HUT68254A - Arthropodical and nematicidal sulfonates and process for their use - Google Patents

Description

Sulphonates with Arthropod and Nematoda activity e.J ο l La {rv \ azc <Jukka.

DUNLENA PTY. LTD. , North Sydney, NSW, AU

Filed on: November 9, 1992. Priority: November 19, 1991 (794,554) US

International Application Number: PCT / US92 / 09337

International Publication Number: WO 93/10096

The present invention relates to sulfonates of general formulas (I) and (II) having anti-arthropod and Nematoda activity,

Q is a group of formula (Q-1), (Q-2), (Q-3), (Q-4), (Q-5) or (Q-6),

X represents oxygen, sulfur or = NR,

Y represents an oxygen or sulfur atom,

Z is hydrogen, halogen, -CN, -NO ₂ , C 1-3 alkyl, C 1-3 haloalkyl,

C 1-3 alkoxy, C 1-3 haloalkoxy, or -S (O) _n R,

R represents a C 1-3 alkyl group,

R ¹ is C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 1 -C 5 alkoxy, C 2 -C 5 alkoxyalkyl, C 2 -C 6 alkenyl, C 2 -C 6 haloalkenyl- C2-C6 alkynyl, C3-C6 haloalkynyl, C3-C6 cycloalkyl, 4-7

C 5 -cycloalkylalkyl, -N (R) R, phenyl optionally substituted with 1 or 2 W, benzyl optionally substituted with 1 or 2 W, or C 1 -C 5 alkyl which is -CN, -N ( R ⁴ ) R ⁵ or -S (O) R ⁷ may be substituted, ⁿ

R is hydrogen, C 1-2 alkyl, C 1-2 haloalkyl, formyl, C 2-3 alkylcarbonyl, C 2-3 alkoxycarbonyl, 3 carbon. • · β · ·· · ··· ···

alkenyl or C 3 alkynyl; or

R ¹ and R ^{2 taken} together may be -CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ -, -CH ₂ CH ₂ CH ₂ CH ₂ - or -CH ₂ CH ₂ OCH ₂ CH ₂ -,

R ^{3 is C} 1 -C 2 alkyl or C 1 -C 2 haloalkyl,

5 · ·

R and R are each independently methyl or ethyl

R ⁴ and R ^{5 taken} together may be -CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ -, -CH ₂ CH ₂ CH ₂ CH ₂ - or -CH ₂ CH ₂ OCH ₂ CH ₂ -,

R ^{6 is} hydrogen, C 1-3 alkyl or C 1-3 haloalkoxy,

R represents C1-C2 alkyl or C1-C2 haloalkyl,

W is halogen, C1-2 alkyl, C1-2 alkoxy, -CF ₃ or -OCF ₃ is and n is 0, 1, or second

1118Μ, ΙΑοίοο THE PUBLIC

COPIES

Representative: Gödölle, Kékes, Mészáros & Szabó Patent and Trademark Office 1024 Budapest, Keleti Károly u. 13 / b.

6 ^ 254 {CTD2v3 | K

Ca> 2I3 | ^

CC4P 213 1 ^ 3 (Cl1MWI®

ÉC ilx hZjyV

Sulfonates with Arthropod and Nematoda Action 6S ai oll ^ (hi2oHaUm ·

DUNLENA PTY. LTD., North Sydney, NSW, AU

Inventor: FINKELSTEIN Bruce Lawrence, Newark, DE, US

Date of filing: 9/11/1992

Preferred November 19, 1991 (794,554) US

International Application Number: PCT / US92 / 09337

International Publication Number: WO 93/10096

The present invention relates to sulfonates having arthropod and nematoda activity.

The compounds of the invention are characterized in that they have a (R ¹ ) (R ² ) NC (= X) - or R ¹ -N- = C (Y R) group at the 1,3-position of the -OSO ₃ r group in a heteroaromatic system. They have. U.S. Pat. No. 3,818,102 discloses certain phenylsulfonate carboxamide with insecticidal activity. The carboxamide group of the compound is unsubstituted and may be in position relative to the sulfonate group.

The present invention includes within its scope the compounds of formulas I and II including all geometric

And stereoisomers, agriculturally useful salts of the compounds, agricultural compositions containing these compounds, and use of the compounds for the control of arthropods and nematodes, both in agriculture and in non-agricultural applications. In formulas I and II

Q is a group of formula (Q-1), (Q-2), (Q-3), (Q-4), (Q-5) or (Q-6),

X represents oxygen, sulfur or = NR,

Y represents an oxygen or sulfur atom,

Z is hydrogen, halogen, -CN, -NO ₂ , C 1-3 alkyl, C 1-3 haloalkyl,

C1-C3 alkoxy, C1-C3 haloalkoxy or -S (O) _n R,

R represents a C 1-3 alkyl group,

R ¹ is C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 1 -C 5 alkoxy, C 2 -C 5 alkoxyalkyl, C 2 -C 6 alkenyl, C 2 -C 6 haloalkenyl- C 2 -C 6 alkynyl, C 3 -C 6 haloalkynyl, C 3 -C 6 cycloalkyl, C 4 -C 7 cycloalkylalkyl, -N (R) R optionally substituted with 1 or 2 W substituents phenyl, benzyl optionally substituted with 1 or 2 W, or C 1 -C 5 alkyl which is -CN, 4 5 7

May be substituted by -N (R) R or -S (O) R, ⁿ

R is hydrogen, C 1-2 alkyl, C 1-2 haloalkyl, formyl, C 2-3 alkylcarbonyl, C 2-3 alkoxycarbonyl, C 3 alkenyl or C 3 alkyl. alkynyl; or

R ¹ and R ^{2 taken} together may be -CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ -, -CH ₂ CH ₂ CH ₂ CH ₂ - or -CH ₂ CH ₂ OCH ₂ CH ₂ -,

R ^{3 is C} 1 -C 2 alkyl or C 1 -C 2 haloalkyl,

5

R and R are each independently methyl or ethyl

R ⁴ and R ^{5 taken} together may be -CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ -, -CH ₂ CH ₂ CH ₂ CH ₂ - or -CH ₂ CH ₂ OCH ₂ CH ₂ -,

R ^{6 is} hydrogen, C 1-3 alkyl or C 1-3 haloalkoxy,

R represents C1-C2 alkyl or C1-C2 haloalkyl,

W is halogen, C1-2 alkyl, C1-2 alkoxy, -CF ₃ or -OCF ₃ is and n is 0, 1, or second

Preferred compounds of formula (A) are those compounds of formula (I) wherein

R ¹ is C 1 -C 4 alic, C 3 -C 5 cycloalkyl, C 4 -C 5 cycloalkylalkyl, or C 1 -C 5 alkyl substituted by -CN,

R is hydrogen or methyl,

R is methyl,

X is O or S and

Z is hydrogen or halogen.

Preferred Compounds (B) are Compounds (A) wherein Q is (Q-1) or (Q-6).

Preferred Compounds (C) are Compounds (B) wherein Q is (Q-1).

Preferred Compounds (D) are Compounds (B) wherein Q is (Q-6).

Particularly preferred compounds (E) for their biological activity and ease of synthesis are the following compounds (C):

N- (1-methylethyl) -6 - [(methylsulfonyl) oxy] -2-pyridine carboxamide,

N- (1-methylethyl) -6 - [(methylsulfonyl) oxy] -2-pyridin-carbothioamide,

N- (1-methylpropyl) -6 - [(methylsulfonyl) oxy] -2-pyridinecarboxamide and

3-chloro-N- (1-methylethyl) -6 - [(methylsulfonyl) oxy] -2-pyridinecarboxamide.

The most preferred compound (F) due to its biological activity is the following compound (E):

N- (1-methylpropyl) -6 - [(methylsulfonyl) oxy] -2-pyridinecarboxamide.

The compounds of the invention also encompass racemic and optically active stereoisomers. "Stereoisomers" refers to all isomers of the compounds of formula (I), including enantiomers, diastereomers and geometric isomers. It will be clear to one skilled in the art that one or the other of said stereoisomers is more effective. It is also known how to separate such enantiomers, diastereomers and geometric isomers. The invention also encompasses racemic mixtures, individual stereoisomers and enriched mixtures of stereoisomers.

As used herein, the term alkyl, alone or as part of other groups, such as haloalkyl, includes both straight and branched chain groups such as methyl, ethyl, η-propyl, isopropyl or various butyl groups. , pentyl or hexyl isomers.

Alkoxy means methoxy, ethoxy, n-propyloxy, isopropyloxy and the various butoxy and pentoxy isomers.

Alkenyl means straight or branched chain alkenyl groups such as vinyl, 1-propenyl, 2-propenyl, 3-propenyl and various butenyl, pentenyl and hexenyl isomers.

Alkynyl refers to straight or branched chain alkynyl groups such as ethynyl, 1-propynyl, 3-propynyl and the various butynyl, pentynyl and hexynyl isomers.

Cycloalkyl means cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.

The term halogen, used alone or as part of other groups, such as haloalkyl, denotes fluorine, chlorine, bromine or iodine. In addition, when used as part of other groups, such as a haloalkyl group, said alkyl group may be partially or completely substituted by halogen atoms, which may be the same or different. Examples of haloalkyl groups include -CH ₂ CH ₂ F, -CF ₂ CF ₃ and -CH ₂ CHFC 1. The definition of haloalkenyl and haloalkynyl is analogous to that of '' haloalkyl.

The sum of the carbon atoms of a substituent is denoted by the live carbon atom of carbon j, where i and j are an integer from 1 to 7. For example, the C 2 -alkylcarbonyl-bonded rt (Ö) ÜH ₃ denotes 4 • · ·

C 5 -C 5 alkylcarbonyl includes -C (O) CH ₂ CH ₂ CH ₃ and -C (O) CH (CH ₃ ), C 2 -C 5 alkoxycarbonyl is -C (O). ) OCH ₃ and C 3 alkoxycarbonyl represent -C (O) CH ₂ OCH ₃ and finally C 3 alkoxyalkyl represents -CH ₂ OCH ₂ CH ₃ , -CH ₂ CH _{2 includes} OCH ₃ and -CH (CH ₃ ) OCH ₃ .

Compounds of formula (I) wherein Q is (Q1) and X is oxygen may be prepared according to the procedure outlined in Reaction Equation 1 with the appropriate pyridone (1) with a suitable sulfonyl halide and a base such as triethyl. reaction with an amine or pyridine in a solvent such as dichloromethane. (R, R, R, R, R, and Z have the meanings given above in the formulas in Reactions 1-13.

The pyridones of formula (1) may be prepared from the corresponding benzyloxy compounds of formula (2) under various conditions depending on the nature of the R, R and Z substituents, such as catalytic hydrogenation, aqueous acid (e.g. aqueous hydrogen bromide). in acetic acid) or treated with iodine trimethylsilane as described in a

Reaction equation 2 shows.

Compounds of formula (2) may be prepared from the corresponding acids of formula (3) by any of a number of known methods for preparing amides. For example, the acids may be treated with thionyl chloride or 1,1'carbonyldiimidazole (CDI) in a solvent such as tetrahydrofuran and then reacted with the appropriate amine as shown in equation (3).

The acids of formula (4) may be prepared from the corresponding halogen compounds of formula (5) by substitution with an alkali metal benzylate such as sodium benzylate in a solvent such as tetrahydrofuran or N, N-dimethylformamide with an additional equivalent amount of base. such as sodium hydride to deprotonate the acid as shown in equation 4.

Compounds of formula (4) are known in the literature or readily prepared by known methods (see, for example, Abramovitch, R. Ed., The Chemistry of Heterocyclic Compounds, Pyridine and its Derivatives, Vol. earlier volumes of the series). Some compounds may be prepared by oxidation of the corresponding methyl compound of Formula 5, wherein the oxidizing agent may be, for example, potassium permanganate as described in

Represented by reaction equation 5.

Compounds of formula (I) wherein Q (Q-2) (Q-3) or (Q-4) and X is oxygen may be prepared in the same manner as those in which Q (ΟΙ) ) and an oxygen atom using appropriate starting materials.

Compounds of formula I wherein Q is Q (Q-5) and X is oxygen may be prepared by reacting the corresponding hydroxy compound of formula 6 with a suitable sulfonyl halide and base such as triethyl. with an amine or pyridine in a solvent such as dichloromethane as shown in Reaction 6.

The hydroxy compounds of formula (6) may be prepared from the corresponding benzyloxy compounds of formula (7) wherein the conditions depend on the nature of the substituents R, R and Z, such as by catalytic hydrogenation, aqueous acid (e.g. aqueous hydrogen bromide). in acetic acid) or treatment with iodine trimethylsilane as shown in equation 7.

Compounds of formula (7) may be prepared from the corresponding acids of formula (8) by any of a number of known processes for preparing amides. For example, the acids may be treated with thionyl chloride or 1,1'-carbonyldiimidazole in a solvent such as tetrahydrofuran, and then reacted with the appropriate amine as shown in equation (8).

The acids of formula (8) may be prepared from the corresponding halogen compounds of formula (9) with an alkali metal benzylate such as sodium benzylate.

Reaction 7 in a solvent such as tetrahydrofuran or N, N-dimethylformamide with the addition of an additional equivalent base such as sodium hydride to deprotonate the acid is illustrated in Reaction 9.

Compounds of formula (9) may be prepared from the corresponding bromo (or iodo) thiazole of formula (10) by reaction with an alkyl lithium such as n-butyllithium in a solvent such as tetrahydrofuran and then reacting the product with carbon dioxide. , this is illustrated in Reaction Equation 10.

Compounds of formula (10) are known in the literature or can be readily prepared by known methods (Metzger, ed., The Chemistry of Heterocyclic Compounds, Generic Synthetic Methods for Thiazole and Thiazolium Salts, Vol. ).

The acids of Formula 8 may also be prepared by reacting the corresponding thiazole of Formula 11 with an alkyl lithium such as n-butyllithium in a solvent such as tetrahydrofuran and reacting the product with carbon dioxide as shown in Reaction Equation 11. .

Compounds of formula I wherein Q is Q-6 and X is oxygen are prepared from the corresponding starting materials in the same way as those wherein Q is Q-5 and X is oxygen.

Compounds of formula (I) wherein X represents a sulfur atom are prepared by reacting a compound of formula (I) wherein X represents an oxygen atom with 2,4-bis (methoxyphenyl) -1, 3-Dithia-2,4-diphosphenate-2,2-disulfide is reacted as shown in equation 12.

Compounds of formula (I) wherein X is -NR may be prepared from compounds of formula (I) wherein X is oxygen by reaction with phosphorus oxychloride followed by amine reaction · · ·

- 8 of them, this is shown in reaction equation 13.

Compounds of formula (II) may be prepared from compounds of formula (I) wherein X is oxygen or sulfur. In this case, the compounds of the formula I are reacted with an alkylating agent such as an alkyl halide or a trialkoxonium tetrafluoroborate or another method described by Sandler et al., Organic Functional Group Preparations, Vol. III, Academic Press. , New York, 1972.).

The invention is further illustrated by the following examples.

Example 1

Preparation of N- (1-methylethyl) -6 - [(methylsulfonyl) oxy] -2-pyridinecarboxamide

Intermediate 1

To a solution of 6- (phenylmethoxy) -2-pyridine carboxylic acid in g (230 mmol) of 6-chloro-2-pyridine carboxylic acid and 31 ml (300 mmol) of benzyl alcohol in 1700 ml of tetrahydrofuran was added 21 g (530 mmol). sodium hydride in the form of a 60% solution in mineral oil. The solution was heated to reflux under reflux. An additional 300 mL of tetrahydrofuran was added and the reaction mixture was refluxed overnight. After cooling in an ice bath, benzyl alcohol (7.1 mL, 69 mmol) and 60% sodium hydride in mineral oil (2.8 g, 69 mmol) were added. The reaction mixture was refluxed overnight. The reaction mixture was cooled and poured into water and washed with ethyl acetate. The aqueous phase was acidified to pH 2 with concentrated hydrochloric acid and extracted with dichloromethane. The organic layer was dried over sodium sulfate and the solvent was removed by rotary evaporation to give 39 g of the title compound as a brown solid.

^{Σ Η} NMR (CDC1 _3): S 5.40 (s, 2), 7.1 (m, 2), 7.4 (m, 5), «·« ·

7.86 (in, 2).

2. Internal product

A suspension of N- (1-methylethyl) -6- (phenylmethoxy) -2-pyridine carboxamide g (87 mmol) in 6-phenylmethoxy) -2-pyridine carboxylic acid in 300 ml of thionyl chloride was heated to reflux. under refrigeration. After a few minutes, the reaction mixture became homogeneous and refluxed for 2 hours. The volatile constituents are removed in a rotary evaporator. The residue was dissolved in dichloromethane (300 mL) and added dropwise to a solution of 2-aminopropane (29.8 mL, 350 mmol) in ice-bath cooled with 100 mL of dichloromethane. After 30 minutes, the volatile components were removed in a rotary evaporator. The residue was dissolved in ethyl acetate and washed with water. The organic phase is dried over sodium sulfate and the solvent is removed on a rotary evaporator. 24.7 g of the title compound are obtained in the form of an orange oil.

¹ H NMR (CDCl ₃ ): δ 1.26 (d, 6), 4.22 (m, 1), 5.38 (s, 2), 6.0 (br, 1), 6.95 (d) , 1), 7.43 (m, 4), 7.75 (m, 3).

3.Next product

1,6-Dihydro-N- (1-methylethyl) -6-oxo-2-pyridinecarboxamide

Ethanol (500 mL) was added to a mixture of 24.7 g of N- (1-methylethyl) -6-phenylmethoxy-2-pyridine carboxamide and 11 g of 10% palladium on carbon. The reaction mixture was vigorously stirred and placed under an atmosphere of hydrogen for 4 hours. (Approximately 2100 mL of hydrogen is absorbed.) The reaction mixture is filtered and the catalyst is washed with tetrahydrofuran. The solvent was removed from the filtrate in a rotary evaporator to give 13.8 g of the title compound as a yellow solid.

^Χ Η NMR (CD ₃ SO ₄ CD ₃ ): δ 1.17 (d, 6), 4.0 (m, 1), 6.67 (d, 1), 7.2 (br, 1), 7.75 (dd, 1), 8.15 (br, 1), 11.5 (br, 1).

Ν- (1-methylethyl) -6 - [(methylsulfonyl) oxy] -2-pyridinecarboxamide

To a solution of 1,6-dihydro-N- (1-methylethyl) -6-oxo-2-pyridinecarboxamide (0.50 g, 2.8 mmol) in dichloromethane (40 mL) was added 0.46 mL (3, 3 mmol) triethylamine. The reaction mixture was cooled in an ice bath and methanesulfonyl chloride (0.26 mL, 3.3 mmol) was added. The reaction mixture was stirred at room temperature overnight, then diluted with dichloromethane, washed with water and dried over sodium sulfate. The solvent was removed by rotary evaporation and the residue was purified by chromatography on silica gel eluting with 25% ethyl acetate in hexane. 0.49 g of the title compound is obtained in the form of a white solid. M.p. 78-79 ° C.

¹ H NMR (CDCl 3): δ 1.29 (d, 1), 3.40 (s, 3), 4.23 (m,

1), 7.30 (d, 1), 7.40 (br, 1), 8.00 (d, 1), 8.19 (d, 1).

Example 2

N- (1-methylethyl) -6 - [(methylsulfonyl) oxy] -2-pyridin-carbothioamide

To a solution of 0.50 g (1.9 mmol) of N- (1-methylethyl) -6 - [(methylsulphonyloxy) -2-pyridinecarboxamide in 25 ml of toluene was added 0.59 g of 2,4- bis (methoxyphenyl) -1,3-dithia-2,4-diphosphetane-2,2-disulfide The reaction mixture was refluxed for 2.5 hours, then the solvent was removed by rotary evaporation and the residue was purified by chromatography on silica gel. The eluent was eluted with a gradient of 10-20% ethyl acetate in hexane to give 0.47 g of a yellow solid, NMR showed the product to be the title compound containing a small amount of impurity. Recrystallize from ether / petroleum ether to give a yellow needle, m.p. 110-112 ° C.

^Τ Η NMR (CDCl 3): δ 1.18 (d, 6), 3.37 (s, 3), 4.87 (m, 1), 7.28 (d, 1), 7.97 (dd, 1), 8.63 (d, 1).

»· 4 *

11 In the same manner as in Examples 1 and 2, and in FIGS. using the procedures outlined in Reaction Equations, the following Examples 1-7 are prepared. Tables 1 to 4. The following abbreviations are used in the tables to denote different alkyl chains and rings:

iPr = isopropyl = -CH (CH ₃ ) ₂ nPr = n-propyl = -CH ₂ CH ₂ CH ₃ cPr = cyclopropyl = -CH (CH ₂ ) 2 tBu = tert-butyl = -C (CH ₃ ) ₃ nBu = n-butyl = - (CH ₂ ) 3 (^ 3 sBu = sec-butyl = -CH (CH ₃ ) CH ₂ CH ₃ iBu = isobutyl = -CH ₂ CH (CH ₃ ) ₂

- <2-

Table 1 Compounds of formula III

r ³ -ch ₃ , X-0, Ζ — H r ³ -ch ₃ , XO, Z-H r ³ -ch ₃ , xo, Z-H B ¹ B ² B ¹ B ² B ¹ B ² ch ₃ H Pr C (O) H CH ₂ CH ₂ Cl ch ₃ ch ₃ ch ₃ Pr C (O) CH ₃ CH- (CF ₃ ) CH ₃ E c ₂ h ₅ H Pr C (O) OCH ₃ OCH 3 E ^C 2 ^K 5 ch ₃ Pr allyl CH ₂ CH ₂ OCH ₃ E C ₂ H 5 C ₂ ^h 5 nBu H Ph E nPr H Bu H PhCH ₂ E nPr ch ₃ CH (CH ₃ ) CH ₂ CH ₃ H N (CH ₂ ) ₃ E nPr ^C 2 «5 cPr H alli 1 E Pr H cPr ch ₃ -ch ₂ ch ₂ ch ₂ ch ₂ ch ₂ - Pr ch ₃ CH ₂ (cPr) H -ch ₂ ch ₂ ch ₂ ch ₂ - Pr C2 ^K 5 ch ₂ cf ₃ H -ch ₂ ch ₂ and ₂ ch ₂ - sBu ch ₃ CH (CH ₃ ) CH ₂ N (CH ₃ ) ₂ Η CH (CH ₃ ) CH ₂ F H r ³ -ch ₃ , X-S, Z-H r ³ -ch ₃ , xs, Z-H R ³ -CH ³ , XS, Ϊ > H ch ₃ H Pr C (O) H CH ₂ CH ₂ Cl ch ₃ ch ₃ ch ₃ Pr C (O) CH ₃ CH (CF ₃ ) CH ₃ E C 2 ^h 5 H Pr C (O) OCH ₃ and ₃ H ^c 2 ^h 5 qh ₃ Pr allyl ch ₂ ch ₂ och ₃ H C ₂ «5 c ₂ h ₅ nBu H Ph E nPr H Bu H PhCH ₂ H nPr ch ₃ CH (CH ₃ ) CH ₂ CH ₃ H N (CH ₂ ) ₃ » nPr c ₂ h ₅ cPr H alli 1 H Pr H cPr ch ₃ -CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ - IPr ch ₃ CH ₂ (cPr) H -ch ₂ ch ₂ ch ₂ ch ₂ - Pr C ₂ «5 ch ₂ cf ₃ H -ch ₂ ch ₂ och ₂ ch ₂

13 ~

R ¹ -iPr, R ² -H X S 0 Ri-i-Pr, R ^{3 is} -CH ₃ . Z. * H B ³ 2 B ² X ^C 2 ^K 5 H H NH ch ₂ ci H H nch ₃ cr ₃ H H nc ₂ h ₅ ch ₃ 3-C1 ch ₃ NH ch ₃ 4-C1 ch ₃ nch ₃ ch ₃ 5-C1 ch ₃ nc ₂ h ₅ ch ₃ 3-CH ₃ ch ₃ 4> CH ₃ ch ₃ 5-CH ₃ ch ₃ 3-CF ₃ ch ₃ 5-CF ₃ ch ₃ 3-CN ch ₃ 3-OCH ₃ ch ₃ 5-OCH ₃ ch ₃ 3-OCF ₂ H

Table 2 Compounds of formula IV

r ³ -ch ₃ , X-O, Z-H r ³ -ch ₃ , X-S, Z-H r ² -h, r ³ -ch ₃ , X B ¹ B ² B ¹ B ² B ¹ 2 ch ₃ H ch ₃ H Pr 2-C1 ch ₃ ch ₃ · ch ₃ ch ₃ Pr 4-C1 c ₂ h ₅ H ^c 2 ^H 5 H Pr € Cl nPr H nPr H Pr 2-CH ₃ Pr H Pr H Pr 4-CH ₃ IPR ch ₃ Pr ch ₃ Pr 6-CH ₃ cPr H cPr H -CH2CH2OCH2CH2- -CH2CH2OCH2CH2-

· -45 -

Table 3 Compounds of formula (V)

r ³ -ch ₃ , X-O, Z-H r ³ -ch ₃ , X-S, Z-H R ² -H, r ³ -ch ₃ , xo B ¹ B ² B ¹ B ² B ¹ 2 ch ₃ H ch ₃ H Pr 2-C1 ch ₃ ch ₃ ch ₃ ch ₃ iPr ' 5-C1 C 2 ^h 5 H c ₂ h ₅ H Pr 6-C1 nPr H nPr H Pr 2-CH ₃ Pr H Pr H IPr 5-CH ₃ Pr ch ₃ Pr ch ₃ Pr 6-CH ₃ cPr H cPr H -CH ₂ CH ₂ OCH ₂ CH ₂ - -ch ₂ ch ₂ and ₂ ch ₂ -

Table 4 Compounds of formula VI

f ³ -ch ₃ , X-O, Z-H r ³ -ch ₃ , X-S, Z-H R ² -H, r ³ -ch ₃ , XO B ¹ B ² B ¹ B ² B ¹ 2 ch ₃ H ch ₃ H Pr 2-C1 ch ₃ ch ₃ ch ₃ ch ₃ Pr 5-C1 c ₂ e ₅ H C ₂ H ₅ E Pr 6-C1 nPr H nPr H Pr 2-CE ₃ Pr H Pr Η Pr 5-CH ₃ Pr ch ₃ Pr ch ₃ Pr € -CH ₃ CPL E CPr H "CH ₂ CH ₂ OCH ₂ CH ₂ - -ch ₂ ch ₂ and ₂ ch ₂ -

Table 5 Compounds of formula VII

r ³ -ch ₃ , X-O, Z-H r ³ -ch ₃ , XO, zh B ¹ B ² B ¹ B ² ch ₃ Η IPr C (O) H ch ₃ ch ₃ Pr C (O) CH ₃ c ₂ h ₅ H Pr C (O) OCH ₃ C ₂ H 5 ch ₃ Pr allyl c ₂ h ₅ c ₂ h ₅ nBu H nPr H Bu H nPr ch ₃ CH (CH ₃ ) CH ₂ CH ₃ H nPr C 2 ^h 5 cPr H IPr ^c 2 ^h 5 cPr ch ₃ Pr H CH ₂ (cPr) Η Pr ch ₃ ch ₂ cf ₃ H Pr c ₂ h ₅ sBu H Bu H CH (CH ₃ ) CH (CH ₃ ) ₂ H r ³ -ch ₃ , X-S, Z-H r ³ -ch ₃ , X— S, Z-H B ¹ B ² B ¹ B ² ch ₃ H Pr C (O) H ch ₃ ch ₃ Pr C (O) CH ₃ c ₂ h ₅ H Pr C (O) OCH ₃ c ₂ h ₅ ch ₃ IPr allyl c ₂ h ₅ c ₂ h ₅ nBu H nPr H Bu H nPr ch ₃ CH (CH ₃ ) CH ₂ CH ₂ H nPr ^c 2 ^h 5 Pr H Pr H Pr ch ₃ Pr ch ₃ CH ₂ (cPx) H Pr C ₂ ^H 5 ch ₂ cf ₃ H

R ³ -CH ₃ , X-0, zh * 1B ch ₂ ch ₂ cich

CH (CF ₃ ) CH ₃ h och ₃ h ch ₂ ch ₂ och ₃ h

Ph

PhCH ₂ H

N (CH ₂ ) ₃ h all 1 H

-ch ₂ ch ₂ ch ₂ ch ₂ ch ₂

-CH ₂ CH ₂ CH ₂ CH ₂ -ch ₂ ch ₂ and ₂ ch ₂ CH (CH ₃ ) CH ₂ CNh

CH (CH ₃ ) ch ₂ ch ₂ ch ₃ h

R ³ -CH 2, xs, ZH ch ₂ ch ₂ cich

CH (CF ₃ ) CH ₃ h och ₃ h ch ₂ ch ₂ och ₃ h

PhΗ

PhCH ₂ H

N (CH ₂ ) ₃ H allylH

-CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ -

Table 6 Compounds of formula VIII

r ³ -ch ₃ , X-O, Z-H r ³ -ch ₃ , X-O, Z-H R ² -H, r ³ -ch ₃ , XO B ¹ B ² B ¹ B ² B ¹ 2 ch ₃ H ch ₃ H Pr cl ch ₃ ch ₃ ch ₃ ch ₃ cPr * cl c ₂ h ₅ H C2H5 H nPr cl nPr H nPr H Pr ch ₃ IPr H Pr H cPr ch ₃ Pr ch ₃ Pr ch ₃ nPr ch ₃ cPr H CPX H -CH ₂ CH ₂ OCH ₂ CH _{2 -} -ch ₂ ch ₂ and ₂ ch ₂ -

Table 7 Compounds of formula IX

Y 0 B B ¹ 2 ch ₃ Pr H ch ₃ sBu H ch ₃ Pr 5-C1 ch ₃ sBu 5-C1 ^C 2 ^K 5 Pr H c ₂ h ₅ SBU H

Y-S B B ¹ 2 ch ₃ IPr H ch ₃ sBu H ch ₃ IPX 5-C1 ch ₃ 8BU 5-C1 c ₂ h ₅ Pr H C2H5 SBU H

··· "

Table A Compounds of Formula III

Veguin B ¹ B ² B ³ 2 2 ftP < ^C C1 1 CH (CH ₃ ) ₂ H ch ₃ 0 H 78-79 2 ch ₂ ch ₂ ch ₃ H ch ₃ She H 84-86 3 N (CH ₃ ) ₂ H ch ₃ 0 H 67-76 4 ch ₂ ch ₂ ch ₃ H ch ₃ s H • 62-65 5 -ch ₂ ch ₂ and ₂ ch ₂ - ch ₃ She H 77-79 6 N (CH ₃ ) ₂ H ch ₂ ci 0 H 91-94 7 CH (CH ₃ ) ₂ ch ₃ ch ₃ 0 H 62-65 8 Ctcloprop »'1 H ch ₃ 0 H 110-112 9 CH (CH ₃ ) ₂ H ch ₃ s H 110-111 10 cyclopropi 1 H ch ₃ s H 124-127 11 C ₂ ^h 5 H ch ₃ s H 94-96 12 c ₂ h ₅ H ch ₃ 0 H 95-99 13 ch ₃ Ή ch ₃ 0 H 97-100 14 Bu H ch ₃ 0 H 70 to 72.5 15 sBu H ch ₃ 0 H 50 16 CH (CH ₃ ) ₂ H ch ₂ ci 0 H 89-90 17 CH (CH ₃ ) ₂ H C ₂ «5 0 H 106-108 18 Ibu H ch ₃ She H oil* 19 CH (CH ₃ ) ₂ H ch ₃ 0 3-C1 129 20 CH (CH ₃ ) ₂ H ch ₃ 0 5-C1 100-101 21 (R) -sBu H ch ₃ 0 H oil ([alpha]] _D -17.5 22 (S) -sBu H ch ₃ 0 H oil ([alpha]] _D +18.4 24 C (CH ₃ ) ₂ CH ₂ CH ₃ H ch ₃ 0 H 45-48 25 CH (C ₂ H ₅ ) CH ₂ CH ₃ H ch ₃ 0 H 88-90 26 SBU H ch ₃ s H 81 -83 27 c / klopent ί1 H ch ₃ 0 H 48-52 28 CH (CH ₃ ) CH (CH ₃ ) ₂ H ch ₃ 0 H 50-53 29 CH (CH ₃ ) CH ₂ CH ₂ CH ₃ H ch ₃ 0 H oil ²

H9- • • · ·· 30 CH (CH ₃ ) CH ₂ OCH ₃ H ch ₃ 0 Η ol «j ³ 31 C2H5 ch ₃ ch ₃ 0 H obj ⁴ 32 CH (CH ₃ ) CH ₂ CN H 1 ch ₃ 0 H 48-52 33 CH (CH ₃ ) ₂ H ch ₃ 0 3-Br 138.5-139.5 34 SBU H ch ₃ 0 3-C1 127-129 35 (R) -CH (CH ₃ ) Ph H ch ₃ 0 H 82-83 36 (S) -CH (CH ₃ ) Ph H ch ₃ 0 H 83-84 37 CH (CH ₃ ) CH ₂ CN H ch ₃ 0 3-C1 122 to 123.5

¹ NMR (CDCl 3): δ 1.09 (d, 6), 1.90 (m, 1), 3.31 (dd, 2), 3.40 (s, 3), 7.29 1, 1.1 ), 7.7 (br, l), 6.01 (dd, l), 8.20 (d, l).

^{2: 1} H NMR (CDCl 3): δ 0.94 (t, 3), 1.25 (d, 3), 1.38 (λ, 2), 1.56 (ir, 2), 3.40 ( s, 3), 4.18 (m, l), 7.31 (d, l), 7.38 (br, l), 8.00 (dd, l), 8.18 (d, 1).

³ NMR (CDCl 3): δ 1.31 (d, 3), 3.40 (s, 3), 3.45 (s, 3), 3.48 (m, 2), 7.25 (d, l) ), 7.8 (br, l), 8.00 (dd, l), 8.18 (d, l).

¹ H NMR. .... rotamer (CDCl 3): δ 1.27 (m, 3), 3.40 3.47 (s, 3),

4.23 (m, l), 6.95 t £> · 7.2 (br, l), 7.10 · $ 7.28 (d, l), 8.00 and

8.18 (dd, l), 8.04 and 8.13 (d, l).

Table B: Compounds of Formula X

Vauiét B ¹ B ² Β ³ X 2 0? ficin 23 CH (OH ₃ ) 2 H ch ₃ 0 2-C1 106 -107 Table C (VII) General compounds Ve ^ UUT B ¹ B ² B ³ X 2 Dp. ro 38 CH (CH ₃ ) ₂ H ch ₃ 0 H 129-131

Formulation / Usage

The compounds of the present invention are generally formulated in formulations with agriculturally acceptable carriers such as liquid or solid diluents or organic solvents. Various formulations suitable for the physical properties of the active ingredient, the mode of application and environmental factors such as soil type, moisture and temperature conditions include powders, granules, baits, pellets, solutions, suspensions, emulsions, wettable powders, emulsifiable concentrates, dry-running preparations and the like. Sprayable formulations are prepared in a suitable medium and can be applied in amounts of about one to several hundred liters per hectare. High concentration formulations are used primarily as starting materials for further formulations. The formulations typically contain an effective amount of the active ingredient, as well as diluents and surfactants, in the approximate ranges indicated in the table below, in a total amount of 100% by weight.

Weight%

agent

Solvent salt

Surfactant

Wettable powders

- 90

0-74

1-10

Oily suspensions, emulsions, solutions (including emulsifiable concentrates)

5-50

- 95

0-15

Powders, granules, baits and pellets 1-25

0.01 - 99

- 99

- 99.99

I ··· ···

High Concentration Preparations 90-99 0-10 0-2

Typical solid diluents are described in Handbook of Insecticide Dusts Diluents and Carriers, 2nd Edition (Watkins et al., Dorland Books, Caldwell, New Jersey). Typical liquid diluents and solvents are described in the Solvents Guide

2nd Edition (Marsáén, Interscience, New York, 1950), McCutcheon's Detergents and Emulsifiers Annual (Allured Publ. Corp., Ridgewood, New Jersey), Encyclopedia of Surface Active Agents (Sisley and Wood, Chemical Publ. Inc., New York, 1964) lists surfactants with specifications for their use. All formulations may contain minor amounts of additives such as foaming, precipitation, corrosion, microbiological contamination, and the like. To avoid.

Solutions are prepared by simple mixing of the ingredients. Fine solid compositions are prepared by blending and are generally comminuted, for example by a hammer grinder or fluid energy mill. Water-dispersible granules can be prepared by compressing fine powders, see, for example, Pesticide Formulations (Cross et al., Washington D.C., 1988, pp. 251-259). The suspensions are prepared by wet milling, see, for example, U.S. Patent No. 3,060,084. Granules and pellets may be prepared by spraying the active ingredients on a pre-formulated granular carrier or by agglomeration as described in Agglomeration (Browning, December 4, 1967, pp. 147-148), Perry's Chemical Engineer's Handbook, 4th Edition. McGraw-Hill, New York, 1963) and International Application Publication No. WO 91/13546. The pellets may be prepared as described in U.S. Patent No. 4,772,714. The water-dispersible and water-soluble granules may also be prepared as described in DE 3.2466.493.

More information about formatting can be found in ί. **. t ··· <* · * '·· »• · í i ···. ··· ♦ ···· ··· · · in U.S. Pat. No. 3,235,361, column 6, line 16 through column 7, line 19 and paragraphs 10-41. Example 3, U.S. Pat. No. 3,309,192, column 5, line 43 to column 7, line 62, and 8, 12, 15, 39, 41, 52, 53, 58, 132, 138-140, 162-164, 166, 167 and 169-182. Example 2, U.S. Pat. No. 2,891,855, Column 3, Line 66 to Column 5, Line 17, and Examples 1-4. Klingman, Weed Control as a Science, John Wiley and Sons, Inc., New York, 1961, 81-96. and Hance et al., Weed Control Handbook, 8th Edition, Blackwell Scientific Publications, Oxford, 1989.

The formulations in the examples below were prepared in the usual manner, all in percent by weight. The numbering of the compounds corresponds to that given in Table A.

Example A

Wettable powder formulation

Compound # 1 65.0 % dodecylphenol polyethylene glycol ether 2.0 % Sodium lignin sulfonate 4.0 % sodium zincoaluminate 6.0 % montmoriHonit (calcined) 23.0 %

Example B Granules

Compound # 1 Attapulgite Granule (Low Volatile Material, 0.71 / 0.30 mm; U.S.S.

- Screen 30)

10.0%

90.0% | »« «J.«.

. «♦ ..., ·

.... * · ·

Example C

Extruded pellets

Compound # 1 is anhydrous sodium sulfate 25.0% 10.0% crude calcium lignin sulfonate sodium alkyl naphthalene sulfonate 5.0% 1.0%

calcium / magnesium bentonite

59.0%

Example D

Emulsifiable concentrate

Compound # 1 Mixture of oil soluble sulfonates and polyoxyethylene ethers in isophorone

20.0%

10.0%

70.0%

The compounds of the present invention are effective against a wide variety of aquatic and terrestrial (arthropod) arthropods (including nematodes), which are growing and stored in agriculture, forestry, greenhouse crops, ornamental plants, seedlings, stored food and fiber. substances, and harm to livestock, households and public health. It is known to those skilled in the art that various compounds are not equally effective against various pests. However, all of the compounds of the present invention are effective in eggs, larvae and adult individuals of the order Lepidoptera, eggs of the order Coleoptera, larvae of leaves, fruits, roots and kernels, and adult individuals of the order Hemiptera and Homoptera. the eggs of the order of the mites, the nymphs and the adults, the eggs of the order of the Thysanopteras, the orthopteras and the Dermapteras, the eggs of the undeveloped and the adults, the eggs and the larvae of the genus Nematodes. The compounds of the invention are also effective against Hymenoptera, Isoptera, ···:. ···.

•.; : ·· *. ··· »........... ·., ·

Against the pests of the order of Phthiropteras, Siphonopteras, Blattarias, Thysanauras and Psocopteras and pests of the Arachnids class and the Platyhelminths tribe. A more detailed description of the pest is found in WO 90/10623 and WO 92/00673.

The compounds of the invention may also be mixed with (one or more) other insecticides, fungicides, nematocides, bactericides, acaricides, semi-chemicals, repellents, attractants, pheromones, nutritional enhancers or other biologically active compounds such as agricultural ingredients, allows an even wider range of defense. Examples of agricultural pesticides for the preparation of the compounds of the invention include insecticides such as monocrotophos, carbofuran, tetrachlorvin, malathion, parathimethyl, methomyl, chlorodimeform, diazinon, deltamethrin, oxamyl, fenvalerate, sulprophos, triflumorone, diflubenzuron, methoprene, buprofezin, thiodicarb, acephate, azinphosmethyl, chlorpyrifos, dimethoate, fipronil, flufenprox, phonophos, isofenfos, methidathion, methamidophos, phosphorus, phalonamide, phosphamide, phosphamide, phosphamide, phosphamide bifenate, cyfluthrin, fenpropathrin, fluvalinate, flucitrinate, tralomatrin, metaldehyde and rotenone, fungicides such as carbendazim, thiuram, dodine, maneb, chloroneb, benomyl, cimoxanyl, fenpropidin, fenpropimorph, triadimefon, captan, thiophene, thiophene , chlorothalonil, dichlorane, metalaxyl, captafol, iprodion, oxadixil, vinclozo lin, casugamycin, mycobutanyl, tebuconazole, difenoconazole, diniconazole, flucinoconazole, ipconazole, metconazole, penconazole, propiconazole, uniconazole, flutriafol, prochloraz, pirifenox, fenarimol, triadimenol, diclobutrazole, diclobutrazol, diclobutrazol, , diclomezine, edifenphos, isoprothiolane, iprobenphos, mepronil, neo-azosine, pencicuron, probenazole, probenazole, pyrocylon, tricyclazole,

validamycin and flutolanyl, nematocides such as aldoxicarb, fenamiphos and phosphitane, bactericides such as oxytetracycline, streptomycin and tri-basic copper sulfate, acaricides such as binapacryl, oxithiokinox, chlorobenzylate, dicofol, dienoclor, and fenbutatin oxide and biological agents such as Bacillus thuringiensis, baculovirus and avermectin B.

In some cases, combinations with other arthropodicides of similar potency but with different modes of action are clearly beneficial to the treatment of resistance.

To control and eradicate arthropod pests that are hazardous to agricultural crops, animals and humans, effective amounts of one or more compounds of the invention are administered to the pest environment, including the infected agricultural and / or non-agricultural area, the protected area, or directly to the pest. The preferred method of application is spraying. Alternatively, granular forms of these compounds can be applied to the foliage of plants or to the soil. Other methods of application include direct and long-term spraying, aerial spraying, systematic (absorbable) uptake, bait, ear tag, pellets, nebulizers, smoke generators, aerosols and many more. The compounds may be incorporated into bait consumed by arthropods or used in traps and the like.

The compounds of the present invention may be used in pure form, but will most often be in the form of a formulation for the desired end use comprising one or more compounds together with a suitable carrier, diluent and surfactant, optionally in admixture with food. A preferred method of application is by spraying an aqueous dispersion or solution of the compounds in a refined oil. In combination with oils and oil concentrates, bulking agents, adhesives, adjuvants, adjuvants, and other solvents such as piperonyl butoxide, the efficacy of the compound can often be enhanced.

The effective dose for effective defense is ···: ···. ι ··· • *. ί; ·· <·· · »... ·

it depends on factors such as the species of arthropod to be controlled, the life cycle, life cycle, size, location of the pest, season, host or animal, nutritional and reproductive behavior, environmental humidity, temperature and the like. Under normal conditions, from about 0.01 to 2 kg of active ingredient per hectare is sufficient to control agricultural ecosystems, but 0.001 kg / ha may be sufficient or may be required to reach 8.0 kg / ha. For non-agricultural applications, the effective amount is from about 1.0 to about 50.0

2 mg / m, but 0.1 mg / m may be sufficient, or up to 150.0 mg / m may be required.

The following experiments illustrate the efficacy of the compounds of the invention in various pests. However, the pest control activity of the compounds is not limited to these species. The compounds are described in A-C. tables.

Experiment A.

Fali Armyworm (Spodoptera frugiperda)

Each of the experimental units was 16 H.I.S. consists of a high (refractive styrene) cell. 12 cells have wet filter paper and about 8 cm of mucilage leaf, while the other 4 cells have 0.5 cm of wheat germ. In a 230 ml plastic container, 15 to 20 larvae of Stodium Spugoptera frugiperda were placed. A solution of each test compound (solvent: acetone: distilled water; 75: 25%) was sprayed onto the tray and into the container. Spraying was performed by placing the tray and container directly on a conveyor belt under a flat vented hydraulic nozzle that sprayed for approx. 0.55 kg / ha at 207 kPa. Insects were placed in the tray (one insect per cell). The trays were covered and kept at 27 ° C for 50 hours at 50% humidity, after which the results of the 12-lima leaf cell were evaluated. The remaining 4 cells were evaluated on Day 7 for delayed (prolonged) toxicity. Among the tested compounds, compound 4 resulted in mortality of 80% or greater (at a dose of 0.13 kg / ha).

Examining).

Experiment B.

Southern Corn Rootworm (Diabrotica undecimpunctata howardi)

Experimental units were prepared by placing 1 germinated corn kernel in 230 ml plastic containers. Three sets of experimental units were sprayed with a unique solution of the test compounds as described in Experiment A. After the pots had dried, 5 Diabrotica undecimpunctata larvae at stage 3 were placed in each pail. A dampened dental swab was placed in each dish to prevent dehydration and then covered. The vessels were then maintained for 48 hours at 27 ° C and 50% relative humidity. After a period of time, a mortality test was performed. Among the compounds tested, the following resulted in 80% mortality or greater: 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14 **, 15, 16, 17, 18, 19, 20, 21, 22, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 38 *.

• ff: tested at 0.13 kg / ha *

: Listed 14-38. The compounds were tested using the same procedure, wherein the dishes contained soybean sprouts and second stage larvae were used.

Experiment C

Aster Leafhopper (Mascrosteles fascifrons)

The experimental units consisted of 350 ml dishes containing 2.54 cm sterilized soil and 1.27 cm sandy oat (Avena sativa) seedlings. The test vessels were sprayed with a unique solution of the compounds listed below as described in Experiment A. After the spray had dried on the oat plant blue, 10 to 15 adult specimens of Mascrosteles fascifrons were placed in pots with a vented lid. The dishes are then heated for 48 hours at 27'C and 50% relative humidity * ♦ · · • · ·

- 28 held. After a period of time, a mortality test was performed. Among the compounds tested, the following resulted in 80% mortality or greater: 1, 2, 7, 15, 16, 21, 22, 25, 26, 38 *.

*: Applied at 0.13 kg / ha

Experiment D.

Boll Weavil (Anthonomus grandis)

Each of a series of 260 ml dishes contained 5 5 adult Anthonomus grandis specimens. The test vessels were sprayed with a unique solution of the compounds listed below as described in Experiment A. The dishes were covered with a ventilated lid and kept for 48 hours at 27 ° C and 50% relative humidity. After a period of time, a mortality test was performed. Among the compounds tested, the following resulted in 80% mortality or greater: 1, 15, 21, 29, 32.

Experiment E

Black Beán Aphid (Aphis fabae)

Watercress (nasturium) leaves were infected with 10 to 15 lice (all stages of development of Aphis fabae) and sprayed upside down as described in Experiment A. The leaves were then placed in a 0.94 mm diameter test tube containing 4 ml of an aqueous sugar solution and covered with a 28 ml transparent flask to prevent lice from falling off the leaf. The vessels were maintained for 48 hours at 27'C and 50% relative humidity. After a period of time, a mortality test was performed. Among the compounds tested, the following resulted in mortality of 80% or more: 19, 20, 33.

Experiment F.

Green Leafhopper (Nephotettix cincticeps)

Three 1.5-leaf, about 10 cm tall rice seedlings are planted on a Rubber Brown artificial soil • ·

- In a 14 ml plastic container containing 29. 7 ml of distilled water are then added to the vessel. The test chemical is first dissolved in acetone and then water is added to form a 75:25 acetone / water mixture. The concentration of the test chemical in the solvent mixture was 100 ppm. Place the four plastic containers (four repetitions) on a rotary table with a spray chamber. The vessels were sprayed with 50 ml of the chemical solution at a pressure of 2.0 kg / cm for 45 seconds using an air spray nozzle. Within 45 seconds, the turntable turns 7.5 turns. After chemical treatment, the dishes should be approx. Keep in a ventilated, closed place for 2 hours to dry. After drying, the pots are placed in conical test units and the soil surface is covered with 2 to 3 mm quartz sand. 8 - 10 specimens of Nephotettix cincticeps with nymph status 3 were placed in the above units using an aspirator. The test units are maintained at 27'C and 65% relative humidity. Live and dead nymphs were counted 24 to 48 hours after infection. Non-walking insects are considered dead. Among the compounds tested, the following resulted in 80% mortality or greater 48 hours after infection: 1, 15, 25, 28, 29, 30, 31, 32.

Experiment G.

Brown Planthopper (Nilaparvata lugens)

Nilaparvata lugens specimens were used as test species in the procedure described in Experiment F. Among the compounds tested, the following resulted in 80% mortality or greater 48 hours after infection: 1, 4, 9, 14, 15, 19, 21, 22, 24, 25, 26, 28, 29, 30, 31 , 32, 33.

Experiment H.

Effect of the absorbed solution on Green Leafhopper (Nephotettix cincticeps) nymphs

The test chemical is directly added to 10 ml of distilled • · · ·

- Add to 30 water and dissolve completely. This solution is poured into a conical test unit. Three rice (Oryza sativa) seedlings were then placed in the experimental unit using a notched sponge disk. The sponge disk allows the root system of the seedling to be completely submerged in the chemical solution, while the above-ground portion of the plant is not in contact with the solution. The sponge also protects the test insects from accidental contact with the test solution. A distance of 7-10 mm between the surface of the chemical solution and the bottom of the sponge disc prevents accidental contamination of the sponge with the chemical. The concentration of the test substance in the chemical solution is 100 ppm. Rice seedlings were kept in a growing chamber for 24 hours at 27'C and 65% relative humidity to allow the chemical to be absorbed. 8 10 specimens of Nephotettix cincticeps of condition 3 nymphs were placed in the above units using an aspirator. The infected units are maintained under the temperature and humidity conditions described above. Counting of living and dead nymphs is performed 24 to 48 hours after infection. Non-walking insects are considered dead. Among the compounds tested, the following resulted in mortality of 80% or greater 48 hours after infection: 1, 15, 16, 21, 22, 28, 29.

Experiment I

Effect of the absorbed solution on the nymphs of Brown Planthopper (Nilaparvata lugens)

The procedure described in Experiment H is repeated, except that Brown Planthopper (Nilaparvata lugens) nymphs are used as test insects. Among the compounds tested, the following resulted in 80% mortality or greater 48 hours after infection: 1, 9, 15, 16, 21, 22, 26, 28, 29.

Claims

Claims (9)

Claims CLAIMS 1. Compounds of general formula (I) and (II) Q is a group of formula (Q-1), (Q-2), (Q-3), (Q-4), (Q-5) or (Q-6), X represents oxygen, sulfur or = NR, Y represents an oxygen or sulfur atom, Z is hydrogen, halogen, -CN, -NO ₂ , C 1-3 alkyl, C 1-3 haloalkyl, C 1-3 alkoxy, C 1-3 haloalkoxy, or -S (O) _n R, R represents a C 1-3 alkyl group, R is C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 1 -C 5 alkoxy, C 2 -C 5 alkoxyalkyl, C 2 -C 6 alkenyl, C 2 -C 6 haloalkenyl, C 2 -C 6 alkynyl, C 3 -C 6 haloalkynyl, C 3 -C 6 cycloalkyl, C 4 -C 7 C 5 cycloalkylalkyl, -N (R) R optionally substituted with 1 or 2 W substituents -, optionally substituted with 1 or 2 W of benzyl or C 1 -C 5 alkyl which is -CN, 4 5 7 It may be replaced by -N (R) R or -S (O) R, 2 " R is hydrogen, C 1-2 alkyl, C 1-2 haloalkyl, formyl, C 2-3 alkylcarbonyl, C 2-3 alkoxycarbonyl, C 3 alkenyl or C 3 alkyl. alkynyl; or R ¹ and R ^{2 taken} together may be -CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ -, -CH ₂ CH ₂ CH ₂ CH ₂ - or -CH ₂ CH ₂ OCH ₂ CH ₂ -, R ^{3 is C} 1 -C 2 alkyl or C 1 -C 2 haloalkyl, 4 5 R and R are each independently methyl or ethyl R ⁴ and R ^{5 taken} together may form -CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ -, -CH ₂ CH ₂ CH ₂ CH ₂ - or -CH ₂ CH ₂ OCH ₂ CH ₂ -, R 6 is hydrogen, C 1-3 represents an alkyl or C 1-3 haloalkoxy group, R represents a C 1-2 alkyl or C 1-2 haloalkyl group: - W 32 is halogen, is 1-2C-alkyl, 1-2C-alkoxy, -CF ₃ or -OCF ₃ group and n is 0, 1, or second Compounds according to claim 1, having the formula R ¹ is C 1 -C 4 alic, C 3 -C 5 cycloalkyl, C 4 -C 5 cycloalkylalkyl, or C 1 -C 5 alkyl substituted by -CN, R is hydrogen or methyl, R is methyl, X is O or S and Z is hydrogen or halogen. Compounds according to claim 2, wherein Q is (Q-1) or (Q-6). Compounds according to claim 3, wherein Q is a group of formula (Q-1). Compounds according to claim 3, wherein Q is a group of formula (Q-6). A compound according to claim 4, which is: N- (1-methylethyl) -6 - [(methylsulfonyl) oxy] -2-pyridine carboxamide, N- (1-methylethyl) -6 - [(methylsulfonyl) oxy] -2-pyridin-carbothioamide, N- (1-methylpropyl) -6 - [(methylsulfonyl) oxy] -2-pyridinecarboxamide and 3-chloro-N- (1-methylethyl) -6 - [(methylsulfonyl) oxy] -2-pyridinecarboxamide. 7. The method of claim 6 N- (1-methylethyl) -6 - [(methylsulfonyl) oxy] -2-pyridinecarboxamide. 8. An arthropodicidal composition which is a compound of any one of claims 1-7. An effective amount of a compound according to any one of claims 1 to 6 and a carrier. 9. A method for controlling Arthropods, wherein the Arthropods or their surroundings are as defined in claims 1 to 7. A compound according to any one of claims 1 to 6, in an amount effective against Arthropods. The Trustee GÖDÖLLE, BLUE, HONEY & HUNGARIAN Patent & Trademark Office 1024 Budapest, Keleti Károly u. 13 / b Enikő Mésíáros is a patent attorney 68 254 I V PUBLICATION LETTER Reaction equation 1 (Q-5) (Q-6) R ³ SO ₂ -halogeno base (Ia) (OQ 1, XO). Hesitant, blue. MTO (^ p8% 8EA8Ó Patent and Trademark Office 1024 Budapest, Keleti Károly u. 13 / b Enikő Mészáros is a patent attorney