compound [III].

The present reaction can be carried out, for example, according to the method described in "Comprehensive Organic Chemistry", Pergamon Press (1979), page 543 or the modified methods.

The amines [III] used in the present reaction are used for the reaction as such or in the form of a salt with an acid as described hereinafter. The amount of the amines [III] used is not specifically limited, and a large excess amount thereof can be used as a solvent. Preferably this is about 0.8 to 5 equivalents.

Good results are sometimes obtained by the use of an acid or a base during the reaction or before or after the reaction for the purpose of accelerating the reaction and reducing by-products. As an acid catalyst, for example, an inorganic protoonic acid such as hydrochloric acid, hydrogen bromide, hydrogen iodide, phosphoric acid, sulfuric acid and the like can be used; an organic protoonic acid such as foormic acid, acetic acid, tartaric acid. Moalic acid, choric acid, oxaolic acid, succonic acid, benzoic acid, trifluoroacetic acid, p-toluene sulfoonic acid and the like; and a Lewis acid such as aluminum chloride, ferric chloride, zinc chloride, titanium tetrachloride, boron trifluoride, and the like. The amount of the acid catalyst used in the reaction is not specifically limited unless the reaction is adversely affected, and is preferably about 0.1 to 2.5 equivalents.

Examples of the base used as the catalyst include organic bases such as alkali metal alcoholates (for example sodium ethylate, sodium methylate, potassium tert-butoxide, etc.), amines (for example triethylamine, diisopropylethyl amine, pyridine , N, N-dimethyl-aniline, etc.), and inorganic bases such as potassium carbonate, sodium carbonate, sodium hydroxide, potassium hydroxide, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium hydride, etc. An amount of the base is not specifically limited unless the reaction is adversely affected. For example, a large amount in excess can also be used as is the case with pyridine which also serves as a solvent.

The present reaction can be carried out using a suitable solvent. Such a solvent is not specifically limited unless it reacts with a substrate, a reagent, and a product to give by-products. Solvent that dissolves both substrate and reagent is preferred. As the solvent, for example, aliphatic hydrocarbons such as pentane, hexane, heptane, petroleum ether, etc; aromatic hydrocarbons such as methyl acetate, ethyl acetate, ethyl formate, ethyl propionate, etc; ketones such as acetone, methyl ethyl ketone, etc; ethers such as diethyl ether, diisopropyl ether, diisobutolic ether, tetrahydrofuran, dioxane, etc; nitriles such as acetonitrile, propionitrile, etc; acid amides such as dimethyl formamide, dimethyl acetamide, etc; sulfooxides such as dimethyl sulfoxide, etc; sulfones such as sulfolane, etc; phosphoric acid amides such as hexamethylphosphoramide, etc; halogenated hydrocarbons such as dichloromethane, chloroform, 1,2-dichloromethane, carbon tetrachloride, etc; aromatic amines such as pyridine, picoline, lutidine, quinoline, etc; a mixed solvent thereof; Water; and a mixed solvent of these solvents and water.

The temperature used for the reaction is usually about -50 to 200^°C, preferably about -30 to 150^°C. The reaction time is usually about 0.1 to 72 hours, preferably about 0.1 to 24 hours.

The compound obtained can be supplied to the subsequent reaction after its isolation and purification by means of a method known per se: concentration, concentration under reduced pressure, conversion of the properties of the liquid, change of solvent, extraction with solvent, distillation, crystallization, recrystallization, chromatography, etc., or supplied as the reaction mixture.

ES 2 187 751 T3

In reaction scheme (B), the starting compound of formula [V] can be produced according to reaction scheme (A).

Compounds [VII] and [VIII] can be produced by reacting compound [V] with an ortho-acid ester of formula [VI]. According to the present reaction, a product such as any one of compound [VII] or [VIII] or a mixture of both compounds is obtained according to the kind of substrate [V] used, reaction conditions, and so on.

The present reaction can be carried out according to the method described in "Comprehensive Organic Chemistry", Pergamon Press (1985), page 108 or the modified methods.

The amount of the orthoacid ester [VI] used in the present reaction is not specifically limited, and a large amount in excess can be used as the solvent. The present reaction can also be carried out in the absence of a catalyst, but is preferably carried out in the presence of a suitable acid catalyst. The classes and amount of the acid catalyst are the same as those for the reaction of reaction scheme (A).

In reaction scheme (C), the reaction of [IX] [XI] can be carried out, for example, according to the method described in "The Chemistry of the Sulfenic Acids and their Derivatives", John Wiley &amp; Sons (1990 ), Chapter 10 or the modified methods.

The amount of the sulfenyl halide [X] used in the present reaction is not specifically limited, and is preferably about 0.8 to 2.5 equivalents. Good results are sometimes obtained by using a base during the reaction or before or after the reaction for the purpose of accelerating the reaction and reducing by-products. The classes and quantity of the base are the same as those for the reaction in reaction scheme (A).

The [XI] [XII] reaction can be carried out, for example, according to the method described in "Organic Functional Group Preparations", Second Edition, Academic Press (1983), Chapter 19 &amp; Chapter 20 or the modified methods.

Examples of the oxidizing agent used in the present reaction include hydrogen peroxide, ozone, peroacids (eg, m-chloro-perbenzoic acid), hydroperoxides (eg, t-butyl hydroperoxide), periodates (eg, sodium periodate). , halogens (eg chlorine, bromine), Nhaloamides (imide) (eg N-bromo-acetamide, N-chlorosuccinimide), etc. The amount of the oxidizing agent used in the present reaction is not specifically limited, and is preferably about 0.8 to 5 equivalents.

In reaction scheme (D), the reaction of [IX] [XIV] can be carried out, for example, according to the method described in "The Chemistry of Cyanates and their Derivatives", Part 1, John Wiley &amp; Sons ( 1997), Chapter 18 or the modified methods.

Examples of the halogenating agent used in the present reaction include chlorine, bromine, etc., preferably bromine.

The amount of the compound [XIII] and the halogenating agent used in the present reaction is not specifically limited, and is preferably about 0.8 to 5 equivalents.

In the [XIV] [XV] reaction, the disulfide [XV] can be obtained by the hydrolysis reaction of thiocyanate [XIV] and the automated oxidation reaction of the thiol that is obtained.

The hydroolysis used in the present reaction can be carried out, for example, according to the known acid hydroolysis, basic hydrolysis, neutral hydrolysis, etc. described in "Survey of Organic Syntheses", Volume 1 and Volume 2, Willey-Interscience (1970 and 1977) , "SHIN JIKKENHAGAKU KOZA (New Experimental Chemistry Handbook)", Maruzen Publishing Co, Ltd, Tokyo, Volume 14-III, page 1363 (1978), etc.

Examples of the acid used in the present reaction include inorganic acids such as hydrochloric acid, bromohydric acid, iodhydric acid, phosphoric acid, sulfuric acid, etc; and organic acids such as formic acid, acetic acid, trifluoro-acetic acid, p-toluene sulfoonic acid, etc.

Examples of bases used in the present invention include inorganic bases such as hi25

ES 2 187 751 T3 sodium hydrogen carbonate, potassium hydrogen carbonate, sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, calcium hydroxide, phenyllithium, butyllithium, sodium hydride, potassium hydride, methoxide sodium, sodium ethoxide, metallic sodium, metallic potassium, etc; and organic bases such as triethylamine, tributylamine, N, N-dimethylaniline, pyridine, lutidine, collidine, 4- (dimethylamino) pyridine, DBU (1,8-diazabicyclo [5.4.0] undecene- 7), etc

In the present reaction, the automatic oxidation proceeds, together with the previous hydroolysis reaction, without requiring any special operation. Good results are sometimes obtained by bubbling air or adding a weak oxidizing agent (eg iodine, etc.) for the purpose of accelerating the reaction.

The reaction of [XV] to [XVI] indicates a process of reacting the disulfide [XV] with the perfluoroalkyl radical generator represented by RfX⁴ o or RfSO2X⁵ in the presence of a radical initiator to produce perfluoroalkyl sulfide [XVI].

RfX Preferred Examples⁴ o or RfSO2X⁵ used in the present reaction include CF3Br, CF3CF2Br, CF3I, CF3SO2Cl, and the like. The amount used is not specifically limited, and is preferably about 0.8 to 5 equivalents.

Preferred examples of the radical initiator used in the present reaction include the organic radical generator such as benzoyl peroxide (BPO), azobisisobutyronitrile (AIBN), etc; and the inorganic radical generator such as Na2S2O4, SmI2, etc. The amount used is not specifically limited, and is preferably about 0.1 to 2.5 equivalents.

The reaction of [XVI] rá [XII] can be carried out according to the methods corresponding to the reaction of [XI] rá [XII] in reaction scheme (C).

In reaction scheme (E), the reaction of [XVII] to [XIX] can be carried out, for example, according to the method described in "Organic Functional Group Preparations", second edition, Volume II, Academic Press (1986 ), Chapter 12 or the modified methods.

The starting compound [XVII] used in the present reaction can be produced, for example, according to the method described in Japanese Unexamined Patent Publication No. 316771/1988, etc. or the modified methods.

The amount of compound [XVII] used in the present reaction is not specifically limited, and is preferably about 0.8 to 2.5 equivalents.

In reaction scheme (F), the reaction of [XX] to [XXI] can be carried out, for example, according to the method described in "Organic Functional Group Preparations", Second Edition, Volume I, Academic Press (1983 ), Chapter 11 or the modified methods.

The starting compound [XX] used in the present reaction can be produced, for example, according to the method described in Japanese Unexamined Patent Publication No.^° 316771/1988, etc or the modified methods.

In the present reaction, R "'is H or the group linked through C described above. When R "'is H, the reaction is preferably carried out in the presence of a suitable condensing agent. As the dehydration and condensation agent, for example, a known condensation agent such as dicyclohexyl-carbodiimide, carbonyl-diimidazole, thionyl chloride, etc. can be used.

The amount of the compound [XVIII] and that of the dehydrating and condensing agent used in the present reaction is not specifically limited, and is preferably about 0.8 to 2.5 equivalents.

The reaction of [XXI] to [XXII] can be carried out, for example, according to the method described in "Reagents for Organic Synthesis", John Wiley &amp; Sons (1967), page 868 or "Comprehensive Organic Chemistry", Volume 2 , Part 8, Pergamon Press (1979), page 469, etc. or the modified methods.

The amount of triphenyl phosphine or phosphorous pentachloride used in the present reaction is not specifically limited, and is preferably about 0.8 to 2.5 equivalents. The amount of carbon tetrachloride used in the present reaction is not specifically limited, and it is preferable26

ES 2 187 751 T3 less than 0.8 equivalent to a large excess amount. Carbon tetrachloride can be used as a solvent.

The reaction of [XXII] [XXIV] can be carried out, for example, according to the method described in "Comprehensive Organic Chemistry", Volume 2, Part 8, Pergamon Press (1979), page 474, etc. or the modified methods.

The amount of XH used in the present reaction is not specifically limited, and is preferably about 0.8 to 10 equivalents.

Good results are sometimes obtained by using a base during or before or after the reaction for the purpose of accelerating the reaction and reducing by-products. The classes and the amount of the base are the same as those for the reaction in reaction scheme (A).

In reaction scheme (G), the reaction of [XXV] [XXVII] can be carried out, for example, according to the method described in "Protective Groups in Organic Synthesis", John Wiley &amp; Sons (1982), page 147 oo the modified methods.

The amount of the compound [XXV] used in the present reaction is not specifically limited and a large excess amount of it can be used as the solvent. Preferably, it is about 0.8 to 10 equivalents.

The present reaction can also be carried out without a catalyst, but is preferably carried out in the presence of a suitable acid catalyst. The classes and the amount of the acid catalyst are the same as those for the reaction of reaction scheme (A).

The reactions of reaction schemes (H) and (I) can each be carried out according to the similar or modified methods of reaction scheme (B).

In reaction scheme (J), the reaction of [XXVIII] [XXX] can be carried out, for example, according to the method described in "Organic Functional Group Preparations", Second Edition, Volume III, Academic Press (1989) , Chapter 6 heard the modified methods.

The starting compound [XXVIII] can be prepared by the method described in reaction schemes (B) or (H).

The amines R²²NH2 used in the present invention are used for the reaction as such or in the form of a salt with the acid as mentioned hereinafter. The amount of the amines R²²NH2 used is not specifically limited and a large excess amount thereof can be used as the solvent. Preferably, it is about 0.8 to 5 equivalents.

In reaction schemes (K) and (L), the starting compounds [XXVIII] and [XXX] can be prepared, for example, according to the method described in reaction scheme (H) and in scheme of Reaction (J), respectively. The kinds and amount of the acid catalyst used in this reaction are the same as those for the reaction of reaction scheme (A).

In reaction scheme (M), compound [XXXIII] can be prepared by reacting compound [XXXII] with an acid anhydride of the formula: (R²³CO) 2O in which R²³ is as defined above or an acid chloride of formula R²³COCl in which R²³ It is as defined above. The amount of the acid anhydride and the acid chloride used in the present reaction is not specifically limited, and is preferably about 0.8 equivalent to a large excess amount. This can be used as a solvent.

Good results are sometimes obtained by using a base during the reaction or before or after the reaction for the purpose of accelerating the reaction and reducing by-products. The classes and the amount of the base are the same as those for the reaction in reaction scheme (A).

Reaction scheme (N) is a process for producing compound [XXXIV] by reacting compound [XXV] with a phosgene (or an equivalent thereof such as diphosgene or triphosgene). The amount of phosgene, diphosgene, or triphosgene used in the present reaction is not specifically limited, and is preferably about 0.8 equivalent to a large excess amount. Diphosgene can be used as a solvent.

ES 2 187 751 T3

Good results are sometimes obtained by using a base during the reaction or before or after the reaction for the purpose of accelerating the reaction and reducing by-products. The classes and quantity of the base are the same as those for the reaction in reaction scheme (A).

The reaction of the reaction scheme (O) can be carried out, for example, according to the method described in "Comprehensive Organic Chemistry", Pergamon Press (1984), Volume 5, paragraph 4.08, page 473 or or the modified methods.

The amount of ethylene diamine used in the present reaction is not specifically limited, and a large excess amount of it can be used as a solvent.

The present reaction can also be carried out without a catalyst, but is preferably carried out in the presence of a suitable acid catalyst. The classes and amount of the acid catalyst are the same as those for the reaction of reaction scheme (A).

In reaction scheme (P), the reaction of [XXXVI] [XXXVII] can be carried out according to methods similar or modified to those described in reaction scheme (A). When R²⁴ is H, compound [XXXVII] and compound [XXXVIII] obtained in the present reaction are tautoomers of each other, as shown in the formula, and can both take the structure of compound [XXXVII] and [XXXVIII].

In reaction scheme (Q), the reaction of [XXXIX] [XL] can be carried out according to methods similar or modified to those described in reaction scheme (B). The reaction of [XL]

[XLI] can be carried out according to the acid hydrolysis described in reaction scheme (K).

The reactions of reaction schemes (R), (S), (T) and (U) can be carried out according to the method described in reaction scheme (D).

The reducing agent used in the reaction of scheme (S) is not specifically limited. Preferably sodium borohydride is used for the reaction. The reactions of reaction schemes (V) and (W) can be carried out according to the methods described in reaction scheme (A) and (G), respectively.

The intermediate compounds [XXXVII], [XXXVIII], [XL], [XLI]. [XLII] and [XLIII] are new compounds. Each reaction from Reaction Scheme (B) to (W) can be carried out using a suitable solvent. Applicable solvents are the same as those used for reaction scheme (A).

The temperature used for each reaction in reaction schemes (B) to (W) is usually about -50 to 200 C, preferably about -30 to 150 C. The reaction time is usually about 0.1 to 72 hours, preferably about 0.1 to 24 hours.

Each compound obtained according to reaction schemes (B) to (W) can be supplied to the subsequent reaction after its isolation or purification by the same methods that are used for the reaction of reaction scheme (A) or as the reaction mixture.

A salt of the compound [I] of the present invention can be any agronomically acceptable salt. That is, when the compound [I] has an acid group such as a carboxyl group, a sulfo group, etc., in the molecule, the compound [I] can form a salt with a base. As the base, for example, inorganic bases such as alkali metal, for example sodium, potassium, and lithium can be used; of alkaline earth metal, for example calcium, and magnesium; ammonia and the like. and orgaonic bases such as pyridine, collidine, triethylamine, triethanolamine, and the like. Inorganic acid salts such as hydrochloric acid, bromhydric acid, iodhydric acid, phosphoric acid, sulfuric acid, perchloric acid and the like can also be used; and salts of orgaonic acids such as foormic acid, acetic acid, tartaric acid, maolic acid, choric acid, oxoalic acid, succonic acid, benzoic acid, potric acid, methanesulfonic acid, p-toluene sulphonic acid and p-toluene sulphonic acid. The compound can form an intramolecular salt and the case is also included in the present invention.

Compound [I] and its salts are effective in preventing horticultural or sanitary insect pests and animal and plant parasites and can exert potent insecticidal activities when applied to living animals or damaged plants. In addition, the compounds [I] and their salts have safety and advantageous properties as agents to prevent insects harmful to health,

ES 2 187 751 T3 horticulture or agriculture, such as no substantial damage to plants and less toxicity to fish.

The compound [I] and its salts can be used as an agricultural chemical, particularly insecticide in any form of application suitable for general purpose agricultural chemicals. That is, one, two, or more of two kinds of compound [I] or its salts are used in the form of preparation such as emulsifiable concentrates, liquid preparation, flowable concentrates, microemulsion, oil dissolution, wettable powders, fine powders , granules, fine granules, seed coatings, fumigation pesticides, microcapsules, tablets, sprays, EW, ointments, poisonous baits or the like, according to the purpose of their use, by dissolving or dispersing them in suitable liquid vehicles or mixing them with or adsorbing them on suitable solid vehicles. These formulations may contain, if necessary, emulsifying agent, suspending agent, dispersing agent, penetrating agent, wetting agent, thickening agent, stabilizer, etc., and can be prepared by any conventional method known per se, for example , mix of each ingredient.

Suitable examples of liquid carriers include solvents such as water, alcohols (eg, methanol, ethanol, n-propanol, iso-propanol, or ethylene glycol), ketones (eg, acetone or methyl ethyl ketone), ethers (eg dioxane, tetrahydrofuran, ethylene glycol monometallic ether, diethylene glycol monometallic ether, or propylene glycol monometallic ether), aliphatic hydrocarbons (eg benzene, toluene, xylene, solvent naphtha, or methyl solvent naphthalene), Halogenated hydrocarbons (for example, dichloromethane, chloroform, or carbon tetrachloride), acid amides (for example, N, N-dimethylformamide or N, N-dimethyl-acetamide), asters (for example, ethyl acetate, butyl acetate or fatty acid esters of glycerol) or nitriles (eg, acetonitrile or propionitrile). These solvents are used individually or as a mixture of two or more of them.

Suitable examples of saline carriers (diluents or powdered carrier) include vegetable powders (for example, soy flour, tobacco flour, finely ground wheat flour, or finely ground wood flour), mineral powders (for example, clays such as kaolin, bentonite, or acidic clay, talcs such as talcum powder or pyrophyllite powder), salices (eg, diatomaceous earth or mica powder), alumina, sulfur powder, or activated vegetable carbonate. They are used singly or as a suitable mixture of two, or more thereof.

Also, suitable examples of ointment bases include polyethylene glycol, pectin, polyol esters of higher aliphatic acids (eg, glycerin monostearate), cellulose derivatives (eg, methyl cellulose), sodium alginate, bentonite, higher alcohols, polyalcohols (eg, glycerin), petrolatum, white petrolatum, liquid paraffin, lard, various vegetable oils, lanolin, dehydrated lanolin, hydrogenated oil, or resins. They are used individually, or as a suitable mixture of two, or more, thereof or together with the surfactants mentioned below.

As surface active agents used as emulsifying agent, dispersing agent, penetrating agent or dispersing agent, non-ionic or anionic surface-active agents such as soaps are used, if necessary; polyoxyethylene alkyl aryl ethers (eg, Noigen® and EA 142® from Dai-ichi Kogyo Seiyaku KK, Japan, and Nonal® from Toho Chemical, Japan); alkyl sulfates (for example, Emal 10® and Emal 40® from Kao KK, Japan), alkyl sulphonates (for example, Neogen® and Neogen T® from Dai-ichi Kogyo Seiyaku, KK, and Neopellex® from Kao KK) ; polyethylene glycol esters (eg, Nonipol 85®, Nonipol 100®, Nonipol 160® from Sanyo Kasei KK, Japan); or polyhydric alcohol esters (eg, Tween 20® and Tween 80® from Kao KK).

Compound [I] or its salts can also be used, as the occasion demands, in combination with or as a mixture with other insecticides (for example, pyrethroid insecticides, organic phosphorus insecticides, carbamate insecticides or natural insecticides) , acaricides, nematicides, herbicides, plant hormones, plant growth regulators, fungicides (e.g. copper fungicides, organic chloride fungicides, organic sulfur fungicides or phenolic fungicides), synergistic agents, attracting agents, repellants, pigments and / or fertilizers.

The amount of the compound [I] or a salt thereof contained in an insecticidal composition of the present invention is suitably from about 0.1 to 80% by weight, preferably from about 1 to 20% by weight, relative to the overall composition. . For example, the amount is suitably about 1 to 80% by weight, preferably about 1 to 20% by weight in the case of emulsifiable concentrates, liquid preparations, or wettable powders.

ES 2 187 751 T3 (for example granulated wettable powders), from about 0.1 to 50% by weight, preferably from about 0.1 to 20% by weight in the case of dissolution in oil or powders, and from about 5 to 50% by weight, preferably from about 1 to 20% by weight in the case of granules.

The other active ingredients for agriculture (for example insecticides, herbicides, acaricides and / or fungicides) incorporated in the composition of the present invention can be used in an amount of about 1 to 80% by weight, preferably about 1 to 20% by weight. weight, with respect to the global composition.

The amount of each of the additives other than the active ingredients described above is usually in the range, which varies depending on the variety and content of the active ingredient for agriculture or the form of the composition, from usually about 0.001 to 99.9 % by weight, preferably about 1 to 99% by weight, relative to the overall composition. More specifically, the surfactant can be used in an amount of about 1 to 20% by weight, preferably about 1 to 15% by weight, the fluidizing agent in an amount of about 1 to 20% by weight, and the carrier in an amount of about 1 to 90% by weight, preferably about 1 to 70% by weight, based on the overall composition. For example, the surfactant can be used in an amount of about 1 to 20% by weight, preferably about 1 to 10% by weight, and water can be used in an amount of about 20 to 90% in the case of preparation. liquid. Emulsifiable concentrates, wettable powders (eg, granulated wettable powders), or the like can be suitably diluted or extended (eg, at about 100 to 5000 times) with water or the like, upon use, and thereafter. apply.

Topical examples of the insecticide, miticide and fungicide that can be used in admixture with the compound [I] or a salt thereof of the present invention are given below:

EPN, acephate, isoxathioon, isophenphos, isoprocarb, etrimphos, oxideprophos, quinalphos, cadusaphos, chlorethoxyphos, chlorpyrifos, chlorpyrifos-methyl, chlorophenvinphos, salitioon, cyanophos, disulfoton, dimethoate, sulprofuporomethiophos, thivinylphosinophos, nazimonophos, trichlorophosphos, thivinyl phosonphosinoles, vamidothioon, pyraclofos, pyridafenthioon, pyrimiphosmethyl, fenitrothioon, fenthioon, fentoate, fostiazato, butathiophos, protiophos, propahos, profenophos, fosalono, fostiazato, malathióon, methidathioon, metolcarb, Monochrome, BPMC, XMC, alanicarb, ethionfencarb, carbaryl, carbosulfóan, carbofuroan, xylylcarb, chloethocarb, thiodicarb, triazamate, pyrimicarb, fenoxycarb, phenothiocarb, furathiocarb, propoxur, bendiocarbotrine, cyclopyron- methomphurane, bendiocarbotrine, cyclo- pyrotron, acrylonitrine, cypermetron, cyyalotron, cyfluthron, cypermetron, silafluophen, teflutron, deltametron, tralometron, fenvalerate, fenpropattern, flucyitrinate, fluvalinate, flufeprox, fluproxygen, flumetron, praletron, beta-cypher benflutron, permetron, acetaprimid, imidacloprid, cartap, thiocyclam, nitenpyram, bensultap, avermectin, emamectin-benzoate, clofentezine, chlorfluazuroon, ziromazine, diafentiuroon, dienechloride, dichloroves, difluzubylphenroline, sulfuropyrazine, tertylpyrine pymetrozine, pyridaben, pyriproxyfen, pyrimidiphen, fipronil, fenazaquin, fenpyroximate, fluazuroon, flucycloxuron, flufenoxuron, buprofezin, hexaflumuroon, hexythiazox, milbemycin, methoxadiazone, lufenuroon, levamisole, AC-303, 630, NC-184, YI-5301, PPI, ampropylphos, ediphenphos, chlorthiophos, tolclofos-methyl, fosetyl, ipconazole, imazilyl, imibenconazole, etaconazole, epoxiconazole, diniciproconazole, difconazole, diniconazole tetraconazole, tebuconazole, triadimenol, triadimephoon, triticonazole, triforon, bitertanol, viniconazole, fenarimol, fembuconazole, fluotrimazole, furconazole-cis, flusilazole, flutriafol, bromuconazole, propiconazole, hexaconazole, pefurazoate, penconazole, penconazole myclobutanil, metconazole, cabendazin, debacarb, prothiocarb, benomyl, maneb, TPN, isoprothiolane, iprodione, iminoctadine-albesil, iminoctadine-triacetate, ethyrimol, etridiazole, oxadixyl, oxycarboxin, oacidine, oxolonic, chloxylazine, chloxylacetamine, oxolonic acid , cyprodinil, ciprofuroan, dietofencarb, diclofluanid, diclomezine, zineb, dimethyrimol, dimethomorph, dimefluazole, thiabendazole, thiophanate-methyl, thifluzamide, teclfthaloam, triazooxide, trichlamide, tricyclazole, tridemorph, triflumizole, validamicon A, hymexazole, pyracarbolid, pyrazophos, pyriphenox, pyrimethanil, pyroquiloon, ferimzone, fenpiclonil, fenpropidin, fenpropimorph, phthalide, furamepyr, furalaxyl, fluazinam, furconayl, fllanquinone, prochloximzone, flulanquinonide, furconayl, flulanquinonyl , probenazole, benalaxyl, benodanil, pencycuron, myclozolon, metalaxyl, metsulfovax, metfuroxam, mepanipyrim, mepronil, kresoxim, azoxystrobon, SSF-126, and carpropamid.

Specifically, the formulations containing the compound [I] or a salt thereof of the present invention are especially effective in the prevention of harmful hemiptera insects such as Eurydema rugosum, Scotinophara lurida, Riptortus clavatus, Stephanitis nashi, Laodelphas striatellus, Nilaparvata lucens , Nephotettix cincticeps, Unaspis vanonensis, Aphis glycines, Lipaphis erysimi, Brevicoryne brassicae, Aphis gossypii, Myzys persicae, Aulacorthum solani, Aphis spiraecola, Bemisia tabaci, Trialeurodes vaporariorum, Sogatella furcifera, Empoasca onukii, Pseudococcus comstocki, Planococcus citri, Icerva

ES 2 187 751 T3 purchasi, Plautia stali, Eysarcoris parvus; Dangerous Lepidopteran insects such as Spodoptera litura, Plutella xylostella, Pieris rapae crucivora, Chilo suppressalis, Autographa nigrisigna, Helicoverpa assulta, Pseudaletia separate, Mamestra brassicae, Adoxophyes orana fasciata, Notarcha derogata, Cnaeaphalocrothorcisory medullary, Cnaeaculecrothorcisoryus, Cnaeaculellacroysorcisory exigua, Agrotis segetum, Agrotis ipsilon, Heliothis armigera, Heliothis virescens, Heliothis zea, Naranga aenescens, Ostrinia nubilalis, Ostrinia furnacalis, Parnara guttata, Adoxophyes sp, Caloptilia theivora, Phyllonorycter ringoneella, Carposina niponensis, Grapholita molesta; Dangerous coleopteran insects such as Elilachna vigintioctopunctata, Aulacophora femoralis, Phyllotetra striotata, Oulema oryzae, Echinocnemus squameus, Lissorhoptrus oryzophilus, Anthonomus grandis, Callosobruchus chinensis, Sphenophorus venatica, Diapotillio spporotes, Diapporicum lineum venatus, Diappotillio spporotes, Diapporicum lineus venaticabri Anthrenus verbasci, Trivolium castaneum, Lyctus brunneus, Anoplophora malasiaca, Tomicus piniperda; Dangerous dipterous insects such as Musca domestica, Culex pipiens pallens, Tabanus trigonus, Delia ancient, Delia platura, Anopheles sinensis, Agromyza oryzae, Hydrellia griseola, Chlorops oryzae, Dacus cucurbitae, Ceratitis capitata, Liriomyza trifolii; harmful orthoptera insects such as Locusta migratoria, Gryllotalpa africana, Oxya yezoensis, Oxya japonica; harmful thysanoptera insects such as Thrips tabaci, Thrips parmi, Frankliniella occidentalis, Bariothrips biformis, Scirtothrips dorsalis; harmful hymenopteran insects such as Athalia rosae; harmful dictyopteran insects such as Blattella germanica, Periplaneta fuliginosa, Periplaneta japonica, Periplaneta americana; tetraniquidaes such as Tetranychus urticae, Panonychus citri, Tetranychus kanzawai, Tetranychus cinnabarinus, Panonychus ulmi, Aculops pelekassi, Polyphagotarsonemus latus, Rhizoglyphus echinopus; and nematodes such as Aphelenchoides besseyi, Meloidogyne incognita, Pratylenchus penetrans, Nothotylenchus acris; termites such as Coptotermes formosanus, Resticulitermes speratus, and Ondototermes formosanus.

The compound [I] or a salt thereof of the present invention can be used as an excellent insecticidal composition having excellent insecticidal effects, regularly low toxicity and good safety. It can be used in a similar way to the conventional insecticidal composition and can exert more excellent effects compared to the conventional composition. For example, the insecticidal composition of the present invention can be applied to the target insects, by seed treatment, nursery treatment, plantation hole treatment, plantation foot treatment, soil treatment, foliar spraying, fumigation, flooding. , and application with water in rice fields. The amount of application can vary widely depending on the season, location, and method of application, and so on. In general, the active ingredient (the compound [I] or a salt thereof) is used in general, in an amount of 0.3 g to 3000 g, preferably 50 g to 1000 g per hectare. When the insecticidal composition of the present invention is in a wettable powder, it can be used by diluting it to as much as 0.1-1000 ppm, preferably 10-500 ppm as the final concentration of the active ingredient.

Best way to carry out the invention

This invention is illustrated in further detail in the Examples.

Elution on a column chromatography in the Reference Examples and in the Examples was carried out while observing with TLC (Thin Layer Chromatography). In the TLC observation, the TLC plate used was Kieselgel ® 60F₂₅₄ manufactured by Merck Co. (70-230 mesh), the developing solvent was the same as that used for elution in column chromatography, and detection was carried out with a UV detector. The solid gel for column chromatography was Kieselgel 60 manufactured by Merck Co. (70-230 mesh). NMR spectra indicate¹H-NMR and were measured using tetramethylsilane as an internal standard with a Varian EM390 (90 MHz) or Brucker AC-200P (200 MHz) spectroometer and all δ values ​​are expressed in ppm. The value shown in () for a mixed solvent as the developing solvent is a mixing ratio by volume of the constituent solvents. The abbreviations used in the Examples, Reference Examples and Tables have the following meanings:

ES 2 187 751 T3

Me: methyl group

Et: ethyl group ph: phenyl group s: singlet br: width d: doublet t: triplet q: quartet m: multiplet dd: doublet of doublets

J: coupling constant

Hz: Hertz

DSMO-d6: deutero-dimethyl-sulfoxide%: percentage by weight

mp: melting point at room temperature means 15-25^°C

Reference example 1

5-amino-1 - (2,6-dichloro-4-trifluoromethylphenyl) -3-pyrazole-carboxamide oxime

5-amino-1 - (2,6-dichloro-4-trifluoromethylphenyl) -3-pyrazole (10.0 g, 31.1 mmol) was dissolved in 150 ml of dry dioxane, followed by hydroxylamine hydrochloride (3.35 g, 46.8 mmol) and triethylamine (6.6 ml, 47.4 mmol) was added with stirring at room temperature. The mixture was stirred at room temperature for 74 hours and the reaction solution was poured into 300 ml of ice water. The solution was stirred for 30 minutes and the deposited crystal was filtered. The resulting crystal was washed with water and then dried under reduced pressure to obtain 8.30 g (23.4 mmol) of the title compound as a colorless crystal. The aqueous layer obtained by combining the above filtrate and the washing was extracted three times with 150 ml of ethyl acetate. The extracted solution was washed three times with 500 ml of a saturated aqueous sodium chloride solution and the organic layer was dried over anhydrous magnesium sulfate. After its concentration under reduced pressure, the resulting crystal was washed with 50 ml of chloroform-hexane (1: 1) and then filtered to obtain 1.19 g (3.36 mmol) of the title compound as a crystal. pale brown. Yield 86%.

mp 235-238^°C (dec.)

NMR (DMSO - ύ₆, δ) 5.28 (2H, brs), 5.51 (2H, brs), 5.55 (1H, s), 8.12 (2H, s), 9.51 (1H, s)

Reference example 2

- (2,6-dichloro-4-trifluoromethylphenyl) -5-methoxymethylideneamino-3 - (1,2,4-oxadiazol-3-yl) pyrazole

5-Amino-1 - (2,6-dichloro-4-trifluoromethylphenyl) -3-pyrazole-carboxamide oxime (4.00 g, 11.3 mmol) and triethyl orthoformate (2.45 g, 22 , 6 mmol) in 40 ml of dry acetonitrile and then p-toluenesulfonic acid monohydrate (0.02 g) was added with stirring at room temperature. After the mixture was stirred at 60^°C for 6 hours, the mixture was cooled to room temperature. The reaction mixture was concentrated under reduced pressure and 50 ml of ethyl acetate was added to the concentrated residue. The orgaonic layer was washed twice with 50 ml of a saturated aqueous sodium chloride solution. The orgaonic layer was dried over anhydrous magnesium sulfate and then concentrated under reduced pressure. The resulting concentrated residue was subjected to solid gel column chromatography [eluent: mixed solvent of ethyl acetate and hexane (volume ratio = 1: 3)] to obtain 3.21 g (7.91 mmol) of the epigraph compound as pale yellow glass. Yield 70%.

mp 113-114^°C

NMR (CDCi₃, 5) 3.70 (3H, s), 6.70 (1H, s), 7.72 (2H, s), 8.19 (1H, s), 8.82 (1H, s)

ES 2 187 751 T3

Reference example 3

- amino-1 - (2,6-dichloro-4-trifluoromethylphenyl) -3 - (1,2,4-oxadiazol-3-yl) pyrazole

1 - (2,6-dichloro-4-trifluoromethylphenyl) -5-methoxymethylideneamino-3 - (1,2,4-oxadiazol-3-yl) pyrazole (2.80 g, 6.89 mmol) was dissolved in a solvent mixture of 50 ml of acetone and 5 ml of water, and then concentrated sulfonic acid (0.70 g, 6.92 mmol) was added with stirring at room temperature. The mixture was stirred at room temperature for 48 hours and the reaction solution was concentrated under reduced pressure. The pH of the residue was adjusted to about 8 by adding a saturated aqueous sodium hydrogen carbonate solution, followed by extraction three times with 30 ml of ethyl acetate. The organic layer was washed three times with 100 ml of water, dried over anhydrous magnesium sulfate and then concentrated under reduced pressure. The resulting concentrated residue was subjected to solid gel column chromatography [eluent: mixed solvent of ethyl acetate and hexane (volume ratio = 1: 2)] to obtain 1.96 g (5.40 mmol) of the epigraph compound as a colorless crystal. Yield 78.1%.

mp 197-198^°C

NMR (CDCi₃, 5) 3.78 (2H, brs), 6.30 (1H, s), 7.76 (2H, m), 8.77 (1H, s)

Reference example 4

- amino-1 - (2,6-dichloro-4-trifluoromethylphenyl) -3 - (1,2,4-oxadiazol-3-yl) -4-thiocyanate pyrazole

Potassium thiocyanate (1.45 g, 14.9 mmol) was dissolved in 20 ml of dry methanol, and then a methanol (5 ml) solution of bromine (0.28 ml, 5.44 mmol) was added dropwise. ) with agitation at -78^°C for 8 minutes (indoor temperature: no higher than -65^°C). After completion of the dropwise addition, the mixture was stirred at -78 ° C for 10 minutes and a methanol solution (15 ml) of 5-amino-1 - (2, 6-dichloro-4-trifluoromethylphenyl) -3 (1,2,4-oxadiazol-3-yl) pyrazole (1.80 g, 4.94 mmol). The solution was stirred at-78^°C for 2 hours, warmed to room temperature and then stirred at the same temperature for 2 hours. The reaction mixture was poured into 100 ml of ice water. After stirring for 30 minutes, the deposited crystal was filtered. The resulting crystal was washed with water and then dried under reduced pressure to obtain 2.04 g (4.85 mmol) of the title compound as a colorless crystal. Yield 98.0%.

mp 195-198^°C

NMR (CDCl₃, 5) 4.50 (2H, brs), 7.79 (2H, m), 8.87 (1H, s)

Reference example 5

Bis (5-amino-1 - (2,6-dichloro-4-trifluoromethylphenyl) -3 - (1,2,4-oxadiazol-3-yl) pyrazol-4-yl) disulfide

1.00 g (2.37 mmol) of 5-amino-1 - (2,6-dichloro-4-trifluoromethylphenyl) -3 - (1,2,4 oxadiazol-3-yl) -4-thiocyanate - pyrazole in 20 ml of dry methanol and then 210 g (5.00 mmol) of 90% sodium borohydride was added at 0 ° C. After the mixture was stirred at 0^°C for 3.5 hours, the reaction mixture was poured into 80 ml of ice water, and then the precipitate was collected by filtration. After drying under vacuum, the resulting yellow crystal was recrystallized from a mixed solvent of ethyl acetate-n-hexane to obtain 512 mg (0.55 mmol) of the title compound as a yellow crystal. Yield 55%.

mp 226-228^°C

NMR (DMSO, £) 6.18 (4H, brs), 8.15 (4H, m), 9.59 (2H, s)

Example 1

5-amino-1 - (2,6-dichloro-4-trifluoromethylphenyl) -4-methylsulfonyl-3-pyrazole-carboxamide oxime (Compound N^° 1-2)

ES 2 187 751 T3

5-amino-3-cyano-1 - (2,6-dichloro-4-trifluoromethylphenyl) -4-methylsulfonyl-pyrazole (500 mg, 1.3 mmol) and hydroxylamine hydrochloride (87 mg, 1.3 mmol) were dissolved ) in 5 ml of dioxane, and then triethylamine (130 mg, 1.3 mmol) was added at room temperature. After the mixture was stirred at room temperature for 5 hours, the reaction mixture was poured into 100 ml of ice water and extracted with 100 ml of ethyl acetate. The extract was dried over anhydrous magnesium sulfate and then concentrated to obtain 470 mg (1.1 mmol) of the title compound as a pale pink crystal. Efficiency 87%

mp 132-134 ° C

NMR (CDCls /) 3.45 (3H, s), 5.18 (2H, br), 5.32 (3H, br), 7.79 (2H, s)

Example 2

5-amino-1 - (2,6-dichloro-4-trifluoromethylphenyl) -4-trifluoromethylsulfinyl-3-pyrazole-carboxamide oxime (Compound N^° 1-4)

5-amino-3-cyano-1 - (2,6-dichloro-4-trifluoromethylphenyl) -4-trifluoromethylsulfinyl-pyrazole (500 mg, 1.1 mmol) and hydroxylamine hydrochloride (79 mg, 1.1 mmol) were dissolved ) in 5 ml of dioxane, and then triethylamine (115 mg, 1.1 mmol) was added at room temperature. After the mixture was stirred at room temperature for 6 hours, hydroxylamine hydrochloride (79 mg, 1.1 mmol) and triethylamine (115 mg, 1.1 mmol) were further added, followed by stirring at room temperature for 2 hours. The reaction mixture was poured into 100 ml of ice water and extracted with 100 ml of ethyl acetate. The extract was dried over anhydrous magnesium sulfate and then concentrated to obtain a brown oily substance. The oily substance was subjected to silica gel column chromatography [eluent: mixed solvent of n-hexane and ethyl acetate (volume ratio = 3: 1)] to obtain 340 mg (0.72 mmol) of the epigraph compound. like a colorless crystal. Yield 63%. mp 203-205^°C

NMR (CDCi₃, 5) 5.03 (2H, br), 5.20 (2H, br), 7.34 (1H, br), 7.82 (2H, s)

Example 3

5-amino-1 - (2,6-dichloro-4-trifluoromethylphenyl) -4-methylthio-3-pyrazole-carboxamide oxime (Compound N^° 1-1)

5-amino-3-cyano-1 - (2,6-dichloro-4-trifluoromethylphenyl) -4-methylthio-pyrazole (7.5 g, 20.4 mmol) and hydroxylamine hydrochloride (1.83 g, 25.5 mmol) in 75 ml of dioxane, and then triethylamine (2.5 g, 24.5 mmol) was added at room temperature. After the mixture was stirred at room temperature for 29 hours, hydroxylamine hydrochloride (720 mg, 10.1 mmol) and triethylamine (1.0 g, 10.2 mmol) were further added, followed by stirring at room temperature. environment for 22 hours. The reaction mixture was poured into 200 ml of ice water and extracted with 250 ml of ethyl acetate. The extract was dried over anhydrous magnesium sulfate and then concentrated to obtain a yellow crystal. The crystal was subjected to silica gel column chromatography [eluent: mixed solvent of n-hexane and chloroform (volume ratio = 1: 1)] to obtain 6.98 g (17.4 mmol) of the epigraph compound as a colorless crystal. Yield 85%.

mp 201-203^°C

NMR (DMSO, δ) 2.29 (3H, s), 5.29 (2H, br), 5.80 (2H, br), 8.12 (2H, s), 9.78 (1H, s)

Example 4

- (2,6-dichloro-4-trifluoromethylphenyl) -5-methoxymethylideneamino-4-methylthio-3 - (1,2,4-oxadiazol-3-yl) pyrazole (Compound N^° 2-1)

5-amino-1 - (2,6-dichloro-4-trifluoromethylphenyl) -4-methylthio-3-pyrazole-carboxamide oxime (1.77 g, 4.4 mmol) was dissolved in 25 ml of trimethyl orthoformate and then p-toluenesulfoonic acid monohydrate (130 mg) was added at room temperature. The mixture was heated under reflux for 2 hours. The trimethyl orthoformate was distilled off under reduced pressure and the

ES 2 187 751 T3 residue was dissolved in 60 ml of ethyl acetate. After the solution was washed with 120 ml of a saturated aqueous solution of sodium chloride and dried over anhydrous magnesium sulfate, the solvent was distilled off to obtain a yellow crystal which was washed with n-hexane to yield 1.47 g (3.3 mmol) of the title compound as a pale yellow crystal. Efficiency 74%

mp 119-121 ° C

NMR (deutero-acetone, δ) 2.41 (3H, s), 3.73 (3H, s), 7.99 (2H, s), 8.67 (1H, s), 9.42 (1H, s)

Example 5

- amino-1 - (2,6-dichloro-4-trifluoromethylphenyl) -3 - (N, N-dimethylamidino) -4-trifluoromethylsulfinyl-pyrazole (Compound N^° 1 - 36)

5-Amino-3-cyano-1 - (2,6-dichloro-4-trifluoromethylphenyl) -4-trifluoromethylsulfinyl pyrazole (0.97 g, 2.22 mmol) was dissolved in 10 ml of 1,4-dioxane and dimethylamine (50% aqueous solution) (1.20 ml, 11.4 mmol) was added, and then the sample was stirred at room temperature for 5 days. After stirring, 20 ml of water and 20 ml of a saturated aqueous sodium chloride solution were added and the solution was extracted twice with 30 ml of ethyl acetate. The extract was dried over anhydrous magnesium sulfate and the solvent was distilled off to obtain a yellow amorphous product. The amorphous product was subjected to solid gel column chromatography [eluent: mixed solvent of ethyl acetate and methanol (volume ratio = 4: 1)] and a small amount of ether was added to crystallize the resulting amorphous product. . This resulting product was filtered to obtain 0.29 g (0.60 mmol) of the title compound as a colorless crystal. Yield 27%.

mp 123-126^°C

NMR (CDCi₃, 5) 3.01 (6H, s), 5.21 (3H, br), 7.80 (2H, s)

Example 6

- amino-1 - (2,6-dichloro-4-trifluoromethylphenyl) -3 - (N-hydroxy-N-methylamidino) -4-trifluoromethylsulfinyl-pyrazole (Compound N^° 1 - 37)

5-amino-3-cyano-1 - (2,6-dichloro-4-trifluoromethylphenyl) -4-trifluoromethylsulfinyl-pyrazole (1.00 g, 2.29 mmol) was dissolved in 10 ml of 1,4-dioxane and N-methyl-hydroxylamine hydrochloride (0.38 g, 4.55 mmol) and triethylamine (0.65 ml, 4.68 mmol) were added, and then the mixture was stirred at room temperature for 3 hours. After 30 ml of water, 60 ml of ethyl acetate and 30 ml of a saturated aqueous sodium chloride solution were added, the reaction mixture was stirred and the ethyl acetate layer was separated. The ethyl acetate layer was washed twice with 50 ml of water and dried over anhydrous magnesium sulfate and the solvent was distilled off to obtain a crystal. This crystal was washed with chloroform and then recrystallized from ethanol-hexane to obtain 0.59 g (1.22 mmol) of the title compound as a colorless crystal. Yield 53%.

mp 187-191^°C

NMR (DMSO - ύ₆, δ) 3.38 (3H, s), 6.90-7.00 (4H, br), 8.21 (2H, s)

Example 7

- (2,6-dichloro-4-trifluoromethylphenyl) -5-methoxymethylideneamino-3 - (1,2,4-oxadiazol-3-yl) 4-trifluoromethylsulfinyl-pyrazole (Compound N^° 2 - 15)

5-amino-1 - (2,6-dichloro-4-trifluoromethylphenyl) -4-trifluoromethylsulfinyl-3-pyrazole-carboxamide oxime (1.81 g, 3.85 mmol) was dissolved in 25 ml of trimethyl orthoformate and p-toluenesulfoonic acid monohydrate (0.08 g) was added, and then the mixture was heated under reflux for 6 hours. After heating, the trimethyl orthoformate was distilled off and 80 ml of ethyl acetate was added to the residue. The ethyl acetate layer was washed three times with 50 ml of a saturated aqueous sodium hydrogen carbonate solution, and then washed with 50 ml of a saturated aqueous sodium chloride solution. After drying over anhydrous magnesium sulfate, the solvent is

ES 2 187 751 T3 was distilled off to obtain a colorless oil. The oil was subjected to solid gel column chromatography [eluent: mixed solvent of ethyl acetate and chloroform (volume ratio = 1:20)] and the resulting crystal was washed with hexane to obtain 1.03 g ( 1.97 mmol) of the title compound as a colorless crystal. Yield 51%.

mp 137-139 ° C

NMR (CDCi₃, 5) 3.71 (3H, s), 7.76 (2H, m), 8.62 (1H, s), 8.87 (1H, s)

Example 8

5-amino-1 - (2,6-dichloro-4-trifluoromethylphenyl) -4-trifluoromethylsulfonyl-3-pyrazole-carboxamide oxime (Compound N^° 1 - 29)

5-amino-3-cyano-1 - (2,6-dichloro-4-trifluoromethylphenyl) -4-trifluoromethylsulfonyl pyrazole (0.86 g, 1.90 mmol) was dissolved in 10 ml of 1,4-dioxane and Hydroxylamine hydrochloride (0.22 g, 3.17 mmol) and triethylamine (0.45 ml, 3.24 mmol) were added, and then the mixture was stirred at room temperature. Ten hours after stirring, hydroxylamine hydrochloride (0.08 g, 1.2 mmol) and triethylamine (0.14 ml, 1.01 mmol) were added again. After the addition was complete, the solution was stirred at room temperature for 23 hours. Thirty milliliters of water and 15 ml of a saturated aqueous sodium chloride solution were added, and then the reaction mixture was washed with 20 ml of a saturated aqueous sodium chloride solution and dried over anhydrous magnesium sulfate. The solvent was distilled off to obtain a colorless crystal. This crystal was washed with a mixed solvent of hexane-ethyl acetate (volume ratio = 1: 1) to obtain 0.82 g (1.68 mmol) of the title compound as a colorless crystal. Yield 89%.

mp 205 - 206^°C

NMR (DMSO - ύ₆, δ) 5.51 (2H, br), 7.28 (2H, br), 8.22 (2H, s), 9.91 (1H, s)

Example 9

- amino-1 - (2,6-dichloro-4-trifluoromethylphenyl) -3 - (1,2,4-oxadiazol-3-yl) -4-trifluoromethylsulfonyl-pyrazole (Compound N^° 2-7)

5-amino-1 - (2,6-dichloro-4-trifluoromethylphenyl) -4-trifluoromethylsulfonyl-3-pyrazole-carboxamide oxime (0.51 g, 1.87 mmol) was dissolved in 12 ml of trimethyl orthoformate and p-toluenesulfoonic acid monohydrate (0.05 g) was added, and then the mixture was heated under reflux for 1 hour. Trimethyl orthoformate was distilled off and 80 ml of ethyl acetate was added to the residue. The ethyl acetate layer was washed twice with 50 ml of a saturated aqueous sodium hydrogen carbonate solution, and then washed once with 50 ml of a saturated aqueous sodium chloride solution. After drying over anhydrous magnesium sulfate, the solvent was distilled off to obtain a colorless crystal. This crystal was washed with a hexane-chloroform mixed solvent (volume ratio = 2: 1) to obtain 0.86 g (1.73 mmol) of the title compound as a colorless crystal. Yield 93%.

mp 205-208^°C

NMR (DMSO - ύ₆, δ) 7.66 (2H, br), 8.26 (2H, s), 9.82 (1H, s)

Example 10

- (2,6-dichloro-4-trifluoromethylphenyl) -5-methoxymethylideneamino-3 - (1,2,4-oxadiazol-3-yl) 4-trifluoromethylsulfonyl-pyrazole (Compound N^° 2 - 16)

A 5-amino-1 - (2,6-dichloro-4-trifluoromethylphenyl) -3 - (1,2,4-oxadiazol-3-yl) -4-trifluoromethylsulfonyl-pyrazole (1.00 g, 2.02 mmol ) and 10 g of trimethyl orthoformate was added or p-toluene sulfoonic acid monohydrate (0.05 g) with stirring at room temperature. The mixture was stirred under heating under reflux for 59 hours. The reaction mixture was cooled to room temperature and then concentrated or under reduced pressure. The residue was dissolved in 50 ml of toluene and then concentrated under reduced pressure. After this procedure was repeated once again, the resulting concentrated residue was purified by subjecting it to column chromatography.

Solid gel ES 2 187 751 T3 [eluent: mixed solvent of ethyl acetate and chloroform (volume ratio = 1:20)]. The resulting crystal was washed with hexane and filtered to obtain 124 mg (0.46 mmol) of the title compound as a colorless crystal. Yield 23.0%

mp 157.5 - 158.5^°C

NMR (CDCl₃, 5) 3.79 (3H, d, J = 0.7 Hz), 7.77 (2H, m), 8.12 (2H, m), 8.89 (1H, s)

Example 11

- (2,6-dichloro-4-trifluoromethylphenyl) -5-dimethylaminomethylideneamino-3 - (1,2,4-oxadiazol-3 yl) -4-trifluoromethylsulfinyl-pyrazole (Compound N^° 2 - 19)

5-amino-1 - (2,6-dichloro-4-trifluoromethylphenyl) -3 - (1,2,4-oxadiazol-3-yl) -4-trifluoromethylsulfinyl-pyrazole (500 mg, 1.04 mmol) and N, N-dimethylformamide dimethyl acetal (90%) (280mg, 2.12mmol) in 20ml dry toluene. The suspension obtained was stirred with heating under reflux for 5 hours. The reaction mixture was cooled to room temperature and then concentrated under reduced pressure. The residue was dissolved in 50 ml of toluene and then concentrated again under reduced pressure. The resulting concentrated residue was purified by subjecting it to the preparative TLC with solid gel [developing solvent: mixed solvent of hexane and ethyl acetate (volume ratio = 3: 1)] to obtain 350 mg (0, 65 mmol) of the title compound as a colorless crystal. Yield 62.5%.

mp 140-140.5^°C

NMR (CDCl₃, 5) 2.81 (3H, s), 3.10 (3H, s), 7.68-7.75 (2H, m), 8.65 (1H, brs), 8.84 (1H, s )

Example 12

- (N-acetoxyamidino) -5-amino-1 - (2,6-dichloro-4-trifluoromethylphenyl) -4-trifluoromethylsulfinyl-pyrazole (Compound N^° 1 - 12)

5-amino-1 - (2,6-dichloro-4-trifluoromethylphenyl) -4-trifluoromethylsulfinyl 3-pyrazole-carboxamide oxime (0.50 g, 1.06 mmol) was dissolved in 8 ml of dichloroethane, and then Pyridine (0.10 ml, 1.2 mmol) was added and then acetyl chloride (99 mg, 1.26 mmol) dissolved in 2 ml of dichloroethane was added dropwise at room temperature. After the completion of the dropwise addition, the mixture was stirred at room temperature for 2 hours and the solvent was distilled off. To the resulting mixture, 50 ml of ethyl acetate was added, then 15 ml of water, and 15 ml of a saturated aqueous sodium chloride solution was added. The ethyl acetate layer was separated and washed once with 30 ml of 0.5N hydrochloric acid, and then washed three times with 30 ml of a saturated aqueous sodium chloride solution. After drying over anhydrous magnesium sulfate, the solvent was distilled off to obtain 0.54 g (1.06 mmol) of the title compound as a colorless amorphous product. Yield 99%.

NMR (DMSO - ύ₆, δ) 2.13 (3H, s), 6.74 (4H, br), 8.20 (2H, s)

Example 13

5-amino-1- (2,6-dichloro-4-trifluoromethylphenyl) -3- (5-oxo-4H-1,2,4-oxadiazolin-3-yl) 4-trifluoromethylsulfinyl-pyrazole (Compound N^° 4-1)

5-amino-1 - (2,6-dichloro-4-trifluoromethylphenyl) -4-trifluoromethylsulfinyl-3-pyrazole-carboxamide oxime (0.78 g, 1.66 mmol) was dissolved in 20 ml of toluene and 10 ml of THF, then triphosgene (0.25 g, 0.84 mmol) was added. The mixture was stirred at room temperature for 4 hours and after the completion of the reaction, 50 ml of ethyl acetate was added. The reaction solution was washed three times with 30 ml of a saturated aqueous sodium hydrogencarbonate solution and then washed twice with 30 ml of a saturated aqueous sodium chloride solution. After drying over anhydrous magnesium sulfate, the solvent was distilled off to obtain a yellow amorphous product. The amorphous product was subjected to solid gel column chromatography [eluent: mixed solvent of ethyl acetate and chloroform (volume ratio = 1: 1)] and the resulting amorphous product was crystallized by adding chloroform. The resulting crystal was washed with a mixed solvent of chloroform and ethyl acetate (= 10: 1) to obtain 304 mg (0.61 mmol) of the compound of the

ES 2 187 751 T3 epigraph as a colorless crystal. Yield 37%.

mp 270-273^°C

NMR (DMSO - ύ₆, δ) 7.06 (2H, br), 8.22 (2H, s), 13.22 (1H, br)

Example 14

- (2,6-dichloro-4-trifluoromethylphenyl) -5-hydroxyaminomethylideneamino-3 - (1,2,4-oxadiazol-3 yl) -4-trifluoromethylsulfinyl-pyrazole (Compound N^° 2 - 14)

To 1 - (2,6-dichloro-4-trifluoromethylphenyl) -5-methoxymethylideneamino-3 - (1,2,4-oxadiazol-3-yl) 4-trifluoromethylsulfinyl-pyrazole (720 mg, 1.38 mmol) were added hydroxylamine hydrochloride (240 mg, 3.45 mmol), dioxane (2.0 ml) and triethylamine (0.40 ml, 2.90 mmol), and then the mixture was stirred at room temperature. Five hours after stirring, triethylamine (0.4 ml, 2.90 mmol) and dioxane (1.0 ml) were added again, followed by stirring at room temperature for 66 hours. After 40 ml of ethyl acetate was added, the organic layer was washed three times with 30 ml of a saturated aqueous sodium chloride solution. After drying over anhydrous magnesium sulfate, the solvent was distilled off to obtain a pale yellow oil. The oil was purified by subjecting it to solid gel preparative TLC [developing solvent: mixed solvent of chloroform and ethyl acetate (volume ratio = 10: 1)] to obtain 284 mg (0.54 mmol) of the epigraph compound as a colorless crystal. Yield 55%.

mp 112-114^°C

NMR (CD₃CN ^) 6.57 (1H, br), 8.02-8.05 (2H, m), 8.60 (1H, br), 9.14 (1H, s), 9.20 (1H, br ).

Example 15

- (2,6-dichloro-4-trifluoromethylphenyl) -5-formylamino-3 - (1,2,4-oxadiazol-3-yl) -4-trifluoromethylsulfinyl-pyrazole (Compound N^° 2 - 21)

1 - (2,6-Dichloro-4-trifluoromethylphenyl) -5-hydroxyamino-methylideneamino-3 - (1,2,4 oxadiazol-3-yl) -4-trifluoromethylsulfinyl-pyrazole (3.50 g, 6.69 mmol) was dissolved ) in 30 ml of acetone and 1.2 N hydrochloric acid (12 ml, 14.4 mmol) was added, and then the mixture was stirred at room temperature for 3 days. After 20 ml of water had been added, the reaction mixture was neutralized with sodium hydrogen carbonate (powder). The solvent was distilled off and 20 ml of water and 100 ml of ethyl acetate were added, followed by partitioning. The aqueous layer was extracted with 10 ml of ethyl acetate and combined with the ethyl acetate layer, followed by washing with 50 ml of a saturated aqueous sodium chloride solution. After drying over anhydrous magnesium sulfate, the solvent was distilled off to obtain a yellow amorphous product. The amorphous product was subjected to solid gel column chromatography [eluent: mixed solvent of ethyl acetate and chloroform (volume ratio = 1:10)] to obtain 453 mg (0.89 mmol) of the title compound as a colorless crystal. Yield 13%.

mp 182-184^°C

NMR (CD₃CN ^) 7.94 (1H, s), 7.97 (1H, s), 8.14 (1H, br), 9.00 (1H, br), 9.16 (1H, br).

At the same time, 5-amino-1 - (2,6-dichloro-4-trifluoromethylphenyl) -3 - (1,2,4-oxadiazol-3-yl) -4-trifluoromethylsulfinyl-pyrazole (1.98 g , 4.12 mmol) by reaction. Yield 62%.

mp 200-202^°C

NMR (DMSO - ύ₆, δ) 6.98 (2H, br), 8.23 ​​(2H, s), 9.79 (1H, s) 12

Example 16

- amino-1 - (2,6-dichloro-4-trifluoromethylphenyl) -3 - (1,2,4-oxadiazol-3-yl) -4-trifluoromethylsulfinyl-pyrazole (Compound N^° 2-2)

ES 2 187 751 T3

1 - (2,6-dichloro-4-trifluoromethylphenyl) -5-methoxymethylideneamino-3 - (1,2,4-oxadiazol-3-yl) -4-trifluoromethylsulfinyl-pyrazole (151 mg, 0.29 mmol) will be dissolved in 5 ml of acetone and 1.2 N hydrochloric acid (0.12 ml, 0.14 mmol) was added, and then the mixture was stirred at room temperature. Seven hours after stirring, 1.2 N ^^ 0x ^ 03 acid (0.12 ml, 0.14 mmol) was added again, followed by stirring at room temperature for 3 days. In addition, 1.2 N hydrochloric acid (0.12 ml, 0.14 mmol) is added, followed by heating at 50 ° C and stirring for another 9 hours. After 5 ml of water and 2 ml of a saturated aqueous sodium hydrogen carbonate solution had been added, the acetone was distilled off and extracted with 40 ml of ethyl acetate. The ethyl acetate layer was washed twice with 30 ml of a saturated aqueous sodium chloride solution and dried over anhydrous magnesium sulfate. The solvent was distilled off to obtain 136 mg (0.29 mmol) of the title compound as a yellowish crystal.

mp 200-202 ° C.

NMR (DMSO - ύ₆, δ) 6.98 (2H, br), 8.23 ​​(2H, s), 9.79 (1H, s)

Example 17

- amino-1 - (2,6-dichloro-4-trifluoromethylphenyl) -3 - (4H-1,2,4-oxadiazolin-3-yl) -4-trifluoromethylsulfinyl-pyrazole (Compound No. 3-5)

5-amino-1 - (2,6-dichloro-4-trifluoromethylphenyl) -4-trifluoromethylsulfinyl-3-pyrazole-carboxamide oxime (1.00 g, 2.13 mmol) was dissolved in 10 ml of acetonitrile and An aqueous solution of formaldehyde (37%) (0.80 ml, 10.7 mmol) and five drops of acetic acid were added, and then the mixture was heated to 50 ° C and stirred for 9 hours. Then, 3 ml of acetonitrile, an aqueous solution of formaldehyde (37% aq) (0.80 ml, 10.7 mmol) and three drops of acetic acid were added again, followed by refluxing for 10 hours. The solvent is distilled off and 50 ml of ethyl acetate is added to the residue. The solution was washed twice with 30 ml of a saturated aqueous solution of sodium chloride, twice with a saturated aqueous solution of sodium hydrogen carbonate and then twice with 30 ml of a saturated aqueous solution of sodium chloride. After drying over anhydrous magnesium sulfate, the solvent was distilled off to obtain a colorless amorphous product. The colorless amorphous product was subjected to silica gel column chromatography [eluent: mixed solvent of ethyl acetate and hexane (volume ratio = 1: 2)] and the resulting crystal was washed with a mixed solvent of hexane and chloroform (volume ratio = 10: 1) to obtain 0.41 g (0.85 mmol) of the title compound as a colorless crystal. Yield 40%. mp 126-130 ° C

NMR (CDCls /) 5.01 (1H, br), 5.19 (2H, br), 5.43 (1H, sm), 5.47 (1H, s), 7.82 (2H, s)

Example 18

5- amino-1 - (2,6-dichloro-4-trifluoromethylphenyl) -3- (2-imidazolin-2-yl) -4-trifluoromethylsulfinyl-pyrazole (Compound N^° 3-1)

5-amino-3-cyano-1 - (2,6-dichloro-4-trifluoromethylphenyl) -4-trifluoromethylsulfinyl pyrazole (0.81 g, 1.85 mmol) was dissolved in 8 ml of THF, and then ethylene was added - diamine (0.40 ml, 5.98 mmol). The mixture was stirred at room temperature for 1 hour, warmed to 50^°C and then stirred for 24 hours. Ethylene diamine (0.40 ml, 5.98 mmol) and THF (3 ml) were then added again, followed by stirring for 14 hours. After the completion of the reaction, 20 ml of water was added and the THF was distilled off and, furthermore, 10 ml of water and 20 ml of a saturated aqueous sodium chloride solution were added. The mixture was extracted twice with 40 ml of ethyl acetate and the ethyl acetate layer was washed twice with 30 ml of a saturated aqueous sodium chloride solution. The product obtained is dried over anhydrous magnesium sulfate and then concentrated to obtain a yellow amorphous product. The yellow amorphous product was subjected to chromatography on a silica gel column [eluent: mixed solvent of ethyl acetate and hexane (ratio by volume = 1: 2)] to obtain 0.34 g (0.71 mmol) of the title compound. as a pale yellow amorphous product. Yield 38%.

NMR (CDCi₃, 5) 3.75 (4H, br), 5.22 (3H, br), 7.80 (2H, s)

ES 2 187 751 T3

Example 19

- amino-1 - (2,6-dichloro-4-trifluoromethylphenyl) -3 - (2,5-dihydro-2-methyl-1,2,4-oxadiazol 3-yl) -4-trifluoromethylsufinyl-pyrazole (Compound N^° 5 - 11)

5-amino-1 - (2,6-dichloro-4-trifluoromethylphenyl) -3 - (N-hydroxy-N-methylamidino) -4-trifluoromethylsulfinyl-pyrazole (1.00 g, 2.07 mmol) was dissolved in 10 ml of acetonitrile, and then 840 mg (10.3 mmol) of aqueous 37% formaldehyde solution and 5 drops of acetic acid were added. After the mixture was stirred at 50 ° for 5 hours, 840 mg (10.3 mmol) of 37% aqueous formaldehyde solution and 5 drops of acetic acid were added again, followed by stirring at 50^°C for 5 hours. The reaction mixture was concentrated under vacuum and ethyl acetate was added to the residual oil and then washed twice with a saturated aqueous solution of sodium hydrogencarbonate, and once with a saturated aqueous solution of sodium chloride. After drying over anhydrous magnesium sulfate, the solvent was distilled off. The resulting concentrated residue was purified by solid gel column chromatography [eluent: mixed solvent of ethyl acetate and n-hexane (volume ratio = 1: 2)] to obtain 260 mg (0.52 mmol) of the compound. of the epigraph as a colorless glass. Yield 25%

mp 165-167^°C

NMR (CDCl₃, 5) 3.31 (3H, s), 5.20 (2H, brs), 5.66 (2H, brs), 7.81 (2H, s)

Example 20

- (2,6-dichloro-4-trifluoromethylphenyl) -5-dimethylamino-3 - (1,2,4-oxadiazol-3-yl) -4-trifluoromethylsulfinyl-pyrazole (Compound N^° 2 - 32)

0.59 g (1.18 mmol) of 1- (2,6-dichloro-4-trifluoromethylphenyl) -5-dimethylamino-4-trifluoromethylsulfinyl-3-pyrazole-carboxamide oxime was dissolved in 5 ml of trimethyl orthoformate , and then 5 mg of p-toluenesulfonic acid monohydrate was added. After the mixture had been stirred at room temperature for 3 hours, the trimethyl orthoformate was distilled off under vacuum, and then 40 ml of ethyl acetate was added. The ethyl acetate solution was washed twice with 15 ml of saturated aqueous sodium hydrogen carbonate solution, and then once with 15 ml of saturated aqueous sodium chloride solution. After drying over anhydrous magnesium sulfate, the solvent was distilled off to obtain 583 mg (1.15 mmol) of the title compound as a colorless crystal. Yield 97%.

mp 82 - 84^°C

NMR (CDCl₃, 5) 2.87 (6H, s), 7.79 (2H, s), 8.86 (1H, s)

Example 21

- (2,6-dichloro-4-trifluoromethylphenyl) -5-methylamino-3 - (1,2,4-oxadiazol-3-yl) -4-trifluoromethylsulfonyl-pyrazole (Compound N^° 2 - 40)

500 mg (1.00 mmol) of 1- (2,6-dichloro-4-trifluoromethylphenyl) -5-methylamino-4-trifluoromethylsulfonyl-3-pyrazole-carboxamide oxime was dissolved in 5 ml of trimethyl orthoformate, and 5 mg of p-toluenesulfonic acid monohydrate was then added. After the mixture had been stirred at room temperature for 6 hours, the trimethyl orthoformate was distilled off under vacuum, and then 20 ml of ethyl acetate was added. The ethyl acetate solution was washed once with 30 ml of saturated aqueous sodium hydrogencarbonate solution, and followed four times with 30 ml of saturated aqueous sodium chloride solution. After drying over anhydrous magnesium sulfate, the solvent was distilled off. The resulting concentrated residue was purified by solid gel column chromatography [eluent: chloroform] to obtain 320 mg (0.63 mmol) of the title compound as a colorless crystal. Yield 63%. mp 156.5 - 157.5^°C

NMR (CDCl₃, 5) 2.63 (3H, d, J = 5.5Hz), 6.48 (1H, q, J = 5.5Hz), 7.78 (2H, s), 8.85 (1H, s)

ES 2 187 751 T3

Example 22

- amino-1 - (2,6-dichloro- 4-trifluoromethylphenyl) -3 - (1,2,4-oxadiazol-3-yl) -4-trifluoromethylsulfenyl-pyrazole (Compound No. 2-12)

1.00 g (1.27 mmol) of bis (5-amino 1 - (2,6-dichloro-4-trifluoromethylphenyl) -3 - (1,2,4-oxadiazole- 3-yl) pyrazol-4-yl, 10 ml of dry 1,4-dioxane, 0.41 ml (3.85 mmol) of trifluoromethanesulfonyl chloride and 0.21 g (1.25 mmol) of azobisisobutyronitrile, and then stirred at 120 C for 7 hours. After the reaction mixture was cooled to room temperature, it was concentrated under vacuum, and then 50 ml of ethyl acetate was added. The mixture was washed once with 50 ml of 1N aqueous hydrochloric acid solution, once with 50 ml of water, once with saturated aqueous sodium hydrogen carbonate solution, and then three times with 30 ml of saturated aqueous chloride solution. of sodium. After drying over anhydrous magnesium sulfate, the solvent was distilled off. The resulting concentrated residue was purified by solid gel column chromatography [eluent: mixed solvent of ethyl acetate and n-hexane (volume ratio = 1: 2]) to obtain 83 mg (0.18 mmol) of the compound of the epigraph as a red crystal Yield 7%.

mp 190-192 ° C

NMR (CDCi₃, 5) 4.42 (2H, br), 7.79 (2H, s), 8.83 (1H, s)

Examples of the present compounds obtained according to the same manner as described in Examples 1 to 22 are shown in Tables 1 to 13 below, together with the compounds obtained in the above Examples.

(See Tables on the following pages)

ES 2 187 751 T3

TABLE 1

<img file="ES2187751T3_D0040.tif" />

ES 2 187 751 T3

TABLE 2

<img file="ES2187751T3_D0041.tif" />

S (0) „R^and ri

<td>Compound N^:</td><td>R⁶</td><td>R</td><td>X</td><td>Y</td><td>n</td><td>Pf-CC)</td>

<td> 1-17</td><td>CF_:</td><td>NH;</td><td>NH;</td><td>NH;</td><td> 2</td><td></td>

<td> 1-18</td><td>Γ * Γ * f 2</td><td>NH;</td><td>NH;</td><td>NHMe</td><td> 2</td><td></td>

<td>1 -1 c Λ. Λ. OR</td><td>C;</td><td>NH;</td><td>NH;</td><td>NMe_:</td><td> 2</td><td></td>

<td> 1-20</td><td>CF;</td><td>NH;</td><td>NH;</td><td>NHCOMe</td><td> 2</td><td></td>

<td> 1-21</td><td>CF;</td><td>NH;</td><td>NH;</td><td>NMeCOMe</td><td> 2</td><td></td>

<td> 1-22</td><td>CF;</td><td>NH;</td><td>NH;</td><td>NHCO; Et</td><td> 2</td><td></td>

<td> 1-23</td><td>CF;</td><td>NH;</td><td>NH;</td><td>OMe</td><td> 9</td><td></td>

<td> 1-24</td><td>CF;</td><td>NH;</td><td>NH;</td><td>OCOMe</td><td> 2</td><td></td>

<td> 1-25</td><td>CF;</td><td>NH;</td><td>NHCOMe</td><td>OMe</td><td> 2</td><td></td>

<td> 1-25</td><td>CF;</td><td>NHCOMe</td><td>NHCOMe</td><td>0 M e</td><td> 2</td><td></td>

<td> 1-27</td><td>CF;</td><td>NH;</td><td>NHMe</td><td>OMe</td><td> 2</td><td></td>

<td> 1-28</td><td>CF;</td><td>NHMe</td><td>NHMe</td><td>OM e</td><td> 2</td><td></td>

<td> 1-29</td><td>CF;</td><td>NH;</td><td>NH;</td><td>Oh</td><td> 2</td><td> 205-206</td>

<td> 1-30</td><td>CF;</td><td>NH;</td><td>NH;</td><td>Oh</td><td> 0</td><td> 185-187</td>

<td> 1-31</td><td>CF;</td><td>NH;</td><td>NH;</td><td>OCO? Me</td><td> 1</td><td>(amorphous)^:</td>

<td> 1-32</td><td>CF;</td><td>NH;</td><td>NH;</td><td>OCO - ^ - Bu</td><td> * 1</td><td>(amorphous) '</td>

<td> 1-33</td><td>CF;</td><td>NH;</td><td>NH;</td><td>^OCOXg&gt;</td><td> 1</td><td> 137-141</td>

<td> 1-34</td><td>CF;</td><td>NH;</td><td>NH;</td><td>OCH (OMe)</td><td> 2 1</td><td> 175-177</td>

<td> 1-35</td><td>CF;</td><td>NH;</td><td>NH;</td><td>I</td><td> 1</td><td> 221-223</td>

<td> 1-36</td><td>CF;</td><td>NH;</td><td>NMe_:</td><td>H</td><td> 1</td><td> 123-126</td>

<td> 1-37</td><td>CF;</td><td>NH;</td><td>N (OH) YES!</td><td>and H</td><td> 1</td><td> 187-191</td>

) NMR (DMSO.

¿) 3. 7S (3H.s), 6.

¿) 1. 33 (93.s). 6. 7. 52Í2H. d. J = 8. 2.19 (2H. S)

73C4E. br ;. 8. 20 (2H.s; 74 (2H. Br ,. 6. 91C2H. Br), 4Hz), 2. I-H2H. d. J = 8.4Kz ;.

co

ES 2 187 751 T3

TABLE 3

<img file="ES2187751T3_D0042.tif" />

ES 2 187 751 T3

TABLE 4

<img file="ES2187751T3_D0043.tif" />

cr 3

<td>Compound N-</td><td>R⁶</td><td>R</td><td>X</td><td>Y</td><td>n</td><td>P-^FC'C)</td>

<td> 1-61</td><td>CF</td><td>NEt:</td><td>NH;</td><td>Oh</td><td> 2</td><td> 88-91</td>

<td> 1-62</td><td>CF_:</td><td>NHPr</td><td>NH;</td><td>Oh</td><td> 2</td><td></td>

<td> 1-63</td><td>CF-</td><td>NPr · '-</td><td>NH;</td><td>Oh</td><td>OR</td><td></td>

<td> 1-64</td><td>CF-</td><td>NHPr-</td><td>NH;</td><td>Oh</td><td> 2</td><td></td>

<td> 1-65</td><td>CF-</td><td>NHCH₂Ph</td><td>NH;</td><td>Oh</td><td> 2</td><td></td>

<td> 1-66</td><td>CF:</td><td>N (CH₂Ph)₂</td><td>NH;</td><td>Oh</td><td> 2</td><td></td>

<td> 1-67</td><td>CF:</td><td>NH:</td><td>N (OH) iie</td><td>H</td><td> 0</td><td> 165-166</td>

<td> 1-68</td><td>CF:</td><td>NHÜe</td><td>N (OH) Ue</td><td>H</td><td> 0</td><td></td>

<td> 1-68</td><td>CF:</td><td>NMe₃</td><td>N (0H) Me</td><td>H</td><td> 0</td><td> 190-192</td>

<td> 1-70</td><td>CF:</td><td>NHEt</td><td>N (0H) iie</td><td>H</td><td> 0</td><td> 127-128</td>

<td> 1-71</td><td>CF:</td><td>NEt ₂</td><td>N (0H) Me</td><td>H</td><td> 0</td><td> 177-178</td>

<td>* no i- i ¿</td><td>CF;</td><td>NHPr</td><td>N (0H) line</td><td>H</td><td> 0</td><td></td>

<td> 1-73</td><td>CF:</td><td>NPr ₂</td><td>N (0H) Me</td><td>H</td><td> 0</td><td></td>

<td> 1-74</td><td>cf₃</td><td>NHPr¹</td><td>N (OH) Me</td><td>H</td><td> 0</td><td></td>

<td> 1-75</td><td>cf₃</td><td>NKCHjPh</td><td>N (OH) lle</td><td>H</td><td> 0</td><td></td>

<td> 1-76</td><td>cf₃</td><td>N (CH₂Ph)_z</td><td>N (0H) tie</td><td>H</td><td> 0</td><td></td>

<td> 1-77</td><td>CF:</td><td>Nfflle</td><td>N (OH) Me</td><td>H</td><td> 1</td><td></td>

<td> 1-78</td><td>CF:</td><td>NMe₂</td><td>N (0H) He</td><td>H</td><td> 1</td><td> 156-162</td>

<td> 1-79</td><td>cf₃</td><td>NHEt</td><td>N (0H) line</td><td>H</td><td> 1</td><td> 220-227</td>

<td> 1-80</td><td>cf₃</td><td>NEt ₂</td><td>N (OH) line</td><td>H</td><td> 1</td><td> 178-181</td>

<td> 1-81</td><td>cf₃</td><td>NHPr</td><td>N (OH) Me</td><td>H</td><td> 1</td><td></td>

<td> 1-82</td><td>cf₃</td><td>NPr ₂</td><td>N (OH) He</td><td>H</td><td> 1</td><td></td>

<td> 1-83</td><td>CF:</td><td>NHPr¹</td><td>N (0H) Se</td><td>H</td><td> 1</td><td> 154-156</td>

ES 2 187 751 T3

TABLE 5

<img file="ES2187751T3_D0044.tif" />

CF₃

<td>Compound N^B</td><td>R⁶</td><td colspan="2">RX</td><td>Y</td><td>n</td><td>mp (° C)</td>

<td> 1-84</td><td>CF-</td><td>NHCH₂Ph</td><td>NCOH) Me</td><td>H</td><td> 1</td><td></td>

<td> 1-35</td><td>cf₃</td><td>NCClhPh ;;</td><td>NCOH) Me</td><td>H</td><td> 1</td><td> £1-84</td>

<td> 1-35</td><td>CF τ</td><td>vw.</td><td>v, 'ninu.-, • '\ &lt;-J ti / -</td><td>Lj i i.</td><td>Λ</td><td> 1^Λ'ΟΠ i V a. X Ú</td>

<td> 1-87</td><td>CF</td><td>NHMe</td><td>NCOIDMe</td><td>or eleven</td><td> 0</td><td></td>

<td> 1-88</td><td>CF_;</td><td>NMe ₂</td><td>N (OH) Me</td><td>H</td><td> 2</td><td></td>

<td> 1-89</td><td>CF</td><td>NHEt</td><td>NCQH) Me</td><td>H</td><td>or</td><td> 96-97</td>

<td> 1-90</td><td>CF;</td><td>NEt 2</td><td>N (OH) Me</td><td>H</td><td> 2</td><td> 166-167</td>

<td> 1-91</td><td>CF:</td><td>NHPr</td><td>N (OE) Me</td><td>H</td><td> 2</td><td></td>

<td> 1-92</td><td>CF;</td><td>NPrⁿ2</td><td>NCOIDMe</td><td>H</td><td> 2</td><td></td>

<td> 1-93</td><td>CF;</td><td>NHPr '</td><td>N (OH) Me</td><td>H</td><td> 2</td><td></td>

<td> 1-94</td><td>CF;</td><td>NHCH₂Ph</td><td>N (OH) Me</td><td>H</td><td>or</td><td></td>

<td> 1-95</td><td>CF;</td><td>N (CE₂Ph;₂</td><td>NiOH) Me</td><td>H 0 Ί</td><td> 2</td><td></td>

<td> 1-96</td><td>cf₃</td><td>nh₂</td><td>NH;</td><td>OCNHEt 0</td><td> 1</td><td> 211-215</td>

<td> 1-97</td><td>CF;</td><td>NH;</td><td>NH;</td><td>j | OCCH₂C1 0 !!</td><td> 1</td><td> 196-197</td>

<td> 1-98</td><td>CF;</td><td>NH;</td><td>NH;</td><td>OCNMe;</td><td> 1</td><td>(amorphous)^4:</td>

<td> 1-99</td><td>CF;</td><td>NHCONHEt</td><td>NH;</td><td>Oh</td><td> 1</td><td> 196-198</td>

<td> 1-100</td><td>CF;</td><td>NHCOPh</td><td>NH;</td><td>Oh</td><td>OR</td><td> 152-154</td>

<td> 1-101</td><td>cf₃</td><td>NHCOPh</td><td>NH;</td><td>Oh</td><td> 1</td><td> 219-221</td>

<td colspan="2">41 NMR (DMSO. ¿) 2.</td><td>98C6H. s).</td><td>5. 20C2H.</td><td>br). 5.43</td><td colspan="2">C2H.br). 7. 80C2H. s&gt;</td>

ES 2 187 751 T3

TABLE 6

<img file="ES2187751T3_D0045.tif" />

<td colspan="2">Compound N^c R6</td><td>R</td><td>J</td><td>R¹⁷</td><td>n</td><td>mp CC)</td>

<td> 2- 1</td><td>I</td><td>\ = Cñ ~~ OMe</td><td> 0</td><td>H</td><td> 0</td><td> 119-121</td>

<td> 2- 2</td><td>CF 2</td><td>\ h₂</td><td> 0</td><td>H</td><td></td><td> 200-202</td>

<td>η π 0</td><td>CF 3</td><td>NH:</td><td> 0</td><td>I</td><td>i</td><td>λλ ·, -or</td>

<td> 2- 4</td><td>CF₃</td><td>\ h₂</td><td>NH</td><td>H</td><td> 1</td><td> 282-284</td>

<td> 2- 5</td><td>cf₃</td><td>NH:</td><td>NH</td><td>I</td><td> 1</td><td></td>

<td> 2- 6</td><td>cf₃</td><td>nh₂</td><td>NM e</td><td>I</td><td> 1</td><td></td>

<td> 2- 7</td><td>cf₃</td><td>nh₂</td><td> 0</td><td>H</td><td> 2</td><td> 205-208</td>

<td> 2- 8</td><td>cf₃</td><td>nh₂</td><td> 0</td><td>I</td><td> 2</td><td></td>

<td> 2- 9</td><td>cf₃</td><td>nh₂</td><td>NH</td><td>H</td><td> 2</td><td></td>

<td> 2-10</td><td>cf₃</td><td>nh₂</td><td>NH</td><td>I</td><td> 9</td><td></td>

<td> 2-11</td><td>cf₃</td><td>NH:</td><td>NMe</td><td>I</td><td> 2</td><td></td>

<td> 2-12</td><td>cf₃</td><td>NH ₂</td><td> 0</td><td>H</td><td> 0</td><td> 190-192</td>

<td> 2-13</td><td>cf₃</td><td>N = Cfi — ΝΗΟΠ</td><td> 0</td><td>H</td><td> 0</td><td> 171-174</td>

<td> 2-14</td><td>cf₃</td><td>N = CH ~ NH0H</td><td> 0</td><td>H</td><td> 1</td><td> 112-114</td>

<td> 2-15</td><td>cf₃</td><td>N = CB * ~ OMe</td><td> 0</td><td>H</td><td> 1</td><td> 137-139</td>

<td> 2-16</td><td>cf₃</td><td>N = CB — OMe</td><td> 0</td><td>H</td><td> 9</td><td>it/. or^--the. or</td>

<td> 2-17</td><td>cf₃</td><td>N = CH * ~ OMe</td><td> 0</td><td>H</td><td> 0</td><td> 119-121</td>

<td> 2-18</td><td>cf₃</td><td>N = CH — NHMe</td><td> 0</td><td>H</td><td> 1</td><td> 220-221</td>

<td> 2-19</td><td>cf₃</td><td>N = CH ~~ NMe₂</td><td> 0</td><td>H</td><td> 1</td><td> 140-140.5</td>

<td> 2-20</td><td>cf₃</td><td>NHCHO</td><td> 0</td><td>H</td><td> 0</td><td> 147-149</td>

<td>9-91 Ul</td><td>cf₃</td><td>NHCHO</td><td> 0</td><td>H</td><td> 1</td><td> 182-184</td>

co to to co co to

ES 2 187 751 T3

TABLE 7

<img file="ES2187751T3_D0046.tif" />

ES 2 187 751 T3

TABLE 8

JN

<img file="ES2187751T3_D0047.tif" />

CFa

<td>n position N²</td><td>R®</td><td>R</td><td>J</td><td>R¹⁷</td><td>n</td><td>Pf (»c)</td>

<td> 2-46</td><td>cf₃</td><td>NHPr '</td><td> 0</td><td>H</td><td> 2</td><td></td>

<td> 2-47</td><td>CF;</td><td>NHCHjPh</td><td> 0</td><td>H</td><td> 2</td><td></td>

<td>9-TtC - -te</td><td>cf₂</td><td>N (C3 «Ph)₂</td><td> 0</td><td>H</td><td> 2</td><td></td>

<td> 2-4£</td><td>cf₃</td><td>NHAc</td><td> 0</td><td>H</td><td> 2</td><td> 163-164</td>

<td> 2-50</td><td>CFa</td><td>NSAc</td><td>n</td><td>or A Λ</td><td>1 J.</td><td> 'l _í 7 * 3</td>

<td> 2-51</td><td>CFa</td><td>ÑECOzMe</td><td> 0</td><td>H</td><td> 2</td><td> 170-174</td>

<td> 2-52</td><td>cf₃</td><td>N = CH — OEt</td><td> 0</td><td>H</td><td> 1</td><td> 88-90</td>

<td> 2-53</td><td>cf₃</td><td>j \ = CH «~ OEt</td><td> 0</td><td>H</td><td> 2</td><td> 104-105</td>

<td> 2-54</td><td>cf₃</td><td>NECOíUe</td><td> 0</td><td>H</td><td> 1</td><td> 145-147</td>

<td> 2-55</td><td>cf₃</td><td>_{N =}/I</td><td> 0</td><td>H</td><td> 1</td><td> 108-109</td>

<td> 2-55</td><td>cf₃</td><td>, OMe N = C3 — OG</td><td> 0</td><td>H</td><td> 0</td><td>(amorphous)^:</td>

<td> 2-57</td><td>cf₃</td><td>NHCONHEt</td><td> 0</td><td>H</td><td> 1</td><td> 166-168</td>

<td> 2-58</td><td>cf₃</td><td>NHCOPh</td><td> 0</td><td>K</td><td> 2</td><td> 202-204</td>

<td> 2-59</td><td>cf₃</td><td>N = CH — OEt</td><td> 0</td><td>H</td><td> 0</td><td> 90-91.5</td>

<td> 2-50</td><td>cf₃</td><td>NHAc</td><td> 0</td><td>H</td><td> 0</td><td>(amorphous)¹</td>

<td>2-6 i</td><td>cf₃</td><td>NHCOPh</td><td> 0</td><td>H</td><td> 1</td><td> 199-202</td>

<td> 2-62</td><td>cf₃</td><td>, OHe N = CH — O OH</td><td> 0</td><td>H</td><td> 1</td><td>(amorphous)</td>

5) NMR: cDCy₃. ¿) 3. S9C3H. s), 6.17C1H. s), 6. 98C1H. d. J = 7. 9Hz). 7.30

7. 37 (2H. M). 7. 74 (23. S). 8. 88 (13. S). 8. 96 (1H. S)

6) nmr (CDC1₃. or) 2.13C3H. s). 7. 30dH.br). 7. 75 (23. S). 8.88 (lH.s)

7) nmr (CDC1₃. or) 3. 22 (33. s). 6. 35ClH.br). 5. 94 (13. D. J = 3.2Hz). 7.22 (1H. D. J = 1.8Bz). 7. 34 (111. Dd. J = l. 8Hz. £. 2Hz). 7 737. 75 (IH. M), 7. 78-7. 80 (13. M;

ES 2 187 751 T3

TABLE 9

<img file="ES2187751T3_D0048.tif" />

S (Oi_nR^and

<td>tax</td><td>N^s R⁶</td><td>R¹⁵</td><td>R</td><td> 2</td><td>L</td><td>n</td><td>mp (° C)</td>

<td> 3- 1</td><td>C Fi</td><td>H</td><td>NH:</td><td>NH</td><td>ch₂</td><td> 1</td><td>(amorphous) ^H</td>

<td> 3- 2</td><td>CF_:</td><td>H</td><td>NH:</td><td>NH</td><td>CH₂CH:&gt;</td><td> 1</td><td></td>

<td>η Π 0 u</td><td>CF;</td><td>H</td><td>NH:</td><td>NH</td><td>AC ₂</td><td> 2</td><td></td>

<td> 3- 4</td><td>C Fi</td><td>H</td><td>NH:</td><td>NH</td><td>CH₂CH:</td><td> 2</td><td></td>

<td> 3- 5</td><td>CF:</td><td>H</td><td>NH:</td><td>NH</td><td> 0</td><td> 1</td><td> 126-130</td>

<td> 3- 6</td><td>CF:</td><td>I</td><td>NH:</td><td>NH</td><td> 0</td><td> 1</td><td>(amorphous)⁵</td>

<td> 3- 7</td><td>CF:</td><td>THE</td><td>NH:</td><td>NH</td><td> 0</td><td> 1</td><td>(amorphous)^10&gt;</td>

<td> 3- 8</td><td>CF:</td><td>H</td><td>nh₂</td><td>NH</td><td> 0</td><td> 0</td><td> 178-179</td>

<td> 3- 9</td><td>CF:</td><td>H</td><td>NHMe</td><td>NH</td><td> 0</td><td> 0</td><td></td>

<td> 3-10</td><td>CF:</td><td>H</td><td>NMe:</td><td>NH</td><td> 0</td><td> 0</td><td></td>

<td> 3-11</td><td>CF:</td><td>H</td><td>NHEt</td><td>NH</td><td> 0</td><td> 0</td><td></td>

<td> 3-12</td><td>CF:</td><td>H</td><td>NEt₂</td><td>NH</td><td> 0</td><td> 0</td><td></td>

<td> 3-13</td><td>CF-</td><td>H</td><td>NHPr</td><td>NH</td><td> 0</td><td> 0</td><td></td>

<td> 3-14</td><td>CF:</td><td>H</td><td>NPr:</td><td>NH</td><td> 0</td><td> 0</td><td></td>

<td> 3-15</td><td>CF:</td><td>H</td><td>NHPr '</td><td>NH</td><td> 0</td><td> 0</td><td></td>

<td> 3-16</td><td>CF,</td><td>H</td><td>NHCH₂Ph</td><td>NH</td><td> 0</td><td> 0</td><td></td>

<td> 3-17</td><td>CF:</td><td>H</td><td>N (CH, Ph)₂</td><td>NH</td><td> 0</td><td> 0</td><td></td>

9) NMR (DMSO, o ') 1.52 and 1.54 (3H. D + d. J = 5.1Hz). 5. OOClH.br). 5. lg mixture (2E.br), 5. 83 (quinr. J = 5.1Hz. 1H), 7. 8l (s. 2H) diastereoisomers

10) nmr (DMSO. 0. 95-1. 05C3H. Ε). 1. 72-1. 83C2H, t). 5. O (1H. Br ;.

mixture 5. 22C2H. br ?, 5. 64 (1H. q. J = 5. OHz), 7. SK2H. s;

diastereoisomers

ES 2 187 751 T3

TABLE 10

<img file="ES2187751T3_D0049.tif" />

C Fa

<td>Compound</td><td>n^and r «</td><td>R '^s</td><td>R</td><td>Z</td><td>L</td><td>n</td><td></td>

<td> 3-18</td><td>cf₃</td><td>H</td><td>NHMe</td><td>NH</td><td> 0</td><td> 1</td><td></td>

<td> 3-19</td><td>CF₃</td><td>H</td><td>NMe_:</td><td>NH</td><td> 0</td><td> 1</td><td></td>

<td> 3-20</td><td>CF₃</td><td>H</td><td>NHEt</td><td>NH</td><td> 0</td><td> 1</td><td></td>

<td> 3-21</td><td>cf₃</td><td>H</td><td>NEt₂</td><td>NH</td><td> 0</td><td> 1</td><td></td>

<td> 3-22</td><td>cf₃</td><td>H</td><td>NHPr</td><td>NH</td><td> 0</td><td> 1</td><td></td>

<td> 3-23</td><td>cf₃</td><td>H</td><td>NPr₂</td><td>NH</td><td> 0</td><td> 1</td><td></td>

<td> 3-24</td><td>cf₃</td><td>H</td><td>NHPr '</td><td>NH</td><td> 0</td><td> 1</td><td></td>

<td> 3-25</td><td>cf₃</td><td>H</td><td>NHCH₂Ph</td><td>NH</td><td> 0</td><td> 1</td><td></td>

<td> 3-26</td><td>cf₃</td><td>H</td><td>NCCH₂Ph)_:</td><td>NH</td><td> 0</td><td> 1</td><td></td>

<td> 3-27</td><td>cf₃</td><td>H</td><td>nh₂</td><td>NH</td><td> 0</td><td> 2</td><td> 202-204</td>

<td> 3-28</td><td>cf₃</td><td>H</td><td>NHMe</td><td>NH</td><td> 0</td><td> 2</td><td></td>

<td> 3-29</td><td>cf₃</td><td>H</td><td>Nlle₂</td><td>NH</td><td> 0</td><td> 2</td><td></td>

<td> 3-30</td><td>cf₃</td><td>H</td><td>NHEt</td><td>NH</td><td> 0</td><td> 0</td><td></td>

<td> 3-21</td><td>cf₃</td><td>H</td><td>NEt₂</td><td>NH</td><td> 0</td><td> 2</td><td></td>

<td> 3-32</td><td>CF₃</td><td>K</td><td>NHPr</td><td>NH</td><td> 0</td><td> 2</td><td></td>

<td> 3-33</td><td>CF₃</td><td>H</td><td>KPr "₂</td><td>NH</td><td> 0</td><td> 2</td><td></td>

<td> 3-34</td><td>cf₃</td><td>H</td><td>HHPr '</td><td>NH</td><td> 0</td><td> 2</td><td></td>

<td> 3-35</td><td>cf₃</td><td>H</td><td>NHCHjPh</td><td>NH</td><td> 0</td><td> 2</td><td></td>

<td> 3-36</td><td>cf₃</td><td>H</td><td>N (CH₂Ph)₂</td><td>NH</td><td> 0</td><td> 2</td><td></td>

<td> 3-37</td><td>cf₅</td><td>H</td><td>N = CB- ~ OMe</td><td>NH</td><td> 0</td><td> 1</td><td> 201-204</td>

ES 2 187 751 T3

TABLE 11

<img file="ES2187751T3_D0050.tif" />

<td>Compound N^AND</td><td>R^and</td><td>R</td><td>z</td><td>L</td><td>n</td><td>mp (° C)</td>

<td> 4- 1</td><td>CF;</td><td>MH;</td><td>\ T XJ 1 * A</td><td>r \</td><td>i</td><td>270-273 (dec.)^{i !;}</td>

11) NMR (D'SO. C) 7.06C2E. br). S.22 (2H.s). 12.22ClE.br)

TABLE 12

<img file="ES2187751T3_D0051.tif" />

CF;

<td>Compound N^B</td><td>R^and</td><td>R</td><td>n Pf- (° C)</td>

<td> 5- 1</td><td>CF;</td><td>NH,</td><td> 0</td>

<td> 5- 2</td><td>CF;</td><td>NHMe</td><td> 0</td>

<td> 5- 3</td><td>CF;</td><td>NUe,</td><td> 0</td>

<td> 5- 4</td><td>CF;</td><td>NHEt</td><td> 0</td>

<td> 5- 5</td><td>CF;</td><td>NEt,</td><td> 0</td>

<td> 5- 6</td><td>CF;</td><td>NHPrⁿ</td><td> 0</td>

<td> 5- 7</td><td>CF;</td><td>NPr;</td><td> 0</td>

<td> 5- 8</td><td>CF;</td><td>NHPr '</td><td> 0</td>

ES 2 187 751 T3

TABLE 13 jN ° ^ N ja _f-S (O) „R ' ¹ ι I

Me N JA.

'Ά

CF 3

<td>Compound</td><td>ic R^and</td><td>R</td><td>n mp (° C)</td>

<td> 5- 9</td><td>CF_;</td><td>NHCB_zPh</td><td> 0</td>

<td> 5-10</td><td>CF_:</td><td>N (CH₂Ph);</td><td> 0</td>

<td> 5-11</td><td>C F-</td><td>NH;</td><td> 1 165-15'</td>

<td> 5-12</td><td>C 7;</td><td>NHMe</td><td> 1</td>

<td> 5-13</td><td>CF ₃</td><td>NMe;</td><td> 1</td>

<td> 5-14</td><td>CF-</td><td>NHEt</td><td> 1</td>

<td> 5-15</td><td>CF:</td><td>NEt;</td><td> 1</td>

<td> 5-16</td><td>CF;</td><td>NHPr</td><td> 1</td>

<td> 5-1?</td><td>CF:</td><td>NPr ";</td><td> 1</td>

<td> 5-18</td><td>CF;</td><td>NHPr '</td><td> 1</td>

<td> 5-19</td><td>CF:</td><td>NHC3₂Ph</td><td> 1</td>

<td> 5-20</td><td>CF;</td><td>N (CH₂Ph)₂</td><td> 1</td>

<td> 5-21</td><td>CF:</td><td>NH;</td><td> 2</td>

<td> 5-22</td><td>CF;</td><td>NHMe</td><td> 2</td>

<td> 5-23</td><td>CF:</td><td>NMe₂</td><td> 2</td>

<td> 5-24</td><td>CF:</td><td>NHEt</td><td> 2</td>

<td> 5-25</td><td>CF;</td><td>NEt 2</td><td> 2</td>

<td> 5-25</td><td>CF;</td><td>NHPr</td><td> 2</td>

<td> 5-27</td><td>CF;</td><td>NPr_:</td><td> 2</td>

<td> 5-28</td><td>CF;</td><td>NHPr '</td><td> 2</td>

<td> 5-29</td><td>CF-</td><td>NHCHjPh</td><td> 2</td>

<td>5-3C</td><td>CF-</td><td>N (CH; Ph);</td><td> 2</td>

CAI

ES 2 187 751 T3

Example 23

An emulsifiable concentrate was produced by sufficiently mixing compound No. 1-1 (20% by weight), xylene (75% by weight) and polyoxyethylene glycol-ether (Nonipol 85 (trade name)) (5% by weight). Example 24

A wettable powder was produced by sufficiently mixing Compound No. 1-1 (30% by weight), sodium lignin sulfonate (5% by weight), polyoxyethylene glycol-ether (Nonipol 85 (trade name)) (5% by weight), white carbon (30% by weight) and clay (30% by weight).

Example 25

A fine powder was produced by sufficiently mixing compound No. 1-1 (3% by weight), white carbon (3% by weight) and clay (94% by weight).

Example 26

A granule was produced by mixing compound No. 1-1 (10% by weight), sodium lignin sulfonate (5% by weight) and clay (85% by weight) with spraying, adding water and kneading them. , followed by granulation and subsequent drying.

Example 27

An insecticidal fine powder was produced by sufficiently mixing Compound No. 1 - 1 (1.275% by weight), cartap (2.2% by weight), white carbon (0.5% by weight) and clay (96.025% by weight ).

Example 28

A fine insecticidal / fungicidal powder was produced by sufficiently mixing compound No. 1-1 (1.275% by weight), validamicón (0.33% by weight), white carbon (0.5% by weight) and clay (97.895% in weigh).

Test of the insecticidal effect of Example 1 against Chilo suppressalis

Five milligrams of each of the test compounds (designated by each compound number assigned to the compound prepared in the Examples described above) were respectively dissolved in 0.5 ml of acetone containing Tween 20 (trade name) and diluted with a Aqueous solution of Dyne 3000 number of times at a given concentration (100 ppm). This solution was applied to the leaves and stems of young rice plants in the stage of 2 to 3 leaves grown in a nursery (plantation of 6 to 7 strains) at a rate of 20 ml / pot by means of a spray gun. After the solution was dried, the young rice seedlings were placed in a test tube (0 (diameter): 3 cm, height: 20 cm) together with 5 ml of tap water. After the release of ten 3-stage larvae between molts of Chio suppressalis in the test tube, the test tube was placed in an incubator (27 ° C). After five days, the total dead larvae were counted and the damage observed. Mortality was calculated using the following equation:

Mortality (%) = (number of dead larvae / number of applied larvae) x 100

Damage to young rice paddies was evaluated according to the following criteria:

<td>Hurt</td><td>Criteria</td>

<td> 0</td><td>Damage is poorly recognized</td>

<td> 1</td><td>Damage is slightly recognized (no more than about 1/10 of untreated young flocks</td>

<td> 2</td><td>Damage is recognized in less than about 1/2 of untreated young sites</td>

<td> 3</td><td>Damage is recognized in no less than about 1/2 of untreated young sites</td>

<td> 4</td><td>Equivalent harm to untreated young schools is recognized</td>

The result is shown in Table 14.

ES 2 187 751 T3

TABLE 14

<td>Co-posited N⁹</td><td>Mortality (¾)</td><td>Damage to campuses young of rice</td><td>Co-bet N⁹</td><td>Mortality (¾)</td><td>Damage to campuses young of rice</td>

<td> 1-1</td><td> 100</td><td> 0</td><td> 2-12</td><td> 100</td><td> 0</td>

<td> 1-2</td><td> 100</td><td> 0</td><td> 2-14</td><td> 100</td><td> 0</td>

<td> 1-3</td><td> 100</td><td> 0</td><td> 2-15</td><td> 100</td><td> 0</td>

<td> 1-4</td><td> 100</td><td> 0</td><td> 2-16</td><td> 100</td><td> 0</td>

<td> 1-11</td><td> 100</td><td> 0</td><td> 2-19</td><td> 100</td><td> 0</td>

<td> 1-12</td><td> 100</td><td> 0</td><td> 2-21</td><td> 100</td><td> 0</td>

<td> 1-29</td><td> 100</td><td> 0</td><td> 2-23</td><td> 100</td><td> 0</td>

<td> 1-30</td><td> 100</td><td> 0</td><td> 2-32</td><td> 100</td><td> 0</td>

<td> 1-35</td><td> 100</td><td> 0</td><td> 2-40</td><td> 100</td><td> 0</td>

<td> 1-36</td><td> 100</td><td> 0</td><td> 2-41</td><td> 100</td><td> 0</td>

<td> 1-37</td><td> 100</td><td> 0</td><td> 2-49</td><td> 100</td><td> 0</td>

<td> 1-39</td><td> 100</td><td> 0</td><td> 2-52</td><td> 100</td><td> 0</td>

<td> 1-49</td><td> 100</td><td> 0</td><td> 2-53</td><td> 100</td><td> 0</td>

<td> 1-58</td><td> 100</td><td> 0</td><td> 2-59</td><td> 100</td><td> 0</td>

<td> 1-59</td><td> 100</td><td> 0</td><td> 3-1</td><td> 100</td><td> 0</td>

<td> 1-67</td><td> 100</td><td> 0</td><td> 3-5</td><td> 100</td><td> 0</td>

<td> 1-69</td><td> 100</td><td> 0</td><td> 3-6</td><td> 100</td><td> 0</td>

<td> 1-86</td><td> 100</td><td> 0</td><td> 3-8</td><td> 100</td><td> 0</td>

<td> 2-1</td><td> 100</td><td> 0</td><td> 3-27</td><td> 100</td><td> 0</td>

<td> 2-2</td><td> 100</td><td> 0</td><td> 3-38</td><td> 100</td><td> 0</td>

<td> 2-3</td><td> 100</td><td> 0</td><td> 4-1</td><td> 100</td><td> 0</td>

<td> 2-4 2-7</td><td> 100 100 —</td><td> 0 0</td><td> 5-11</td><td> 100</td><td> 0</td>

From Table 14, it follows that the compound [I] of the present invention has excellent insecticidal activities and are excellent harm-free compounds.

ES 2 187 751 T3

Industrial applicability

The 1-aryl-pyrazole derivatives [I] or their salts of the present invention have excellent insecticidal activities and less toxicity to fish. Therefore, the insecticidal compositions containing the compound [I] or a salt thereof of the present invention protect crops, etc. from harmful pests and can contribute to an agricultural success.