HU204260B - Insecticide compositions containing substituted indazol derivatives as active components and process for producing the active components - Google Patents

Abstract

The insecticidal compositions of the present invention comprise from 0.00181 to 95% by weight of substituted indazole derivatives and agriculturally acceptable metal salts thereof, wherein A is oxygen, sulfur, -CH2-, -CH (CH3) -, -; CH 2 CH 2 -, -N (R 6) -, -SO (a) -, -SO (p) - or -SO 2 -; B is hydrogen, C 1 -C 6 alkyl, C 2 -C 6 alkenyl, cyano (C 2 -C 6 alkyl), phenyl, halogen or C 1-4 alkoxy, benzyl, or phenyl ring halogen substituted benzyl, CO2R / j 'or C (O) NR3' R4, wherein R1 is hydrogen, alkali metal, or C1-4 alkyl optionally substituted with 1 to 3 carbon atoms, R3 'is hydrogen or 1- C 4 alkyl, R 4 is hydrogen, C 1-4 alkyl, C 2-6 alkenyl or halogen substituted phenyl, or R 3 'and R 4 together with the nitrogen to which they are attached form a 5- or 6-membered heterocyclic ring containing a nitrogen atom; 1 is hydrogen or substituted phenyl; © CD CM © CM □ Scope of description: 32 pages (including 8 pages)

Description

K is hydrogen;

R 1 is halogen, trihaloalkyl, alkoxy substituted 2-3 times with halogen, SR ₃ '' - or CO 2 R ₃ '', where R ₃ '' is alkyl, then m is 1, __ m is 2 for R 1 represents two halogens at the 4 and 3 or 5 position;

R 2 is hydrogen, halo, alkyl, trihaloalkyl, or alkoxy substituted with halo;

R is hydrogen, alkyl or benzyl; R8 is alkyl;

n is 1 or R 2 is 1 or 2;

g is 0.1 or 2;

Y is hydrogen, alkyl, alkylcarbonyl, or alkoxycarbonyl

The invention also relates to the preparation of an active ingredient in the above compositions.

The present invention relates to insecticidal compositions containing substituted indazole compounds and their agriculturally acceptable metal salts and to a process for the preparation of indazole slides.

U.S. Pat. No. 4,070,365 discloses insecticidal compounds of formula (I) wherein:

R 2 and R ₃ are each independently optionally substituted with one or two halogen atoms, alkyl, haloalkyl, cycloalkyl, AL, alkylthio, alkoxy, mono- or dialkylamino, nitro or optionally substituted with halogen or cyano, phenyl, alkyl, cycloalkyl, pyridyl or thienyl substituted with phenyl;

Y is halogen, nitro, alkyl, haloalkyl, cycloalkyl, alkylthio, alkoxy, dialkylamino, alkylsulfonyl, acyl, acylamino, cyano or optionally substituted by halogen. ; and

X is oxygen or sulfur.

U.S. Pat. No. 4,663,341 discloses an insecticidal compound of formula 2 wherein A is optionally substituted phenyl;

B is optionally substituted phenyl;

U is O, S or NR;

Y is optionally substituted alkyl, carbonyl or phenyl; and

Z is an organic group with the proviso that it cannot be hydrogen,

Y is hydrogen, C3-C6 cycloalkyl, substituted or unsubstituted aryl, or R4-Q.

FIELD OF THE INVENTION The present invention relates to pesticide formulations containing the compounds of formula (I), including all geometric and stereoisomers thereof, and their agriculturally suitable metal salts, and to processes for the preparation of the active ingredient. In the formula (I)

A is oxygen, sulfur, -CH 2 -, -CH (CH ₃ ) -,

-CH2CH2-, -N (Rfi) -, -SO (a) -, -SO (O) -, or -SO2;

B is hydrogen, C 1-6 alkyl, C 2-6 alkenyl, cyano (C 2-6 alkyl), E substituted with phenyl, halogen or C 1-4 alkoxy, benzyl or phenyl in the phenyl ring benzyl substituted by halogen, CO2R / or C (O) NR ₃ 'R 4 of our existence kép20 group, wherein

R ₃ 'is C 1-4 alkyl substituted with 1 to 3 times hydrogen, alkali metal or optionally substituted with halogen,

R ₃ 'is hydrogen or C 1-4 alkyl,

R 4 is hydrogen, C 1-4 alkyl, C 2-6 alkenyl or phenyl substituted with halogen, or

R ₃ 'and R 4 together with the nitrogen atom to which they are attached form a 5 to 30 or 6 membered heterocyclic ring containing one nitrogen atom;

J is hydrogen or phenyl substituted with halogen;

K is hydrogen;

R 1 is halogen, C 1 -C 4 alkoxy, tri-halo (C 1 -C 4) alkyl, substituted with 2-3 times halogen, SR ₃ "'- or CO ₂ R ₃ "' where R ₃ '' is C 1 -C 4 alkyl, where m is 1, for m 1 2, R 1 at the 4 and 3 or 5 position is two halogen;

R 2 is hydrogen, halogen, C 1-4 alkyl, trihalogenC 1-4 alkyl, or C 1-4 alkoxy optionally substituted with halo;

Re is hydrogen, (C1-C4) -alkyl or benzyl;

R5 is C1-C4 alkyl; n is 1 or R 2 is 1 or 2;

g is 0.1 or 2;

Y is hydrogen, (C1-C4) alkyl, (C14-alkyl) carbonyl or (C1-C6) alkoxy) carbonyl.

Preferred compounds of formula I are those in which

A is as defined above;

B is hydrogen, C 1-6 alkyl, C 26 alkenyl, CO x R

HU 204260 Β

C (O) NR3 'phenyl of the formula (R.4), singly substituted by phenyl or halo or C1-C4 alkoxy;

J is hydrogen;

K, R 1, m, R ₂ , R 3 '. R3 ', R4 and R5 are as defined above,

Re is hydrogen or C1-C4 alkyl;

n is 1; g is 0.1 or 2;

Y is hydrogen, C 1 -C 4 alkyl, C (O) CH 3, or CO 2 CH 3 or C 6 CH 2 CH 3 -CO 2.

Particularly preferred are compounds in which

B is hydrogen, C 1-4 alkyl; A carbonyl group, a phenyl group or a phenyl group substituted by a halogen atom or a methoxy group;

J is hydrogen;

K is hydrogen;

R 1 is halogen, SR 3 '', CO 2 R 3 '';

R 2 is hydrogen, halogen, or C 1-4 alkoxy;

R3 is C1-C4 alkyl;

R4 is hydrogen or methyl;

R5 is methyl;

m is 1,

Within this narrower group, compounds in which

R 1 is chloro, fluoro, or bromo, CF ₃ , OCF ₃ , or OCF 2 H;

R2 is hydrogen, chlorine, fluorine or bromine, OCF ₂ H group;

Re is hydrogen or CH3;

B is hydrogen, CH3, CH2CH3, CO2CH3,

CO2CH2CH3, phenyl substituted with phenyl or halogen; and

Y is hydrogen.

Particularly preferred are: 3,3a, 4,5-Tetrahydro - {[4- (trifluoromethyl) phenylamino] carbonyl} -2H-benz [g] indazole-3-methylcarboxylate, (G 7-Chloro-3,3a, 4,5-tetrahydro-2 - {[4- (trifluoromethyl) phenylamino] carbonyl} -2H-benz (g) indazole-3a-methylcarboxylate, ( H)

7-Chloro-3,3a, 4,5-tetrahydro-N- [4- (trifluoromethyl) phenyl] -2H-benz [g] indazole-2-carboxamide, (I)

6-Fluoro-3,3a, 4,5-tetrahydro-2 - {[4- (trifluoromethyl) phenylamino] carbonyl} -2H-benz [g] indazole-3a-methylcarboxylate (J ).

The leaf and soil insecticidal compositions of the present invention may also be used in combination with other agricultural pesticides, as will be apparent to those skilled in the art.

The compositions of the present invention may also contain as active ingredient the geometric and stereoisomers of the compounds of formula (I) and their agriculturally suitable metal salts.

In the following description and tables, the numbering of the group of formula (a ') is applied to the corresponding moiety of the compounds of formula (I).

In the process of the present invention, compounds of formula I are prepared by reacting an aryl isocyanate of formula H with an indazole derivative of formula kívánt and optionally forming a compound of formula I containing a hydrogen atom instead of a B obtained. with a base and then with a suitable electrophilic reagent to form a compound of formula (I) wherein B is other than hydrogen, phenyl or substituted phenyl and optionally a resulting compound of formula (I) with an hydroxide, alkoxide or hydride of an agriculturally suitable metal by reaction to form an agriculturally suitable metal salt.

The procedure is described in more detail below:

Compounds of formula (I) may be prepared by reacting a compound of formula (Π) with a substituted indazole compound of formula (III) as shown in Scheme 1. The reaction is usually carried out in equimolar amounts with compounds of formulas (H) and (III) in conventional organic solvents such as ether, tetrahydrofuran (THF), methylene chloride, chloroform or benzene. The reaction temperature may range from -20 'C to 100 ° C, preferably from -10' C to 30 'C.

Compounds of formula (IH) wherein B is hydrogen may be prepared by reacting hydrazine with an α, β-unsaturated ketone or a precursor compound of formula (IV) according to a method known in the chemical literature. The reaction is illustrated in Scheme 2, For a review of pyrazoline synthesis, see El-Rayyes and Al-Awadi Synthesis, 1028 (1985). Synthesis of 3,4- and 3,5-disubstituted plrazolines for the preparation of compounds of formula III wherein B is hydrogen are described in U.S. Patent Nos. 3,991,073 and 4,070,365.

Compounds of formula (I) wherein B is other than hydrogen, phenyl or substituted phenyl may be prepared by converting a compound of formula (I) wherein B is hydrogen into a 3-position metal compound followed by a suitable electrophilic reaction. Reaction reagent as shown in Scheme 3. A process for the conversion of 4-substituted pyrazolines to 4,4-disubstituted pyrazolines and the preparation of indazole compounds of formula I is described in EP-A-153 127. The metal compound formation is effected by proton deprotection with a strong base in a suitable solvent,

Temperature range from -78 'C to 100' C. Examples of suitable bases for the reaction include lithium dialkyl amides such as lithium diisopropylamide

EN 204260 Β and lithium tetramethylpiperidine, alkyl lithium reagents such as n-butyllithium, and metal hydrides such as sodium hydride and potassium hydride. Compounds of formula (I) wherein B and Y are both hydrogen may be deprotonated with two equivalents of a base. The reaction may be carried out in a variety of conventional organic solvents and may in some cases be effective in the use of co-solvents. Examples of the solvent include diethyl ether, tetrahydrofuran, dimethylformamide, hexamethylphosphoramide and benzene. Alkyl halides, substituted alkyl halides, alkyl chloroformates, acyl halides, isocyanates, dialkylcarbamoyl halides, and other compounds known in the art can be used as electrophilic reagents for the reaction of the metal compound of formula (I). electrophilic compounds

The substituent 3a can also be introduced, in certain preferred cases, via compounds of formula V wherein the 2-position nitrogen is protected with an appropriate protecting group (PG). Such a process results in higher yields and / or simpler synthesis. The proton deprotection is effected by reaction with a strong base such as a generally stoichiometric amount of lithium diisopropylamide followed by an electrophilic reagent as described above to give a compound of formula V wherein B is other than hydrogen, phenyl or substituted phenyl. Removal of the nitrogen protecting group affords the desired intermediate of formula (() (See Scheme 4). Nitrogen protecting groups and their preparation and purification can be found in the chemical literature, such as acetyl, trifluoro acetyl, benzoyl, substituted benzoyl, alkoxycarbonyl, benzyl, and substituted benzyl For a review of the literature, see Green, Protective Groups in Organic Synthesis (New York: John Wiley and Sons, 1981), pp. 218-287. .

Compounds of formula (IH) wherein B is phenyl or substituted phenyl can be prepared by reacting a substituted ketone of formula (VHI) with hydrazine. The compounds of formula (VHI) ^{2 can} be prepared from the compounds of formula (VH) by a two-step process by first subjecting a compound of formula (VH) to a sacrificial or Mannich reaction followed by the hydroxyl or dialkylamino group. Converting L to a leaving group; such methods for converting it into chloride, bromide, tosylate or mesylate are well known in the art. (See Scheme 5).

Compounds of formula (IV) (or precursor compounds thereof) can be readily prepared from compounds of formula (IX) by aldol condensation followed by dehydration of the resulting aldol or, if J and K are hydrogen, by Mannich reaction followed by removal of the dialkylamino group

By intoxicated. (See Scheme 6.) An overview of these reactions can be found in March, "Advanced

Organic Chemistry, 3rd ed., (New York: John Wiley and Sons, 1985), p. 829 to 834, and House, Modem

Synthetic Reactions', 2nd ed., (Menlo Park, CA: N.A. Benjamin 1972) p. 665 to 660 in publications.

Intermediate compounds of formula IX are known to those skilled in the art, such as, for example, indanone, tetralone, chroma non, thiochromanone, the preparation of which can be found in the chemical literature. Some compounds of formula IX are also commercially available.

The agriculturally suitable metal salts of the compounds of formula (I) may be prepared by subjecting the compounds of formula (I) to an agriculturally suitable metal such as a compound of formula (I). with an alkali metal or alkaline earth metal, hydroxide, alkoxide or hydride.

The following examples illustrate the invention in more detail.

Example 1

3,3a, 4,5-Tetrahydro-N- [4- (trifluoromethyl) phenyl] -2H-benz [g] indazol-2-carboxamide

In 2Q ml of ethanol, 10.0 g of α-tetralone, 2.0 g of parafoimaldehyde, 6.5 g of dimethylamine hydrochloride and 1.75 ml of concentrated hydrochloric acid were heated at reflux for 24 hours and then cooled to room temperature and the ether and the water. The aqueous extracts were made basic with 1 N aqueous sodium hydroxide solution and extracted with ether. The ethereal extracts were then dried over magnesium sulfate and concentrated to give 12.3 g of a yellow oil. The resulting oil was dissolved in n-propyl alcohol (40 mL), combined with hydrazine hydrate (6.7 mL) and heated at reflux for 1 h. The reaction mixture was concentrated in vacuo and partitioned between 5% aqueous sodium bicarbonate and methylene chloride and dried over magnesium sulfate. To the methylene chloride extracts was added 125 g of 4-trifluoromethylphenyl isocyanate, and the mixture was refluxed for one hour, then cooled to room temperature and concentrated to give 26.1 g of a brown oil. This was subsequently chromatographed on silica gel to give 11.78 g of the title compound as a powder, m.p. 149-151 ° C.

Atomic mass spectrometry:

1 H-NMR (CDCl 3) δ: 1.9 (m, 1H), 2.4 (m, 1H), 3.0 (m,

2H), 3.0 (m, 2H), 3.5 (m, 2H), 4.4 (m, 1H), 7.3 (m, 3H), 7.58 (d, 2H), 7, 65 (d, 2H), 8.0 (d, 2H), 8.3 (broad s, 1H).

Example 2

3,3a, 4,5-Tetrahydro-3a-methyl-N- [4- (trifluoromethyl) phenyl] -2H-benz [g] indazole-2-carboxamide to 0.9 ml of diisopropylamine in 0.9 ml of tetrahydrofuran At C was added 2.3 ml of a 2.5 M solution of n-butyllithium in hexane and the mixture was stirred for 5 minutes.

HU 204260 Β

To this solution of -78'C was added 1.0 g of the compound prepared in Example 1 dissolved in 5 ml of tetrahydrofuran. The reaction mixture was warmed to 0 'C, then cooled again to -78' C and 0.4 ml of methyl iodide was added. The reaction mixture was then stirred for 24 hours, gradually warming to room temperature, then washed with glacial acetic acid (0.5 ml) and poured into 5% aqueous sodium bicarbonate. The reaction mixture was extracted with chloroform, then dried over magnesium sulfate and concentrated. Crystallization from 1: 1 ethyl acetate: hexane gave 0.41 g of a yellow solid, m.p. 130-135 ° C. The filtrate was chromatographed on silica gel with 30% EtOAc / EtOAc / hexane to give the title compound (0.17 g, m.p. 152.5-153.5 C).

Mass spectrometric analysis:

1 H-NMR (CDCl 3) δ: 1.29 (s, 3H), 2.1 (m, 2H), 2.9-3.3 (m, 2H), 3.70 (d, 1H), 4, 12 (d, 1H), 7.3 (m, 3H), 7.57 (d, 2H), 7.68 (d, 2H), 7.98 (d, 1H), 8.3 (broad s, IH).

Example 3

3,3a, 4,5-tetrahydro-2 - {[4- (trifluoromethyl) phenylamino] carbonyl} -2H-benz [g] indazole-3a-carboxylate

Following the procedure of Example 2, using 0.75 ml of methyl formic acid, after chromatography on silica gel, 0.25 g of the title compound is obtained in the form of a white solid, m.p. 177-180 ° C.

Mass spectrometric analysis:

1 H-NMR (CDCl 3) δ: 2.1 (m, 1H), 2.7 (m, 1H), 3.0 (m, 2H), 3.71 (s, 3H), 3.76 (d, 1H), 4.58 (d, 1H), 7.3 (m, 3H), 7.57 (d, 2H), 7.66 (d, 2H), 8.0 (d, 1H), 8, 22 (s, 1H).

Example 4

7-Chloro-3,3a, 4,5-tetrahydro-N- [4- (trifluoromethyl ') - phenyl] -2H) benz [g] indazol-2-carboxamide

The reaction is [(2- (3-Chloro-phenyl) -ethyl) -methanesulfonate

To a mixture of 3-chlorophenethyl alcohol (30.0 g) in tetrahydrofuran (150 mL) and methanesulfonyl chloride (15.3 mL) was added triethylamine (28.0 mL) in tetrahydrofuran (50 mL). The reaction mixture was warmed to room temperature, stirred overnight and filtered. The filtrate was partitioned between aqueous sodium bicarbonate solution and ether. The organic extracts were dried over anhydrous magnesium sulfate, filtered and concentrated under reduced pressure to give 45.93 g of a clear, colorless oil. -The structure was determined by Ή-NMR mass spectrometry.

Step B

Chloro-benzene-butanoic acid

A solution of 8.0 g of 60% w / w sodium hydride in 300 ml of tetrahydrofuran was added dropwise to a solution of 50 ml of tetrahydrofuran in a nitrogen atmosphere.

31.0 ml of diethyl malonate. Upon completion of the diethyl malonate addition, a light yellow, homogeneous solution was obtained. To this was added a solution of 45.93 g of the sulfonate obtained in Step A, and the mixture was refluxed overnight. The reaction mixture was cooled to room temperature, poured into almost 400 ml of 1 N hydrochloric acid and extracted with ether. The ethereal extracts were dried over magnesium sulfate, filtered and concentrated under reduced pressure to give 68.9 g of a yellow oil. The crude oil was dissolved in a mixture of 400 ml of methanol, 100 ml of water and 40 ml of 50% w / w sodium hydroxide solution. The reaction mixture was stirred overnight and then methanol was removed under reduced pressure. The resulting crude residue was partitioned between water and ether, the aqueous extracts acidified with concentrated hydrochloric acid and extracted several times with ether. The ethereal extracts were dried over magnesium sulfate, filtered and concentrated to give 51.7 g of a yellow oil. The crude residue was dissolved in toluene (200 mL) and refluxed under nitrogen to effect decarboxylation. The toluene was then removed by concentration under reduced pressure to give 35.72 g of a yellow oil. Mass spectrometry by Ή-NMR showed the purity of 3-chlorobenzene butanoic acid to be 80%. The crude product was used in the next step without further purification.

Operation C

6-Chloro-3,4-dihydro-1 (2H) -naphthalenone

A mixture of 35.72 g of the product of Step B and 50 ml of thionyl chloride was heated at reflux for 2 hours and then stirred at room temperature for 18 hours. The thionyl chloride was then removed under reduced pressure, the product dissolved in carbon tetrachloride and concentrated under reduced pressure. The residue was dissolved in dichloroethane (150 mL), cooled to 0 ° C, and aluminum chloride (28 g) was added in about 3 portions over 1 hour. After stirring for 3 hours, the reaction mixture was poured into ice / 1 N hydrochloric acid and extracted three times with methylene chloride. The organic extracts were dried over magnesium sulfate and concentrated to give 30 g of a brown oil. The resulting residue was chromatographed on silica gel with 10% ethyl acetate / hexane to give 17.83 g of a brown oily 6-chloro-3,4-dihydrol (2H) -naphthalenone. The structure was determined by Ή-NMR mass spectrometry.

Operation D

7-Chloro-3,3a, 4,5-tetrahydro-N- [4- (trifluoromethyl) phenyl] -2H-benz [g] indazole-2-carboxamide

A mixture of 6-chloro-3,4-dihydro-1 (2H) naphthalenone from step C, 2.5 g dimethylamine hydrochloride, 1.0 g paraformaldehyde, 0.7 ml concentrated hydrochloric acid and 15 ml ethanol was refluxed. heated for 18 hours. The reaction mixture was then concentrated under reduced pressure and partitioned between water and ether. THE

The aqueous extracts were basified with 1N sodium hydroxide solution and extracted three times with ether. The ethereal extracts were dried over magnesium sulfate and concentrated to give 4.64 g of a yellow oil. This compound was dissolved in ethanol (25 mL) and hydrazine hydrate (1.5 mL) was added followed by 5-6 drops of 50% w / w sodium hydroxide. The reaction mixture was heated at reflux under nitrogen for 2-3 hours, then cooled and most of the ethanol removed by concentration under reduced pressure. The crude residue was partitioned between saturated aqueous sodium bicarbonate and methylene chloride. The methylene chloride extracts were dried over magnesium sulfate and filtered. The methylene chloride extract was then added with 3.5 g of trifluoromethyl femyl isocyanate and stirred overnight under a nitrogen atmosphere. The reaction mixture was then concentrated and the crude residue was triturated with ether to give 3.35 g of the title compound as a white powder.

M.p .: 196-199 'C.

Result of pond spectrometry analysis:

1 H-NMR (CDCl 3) δ: 1.9 (m, 1H), 2.2 (m, 1H), 3.0. (m, 2H), 3.5 (m, 2H), 4.43 (m 1H), 7.24 (m, 2H), 7.55 (tfd, 2H), 7.67 (d, 2H), 7 , 92 (d, 1H), 8 _s 20 (s, 1H).

Example 5

7-Chloro-3,3a, 4,5-tetrahydro-2 - {[4- (trifluoromethyl) phenylamino] carbonyl} -2H-benz [g] indazole-3a-methylcarboxylate ~ 50 mL 6.7 ml of diisopropylamine in tetrahydrofuran were cooled to -78 ° C under nitrogen and 17.5 ml of a 2.5 molar solution of n-butyllithium in hexane dissolved in 15 ml of tetrahydrofuran after 7.8 g of Example 4 were added. compound was added dropwise and the resulting dark red solution was stirred at -78 ° C for an additional 15 minutes. Then, 4.6 ml of methyl formic acid chloroformate was added dropwise in 10 ml of tetrahydrofuran, causing the red color to disappear rapidly. The reaction mixture was warmed to room temperature and after 1 hour, washed with 5% aqueous sodium bicarbonate solution. The reaction mixture was partitioned between ether and 5% w / w aqueous sodium bicarbonate. The ethereal extracts were dried over magnesium sulfate and concentrated to give 14.1 g of a yellow oily solid. The crude product was triturated with ether and the resulting white precipitate was filtered off and dried, yielding 5.56 g of a white solid, m.p. 234-236 ° C.

Mass spectrometric analysis:

1 H-NMR (CDCl 3) δ: 2.1 (m, 1H), 2.75 (m, 1H), 2.95 (m, 2H), 4.71 (s, 3H), 3.75 (d, 1H, J-6Hz), 4.59 (d, 1H, J-6Hz), 7.25 (m, 2H), 7.57 (d, 2H), 7.66 (d, 2H), 7 , 94 (d, 1H), 8.18 (d, 1H).

Example 6

7-chloro-2,3,3a, 4-tetrahydro-N- [4- (trifluoromethyl) phenyl] - [l] benzo thiopyrano [4,3-c] pyrazole-2-carboxamide

The operation

7-Chloro-3 - [(dimethyl-amino) methyl] -2,3-dihydro-4H-l-benzofuran-thio-pyran-4-one

15.0 g (75.7 mmol) of 7-chlorothiochroman-4-one (see

Chu et al., Hua Hsieh Hsueh Pao 1956, 22, 371-8; Chem. Abstracts, 1958, 52, 11044a), a mixture of 7.41 g (90.8 mmol) dimethylamine hydrochloride, 3.41 g (113 mmol) paraformaldehyde and 1.26 mL (15 mmol) concentrated hydrochloric acid in 25 mL ethanol was refluxed under nitrogen for 22 hours. The reaction mixture was poured into water (150 mL) and extracted with ether (2 x 50 mL). The aqueous layer was basified with 1N sodium hydroxide solution (pH-10) and extracted with 3400 mL of ethyl acetate. The ethyl acetate extracts were dried over magnesium sulfate and concentrated under reduced pressure to give 14.9 g of a yellow oil.

The title compound was determined by NMR mass spectrometry.

Step B

7-chloro-2,3,3a, 4-tetrahydro-N- [4- (trifluoromethyl) phenyl] - [l] benzo thiopyrano [4,3-c] pyrazole-2-carboxamide

To a stirred mixture of 14.0 g (54.7 mmol) of Mannich base (36.0 mL) and hydrazine hydrate (6.19 mL, 6.38 g, 110 mmol) in nitrogen (0.29 mL) was added under stirring. 5.5 mmol) of 50% aqueous sodium hydroxide solution and the mixture was heated at 100 ° C for 2 hours. The reaction mixture was concentrated under reduced pressure, diluted with 250 ml of dichloromethane and 200 ml of washed with aqueous sodium bicarbonate solution. The aqueous layer was extracted with dichloromethane (50 mL). The combined organic layers were dried over magnesium sulfate and filtered to give 370 mL of solution. 120 mL of the solution was treated with nitrogen (3.75 g, 20.0 mmol) 4- (trifluoromethyl) phenyl isocyanate and stirred overnight. The reaction mixture was concentrated under reduced pressure and the resulting residue was triturated with 35 mL of ether and filtered to give 4.51 g (63%) of the title compound as a yellow solid, m.p. 188-192 ° C.

Mass spectrometric analysis:

1 H-NMR (CDCl 3, 200 MHz) δ 3.19 (dd, 4.5 Hz, 12.0 Hz, 1H), 3.32 (t, 12.0 Hz, 1H), 3.69 (t, 10 , 8 Hz, 1H), 3.86 (dq, 4.5 Hz, 11 Hz, 1H), 4.43 (t, 10.5 Hz, 1H), 7.13 (dd, 1.9 Hz, 8 , 8 Hz, 1H), 7.24 (d, 1.9 Hz, 1H), 7.58 (d, 8.8 Hz, 2H), 7.66 (d, 8.8 Hz, 2H), 7 , 93 (d, 8.4

Hz, 1H), 8.13 (s, 1H).

Example 7

7-Chloro-2,3,3a, 4-tetrahydro-4,4-dimethyl-N- [4- (trifluoromethyl) phenyl] - [1] benzothio55-pyrano [4,3-c] pyrazole -2-Carboxamide The operation

3- (3-Chloro-phenyl-lio) -3-methyl-butyric acid

20.0 g (138 mmol) of 3-chlorothiophenol, 13.85 g (138 mmol) of 3-methyl-2-butanoic acid and 4.1 mL (3.5 g) of

42 mol) of piperidine in a nitrogen atmosphere

HU 204260 Β was heated under reflux at 105 ° C for 28 hours. The reaction mixture was poured into 200 mL of ether and washed with 2 x 80 mL of 1 N hydrochloric acid, and the aqueous layers were extracted with 50 mL of ether. The combined organic layers were dried over magnesium sulfate, concentrated under reduced pressure to give 33.1 g of a yellow oil.

The structure of the title compound was determined by Ή-NMR mass spectrometry.

Step B

7-Chloro-2,3-dihydro-2,2-dimethyl-4H-benzo-l-thio-pyran-4-one

To 270 g of polyphosphoric acid heated to 70 'C, 31.9 g of the product of Step 15 were added portionwise over 15 minutes under mechanical stirring under a nitrogen atmosphere. The reaction mixture was then heated at 70 'C for a further 45 minutes, then cooled to 0' C, water (150 mL) was added carefully, followed by ether (100 mL). The resulting mixture was diluted with water (170 mL) and ether (110 mL). The layers were separated and the aqueous layer was extracted with ether (2 x 200 mL). The combined ether layers were washed with 100 mL of 1 N sodium hydroxide solution, then dried over magnesium sulfate and concentrated under reduced pressure to give 25.8 g of a yellow solid.

1 H NMR mass spectrometry showed the presence of 68:32 by weight of the title compound and its 5-chloroisomer.

Operation C

7-Chloro-3 - [(dimethylamino) methyl] -2,3-dihydro-2,2 ·

dimethyl-4H-benzo-l-thio-pyran-4-one

10.0 g (44.1 mmol) of thiochromanone isomeric mixture obtained in Step B, 1.99 g (66.2 mmol) of paraformaldehyde bridge, 4.32 g (52.9 mmol) of dimethylamine hydrochloride and 0, 74 ml of concentrated hydrochloric acid mixture was heated under reflux in 15 ml of ethanol under nitrogen for 49 hours. The reaction mixture was poured into 1000 mL of water and extracted with ether (5 x 200 mL). The aqueous layer was basified with 1N 40 NaOH (pH 10) and extracted with ethyl acetate (3 x 200 mL). The ethyl acetate extracts were concentrated under reduced pressure to give 3.59 g of an oily product.

1 H-NMR mass spectrometry showed the presence of 80:20 to 45% of the title compound and its 5-chloroisomer.

Operation D

7-Chloro-2,3,3a, 4-tetrahydro-4,4-dimethyl-N- [4-50]

- (trifluoromethyl) phenyl] - [1] benzothiopyrano [4,3-c] pyrazole-2-carboxamide

A mixture of 3.20 g (11.3 mmol) of the Mannich base from Step C and 1.28 mL (1.32 g, 22.6 mmol) of hydrazine hydrate was stirred in 7.5 mL of n-propanol and under a nitrogen atmosphere. 90 mg (1.1 mmol) of a 50% aqueous sodium hydroxide solution was added and the resulting mixture was heated at 100 ° C for 2 hours. The reaction mixture was then concentrated under reduced pressure, diluted with dichloromethane (50 mL) and washed with dilute aqueous sodium bicarbonate (100 mL). The aqueous layer was extracted with dichloromethane (20 mL). The combined organic layers were dried over magnesium sulfate and filtered to give 93 mL of solution. 27 ml of this solution was treated with 0.68 g (3.6 mmol) of 4- (trifluoromethyl) phenyl isocyanate and stirred at room temperature for 2.5 hours. The reaction mixture was concentrated under reduced pressure, and the residue was triturated with 15 mL of food and filtered to give 1.03 g (71%) of the title compound as a solid, m.p. 200-202 ° C.

Mass spectrometry analysis: δ-NMR (CDCl3, 200 MHz) δ: 1.35 (s, 3H), 1.45 (s,

3H), 3.83 (m, 2H), 4.21 (m, 1H), 7.14 (dd, 2.0 Hz, 8.4 Hz, 1H), 7.22 (d, 1.8 Hz) , 1H), 7.58 (d, 8.8 Hz, 2H), 7.66 (d, 8.9 Hz, 2H), 7.95 (d, 8.1 Hz, 1H), 8.13 ( s, 1H).

Example 8

3a- (4-Chloro-phenyl) -3,3a, 4,5-tetrahydro-N- (4-trifluoromethyl) -phenyl] -2H-benz [g] indazole-2-carboxamide

4-Chloro-2- (2-phenylethyl) -benzene acetic acid methyl ester was added dropwise to 4.35 g of 60% w / w sodium hydride in 50 ml of dimethylformamide. methyl acetate in 25 ml of dimethylformamide. After the reaction was complete, 20.0 g of 2-bromomethylbenzene was added in 25 ml of dimethylformamide and the reaction mixture was stirred overnight at room temperature. The reaction mixture was then partitioned between 400 mL of food and 200 mL of water. The ethereal extracts were washed with water and dried over magnesium sulfate, filtered and concentrated. This gave 32.9 g of a yellow oil. The resulting residue was chromatographed on silica gel with ethyl acetate / hexane (5% v / v) to give the title compound (12.6 g) as a clear, colorless oil.

Step B

2- (4-Chlorophenyl) -3,4-dihydro-1 (2H) -naphthalenone 12.6 g, Compound A, 100 ml methanol, 30 ml water and 10 ml, 50% w / w sodium hydroxide solution was heated to reflux under nitrogen overnight. The reaction mixture was then concentrated under reduced pressure and acidified with concentrated hydrochloric acid. The mixture was extracted three times with ether and then dried over magnesium sulfate and concentrated to give 12.14 g of a yellow oil. The resulting residue was dissolved in 20 mL of thionyl chloride and heated at reflux under nitrogen overnight. The thionyl chloride was removed by concentration under reduced pressure and the residue was concentrated twice from carbon tetrachloride. The crude product was dissolved in dichloroethane (50 mL) then cooled to 0 ° C under nitrogen and 5.9 g of aluminum trichloride were added. After stirring overnight at room temperature, the reaction mixture was poured into 50 ml of 1 N hydrochloric acid and extracted with methylene chloride. The organic extracts were dried over magnesium sulfate, filtered and concentrated to give 12.3 g of a brown solid. The resulting residue was taken up in 10% ethyl acetate

I

Chromatography on silica gel with ethyl acetate / hexane (260 Β) followed by trituration with methanol gave 5.51 g of a brown solid, m.p. 97-99 ° C.

Operation C _

2- (4-chloro-phenyl) -3,4-dihydro-2- (hydroxymethyl) -l (2H) -naphthalene-one.

To the mixture was added 1.5 g of 37% w / w formaldehyde and 7.8 ml of 0.5 M sodium hydroxide in 10 ml of toluene. The reaction mixture was stirred under nitrogen at room temperature for 4 hours. Subsequently, thin layer chromatography analysis revealed that the starting tetralone had disappeared from the mixture. The reaction mixture was poured into 100 ml of a 5% w / w aqueous sodium bicarbonate solution and 100 ml of ethyl acetate. The aqueous extracts were then washed twice with ethyl acetate, and the organic extracts were dried over magnesium sulfate, filtered and concentrated under reduced pressure. The resulting residue was chromatographed on silica gel with 20% ethyl acetate / hexane to give 1.19 g of a brown oil.

The structure of the title compound was determined by Ή-NMR mass spectrometry.

Operation D

2- (4-Chloro-phenyl) -3,4-dihydro-2 - [(methylsulfonyl-oxy) -methyl] -1 (2H) -naphthalenone

To a mixture of 0.99 g of the compound obtained in Step C and 0.6 ml of methanesulfonyl chloride in 20 ml of tetrahydrofuran was added 1.05 ml of triethylamine at 0 ° C. After stirring overnight at room temperature, the reaction mixture was partitioned between 5% (w / w) aqueous sodium bicarbonate and chloroform, dried over magnesium sulfate and concentrated. The resulting residue was chromatographed on silica gel with ethyl acetate / hexane (30% v / v ethyl acetate). This gave 1.1 g of the title compound as a yellow viscous oil. 40

This operation

3a- (4-Chloro-phenyl) -3,3a, 4,5-tetrahydro-N- [4- (trifluoromethyl) -phenyl] -2H-benz [d] indazole-2-carboxamide 0.9 g, Compound obtained in Step D, 10 ml ethanol and ethyl acetate

0.4 ml of hydrazine hydrate mixture was heated at reflux under nitrogen for 4 days. The reaction mixture was cooled to room temperature and the white precipitate formed was filtered off. The filtrate was partitioned between saturated aqueous potassium bicarbonate and ethyl acetate. The organic extracts were dried over magnesium sulfate, filtered and concentrated under reduced pressure. 0.58 g of a yellow gum is obtained. The crude residue was dissolved in 5 mL of tetrahydrofuran and 0.4 mL of 4-trifluoromethylphenyl isocyanate was added. After 15 minutes, a thin layer analysis was carried out on silica gel (30% ethyl acetate / hexane) to reveal the presence of a fluorescent product. The reaction mixture was concentrated under reduced pressure and chromatographed on silica gel with 20% ethyl acetate / hexane / 10% methylene chloride / 10% methylene chloride / n-butyl chloride and then triturated with hexane. a crude wool color powder was obtained.

Mass spectrometric analysis:

1 H-NMR (CDCl 3) δ: 2.30 (dt, 1H), 2.5-2.9 (m, 3H), 3.90 (d, 1H), 4.33 (d, 1H), δ 14 (m, 3H), 7.2-7.4 (m, 3H), 7.56 (d, 2H), 7.65 (d, 2H), 8.11 (m, 1H), 8.28 (bs, 1H).

The commonly used procedures described herein, or appropriate modifications thereof, are described in FIGS. The compounds listed in Table II can be prepared.

1-11. The following compounds are found in Tables:

A compound of formula XI wherein Q is a group of formula a as defined below.

Table ¹ serial number in the general formula (a) First A = CH ₂ or CH ₂ -CH ₂ J-K-H Second AO, S, SO (a), δθ (β) or SO ₂ J-K-H Compound of Formula (ΧΠ) wherein Q is is defined by the following formula (a) group: Spreadsheet in the general formula (a) number Third A-CH ₂ J = K = H 4th A = S J = K = H Compound of Formula (ΧΠΙ) wherein Q is Formula (a) is defined below group: Spreadsheet in the general formula (a) number 5th a-ch ₂

Compound of Formula (XHI) wherein Q is (a7): Table 6;

Compound of Formula XVI: Table 7;

Compound (XVH): Table 8;

Compound (XV) Table 9;

Compound (XVHI): Table 10; Compound of Formula XIX: Table 11.

In Table 6, for ease of reference, only one of the possible enantiomers of the group (a7) is shown.

HU 204 260 Β

Table 1

Ri R j . r ₂ B THE Physical Properties Op. ('C) 4-C1 H H H ch ₂ 91.5 to 96 4-Br H H H ch ₂ 151-152 4-CF ₃ H H H ch ₂ 149-151 4-OCF3 H H H ch ₂ 104-107 4-CF3 H H Me ch ₂ 151.5 to 153.5 4-CF3 H H et ch ₂ 120-123 4-CF3 H H allyl ch ₂ 158-163 4-CF3 H H CH ₂ Ph ch ₂ 51-55 4-CF3 H H (CH ₂ ) ₂ CN ch ₂ 165-169 4-CF3 H H (CH ₂ ) ₃ CN ch ₂ 186-188 4-CF3 H H CO ₂ Me ch ₂ 177-180 4-C1 H H CO ₂ Me ch ₂ 175-177 4-Br H H CO ₂ Me ch ₂ 175-178 4-CF3 H H CO ₂ Et ch ₂ 220-222 4-Br H H CO ₂ Et ch ₂ 179-182 4-C1 H H CO ₂ Et ch ₂ 172-174 4-CF3 H H CO ₂ H ch ₂ 182-183 4-CF3 H H CO ₂ Well ch ₂ 230 4-CF3 H H CO ₂ CH ₂ CC1 ₃ ch ₂ 194-196 4-CF3 H H CO ₂ (CH ₂ ) Cl ch ₂ 185-188 4-CF3 H H CO ₂ (CH ₂ ) Br ch ₂ 162-167 4-CF3 H H C (O) NH ₂ ch ₂ 250 4-CF3 H H C (O) NMe ₂ ch ₂ 226-230 4-CF3 H H C (O) NHMe ch ₂ 220 4-CFj H H C (O) NH-allyl ch ₂ 250 4-CF3 H H C (O) N (Me) Allyl ch ₂ 219-221 4-CF3 H H C (O) NHPh-4-Cl ch ₂ 255 4-CF3 H H C (O) -piperidinyl ch ₂ 235 4-C1 H H H ch ₂ ch ₂ 136.5-138 4-CF3 H H H ch ₂ ch ₂ 167 to 168.5 4-C1 H H Me ch ₂ ch ₂ 137 to 141.5 4-CF3 H H Me CH2CH2 134-139 4-Br H 5-C1 H ch ₂ 164-166 4-Cl H 5-C1 H ch ₂ 155-157 4-SMe H 5-C1 H ch ₂ 159-161 4-CO ₂ Et H 5-C1 H ch ₂ 153-156 4-Br H 5-C1 CO ₂ Me ch ₂ 234-236 4-SMe H 5-C1 CO ₂ Me ch ₂ 202-204 4 COjEt H 5-C1 CO ₂ Me ch ₂ 197-199 4-C1 H 5-C1 CO ^ e ch ₂ 222-233 4-CF3 H 5-F H ch ₂ 175-178 4-CF3 H 5-F CO ₂ Me ch ₂ 223-225 4-CF3 H 5-OMe CO ₂ Me ch ₂ 180-186 4-CF3 H 5-OMe CO ₂ Et ch ₂ 160-166 4-CF3 H 5-OMe H ch ₂ 158-160 4-C1 H 5-OMe H ch ₂ - 169-171 4-CF3 H 5,6-di-Cl H ch ₂ 229-230 4-CF3 H 5,6-di-Cl CO ₂ Me ch ₂ 238-241 4-CF3 H 4-F H ch ₂ 183-184 4-CF3 H 4-C1 H ch ₂ 179-180 4-CF3 H 4-F CO ₂ Me ch ₂ 206-212 4-CF3 H 4-C1 CO ₂ Me ch ₂ 209-211

HU 204260 Β

Ri

Ri

Ri

4-CF3 H H 4-C1 3-C1 H 4-Br H H 3-CFA H H 4-C1 H H 3-C1 H H 4-CFS H 5-Br 4-C1 H 5-Br 4-Br H 5-Br 4-C1 H 7-Br 4-CF3 H 7-Br 4-Br H 7-Br 4-CF3 H 5-C1 4-C1 H 5-C1 4-Br H 5-C1 4-CF3 H 7-C1 4-C1 H 7-C1 4-Br H 7-C1 4-CF3 H H 4-C1 3-Cl H 4-Br H H 3-CF3 H H 4-C1 H H 3-CF3 H 5-Cl 4-C1 H 5-Cl 3-C1 H 5-Cl 4-Br H 5-C1 4-C1 3-C1 5-C1 4-CF3 H 6-C1 3-CF3 H 6-C1 4-C1 H 6-C1 3-C1 H 6-C1 4-Br H 6-C1 4-C1 3-C1 6-C1 4-CF3 H 5-Br 3-CF3 H 5-Br 4-C1 H 5-Br 3-C1 H 5-Br 4-Br H 5-Br 4-C1 3-C1 5-Br 4-CF3 H 4-C1 4-C1 H 4-C1 4-Br H 4-Cl 4-CF3 H H 4-C1 3-C1 H 4-Br H H 3-CF3 H H 4-C1 H H 3-C1 H H 4-CF3 H 5-C1 3-CF3 H 5-Cl 4-C1 H 5-Cl 3-C1 H 5-Cl 4-Br H 5-C1 4-C1 3-C1 5-Cl

Table 2

H

H

H

H

H

H

H

H

H

H

H

H

H

H

H

H

H

H

H

H

H

H

H

H

H

H

H

H

H

H

H

H

H

H

H

H

H

H

H

H

H

H

H

H

H

H

H

H

H

H

H

H

H

H

H

Physical Properties Op. ('C)

0 161-164 0 220-224 0 215-220 0 165-167 0 192-199 0 162-171 0 192-195 0 144-150 0 218-221 0 180-184 0 161-182 0 179-202 0 152-182 0 193-207 0 228-232 0 178-202 0 179-193 0 201-208 s 170-171 s 235-239 s 189-192 s 203-204 s 178-180 s 197-200 s 202-206 s 224-227 s 207-211 s 220-232 s 195-202 s 207-213 s 180-188 s 230-240 s 184-189 s 227-237 s 212-215 s 187-200 s 192-209 s 175-190 s 188-215 s 187-200 s 207-210 s 191-193 s 188-190 so ₂ 255-260 so ₂ 250-255 SO2 272-274 SO2 261-263 SO2 247-250 SO2 245-249 SO2 293-297 SO2 217-234 SO2 318-321 SO2 241-270 SO2 290-292 SO2 280-285

HU 204260 Β

Ri Ri R2 B THE Physical Properties Op. ('C) 4-CF ₃ H 6-Cl H SO ₂ 290-292 3-CF3 H 6-Cl H SO ₂ 175-182 4-C1 H 6-Cl H SO ₂ 230-280 3-C1 H 6-C1 H SO2 245-269 4-Br H 6-Cl H SO ₂ 307-310 4-C1 3-C1 6-C1 H SO ₂ 275-278 3-CF3 H H H SO (a) 255-260 4-CF3 H H H SO (a) 250-255 4-Br H H H SO (a) 278-282 4-Br H H H © SO 258-260 4-C1 3-C1 H H SO (a) 275-280 4-C1 3-C1 H H © SO 265-269 4-C1 H H H SO (a) 262-264 4-C1 H H H © SO 247-250 3-C1 H H H SO (a) 231-232 3-C1 H H H © SO 255-258 4-CF3 H 5-C1 H SO (a) 271-275 4-CF3 H 5-C1 H δθ (β) 256-277 3-CF3 H 5-C1 H SO (a) 210-213 3-CF3 H 5-C1 H © SO 250-252 4-C1 H 5-C1 H SO (ct) 284-286 4-C1 H 5-C1 H © SO 278-283 3-C1 H 5-C1 H SO (a) 240-241 3-C1 H 5-C1 H © SO 230-246 4-Br H 5-C1 H SO (a) 285-287 4-Br H 5-C1 H so © 267-272 4-C1 3-C1 5-C1 H SO (a) 276-280 4-C1 3-C1 5-C1 H © SO 254-268 4-CF3 H 6-Cl H SO (a) 252-256 4-CF3 H 6-Cl H so © 218-232 3-CF3 H 6-Cl H SO (a) 263-265 3-CF3 H 6-Cl H © SO 4-C1 H 6-Cl H SO (ct) 243-245 4-C1 H 6-Cl H © SO 269-272 3-C1 H 6-Cl H SO (ct) 154-160 3-C1 H 6-Cl H © SO 4-Br H 6-Cl H SO (ct) 248-250 4-Br H 6-Cl H © SO 283-285 4-C1 3-C1 6-Cl H SO (a) 272-275 4-C1 3-C1 6-Cl H © SO 289-295 3-CF3 H H H © SO 229-236 4-CF3 H H H © SO 235-258

Table 3 rl R2 B THE Y Me Physical Properties Op. ('C) 4-CF3 H C0 ₂ Me CH ₂ C (O) Me 110-115 4-CF3 H H CH ₂ CO2 t-Bu 178-179

HU 204260 Β

Table 4

Ri R ₂ B Y THE Physical Properties Op. ('C) 4-CFj H H Me S 151-152 4-CF ₃ H H C0 ₂ Me S 150-158 4-CFj H H C (0) Me S 80-85 4-CF ₃ 5-C1 H C (0) Me S 97-99 4-CF ₃ 5-C1 H Colman S 170-172 4-CF ₃ 5-C1 H Me S 180-183 4-C1 H H C (O) Me S 140-150 4-Cl H H Me S 125-127 4-Cl 5-C1 H C (O) Me S 127-142 4-Cl 5-C1 H Me S 160-165

Table 5 Ri R ₂ B THE J K Physical properties Op.fC) 4-CF ₃ H H ch ₂ 4-F-Ph H 199-201 4-CF ₃ H H ch ₂ 4-Cl-Ph Η 187-188 4-Cl H H ch ₂ 4-F-Ph H 208-209 4-Cl H H ch ₂ 4-Cl-Ph Η 179-181

Table 6

Physical properties

Ri R ₂ Β Α 2? G rl Op.fC) 4-CF ₃ H Η S Me H 208-210 4-Cl H Η S Me H 172-178 4-Br Η Η S Me H 185-187 4-CFj Η Η S Η Me 168-170 4-Cl Η Η S Η Me 155-156 4-Br Η Η S Η Me 172-180 4-CF ₃ Η Η S Me Me 183-184 4-Cl Η Η S Me Me 181-186 4-Br Η Η S Me Me 182-185 4-CF ₃ 5-C1 Η S Me H 251-255 4-C1 5-α Η S Me H 222-226 4-Br 5-C1 Η S Me H 228-230 4-CF ₃ 5-C1 Η S H Me 171-173 4-C1 5-C1 Η S H Me 170-176 4-Br 5-C1 Η S H Me 120-125 4-CF ₃ 5-C1 Η S Me Me 200-202 4-Cl 5-C1 Η S Me Me 190-193 4-Br 5-C1 Η S Me Me 204-207 4-CF ₃ 5-Br Η S Me Me 190-196 4-Cl 5-Br Η S Me Me 165-186 4-Br 5 Βγ Η S Me Me 208-211 4-CF ₃ 4-C1 Η S Me Me 170-173 4-Cl 4-C1 Η S Me Me 150-168 4-Br 4-C1 Η S Me Me 158-170

HU 204260 Β

Table 7

Compound number Ri r ₂ Y THE B Mp. (° C) 182 4-C1 H H ch ₂ 4-Cl-Ph 171-173 183 4-Br H H ch ₂ 4-Cl-Ph 185-187 184 4-CF ₃ H H ch ₂ ch ₂ CO ₂ Me 115-117 185 4-C1 H H ch ₂ ch ₂ CO ₂ Me 173-176 186 4-Br H H ch ₂ ch ₂ CO ₂ Me 184-186 187 4-CF ₃ 5-C1 H ch ₂ 4-Cl-Ph 226-228 188 4-Br 5-C1 H ch ₂ 4-Cl-Ph 208-210 189 4-CF3 H H ch ₂ 4-F-Ph 209-211 190 4-CF3 5-C1 Me ch ₂ CO ₂ Me 135-136 191 4-CF3 5-C1 C (O) Me ch ₂ Cozma 154-155 192 4-CF3 5-C1 CO ₂ Me ch ₂ CO ₂ Me 173-175 193 4-CF3 5-Br H ch ₂ H 203-205 194 4-CF3 5-Br H ch ₂ CO ₂ Me 210-218 195 4-CF3 5-Me H ch ₂ H 166-168 196 4-CF3 5-Me H ch ₂ CO ₂ Me 199-201 197 4-CF3 5-C1 H ch ₂ CO-L-Pr 207-209 198 4-CF3 5-C1 H ch ₂ CO ₂ CH ₂ CF ₃ 165-167 199 4-CF3 5-C1 H ch ₂ co ₂ h 200-202 274 cl 4-F H ch ₂ 4-Br-Ph 244-246 275 Br 4-F H ch ₂ 4-BrPh 243-245 276 CF ₃ 4-F H ch ₂ 4-Br-Ph 227-229 277 cl 4-F H ch ₂ Ph 218-219 278 Br 4-F H ch ₂ Ph 223-225 279 CF ₃ 4-F H ch ₂ Ph 219-221 280 cl 4-F H ch ₂ 4-F-Ph 217-219 281 Br 4-F H ch ₂ 4-F-Ph 231-233 282 cf ₃ 4-F H ch ₂ 4-F-Ph 196-198 283 cf ₃ 4-F H ch ₂ 4-MeO-Ph 196-198 284 Br 4-C1 H ch ₂ Ph 236-238 285 CF ₃ 4-C1 H ch ₂ Ph 182-183 286 Br 4-C1 H ch ₂ 4-F-Ph 198-200 287 cf ₃ 4-C1 H ch ₂ 4-F-Ph 207-209 288 cl 4-C1 H ch ₂ 4-Br-Ph 209-211 289 Br 4-C1 H ch ₂ 4-Br-Ph 220-223 290 CF ₃ 4-C1 H ch ₂ 4-Br-Ph 238-240

Table 8

Compound number Ri RZ B Op. ('C) 200 4-CF3 H H 152-159 201 4-C1 H H 120-123 202 4-Br H H 124-126 203 4-CFj H CO ₂ Me 170-172 204 4-C1 H Cozma 166-170 205 4-Br H CO ₂ Me 185-188

HU 204 260 Β

Compound number Ri Ra THE 206 4-C1 5-F S 207 4-CF3 5-F S 208 4-Br 5-F S 209 4-CF3 N S 210 4-CFj 5-CF3 S 211 4-C1 5-CF3 S 212 4-Br 5-CF3 S 213 4-CF3 5-F S 214 4-Cl 5-F S 215 4-Br 5-F S 216 4-CF3 5-CF3 S

Table 9

B Ri $

Η Η Η

Η Η Η

Η Η Η

COzMe Η Η

Η Η Η

Η Η Η

Η Η Η

Η Me Me

Η Me Me

Η Me Me

H Me Me

Compound Number R ₂

217 4-F 218 4-F 219 4-F 220 4-F 221 5-C1 222 5-C1 223 5-C1 224 5-a 225 5-a, 226 5-a 227 4-F 228 4-F 229 4-F 230 5-F 231 5-F 232 5-F 233 5-F 234 5-F 235 5-CF ₃ 236 5-a 237 5-F 238 5-C1 239 5-F 240 5-C1 241 5-a 242 5-a 243 5-a 244 5-a 245 5-Cl 246 5-a 247 5-a 248 5-a 249 5-a 250 5-a 251 5-a 252 5-0¾ 253 5-CF ₃ 254 5-O? 3

Op. ('C)

179-181

180-181

188- 192 195-207 188-200 208-210 212-218 200-208 182-185

189-202 208-215

Table 10

Rj Y θΡ · (° ^c )

CO2CH3 cf ₃ Ph cf ₃ 4-F-Ph cf ₃ 4-in-Ph cf ₃ ch ₃ cf ₃ CO2CH3 cf ₃ Ph cf ₃ 4-F-Ph cf ₃ 4-Cl-Ph cf ₃ 4-Cl-Ph cf ₃ 4-in-Ph the 4-in-Ph Br 4-F-Ph CF ₃ ch ₃ cf ₃ CH ₃ the ch ₃ Br CO2CH3 cf ₃ Ph cf ₃ CO2CH3 cf ₃ Ph cf ₃ CO2CH3 cf ₃ CH ₃ cf ₃ ch ₃ cf ₃ ch ₃ ocf ₃ CO2CH3 0CF3 CH ₃ the ch ₃ Br CO2CH3 Br CO2CH3 cf ₃ LPR cf ₃ LPR Br LPR OCF ₃ LPR the et cf ₃ et OCF ₃ CO2CH3 OCF ₃ LPR cf ₃ ch ₃ CFj

H 217-220 H 227-228 H 185-187 H 189-190 H 179-180 H 214-215 H 192-193 H 231-232 H 222-224 COCH3 103-106 H 235-239 H 228-230 COCH3 155-156 H 144-146 H > 250 H 145-149 H 200-202 H 206-208 H 189-190 COCH3 195-197 COCH3 158-160 COCH3 63-70 H 192-194 H 132-135 H 195-197 H 165-169 H 161-162 H 211-215 COCH3 198-200 H 150-152 H 154-155 H 167-168 H 152-153 H 155-157 H 120-122 H 161-163 H 160-161 H 177-179

HU 204260 Β

Compound number r ₂ B Ri Y Mp. (° C) 255 5-CF ₃ IPr OCF 3 H 148-149 256 5-CF ₃ CH ₃ OCF 3 H oil 256 5-CF3 CO2CH3 cf ₃ COCH3 180-181 257 5-C1 IPr cf ₃ COCH3 115-116 259 5-CF3 CO2CH3 cf ₃ CO2CH3 157-159 260 5-C1 CO2CH3 cf ₃ CO2CH3 218-220 261 5-C1 ch ₃ cf ₃ CO2CH3 112-115 262 4-F 4-F-Ph cf ₃ CO2CH3 100-104 263 5-C1 sec-Bu cf ₃ H 177-178 264 5-C1 t-Bu cf ₃ H 181-183 265 5-C1 1-Pr cf ₃ CO ₂ CH ₃ 180-181 266 5-C1 sec-Bu cf ₃ CO2CH3 158-159 267 5-CF3 CO2CH3 cl H 208-210 268 5-CF3 CO2CH3 Br H 201-202 269 5-CF3 4-F-Ph cf ₃ H 216-217 270 5-CF3 4-F-Ph cl H 195-197 271 5-CF3 H cf ₃ H 160-165 272 5-CF3 H cl H 180-190 273 5-CF3 H Br H 175180

Table 11 Compound number Ri R2 from Y B Op. ('C) 291 cf ₃ cl ch ₃ H ch ₃ 149-153 292 cf ₃ cl ch ₃ H co ₂ ch ₃ 187-190 293 cf ₃ cf ₃ ch ₃ H co ₂ ch ₃ 200-203 294 cf ₃ H ch ₃ H ch ₃ Solid 295 cf ₃ cl CH ₂ Ph H co ₂ ch ₃ 207-210 296 cf ₃ cl CH ₂ Ph H ch ₃ 190.5 to 193 297 cf ₃ cf ₃ ch ₃ H ch ₃ 183-185 298 cf ₃ cl H H ch ₃ 86.5 to 90 299 cf ₃ cf ₃ CH ₂ Ph H ch ₃ 175-179 300 cf ₃ cf ₃ H H ch ₃ 190.5 to 193

Formulation and Application Examples The active compounds of the present invention are formulated with a carrier suitable for agricultural use, such as a liquid or solid carrier or an organic solvent. Formulations containing the active ingredient of formula (I) may be prepared by conventional methods. Such formulations include, for example, powders, granules, pellets, solutions, suspensions, emulsions, wettable powders, emulsifiable concentrates and dry powder formulations. Most of these formulations are directly applicable. The spray formulations are diluted with a suitable material and the amount of spray applied ranges from 1 liter to a few hundred liters. Concentrated formulations are used as intermediates in further formulations. The formulations contain from 1 to 99% by weight of active ingredient (s), from 0.1 to 20% by weight of surfactant (s) and from 5 to 99% by weight of solid or liquid diluent (s). The effective amounts of the components in the various formulations are as follows:

45 E preparation photo material thinner Material crowd% surfactant material Wettable powder 25-90 0-74 1-10 50 Oil suspensions, emulsions, solutions - (including emulsifiable concentrates) 5-50 40-95 0-15 55 powders 1-25 70-99 0-5 granules, pellets 1-95 5-99 0-15 60 High concentration preparations 90-99 0-10 0-2

HU 204260 Β

The amount of active ingredient in the composition will, of course, depend on the intended use and the physical properties of the active ingredient. It is sometimes desirable to have a higher concentration of surfactant relative to the active ingredient, which may be achieved either by incorporation into the formulation or by tank mixing.

Commonly used solid diluents are described in Watkins et al., Handbook Dust Diluents and Carriers, 2nd Ed., Dorland Books, Caldwell, 10 New Jersey. Higher absorbency diluents are preferred for wettable powder formulations, more dense for powder formulations. Commonly used liquid diluents and solvents are described in Marsden, 15 Solvents Guide, 2nd Ed., Interscience, New York.

In the 1950 edition. The suspension concentrates preferably have a solubility of 0.1% by weight and preferably no phase separation at 0 ° C. Surfactants and recommended uses are described in "Mc Cutcheon's Detergents and Emulsifiers Annual", Allured Publ. Corp., Ridgewood, New Jersey, and Sisely and Wood, "Encyclopedia and Surface Activating Agents", Chemical Publ.

Co., Inc., New York 1964, in publications. Each composition may contain minor amounts of additives such as antifoam, anemone, antifoam, an anticorrosive, and an antibacterial agent. (Applicable additives should preferably be approved by the United States Environmental Protection Agency.) _

The process for preparing such compositions is well known. The solutions are obtained by simple mixing of the ingredients. Fine granular solid compositions are prepared by mixing and generally grinding in a hammer or 35 fluid mills. The suspensions are prepared by wet milling (such as that described in U.S. Patent No. 30,608,084). Granules or pellets are prepared by spraying or agglomerating the preformed granules 40. See J.E. Browing, Agglomeration,

Chemical Engineering, December 4, 1967, p. Article 147 and the "Perry's Chemical Engineer's Handbook",

4th Ed., McGraw-Hill, New York, 1963. p. 8-59. 45 publications.

The formulations of the active compounds prepared by the process of the present invention are illustrated in the following examples, in which the term "%" refers to% by weight.

The ingredients were mixed and stirred under slight heating to accelerate dissolution. The undissolved materials were removed by filtration through a fine sieve during the packaging operation.

Example B)

Wettable powder making ~

We made a wettable powder from the following ingredients:

3,3a, 4,5-Tetrahydro-2 - {[4- (trifluoromethyl) phenylamino] carbonyl} -2H-benz [g] indazole-3a-carboxylate

Sodium alkylnaphthalenesulfonate

Sodium lignosulfonate

Synthetic amorphous silica

kaolinite

30%

2%

2%

635

Example C)

Dust Preparation Dust Preparation The following ingredients were prepared: The active ingredient was heated to reduce viscosity and sprayed onto inert materials in the mixer. The material was then ground in a hammer mill, mixed again and passed through a sieve of 270 µm.

10%

90%

The wettable powder formulation of Example B)

Pyrophylls (powder)

The wettable powder and pyrophyll diluent were thoroughly mixed and then packaged. Products made in this way can be used as a dusting agent.

Example D)

Granules

Granules were prepared from the following ingredients:

3,3a, 4,5-Tetrahydro-3a-methyl-N- [4- 10%

- (trifluoromethyl) phenyl] -2H-benz [g] indazol-2-carboxamide

Attapulgite Granulate (Low Volatile 90%, 0.71 / 0.30 mm; Passes through U.S.S. No. 25-30)

The active ingredient was mixed in a suitable solvent and then sprayed onto a dust-free attapulgite granulate in two cone mixers. The granulate was then heated to deflate the solvent 50, then cooled and packaged.

Example E)

granule

Example A)

Preparation of Emulsifiable Concentrate An emulsifiable concentrate was prepared from the following ingredients:

3,3a, 4,5-Tetrahydro-3a-methyl-N- [4- 5% We made pellets the following fall - (trifluoromethyl) phenyl] -2H-benz [gJ vesicle: indazol-2-carboxamide Wettable according to Example D) 15% Oil-soluble sulfonates and poly (oxy) 4% powder ethylene) ethers Gypsum 69% xylene 91% 60 Potassium sulphate 16%

HU 204260 Β

The ingredients were mixed in a rotary mixer and water was sprayed onto the mixture for granulation. When most of the material reached a particle size of 0.1-0.42 mm (U.S.S. No. 18-40), the granulate was removed, dried and sieved. The larger particle size materials were broken into the desired particle size range. The granulate thus obtained contains 43% of the active ingredient.

Example F)

solution Preparation

We made a solution of the following ingredients:

3,3a, 4,5-Tetrahydro-2 - {[4- (trifluoro-10%)

-methyl) -phenylamino] -carbonyl} -2H-benz- [g] indazole-3a-carboxylate

Isophorone 90%

The ingredients were mixed and mixed to provide a solution for immediate, low volume application.

Example G)

Highly active concentrate

We made a concentrate of the following ingredients:

3,3a, 4,5-Tetrahydro-3a-methyl-N- [4- 95.0%

- (trifluoromethyl) phenyl] -2H-benz [g] -indazole-2-carboxamide silica aerogel 0.5% synthetic amorphous silica 4.5%

The ingredients were mixed and ground in a hammer mill and sieved through a 3 mm mesh sieve.

The active compounds of formula (I) may be admixed with one or more other insecticides, fungicides, nematocides, bactericides, acaricides or other biologically active substances to form multi-component, broad-spectrum pesticides.

Other agricultural pesticides which can be mixed with the active compounds of formula (I) according to the invention include:

Insecticides

3- (Dimethoxy-phosphinoyloxy) -N-methyl-cis-rotonamide (Moncrotophos)

2,3-dihydro-2,2-dimethyl-7-benzofuranyl-N-methylcarbamate (carbofuran)

O, O-Dimethyl-1- (2,4,5-trichlorophenyl) -2-chloro-vinyl phosphate (Tetrachlorvinphos)

O, O-Dimethyl-2- (dicarbethoxyethyl) dithiophosphate (malathion)

O-O-Dimethyl-O- (p-nitrophenyl) thiophosphate (methyl parathion)

N-methyl-1-naphthylcarbamate (carbaryl)

S-methyl-N- (methylcarbamoyloxy) thioacetimidate (methomyl)

N '- (4-chloro-o-tolyl) -N, N-dimethylformamide (Chlorodimeform)

O, O-Diethyl-O- (2-isopropyl-4-methyl-pyrimidinyl) -thiophosphate (diazinon) chlorinated camphene (toxafen)

O-Ethyl-Op-nitrophenyl-phenyl-phosphonation (EPN) (1R, 3R) -3- (2,2-dibromo-vinyl) -2,2-dimethyl-cyclopropanecarboxylic acid (S) -ct- cyano-m-phenoxybenzyl ester (deltamethrin)

S-methyl - [(dimethylcarbamoyloxy)] thioformimidate (oxamyl) α-cyano-m-phenoxybenzyl-α-isopropyl-p-chlorophenyl acetate (fenvalerate) (±) -cis, trans-3- (2,2-Dichloro-vinyl) -2,2-dimethyl-cyclopropanoic acid 3-phenoxybenzyl ester (permethrin)

2,2-Dimethyl-3- (2,2-dichloro-vinyl) -cyclopropanecarboxylic acid (a-cyano-3-phenoxybenzyl) ester (cypermethrin)

O-Ethyl S- (p-chlorophenyl) ethyl phosphonodithioate (profenophos)

0-ethyl-O- [4- (methylthio) phenyl] -S-n-propylphosphorothiol thionate (sulprophos).

In addition, the following insecticides may also be used: triflumuron, diflubenzuron, metopren, buprofezin, thiodicarb, acephate, azinphos-methyl, chlorpyrifos, dimethoate, phonophos, isofentos, methidathion, methamidophos, monocrotophos, phosfm, , profenofos, terbufos, trichlorphos, methoxychlor, bifenthrin, bifenate, cyfluthrin, fenpropathrin, fluvalinate, flucitrinate, tralomethrin, metaldehyde and rotenone.

Fungicides

2-Methoxycarbonylamino) -benzimidazole (carbendazim) tetramethyluran disulfide (thiurane) n-dodecylguanidine acetate (dodine) manganese ethylene bis-dithiocarbamate (maneb)

1,4-Dichloro-2,5-dimethoxybenzene (chloroneb) 1-butylcarbamoylbenzimidazole-2-methylcarbamate (benomyl)

1- [2- (2,4-Dichlorophenyl) -4-propyl-1,3-dioxalan-2-ylmethyl] -1H-1,2,4-triazole (propiconazole)

2-Cyano-N- (ethylaminocarbonyl) methoxyiminoacetamide (cymoxanyl) 1- (4-chlorophenoxy) -1- (1 H -1,2,4-triazol-1-yl) -3,3-dimethyl-2-butanone (triadimphone)

N- (trichloromethyl-thio) phthalimide (folpet)

- {[bis (4-fluorophenyl)] - (methyl) silylmethyl} -1H1,2,4-triazole

nematicides

S-methyl-l- (dimethylcarbamoyl) -N- (methyl-carbamoyloxy) -tioformimidát

S-methyl l-carbamoyl-oxy-N-methylcarbamoyl) -tioformimidát

0-ethyl-0 '- [4- (methylthio) -m-tolyl] -N-isopropylphosphoramidate (fenamiphos)

Bactericides tribasic copper sulfate streptomycin sulfate

HU 204260 Β

acaricide

2-sec-butyl-4,6-dinitrophenyl-senecionate (binapacryl) -methyl-LS-dithio-H-PjkinoxaEn-4-one (oxithiokinox) -1,1-bis (p-chlorophenyl) -2,2 , 2-trichloroethanol (dicofol) 4,4'-dichloroethylbenzylate (chlorobenzylate) bis (pentachloro-2,4-cyclopentadien-1-yl) (diene chloro) tricyclohexyltin hydroxide (cyhexatin) trans -5- (4-Chloro-phenyl) -N-cyclohexyl-4-methyl-2-oxo-thiazolidine-3-carboxamide (hexylthiazox) amitraz propargite fenbututa tin oxide bisclofentezine

Biological agents Bacillus turingiensis Avennectin B.

The composition of the present invention is widely applicable to leaf pests and soil insects. The composition of the present invention is effective against a number of insects which cause very significant economic damage, such as insects of the order Lepidoptera, Homoptera and Coleoptera. The following insects were tested: Spodoptera frugipedra, Antonomus grandis, Ostrinia nubilatis, Diabrotica undecimpunctata howardi, Mecrosteles fascifrons and Heliotis virescens. However, the compositions of the present invention are not only useful against the insects listed above.

The composition of the present invention containing the active ingredient of the formula I is applied to the agricultural product as an insecticide with an effective amount of the active ingredient at the site of infection, in the protected area or directly on the insects.

A preferred application is spraying with a sprayer, which enables the active ingredient to be uniformly distributed over foliage, soil or the infected or protected part of the plant. Granule formulations of the active compounds may also be applied to the soil, to the foliage or, if appropriate, may be incorporated into the soil. Surface or soil treatment can be used.

The active compounds of the present invention are formulated together with an agricultural carrier or diluent. The most preferred treatment method is spraying with an aqueous dispersion or refined oily suspension of the active ingredient of formula (I) prepared by the process of the present invention.

The effective amount of the active ingredient of the formula I employed will depend on the species, stage of development, size, location of the insect to be killed, host plant, period of application, air humidity, temperature conditions, and the like. Under normal conditions, generally 0.05 to 2 kg of active ingredient per hectare are required for adequate field protection, but in some cases 0.01 kg / ha may be sufficient, but in some cases up to 8 kg / ha may be required. may also be necessary.

The following examples illustrate the activity of the active compounds of the formula I against various insects. In the assays, the active compounds 1-8 are the same as the compounds 1-8. with the active compounds prepared in Examples 9-181. 12-13. Tables 182-300. s. 7-11. tables. The active ingredient not listed in the tables was either not tested or had at least 35 killing activity of at least 80%.

Table 12

In the formula (XIV), the substituent represents

Dry. number rr r ₂ J Y THE B 9 4-Cl H H H CH H 10 4-Br H H H ch ₂ H 11 4-OCFs H H H CH ₂ H 12 4-Cl 5-C1 H H CH ₂ H 13 4-Br 5-C1 H H CH ₂ H 14 4-CF ₃ 5-OMe H H CH ₂ H 15 4-CF3 5 OCFzH H H CH ₂ H 16 4-CFj 5-F H H CH H 17 4-CF3 4-CI - H H ch ₂ H 18 4-CF3 4-F H H ch ₂ H 19 4-CF3 5,6-di-Cl H H CH ₂ H 20 4-CF3 5-F H H CH ₂ Cozma 21 4-CF3 5-OMe H H CH ₂ Cozma 22 4-CF3 4-Cl H H CH ₂ Cozma 23 4-CF3 4-F H H CH ₂ CO ₂ Me 24 4-CF3 5,6-di-Cl H H CH ₂ Cozma 25 4-CF3 H H H CH ₂ et

HU 204260 Β

Dry. number Ri r ₂ J Y THE B 26 4-CF ₃ H H H ch ₂ CH ₂ -Ph-4-F 27 4-CF3 H H H ch ₂ (CH ₂ ) ₂ CN 28 4-CF3 H H H ch ₂ (CH ₂ ) ₃ CN 29 4-CF3 H H H ch ₂ CO ^ t 30 4-CF3 H H H ch ₂ CO ₂ (CH ₂ ) ₂ Cl 31 4-CF3 H H H ch ₂ CO ₂ (CH ₂ ) ₂ Br 32 4-CF3 H H H ch ₂ CO ₂ CH ₂ CF ₃ 33 4-CF3 H H H ch ₂ co ₂ ch ₂ cci ₃ 34 4-CF3 H H H ch ₂ conh ₂ 35 4-CF3 H H H ch ₂ CONHMe 36 4-CF3 H H H ch ₂ CONMe ₂ 37 4-CF3 H H H ch ₂ CON (H) CH ₂ CH = CH ₂ 38 4-CF3 H H H ch ₂ CON (Me) CH ₂ CH = CH ₂ 39 4-CF3 H H H ch ₂ CONH (4-Cl-Ph) 40 4-C1 5-C1 H H ch ₂ CO ₂ Me 41 4-Br 5-C1 H H ch ₂ CO ₂ Me 42 4-CF3 H H H ch ₂ CO-piperidinyl 43 4-CF3 H H H ch ₂ CO ₂ H 44 4-CF3 H H H ch ₂ CO ₂ Well 45 4-CF3 H H C (0) Me ch ₂ C0 ₂ Me 46 4-CF3 H H Me ch ₂ CO ₂ Me 47 4-CF3 H H CO ₂ Me ch ₂ CO ₂ Me 48 4-CF3 H H C (O) Me ch ₂ H 49 4-CF3 H 4-F-Ph H ch ₂ H 50 4-C1 H 4-F-Ph H ch ₂ H 51 4-CF3 H 4-Cl-Ph H ch ₂ H 52 4-C1 H 4-Cl-Ph H ch ₂ H 53 4-CF3 H H H ch ₂ CH ₂ CH-CH ₂ 54 4-CF3 H H H ch ₂ CH ₂ Ph 55 4-CF3 H H H ch ₂ CO ₂ Et 56 4-C1 H H H ch ₂ CO ₂ Et 57 4-Br H H H ch ₂ COjMe 58 4-Br H H H ch ₂ Coze 59 4-C1 H H H ch ₂ CO ₂ Me 60 4-C1 5-OMe H H ch ₂ H 62 4-CF3 H H CO ₂ -t-Bu ch ₂ H 63 4-SMe 5-C1 H H ch ₂ H 64 4-CO ₂ Et 5-C1 H H ch ₂ H 65 4-SMe 5-C1 H H ch ₂ CO ₂ Me 66 4-CO ₂ Et 5-C1 H H ch ₂ CO ₂ Me 67 4-CF3 H H H ch ₂ ch ₂ H 68 4-CF3 H H H ch ₂ ch ₂ Me 69 4-C1 H H H ch ₂ ch ₂ H 70 4-C1 H H H ch ₂ ch ₂ Me

Table 13

In formula (XV), substituent meanings

Dry. number Ri r ₂ Y THE R8 71 4-CFj H H SHE H H 72 4-CF3 H H S H H 73 3,4-Cl H H 0 H H 74 4-Br H H 0 H H

HU 204260 Β

Dry. number Ri Ri Y THE 75 3-CFj H H 0 76 4-Cl H H 0 77 3-Cl H H 0 78 3,4-Cl H H s 79 4-Br H H s 80 3-CFj H H s 81 4-C1 H H s 82 3-Cl H H s 83 3-CFj H H SO (ct) 84 4-CFj H H so ₂ 85 4-CFj H H SO (a) 86 3,4-Cl H H SO2 87 4-Br H H SO (a) 88 4-Br H H © SO 89 3,4-Cl H H SO (a) 90 3,4-Cl H H so © 91 4-C1 H H SO (a) 92 4-C1 H H © SO 93 3-Cl H H SO (ct) 94 3-Cl H H © SO 95 4-Br H H so ₂ 96 3-CFj H H SO2 97 4-C1 H H SO2 98 3-Cl H H so ₂ 99 3-CFj H H © SO 100 4-CF ₃ 5-C1 H s 101 3-CFj 5-C1 H s 102 4-C1 5-C1 H s 103 3-Cl 5-C1 H s 104 4-Br 5-C1 H s 105 3,4-Cl 5-C1 H s 106 4-CFj 6-Cl H s 107 3-CFj 6-C1 H s 108 4-C1 6-C1 H s 109 3-Cl 6-C1 H s 110 4-Br 6-Cl H s 111 3,4-Cl 6-Cl H s 112 4-CF ₃ 5-C1 H SO2 113 3-CF ₃ 5-C1 H so ₂ 114 4-C1 5-C1 H so ₂ 115 3-Cl 5-C1 H SO2 116 4-Br 5-C1 H SO2 117 3,4-Cl 5-C1 H SO2 118 4-CFj 6-C1 H SO2 119 3-CFj 6-C1 H SO2 120 4-C1 6-C1 H SO2 121 3-Cl 6-Cl H SO2 122 4-Br 6-Cl H SO ₂ 123 3,4-Cl 6-Cl H SO2 124 4-CF ₃ 5-C1 H SO (a) 125 4-CFj 5-C1 H © SO 126 3-CFj 5-C1 H SO (a) 127 3-CFj 5-C1 H © SO 128 4-C1 5-Cl H SO (a) 129 4-0 5-C1 H © SO 130 3-Cl 5-C1 H SO (ct)

Η

Η

Η

Η

Η

Η

Η

Η

Η

Η

Η

Η

Η

Η

Η

Η

Η

Η

Η

Η

Η

Η

Η

Η

Η

Η

Η

Η

Η

Η

Η

Η

Η

Η

Η

Η

Η

Η

Η

Η

Η

Η

Η

Η

Η

Η

Η

Η

Η

Η

Η

Η

Η

Η

Η

Η $

HU 204260 Β

Dry. number Ri r ₂ Y THE rg rl 131 3-C1 5-C1 H SO (p) H H 132 4-Br 5-C1 'H SO (a) H H 133 4-Br 5-C1 H so (3) H H 134 3,4-Cl 5-C1 H SO (a) H H 135 3,4-Cl 5-C1 H δθ (β) H H 136 4-CF ₃ 6-C1 H SO (a) H H 137 4-CF ₃ 6-C1 H δθ (β) H H 138 3-CF ₃ 6-C1 H SO (a) H H 139 3-CF ₃ 6-C1 H δθ (β) H H 140 4-Cl 6-C1 H SO (a) H H 141 4-Cl 6-C1 H δθ (β) H H 142 3-C1 6-C1 H SO (a) H H 143 3-C1 6-C1 H δθ (β) H H 144 4-Br 6-C1 H SO (a) H H 145 4-Br 6-C1 H δθ (β) H H 146 3,4-Cl 6-C1 H SO (a) H H 147 3,4-Cl 6-C1 H δθ (β) H H 148 4-CF ₃ 5-Br H s H H 149 3-CF ₃ 5-Br H s H H 150 4-Cl 5-Br H s H H 151 3-C1 5-Br H s H H 152 4-Br 5-Br H s H H 153 3,4-Cl 5-Br H s H H 154 4-CF ₃ H H δθ (β) H H 155 4-CF ₃ H H s H H 156 4-CF ₃ H H s H H 157 ... 4-CF ₃ H H s H H 158 4-CF ₃ 5-C1 C (0) Me s H H 159 4-CF ₃ 5-C1 CO ₂ Me s H H 160 4-CF ₃ 5-C1 Me s H H 161 4-Cl H C (0) Me s H H 162 4-Cl H Me s H H 163 4-Cl 5-C1 C (O) Me s H H 164 4-Cl 5-C1 Me s H H 165 4-CF ₃ H H s Me Me 166 4-Cl H H s Me Me 167 4-Br H H s Me Me 168 4-Cl 5-C1 H s Me Me 169 4-Br 5-C1 H s Me Me 170 4-CF ₃ H H s Me H 171 4-CF ₃ H H s H Me 172 4-Cl H H s Me H 173 4-Cl H H s H Me 174 4-Br H H s Me H 175 4-Br H H s H Me 176 4-CF ₃ 5-C1 H s Me H 177 4-CF ₃ 5-C1 H s H Me 178 4-Cl 5-C1 H s Me H 179 4-Cl 5-C1 H s H Me 180 4-Br 5-C1 H s Me H 181 4-Br 5-C1 H s H Me

Example 9 was carried out in small, 237 cm ³ plastic bowls. To each of the effects of Totpodoptera frugiperda, ten third developmental animals were assayed with 0.5 cm thick wheat germ on a Spodoptera frugipedra larva. Ez21

After 204260 Β, 0.1% (w / v) acetone / distilled water (75:25 in volume) solutions of the active ingredient to be tested were sprayed into the bowls using different active ingredients per bowl. Spraying was carried out by placing the dishes on an endless belt underneath the spray nozzle's hydraulic nozzle, which delivered 0.55 kg / ha of active ingredient at a pressure of 300 kPa. The plates were then covered and kept at 27 ° C, 50% RH for 72 hours, and then assayed for mortality. Among the active substances tested, the following resulted in 80% or more deaths of Spodoptera frugiperda larvae: 3, 4, 5, 7, 15, 17, 20, 22, 15 23,25, 45,59,72,100,125,148,158,159,160,165,

166, 168, 169, 170, 173, 177, 179, 181, 182, 183,

187, 188, 189, 190, 191, 192, 193, 194, 195, 196,

197, 198, 199, 203, 204, 209, 210, 213, 214, 217,

218, 219, 220, 221, 222, 223, 224, 225, 226, 227, 20

228, 229, 230, 231, 233, 234, 235, 236, 242, 243,

246, 247, 248, 249, 250, 251, 259, 262, 263, 264,

266, 268, 269, 270, 271, 273, 274, 276, 277, 278,

279, 280, 281, 282, 284, 285, 286, 287, 288, 289,

290,291,292,293,295,296,297,298,299. 25

Example 10

Test against Ostrinia nubilalis The tests were carried out in 237 cm ³ plastic bowls containing a mixture of wheat germ with a surface of 6 cm ² and soy flour. Five Ostrinia nubilalis larvae in the third stage of development were placed in each bowl. Then, solutions containing 0.1% w / w of the test substance listed below were sprayed into the bowls, using 35 different active ingredients per bowl, as described in Example 9. The plates were then covered and kept at 27 ° C, 50% RH for 48 hours.

We then examined the extent of death. Of the 40 active compounds tested, the following resulted in 80% or greater death of Ostrinia nubilalis at 2, 3, 4, 5, 15, 22, 23, 29, 45, 47, 53, 54, 55, 56,

58,59,71,72,81,84,91,95,97,100,165,177.

Example 11

Diabrotica undecimpunctata howard test

The tests were carried out in 237 cm ³ plastic bowls containing sprouted wheat kernels. Three assay units of 50 plates each were prepared and pre-injected with solutions containing 0.1% w / v of the test compound. Different active ingredients were used per unit, and spraying was carried out using the procedure described in Example 9. After the spray was dried in the bowls, five diabrotica undecimpunctata howard larvae in the third stage of development were placed in each bowl. To prevent dehydration, damp cotton wool was placed in each bowl, and 60 µl were covered. The plates were then stored at 27 ° C and 50% relative humidity for 48 hours.

n The mortality rate was then examined. Among the active substances tested, the following resulted in a

- 80% or more mortality of 5 diabrotica undecimpunctata howard: 1,2,3,4,5,7, -15,16,17,20,21, t 22,23,25,27,29,35,36, 45,47,53,54,56,58,59,72, t 76,79,81,84,91,95,97,100,124,125,132,133,148,

154,157,158,160,162, 165,166,168,169,170,172,

- 10,173,174,175,180, 182,183,184,187,188,189, 190, i 191,192,193,194,195,196,198,199,200,201,202,

203,204,205,207, 209,210,211,212,213,214,215,

217,218,219,220,221,222,223,224,225,226,227,

228,229,230,233,234,235,236,237,242,243,244,, 15,246,247,248,249,250,251,259,260,261,263,264,, 265,267,268,269,270,273,276,277,278,279,280,

281,282,285,286,287,288,289,290,291,292,293,

294,295,297,298,299.

Example 12

Anthonomus grondis Assay We placed one adult Anthonomus grandist in a series of 255 cm? The treatment was carried out according to the procedure described in Example 9 and the mortality was determined 48 hours after the treatment. Among the active substances tested, the following resulted in 80% or more death of Anthonomus grandis: 1,2, 3,4,5,7,14,15,22,23,35,45,47,53,58,59,61 , 67.71, 72,76,81,84,91,97,104,165,177,195,196,210,211, 30,212, 217,218, 219, 220,222, 223,225, 226, 227,228, 229, 230, 231, 233,234,235,236, 239, 242, 243,244, 246, 247 248, 249, 250, 251, 259,260, 261,262,263, 265, 266, 267, 268, 269, 270, 271, 273, 274, 275,276, 277, 278, 279, 280, 281, 282, 285, 286, 287, 288,289, 35,290,291,292,293,294,295,296,297,298,299.

Example 13

Assay against Mascrosteles fascifrons Assays were carried out in a series of 340 cm ³ , 24.5 mm 40 thick sterilized soils containing oat (Avena sativa) seedlings.

The bowls were then sprayed with solutions containing 0.1% (w / w) of the test substance listed below. Different active ingredients were applied to the bowl and sprayed according to the procedure described in Example 9. After the spray liquid in the bowl had dried, 10-15 adult Macrosteles fascifrons were added to each covered bowl. The plates were then maintained at 27 ° C, 50% relative humidity for 48 hours. The percent mortality was then determined. Among the active compounds tested, the following resulted in 80% or greater death of Mascrosteles fascifrons: 2, 3, 4,5, 7,15,16, 20,22,23, 25, 45, 47,53,

59, 72, 100, 104, 157, 158, 159, 160, 162, 162, 165,166,168,169,171,172,173,174,175,177,179,181,182,184,189,190,191,192,193,194,197,198,203, 204,205,207,208,209,205,207,208,209,205,207,208,29,25,27,220,2,2,2

242,243,244,245,246,247,248,249,250,259,260,

HU 204260 Β

261, 262,263,264, 265, 266,268,269, 270,273,277,

278,280,281,285,286,291,292,294,297,298.

Example 14

Test against Heliothis virescens

Heliothis virescens larvae in the third stage of development were treated according to the procedure described in Example 9, but the extent of death was determined 48 hours after the treatment. Among the active compounds tested, the following resulted in 80% or more mortality of Heliothis virescens larvae: 5,7,15,23,25,39, 100, 160, 165, 168, 177, 182,183, 184, 187, 188, 190, 191, 192.194, 195.196, 197.198, 203, 213, 214, 217, 218, 219, 220, 221, 222, 223, 224, 225, 226, 227, 228, 229, 230, 233, 234, 235, 236, 242, 243, 246, 247, 248, 249, 250, 251, 259, 262, 263, 264, 266, 268, 269, 270, 271, 273, 276, 279, 281, 282, 284, 285, 286, 287, 288,

289,290,291,292,293,295,296,297,298,299.

Example 75

Soil treatment against Diabrotica undecimpunctata howard

The tests were carried out in a 73 mm cylindrical flask containing 200 g of wet safflower wood material and 2 Dekalb T1100 maize kernels.

The treatment was carried out by placing the cylindrical vessels on an endless belt beneath the nozzle of a spraying machine and applying 0.112 kg / ha of active ingredient (about 2 ppm soil concentration) from the nozzles to a pressure of 300 kPa. After spraying, the corn kernels were covered with soil and 10 Diabrotica undecimpunctata howardis in third development were added to each roll. The rollers were then stored at 24 ° C, 70% relative humidity for 16 hours in the light, 8 hours in the dark for 7 days and then tested for effect. A scale of 1 to 5 was used for the assay, with 1 indicating that the root system was not damaged and 5 being indicating that the root system was completely damaged. Control was done by determining the percentage of emerged seedlings.

The result is summarized in the following table:

Compound number root damage Rising% 2 1.5 100 3 1.0 88 5 1.0 100 15 1.3 88 20 1.6 75 22 2.0 75 23 1.0 75 29 1.0 100 59 1.1 100 190 1.1 88 191 1.1 88 194 1.5 100 203 1.1 100 205 1.2 75 213 1.2 83

9-15. in test examples 223, 224, 225, 228, 236, 269 and 270 were tested at 0.14 kg / ha and compounds 231 and 232 at 0.028 kg / ha. For compounds 228, 231, 232, 236, 269, and 270, only one assay unit was used.

Example 16

Comparison of compound 222 against Spodoptera jrugiperda (FAW), Anthonomus grondis (BW) and Heliothis virescens (TB)

The tests were carried out according to the procedure described in Examples 9, 12 and 14. The active ingredient was administered at the doses given in Table 21. At a dose of 0.01 kg / ha, a solution of 0.0018% by weight was sprayed.

Claims (2)

Insecticidal compositions comprising a biologically active agent and a solid carrier preferably kaolinite and / or gypsum - or a liquid carrier, preferably xylene - and optionally a surfactant, preferably sodium alkylnaphthalenesulfonate and / or a nonionic emulsifier, containing from 0.00181% to 95% by weight of the active ingredient substituted indazole derivatives and their agriculturally suitable metal salts having the formula: wherein A is oxygen, sulfur, -CH ₂ -, -CH (CH ₃ ) -, -CH ₂ CH ₂ -, -N (R 6) -, -SO (a) -, -SO (P) - or -SO ₂ ; B is hydrogen, phenyl substituted with (C 1 -C 6) alkyl, (C 2 -C 6) alkenyl, cyano (C 2 -C 6) alkyl, phenyl, halo or (C 1 -C 4) alkoxy, benzyl or halo in the phenyl ring benzyl, CO ₂ R ₃ 'or C (O) NR ₃ ' R _{4 in} which R ₃ 'is C 1-4 alkyl substituted with 1 to 3 times hydrogen, alkali metal or optionally substituted with halogen, R 3 'is hydrogen or C 1-4 alkyl, R ₄ is hydrogen, C 1 -C 4 alkyl, C 2 -C 6 alkenyl or phenyl substituted by halogen, or HU 204260 Β R ₃ 'and R 1 together with the nitrogen atom to which they are attached form a 5 or 6 membered heterocyclic ring containing one nitrogen atom; J is hydrogen or phenyl substituted with halogen; 5 K is hydrogen; R 1 is halogen, C 1 -C 4 alkoxy, tri-halo (C 1 -C 4 alkyl) -, substituted 2-3 times with halogen, SR 3 '' - or CO 2 R 3 '' where R 3 '' is 1- Alkyl having 4 carbon atoms, m being 1, m being 2, R 1 being 2 and 3 or 5 at the 4 or 3 position; R 2 is hydrogen, halogen, C 1 -C 4 alkyl, tri-halo (C 1 -C 4 alkyl), or C 1 -C 4 alkoxy optionally substituted with halo; R5 is hydrogen, (C1-C4) -alkyl or benzyl; 20 R5 is C1-C4 alkyl; n is 1 or R _{2 is} halogen or 1 or 2; g is 0.1 or 2; Y is hydrogen, (C 1 -C 4) alkyl, (C 1 -C 4) alkylcarbonyl, or (C 1 -C 6) alkoxy) carbonyl. 2. A process for the preparation of substituted indazole derivatives of the general formula φ, their geometric and stereoisomers, and their agriculturally suitable metal salts, wherein A is oxygen, sulfur, -CH ₂ -, -CH (CH 3) -, -CH ₂ CH ₂ -, -N (R 6) -, -SO (a) -, -SO (P) - or -SO ₂ ; B is hydrogen, phenyl substituted with C 1 -C 6 alkyl, C 2 -C 6 alkenyl, cyano (C 2 -C 6 alkyl), phenyl, halogen or C 1 -C 4 alkoxy, benzyl, or halogen in the phenyl ring substituted benzyl, CO2R3 'or C (O) NRj' R + in which R 1 'is C 1 -C 4 alkyl substituted with 1 to 3 times hydrogen, alkali metal or optionally substituted by halogen, R 3 'is hydrogen or C 1 -C 4 45; alkyl; R 1 is hydrogen, C 1 -C 4 alkyl, C 2 -C 6 alkenyl or phenyl substituted by halogen, or R3 'and R1 together with the nitrogen atom to which they are attached form a 5 or 6 membered heterocyclic ring containing one nitrogen atom; J is hydrogen or phenyl substituted with halogen; K is hydrogen; ) Ri is halogen, ogén- trihydrate (Ci-C4 alkyl) -!, 2-3-fold substituted by halogen C 1-4 alkoxy, SR 3 '' - or CO ₂ R "'group, wherein R 3''represents C 1-4 alkyl, where m is 1, m for 2, R 1 is at the 4 and 3 or 5 position two halogen atoms; R ₂ is hydrogen, halogen, C 1 -C 4 alkyl, trihalogen (C 1 -C 4 alkyl), or C 1 -C 4 alkoxy optionally substituted with halo; R a is hydrogen, C 1-4 alkyl or benzyl; R5 is C1-C4 alkyl; n is 1 or R _{2 is} halogen or 1 or 2; g is 0.1 or 2; Y is hydrogen, (C 1 -C 4) alkyl, (C 14 -alkyl) carbonyl, or (C 1 -C 6) alkoxy) carbonyl, characterized in that an arylisocyanate of formula (Π) is indazole derivative of formula (EH). reacting - in the formulas, the substituents are alkylating a compound having the above formula (ii) and optionally where B is (C 1 -C 6) alkyl, or (ii) optionally, (B) (C 1 -C 5) alkoxycarbonyl; and (iii) optionally reacting the resulting compound of formula (I) with an hydroxy, alkoxide or hydride of an agriculturally suitable metal to form the agriculturally suitable metal salt.