CA2123902A1 - Arthropodicidal and nematicidal sulfonates - Google Patents

Abstract

Arthropodicidal and nematicidal compounds of formulae (I, II), wherein Q is selected from the group Q-1, Q-2, Q-3, Q-4, Q-5 and Q-6, and R, R1, R2, X, Y and Z and R3 are as defined in the text, compositions containing the compounds and methods employing the compounds to control pests.

Description

r~ 2123~2 TITLE
ARTHROPODICIDAL AND NEMATICIDAL SULFONATES
The compounds of this invention are characterized by having a substituted (R1)(R2)N-C(=X)- or R1-N=C~YR)-moiety located in a 1,3 relationship to an oS02R3 substituent in a heteroaromatic system. U.S. Patent 3,818,102 discloses a certain insecticidal phenyl sulfonate carboxamide. The disclosed carboxamide moiety is unsubstituted and its position is variable relative to the sulfonate moiety. EPA 356,029 discloses insecticidal compounds that differ from those i of the present invention, among ot~er things, in having a sulfonyl group rather than a carbonyl or thiocarbonyl directly attached to the pyridine ring.
This invention pertains to compounds of Formulae I
and II, including all geometric and stereoisomers, agriculturally suitable salts thereof, agricultural compositions containing them and their use for the control of arthropods and nematodes in both agronomic and nonagronomic uses. The compounds are X ,R
R~
~N--C--Q Rl--N=C--Q

II
, wherein:
Q is selected from the group ~CN10SO~R~ oso~R

Q-l Q-2 SU~TITUTE ~

WO~3/10096 2 1 2 3 ~ {~ 2 PCT/US92/09337 OSO2R3 ¦ ~
1~z. l~z Z ~OSO2R3 S OS02R' /~ z ;

X is selected from the group O, S and NR6;
Y is selected from the group O and S;
Z is Qelected from the group H, halogen, CN, NO2, C1-C3 alkyl, C1-C3 haloalkyl, Cl-C3 alkoxy, Cl-C3 haloalkoxy and S(o)nR7;
R is selected from Cl-C3 alkyl;
Rl is selected from the group Cl-C6 alkyl, Cl-C6 haloalkyl, C1-C5 alkoxy, C2-C5 alkoxyalkyl, C2-C6 alkenyl, C2-C6 haloalkenyl, C2-C6 alkinyl, C3-C6 haloalkynyl, C3-C6 cycloalkyl, C~-C7 cycloalkylalkyl, N~R4)R5, phenyl optionally substituted with l or 2 substituents selected .
from the group W; benzyl optionally substituted with 1 or 2 substitutents sele~ted from the group 15 W; and Cl-C5 alkyl substituted with a group selected from CN, N(R4)R5 and S(O) nR7;
R2 is selected from the group H, Cl-C2 alkyl, Cl-C2 haloalkyl, formyl, C2-C3 alkylcarbonyl, C2-C3 . alkoxycarbonyl, C3 alkenyl and C3 alkynyl; or R1 and R2 can be taken together to form -CH2CH2CH2CH2CH2-, -CH2CH2CH2CH2- or -CH2cH2OcH2cH2-;

WO93/1009~ 2 ~ 2 ~ 3 0 2 PCT/US92/09337 R3 is selected from the group Cl-C2 alkyl and C1-C2 haloalkyl;
R4 and R5 are independently selected from methyl and ethyl; or R4 and R5 can be taken together to form -CH2CH2CH2CH2C~2-, -CH2CH2CH2CH2- or -CH2CH2OCH2cH2-;
R6 is selected from the group H, Cl-C3 alkyl and C1-C3 `
haloalkoxy;
R7 iS from the group Cl-C2 alkyl and C1-C2 haloalkyl;
W is selected from the group halogen, Cl-C2 alkyl, Cl-C2 alkoxy, CF3 and OCF3; and ::
n is 0, 1 or 2.
Preferred compounds A are compounds of Fa,rmula I
wherein:
R1 is selected from the group Cl-C4 alkyl, C3-Cs cycloalkyl, C4-C5 cycloalkylalkyl and C1-Cs alkyl substituted with CN;
R2 is selected from the group H and CH3;
R3 is CH3;
X is selected from the group O and S; and Z is selected from the group H and hl~logen.
Preferred compounds B are compounds of Preferred A
wherein Q is selected from the group Q-l and Q-6.
Preferred compounds C are compounds of Preferred B
wherein Q is Q-l.
Preferred compounds D are compounds of Preferred B
wherein Q is Q-6.
Specifically preferred compounds E for biological activity and ease of synthesis are the compounds of Preferred C which are:
N-~l-methylethyl)-6-[(methylsulfonyl)oxy]-2-pyridinecarboxamide;
N-(1-methylethyl)-6-~(methylsulfonyl)oxy]-2-pyridinecarbothioamide;

W O 93/10096 21 2 3 9 ~! ~ PC~r/US92/09337 N~ methylpropyl)-6-[(methylsulfonyl)oxy]-~
pyridinecarboxamide; and ~;~
3-chloro-N-(1-methylethyl)-6-[(methylsulfonyl)oxy]-2-pyridinecarboxamide.
Most preferred compound F for biological activity is the compound of Preferred E which is:
N-(1-methylpropyl)-6-[(methylsulfonyl)oxy]-2-pyridinecarboxamide.
Compounds of the instant invention include racemic and optically activs stereoisomers. By "stereoisomers"
we mean all of the isomers of the Formula I compounds which include enantiomers, diastereomers, and geometric isomers. One skilled in the art will appreciate that one or the other of said stereoisomer(s) will be the more active. It is also known how to separate such enantiomers, diastereomers, and geometric isomers.
Accordingly, this invention includes racemic mixtures, each indi~idual stereoisomer and enriched mixtur~s of stereoisomers.
In the above recitations, the term "alkyl'~ used either alone or in compound word such as "haloalkyl", denotes straight or branched alkyl such as methyl, ethyl, n-propyl, isopropyl, or the different butyl, pentyl or hexyl isomers.
Alkoxy denotes methoxy, ethoxy, n-propyloxy, isopropyloxy and the different butoxy or pentoxy isomers.
AlkenyI denotes straight or branched chain alkenes such as vinyl, 1-propenyl, 2-propenyl, 3-propenyl and the different butenyl, pentenyl and hexenyl isomers.
Alkynyl denotes straight chain or branched alkynes such as ethynyl, 1-propynyl, 3-propynyl and the different but~nyl, pentynyl and hexynyl isomers.
Cycloalkyl denotes cyclopropyl, cyclobutyl, ` cyclopentyl and cyclohexyl.

W O 93/10096 2 1 2 3 9 ~ 2 PC~r/US92/09337 The term "halogenT', either alone or in compound words such as "haloalkyl", denotes fluorine, chlorine, bromine or iodine. Further, when used in compound words such as "haloalkyl" said alkyl can be partially or fully substituted with halogen atoms, which can be the same or different. Examples of haloalkyl include CH2CH2F, CF2CF3 and CH~CHFCl. The terms "haloalkenyl" and "haloalkynyl"
are defined analogously to the term "haloalkyl".
The total number of carbon atoms in a substituent group is indicated by the "Ci-Cj" prefix where i and j are numbers from 1 to 7. For example, C2 alkylcarbonyl designates C(O~CH3 and C4 alkylcarbonyl includes C(O~CH2CH2CH3 and C~O)CH(C~3)2; C2 alkoxycarbonyl designates C(O)OCH3 and C3 alkoxycarbonyl designates C(O)OCH2CH3: and as a final example C3 alkoxyalkyl designates CH2OCH2CH3, CH2CH2OCH3 and C~(CH3)OCH3.

Compounds of Formula I wherein Q is Q-1 and X is O
can be prepared by reaction of the corresponding pyridones (1) with the appropriate sulfonyl halide and a base such as triethylamine or pyridine in a solvent such as dichloromethana as shown in Equation 1. (In Equations 1 to 13, Rl, R2, R3, R6 and Z are as previously defined.) ~quation 1 '~ R3S02-halogen NC N O E~ase \ NC N OS02R

I ~ l, X--O) - ~he pyridones 1 can be prepared from the corresponding benzyloxy compounds (2~ under a variety of conditions depending on the nature of the substituents R1, R2 and Z, such as catalytic hydrogenation, heating with

2 1 2 3 3 3 2 PCT/US92/09337 aqueous acid, (e.g., aqueous hydrobromic acid in acetic acid) or treatment with iodotrimethylsilane as shown in Equation 2.
~uatiQn 2 Z H2, catalyst \NC--~NC~lo----Ph Acid or T~SI

The compounds of Formula 2 can be prepared from the corresponding acids (3~ by any one of a numb~r of methods for forming amides known to one skilled in the art. For example treatment of the acids ~ith thionyl chloride or with l,l'-carbonyldiimidazole (CDI~ in a solvent such as tetrahydrofuran followed by treatment with the appropriate amine as shown in Equation 3.
Equation ~

,Cl ~ ,. RlR2NH
H~2C N O

The acids 4 can be prepared from the corresponding halogen compound (5) by displacement with an alkali metal benzyloxide such as sodium benzyloxide in a solvent such as tetrahydrofuran or N,N-dimethyl-formamide with the addition of an extra equivalent of base, such as sodium hydride, to deprotonate the acid as shown in Equation 4.

WO93~10096 2 ~ 2 3 9 ~ 2 PCT/US92/09337 E~uation 4 CC~1 NaOCH2Ph H02C N halogen Base The acids 4 are compounds known in the art or readily prepared by methods known to one skilled in the art. For example, see Abramovitch, R. ed., The Chemis~ry S of ~eteroc:yclic Compounds, Pyridine and its Derivatives, vol 14 supplement 1, Wiley, New York and earlier volumes in that series. In some instances, they can be prepared by oxidation of the corresponding methyl compounds (5) with an oxidant such as potassium premanganate as shown in Equation 5.
E~uation 5 ~ 4 CH3 N halogen The compounds of Formula I wher~in Q is Q-2, Q-3 or Q-4 and X is O can be prepared in similar fashion to those wherein Q is Q-1 and X is O, from the appropriate starting materials.
The compounds of Formula I, wherein Q is Q-5 and X
is O can be prepared by reaction of the corresponding hydroxy compound ~6) with the appropriate sulfonyl halide and a base such as triethylamine or pyridine in a solvent such as dichloromethane as shown in E~uation 6.

W~93/10~96 P~T/US92/09337 2123~2 8 ~quatiQn 6 OH oS02R3 N ~ ~3S02-halogen Rl ll N 3_ ~NC 5 z Base 2 / Z

6 I ~Q~Q-6, X~O) The hydroxy compounds of Formula 6 can be prepared from the corresponding benzyloxy compounds t7) under a variety of conditions depending on the nature of the substituents Rl, R2 and Z, such as catal~tic hydrogenation, heating with aqueous acid, (e.g., aqueous hydrobromic acid in acetic acid) or treatment: with iodotrimethylsilane as shown in Equation 7.
E~ua~ion 7 ~ C ~ ~ H2, catalyst R2 s acid or TMSI

The compounds of Formula 7, can be prepared from the corresponding acids (8) by any one of a number of methods for forming amides known to one skilled in the art. For example, treatment of the acids with thionyl chloride or :
with 1,1'-carbonyldiimidazole in a solvent such as tetrahydrofuran followed by treatment with the appropriate amine as shown in Equation 8. -`

WO93/10~96 2 1 2 3 4~ ~ ~ PCT/US92/09337 E~uatiQn 8 o--Ph N~ 1 CDI

H02C ~~ S ~~ Z 2 R1R2NH

The acids (8) can be prepared from the corresponding halogen compound (9) by displacement with an alkali metal benzyloxide such as sodium benzyloxids in a solvent such as tetrahydrofuran or N,N-dimethyl-formamide with the addition of an extra equi~alent of base, such as sodium hydride, to deprotonate the acid as shown in Equation 9.

llalogen N 3 NaOCH2Ph E102C Z Base g . - :.
The compounds of Formula 9 can be prepared from the corresponding bromo- (or iodo-)thiazole (10) by reaction with an alkyllithium, such as n-butyllithium, in a solvent such as tetrahydrofuran followed by reaction with carbon diox~ide as shown in Equation 10.
~.

W O 93/10096 PC~r/US92/09337 2123~

Equa~ion 1 0 halogen N~ ' 1. alkyllithium - g S 2. C2 The thiazoles (10) are compounds known in the art and are readily prepared by methods known to one skilled in the art (Met~ger, ed., The Chemistry of. He~terocyclic 5 Compounds, General Synthe~ic Methods for Thialzole 2nd Thiazolium Salts, Vol 34, Part 1, Wiley, New York, 1979).
Alternati~elyr the acids (8) can be prep~red by reaction of the corresponding thiazole ~11) with an alkyllithium, such as n-butyllithium, in a sol~ent such as tetrahydrofuran followed by reaction with carbon dioxide as shown in Equation 11.
E~uation 11 O Ph N~ 1. allcyllithium ~ ~;
~~ z 2 C02 ~ 8 The compounds of Formula I wherein Q is Q-6 and X is O can be prepared in similar fashion to thsse wherein Q

is Q-5 and X is O, from the appropriate starting materials.
The compounds of Formula I, wherein X is S, can be prepared by reaction of the compounds of Formula I
wherein X is O with 2,4-bis(methoxyphenyl)-1,3-dithia-2,4-diphosphetane-2,2-disulfide as shown in Equation 12.

WO93/10096 ~ ~ 2 3 ~ ~ 2 PCT/US92/09337 tion 12 ~NCQ Cil30~ 5 5 5 R 2 I (X~O) I (X~S) The compounds of Formula I, wherein X is NR6, can be prepared from the compounds of Formula I, wherein X is O, by reaction with phosphorous oxychloride, followed by reaction with an am~ne as shown in Equation 13.
E~uation 13 o NR6 Rl ~ ll 1. POC13 Rl 11 NCQ ~ ,NCQ
R2 / 2 . E~6NH2 R2 /

I ~X--O) Compounds of Formula II can be prepared from compounds of Formula I, wherein X is O or S, by treatment with an alkylating agent such as an alkyl halide or a trialkyloxonium tetrafluorborate or by other methods as described in Sandler et al., Qr~ani~ Functional_~rQ~
aL~iQn~, Vol. III, Academic Press, New York, 1972.

21~,39~

~ak~,~
aration of N-~l-Methylethyl)-6- r (methylsul~Qnyl)oxyl-Intermediate 1 6-lPhenylmetho~y)-2-~yridinecarboxylic acid To a solution of 36 g (230 mmol) of 6-chloro-2-pyridinecarboxylic acid and 31 mL (300 mmol) of benzyl alcohol cooled in an ice bath in 1700 mL of tetrahydrofuran (THF) was added 21 g (530 mmol) of 60%
sodium hydride in mineral oil. The solution was heated to reflux. An additional 300 mL of THF was added. The reaction was refluxed overnight. It was cooled in an ice bath and 7.1 mL (69 mmol) of be~zyl alchol and 2.8 g (69 mmol) of 60% ~odium hydride in mineral oi.l were added. The reaction mixture was refluxed o~ernight. The reaction mixture was cooled and was poured into water and washed with ethyl acetate. The aqueous layer was acidified to pH 2 with concentrated HCl and extracted with dichloromethane. The or~anic layer was dried `;~
20 ~sodium sulfate) and the solvent was removed with a ;~
rotary evaporator to afford 39 g of the title compound as a tan solid.
lH NMR (CDC13): ~ 5.40 (s, 2), 7.1 (m, 2), 7.4 (m, 5), 7.86 (m, 2). ;
Intermedi~ 2 N-(1-Metbylethyl)-6-(Dhenylmethoxy)-2-Dyridin~carboxamide A suspension of 20 g (87 mmol) of 6-(phenyl-methoxy)-2-pyridinecarboxylic acid in 300 mL of thionyl chloride was heated to reflux. After a few minutes the reaction mixture became homogeneous and it was refluxed for 2 h. The volatiles were removed with a rotary evaporator. The residue was disolved in 300 mL of dichloromethane and added dropwise to 29.8 mL (350 mmol) of 2-aminopropane in 100 mL of dichloromethane cooled in an ice bath. After 30 min. the volatiles were removed WO93/10096 l3 PCT/US92/09337 with a rotary evaporator. The residue was disolved in ethyl acetate and washed with water. The organic layer was dried (sodium sulfate) and the solvent was removed with a rotary evaporator ~o give 24.7 g of the title compound as an orange oil.
1H NMR (CDCl3): ~ 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).
Interme~
1 6-Dihydro-N-~l-meth~lQ~ 6-oxo-2-~y~idinecarh To a mixture of 24.7 g of N~ methylethyl)-6-(phenyl-methoxy)-2-pyridinecarboxamide and 11 g of 10% Pd on carbon was added 500 mL of ethanol. The reaction mixture was vigorously stirred and placed under 1 atmosphere of hydrogen for 4 hours. (Approximately 2100 mL of hydrogen was absorbed.) The reaction mixture was filtered and the catalyst was washed with THF. The solvent was removed from the filtrate with a rotary e~aporator to give 13.B g of the title compound as a yellow solid.
1H NMR (CD3SOCD3): ~ 1.17 (d, 6), 4.0 (m, 1), 6.67 (d, 1) and 7.2 (br, 1), 7.75 (dd, 1), 8.15 ~br, 1), 11.5 (br, 1).
~=ll=~9~yL~thyl~-~-rlmethv~sulfonvl)oxvl-2-To a solution of 0.50 g (2.8 mmol) of 1,6-dihydro-N-~l-methylethyl)-6-oxo-2-pyridinecarboxamide in 40 mL of dichlorome~hane was added 0.46 mL (3.3 mmol) of triethylamine. The reaction mixture was cooled in an ice bath and 0.26 mL (3.3 mmol) of methanesulfonyl chloride was added. The reaction mixture was stirred at room temperature overnight~ The reaction mixture was diluted with dichloromethane, washed with water and dried ~sodium sulfate). The solvent was removed with a rotary evaporator and the residue was purified by flash chromatography on silica gel with 25% ethyl acetate in WO93/10096 2 ~ 2 3 9 a 2 PCT/US92/09337 hexanes as eluant to give 0.49 g of the title compo~nd as a white solid, mp 78-79C.
1H NMR (CDCl3): ~ 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).
E~ IE_2 2-~yridi.necarkQthioamid~
To a solution of 0.50 g (l.9 mmol) of N-(1-methyl-ethyl)-6-methylsulfonyloxy)-2-pyridinecarboxamide in 25 mL of toluene was added 0.59 g of 2,4-bis(methoxy- ~
phenyl)-1,3-dithia-2,4-diphosphetane-2,2-disulfide. The ~-reaction mixture was refluxed for 2.5 hours. The solvent was removed with a rotary evaporator. The residue was purified by flash chromatography on silica gel with a gradient of 10-20% ethyl acetate in hexanes as eluant to give 0.47 g of a yellow solid. lH NMR indicated this to be the title compound with a small impurity. The solid was recrystallized from a mixture of et~er/petroleum ether to give yellow needles, mp 110-112C.
lH NMR (CDCl3): ~ 1.18 (d, 6), 3.37 (s, 3), 4.87 (m, 1), 7.28 (d, 1), 7.97 (dd, 1~, 8.63 (d, 1).
By applying the procedures of Examples 1 and 2 and Equations l through 13, one skilled in the art can prepare the compounds in Tables 1 through 7. In the 2~ following Tables, abbreviations for various alkyl chains and rings have been used with the following corresponding definitions.
iPr = isopropyl = CH(CH3)2 nPr = n-propyl = CH2CH2CH3 cPr = cyclopropyl = CH(CH2)2 tBu = tert-butyl = C(CH3) 3 nBu ~ n-butyl = (CH2) 3CH3 sBu -- ~ec-butyl ~ CH (CH3) CH2CH3 iBu ~ iso-butyl ~ CH2CH (CH3) 2 WO 93/10096 2 1 ~ 3 9 ~ 2PC~/US92/09337 ~NC ~N~10502R3 R33CH3, X-O, Z~H R3-CH3, X=O, Z-HR3-CH3, X~O, Z~H
Bl B2 ~1 B2 Bl B
CH3 H iPr C(O)H CH2CH2Cl CH3 :~
CH3 CH3 iPr C(O)CH3 C~CF3)CH3 H
C2H5 H iPr C(O)OCH3 OCH3 H :
C2H5 CH3 iPr allyl CH2CH2OcH3 H :-C2H5 C2H5 n3u H Ph H
nPr H tBu H PhCH2 H
nPr CH3 CH(c~3)cH2cH3 H N~cH2)3 H
nPr C2HS cPr H allyl H
iPr H cPr CH3 -CH2CH2C~2cH2cH2 iPr CH3 CH2~cPr) H -CH2CH2CH2cH2-iPr C2H5 CH2CF3 H -CH2CH2OCH2CH2-sBu CH3 CH~cH3)cH2N~cH3)2 H CH~cH3)cH2F H

R3-CH3, X~S, Z-H R3-CH3, X~S, Z-H R3-CH3, X~S, Z-H
CH3 H iPr C~O)H CH2CH2Cl CH3 CH3 CH3 iPr C~O)CH3 CH~CF3)CH3 H
C2H5 H iPr C~O)OCH3 OCH3 H
C2H5 ÇH3 iPr allyl CH2CH2OcH3 H
C2H5 C2H5 nBu H Ph H
nPr H tBu H P~CH2 H
nPr CH3 CH~cH3)cH2cH3 H N~cH2)3 H
nPr C2H5 cPr H allyl iPr H CPr CH3 -CH2CH2CH2cH2cH2-iPr CH3 CH2~cPr) H -CH2CH2CH2cH2-iPr C2H5 CH2CF3 H -CH2CH2OcH2cH2~

W O 93/}0096 ~ l 2 ~3 9 ~ ~ PCT/US92/Og337 Rl=iPr, R2~H and X is O Rl~iPr, R3 CH3 and Z is H
B3 ~ B2 ~ :

C~2Cl H H NCH3 C~3 3-Cl CH3 NH
CH3 4-Cl CH3 NCH
CH3 S-Cl c~3 NC2H5 CH3 4-GH3 :.

WO 93/lOOg6 2 1 2 3 9 ~J 2 PCI /US92/09337 \NIl 0502R

R3-CH3, X-O, ZDH R3~CH3, X-S, Z=H R2-H, R3-CH3, X-O
Bl B2 Bl B2 B
CH3 H CH3 H iPr 2-Cl CH3 CH3 CH3 CH3 lPr 4-Cl C2H5 H . C2H5 H iPr 6-Cl nPr H nPr H lPr 2-CH3 iPr H iPr H iPr 4-CH3 iPr CH3 iPr CH3 iPr 6-CH3 cPr H cPr H
-cH2cH2ocH2cH2 --CEi2CH20CH2C~2 W O 93/10096 PC~/U~2/0~337 `~'~3i~ 18 TA~I~ 3 oso2R3 R~

R3~CH3, X~O, Z~H R3=CH3, X~S, Z-H R2~H, R3~CH3, XYO
E31 B2 B,l B2 Bl .~
CH3 H CH3 H iPr 2-Cl CH3 CH3 CH3 ~H3 iPr 5-Cl C2H5 H C2~5 H iPr 6-Cl nPr H nPr H . tPr 2-C~3 iPr H iPr H . lPr 5-CH3 iPr CH3 iPr CH3 iPr 6-CH3 cPr H cPr H
-CH2CH20CH2CH2--CH2CH20CH2CH2 ~ ~

. ~ .

Il CN

R3-CH3, X~O, Z-HR3-CH3, X-S, Z-H R2-H, R3-CH3, X-O
Bl ~2 Bl ~2 Bl CH3 ~ CH3 H iPr 2-Cl CH3 CH3 CH3 CH3 iPr 5-Cl C2H5 H C2H5 H iPr 6-Cl nPr H nPr H iPr 2-CH3 iPr H iPr H iPr 5-CH3 iPr ` CH3 iPr CH3 iPr 6-CH3 cPr H cPr H
-CH2CH20C82CH2--CH2CH20C~2CH2 -W O 93/10096 2 1 ~ 3 3 ~ 2 PCT/USg2/09337 TA~h~ 5 oso2R3 NC

R3-CH3, X~O, Z~H R3~CH3, X=O, ZDH R3-CH3, X~O, Z-H
~1 B2 B1 ~2 ~1 R2 CH3 H iPr C(OlH CH2CH2Cl CH3 CH3 CH3 iPr C(O)CH3 CH(cF3)cH3 H
C2H5 H iPr C~O)OCH3 OCH3 H
C2H5 CH3 iPr allyl CH2CH2OcH3 H
C2H5 C2H5 nBu H Ph H
nPr H tBu H PhCH2 H
nPr CH3 CH~CH3)CH2CH3 H N~CH2)3 H
nPr C2H5 cPr H allyl H
iPr C2H5 CPr CH3 -CH2C~2CH2cH2cH2-iPr H CH2(cPr) H -CH2CH2CH2cH2 ~Pr CH3 CH2CF3 H -CH2CH2OcH2cH2 iPr C2H5 s3u H CH(CH3~CH2CN
tBu H CH(cH3)cH(cH3)2 H ~H(CH3)CH2CH2CH3 H

R3-CH3, X-S, Z~H R3-CH3, X~S, 2~H R3~CH3, X-S, Z~H
Bl B2 Bl B2 Bl B
CH3 H iPr C(O)H CH2CH2Cl CH3 CH3 CH3 iPr C(O)CH3 CH~CF3)CH3 H
C2~5 H iPr C~O~OCH3 OCH3 H
2H5 C-H3 iPr allyl CH2CH2OcH3 H
C2H5 C2H5 nBu H Ph H
nPr H tBu H PhCH2 H
nPr CH3 CH(CH3)CH2cH2 H N(CH2)3 nPr C2H5 iPr H allyl H :
iPr ` H iPr CH3 -CH2CH2CH2cH2cH2 iPr CH3 CH2(cPr) H -CH2CH2CH2cH2 iPr C2H5 CH2CF3 H -CH2cH2OcH2cH2 WO 93tlO096 PCI'/US92/Og337 21233 ~2 2~

1 ~ X N ~
NC ~ ~ oS02R3 R3-CH3, X-O, Z~H R3-CH3, X~O, Z-H R2-H, R3-CH3, X~O
Bl B2 Bl B2 ~1 ~
CH3 H CH3 H iPr Cl C~3 CH3 CH3 CH3 cPr Cl C2H5 H C2HS H nPr Cl nPr H nPr ~ iPr CH3 lPr H iPr H cPr CH3 iPr CH3 ~Pr CH3 nPr CH3 cPr H cPr H

~aEII~ 7 R'--N=C N OS02CE13 Y-O Y-S
B Bl ~ B Bl CH3 iPr H CH3 lPr CH3 sBu H CH3 sBu H
CH3 iPr 5-Cl CH3 iPr 5-Cl CH3 sBu 5-Cl CH3 sBu 5-Cl C2HS iPr H C2H5 iPr H
C2H5 sBu H C2H5 sBu H
.

W O 93/10096 2 ~ 2 3 9 ~ 2 PCT/US92/09337 INDEX TABLE A

\ ll ~ N 1 OSO ~3 CMPD ~1 B2 B3 ~ ~ mP ~C) 1 CH(CH3)2 H CH3 O H 78-79

3 N(CH3)2 H CH3 O H 67-76

4 CH2CH2CH3 H CH3 S H . 62-65 6 N(CH3)2 H CH2C1 O H 91-94 7 CH(CH3)2 CH3 CH3 O H 62-65 8 CYC1OPrOPY1 H CH3 O H 110-112 9 CH~CH3)2 H CH3 S H 110-111 CYC1OPrOPY1 H CH3 S H 12g-127 12 C2H5 H CH3 H 95~99 13 CH3 ~ CH3 O H 97-100 14 tBU H CH3 O H 70-72.5 16 CH(CH3)2 H CH2C1 O H 89-90 17 CH~CH3)2 H C2H5 O H 106-108 18 iBU H CH3 O H Oi11 19 CH~CH3)2 H CH3 O 3-C1 129 CH~CH3~2 H CH3 O 5-C1 100-101 ~;
21 ~R)-S8U H CH3 O H Oi1 [a1D~ -17.5 22 ~S)-SBU H CH3 O H Oi1 ~a~D- +18.4 24 C~CH3)2CH2CH3 H CH3 O H 45-48 CH~C2H5)CH2CH3 H CH3 O H 88-90 27 CYC1OPe~tY1 H CH3 O H 48-52 28 CH~CH3)CH(CH3)2 H CH3 O H 50-53 29 CH~CH3)CH2CH2CH3 H CH3 O H Oi12 W O 93~10096 21 2 3 ~ ~ 2 22 PCT/US92/09337 CH~CH3)C~2OCH3 H CH3 O H oil3 31 C2H5 C~3 CH3 O H oil4 32 CH~CH3)CH2CN H CH3 O H 48-52 33 CH(CH3)2 H CH3 O 3-Br 138.5-139.5 34 sBu HCH3 O 3-C1 127-129 (R)-CH~CH3)P~ H CH3 O H 82-83 36 ~S)-CH~CH3)Ph H CH3 O H 83-84 37 _CH~CH3)CH2CN H CH3 _O 3-C1 122-123.5 1 1H NMR ~CDC13): ~ 1.09 ~d,6), 1.90 ~m,1), 3.31 ~dd,2), 3.40 ~s,3), 7.29 (d,l), 7.7 ~br,l), 8.01 ~dd,l), 8.20 ~d,l).
2 lH NMR ~CDC13): ~ 0.~4 ~t,3), 1.25 ~d,3), 1.38 ~m,2), 1.56 ~m,2), 3.40 (s,3), 4.18 ~m,1), 7.31 ~d,1), 7.38 (br,l), 8.00 ~dd,1), 8.18 (d,l).
3 1H NMR (CDC13): ~ 1.31 (d,3), 3.40 ~s,3), 3.45 (s,3), 3.48 (m,2), 7.25 (d,1), 7.8 ~br,l), 8.00 (dd,1), 8.18 ~d,l).
4 1H NMR shows rotamers ~CDC13): ~ 1.27 ~m,3), 3.40 and 3.47 ~s,3), 4.23 ~m,l), 6.g5 and 7.2 ~br,1), 7.10 and 7.28 ~d,1), 8.00 and 8.18 ~dd,l), 8.04 and 8.13 ~d,l).

IN~EX ~2 X ,R~

CEI,SO,O~ ~

~m~ Bl B2 ~3 ~ ~ m~ L
23 CH~C83)2 H CH3 O 2-C1 106-107 WO 93/100!~6 2 1 2 3 ~ 0 2 PCT/US92/09337 INDEX TABLE C

Rl X ~ Z

.~ R2 ~, Bl B2 B3 ~ ;~ mD 1 C) 38CH ~CH3) 2 H CH3 H 129-131 .
, Compounds of this invention will generally be used in formulation with an agriculturally suitable c:arrier comprising a liquid or solid diiuent or an organic solvent. Vse formulations include dusts, granules, baits, pellets, solutions, suspensions, emulsions, ~-wettable powders, emulsifiable concentrates, dry flowables and the like, consistent with the physical properties of the active ingredient, mode of application and environmental factors such as soil type, moisture and temperature. Sprayable formulations can be extendec in suitable media and used at spray volumes from about one to several hundred liters per hectare. High strength compositions are primarily used as intermediates for further formulation. The formulations will typically contain effective amounts of active ingredient, diluent and surfactant within the following approximate ranges which add up 100 weight percent.

....

2i23~2 24 _ Wei~ht Percent _ ~;iQ~ :
Wettable Powders 25-90 0-74 l-10 ~-Oil Suspensions, 5-50 40-95 0-15 Emulsions, Solutions, (includlng Emulsifiable Concentrates) :
Dust~ 1-25 70-99 0~5 Granules, Baits and 0.01-99 5-99.99 0-lS
Pellets High Strength 90-99 0-10 0-2 Compositions Typical solid diluents are described in Watkins, et al., Handbook of Insecticide Dust Diluents and Carriers, 2nd Ed., Dorland Books, Caldwell, New Jersey .
Typical liquid diluents and solvents are described in Marsden, Solvents Guide, 2nd ~d., Interscience, New York, 1950. NcCutcheon 's De~ergents and Emulsifiers Annual, Allured Publ. Corp., Ridgewood, New Jersey, as well as Sisely and Wood, Encyclopedia of Surface Active Agentst Chemical Publ. Co., Inc., New York, 1964, list surfactants and recommended uses. All formulations can contain minor amounts of additives to reduce foam, caking, corrosion, microbiological growth, etc.
Solutions are prepared by simply mixing the ingredients. Fine solid compositions are made by blending and, usually, grinding as in a hammer mill or fluid energy mill. Water-dispersible granules can be produced be agglomerating a fine powder composition; see for example, Cross et al., Pesticide Formulations, Washington, D.C., 1988, pp 251-259~ Suspensions are prepared by wet-milling; see, for example, U.S.
3,060,084. Granules and pellets can be made by spraying the active material upon preformed granular carriers or W093/l0~96 2 ~ ~ 3 ~ ~ 2 PCT/~S92to9337 by agglomeration techniques. See Browning, "Agglomeration", Chemical Engineering, December 4, 1967, -~
pp 147-148, .Perry's Chemical Engineer's ~landbook, 4th Ed., McGraw-Hill, New York, 1963, pages 8-57 and following, and WO 91/13546. Pellets can be prepared as described in U.S. 4,172,7.14. Water-dispersible and water-soluble granules can also be prepared as taught in DE 3,246,493.
For further information regarding the art of formulation, see U.S. 3,235,361, Col. 6, line 16 through Col. 7, line 19 and Examples 10-41; U.S. 3,309,192, Col.

5, line 43 through Col. 7, line 62 and Examples 8, 12, 15, 39, 41, 52, 53, 5~, 132, 138-140, 162-164, 16~, 167 and 169-182; U.S. 2,891,855, Col. 3, line 66 through Col. 5, line 17 and Examples 1-4; Klingman, Weed Control as a Science, John Wiley and Sons, Inc., New York, 1961, pp 81-96; and Hance et al., Weed Control Handbook, 8th .
Ed., Blackwell Scientific Publications, Oxford, 1989.
In the following Examples, all percentages are by weight and all formulations are worked up in conventional ways. Compound numbers refer to compounds in Index Table A.

Wetta~le Powder Compound 1 65.0%
dodecylphenol polyethylene glycol ether 2.0%
sodium ligninsulfonate 4.0 sodium silicoaluminate 6.0%
montmorillonite (calcined) 23.0 E~dmG
~an~
~Compound 1 10.0 attapulgite granules (low volative matter, 0.71/0.30 mm; U.S.S. No.
25-50 sieves) 90.0% :`

6 PCT/US92/09337 2 ~ 26 E~ample C
~

Compound 1 25.0%
anhydrous sodium sulfate 10.0%
crude calcium ligninsulfonate 5.0%
sodium alkylnaphthalenesulfonate 1.0%
calcium/magnesium bentonite 59.0%
E~ample D
. ~h~
Compound 1 20.0%
blend of oil soluble sulfonates and polyoxyethylene ethers 10.0%
isophorone 70.0%
The compounds of this invention exhibit acti~ity against a wide spectrum of foliar-feeding, fruit-feeding, seed-feeding, aquatic and soil-inhabiting arthropods (term includes ~ematodes) which are pests of growing and stored agronomi~ crops, forestry, greenhouse crops, ornamentals, nursery crops, stored food and fiber products, livestock, household, and public and animal health. Those skil~ed in the art will appreciate that not all compounds are equally effective against all pests. Nevertheless, all of the compounds of this invention display activity against pests that include:
eggs, lar~ae and adults of the Order Lepidoptera; eggs, foliar-feeding, fruit-feeding, root-feeding, seed-feeding larvae and~adults of the Order Coleoptera; eggs, immatures and adults of the Orders Hemiptera and Homoptera; eggs, larvae, nymphs and adults of the Order Acari; eg~s, immatures and adults of the Orders Thysanoptera, Orthoptera and Dermaptera; eggs, immatures and adults of the Order Diptera; and eggs, jun~eniles and adults of the Phylum Nemata. The compounds of this invention are also active against pests o~ the Orders Hymenoptera, Isoptera, Phthiraptera~ Siphonoptera, WO93/10096 2 1 ~ 3 9 ^~ 2 PCT/USg2~09337 2`i Blattaria, Thysanaura and Pscoptera; pests belonging to the Class Arachnida and Phylum Platyhelminthes. See Wo 90/10623 and wo 92/00673 for more detailed pest descriptions.
Compounds of this invention can also be mixed with one or more other insecticides, fungicides, nematocides, bactericides, acaricides, semiochemicals, repellants, attractan~s, pheromones, feeding stimulants or other biologically active compounds to form a multi-component pesticide giving an even broader spectrum of agricultural protection. Examples of other agricultural protectants with which compounds of this invention can be formulated are: insecticides such as monoc.rotophos, carbofuran, tetrachlorvinphos, malathion, p~rathion-methyl, methomyl, chlordimeform, diazinon, deltamethrin, oxamyl, fenvalerate, esfenvalerate, permethrin, profenofos, sulprofos, triflumuron, diflubenzuron, methoprene, buprofezin, thiodicarb, acephate, azinphosmethyl, chlorpyrifos, dimethoate, fipronil, flufenpxox, fonophos, isofenphos, methidathion, methamidophos, phosmet, phosphamidon, phosalone, pirimicarb, phorate, terbufos, trichlorfon, methoxychlor, bifenthrin, biphenate, cyfluthrin, fenpropathrin, fluvalinate, flucythrinat~, tralomethrin, metaldehyde and rotenone; fungicides such as carbendazim, thiuram, dodine, maneb, chloroneb, benomyl, cymoxanil, fenpropidine, fenpropimorph, triadimefon, captan, thiophanate-methyl, thiabendazole, phosethyl-Al, chlorothalonil, dichloran, metalaxyl, captafol, iprodione, oxadixyl, vinclozolin, kasugamycin, myclobutanil, tebuconazole, difenoconazole, diniconazole, fluquinconazole, ipconazole, metconazole, penconazole, propiconazoler uniconzole, flutriaol, prochloraz, pyrifenox, fenarimol, triadimenol, diclobutrazol, copper oxychloride, furalaxyl, folpet, flusilazol, blasticidin S, diclomezine, edifenphos, isoprothiolane, iprobenfos, WO93~10096 PCT/~S~2/09337 21~3~2 - mepronil, neo-asozin, pencycuron, probenazole, pyroquilon, tricyclazole, validamycin, and flutolanil;
nematocides.such as aldoxycarb, fenamiphos and fosthietan; bactericides such as oxytetracyline, streptomycin and tribasic copper sulfate; acaricides such as binapacryl, oxythioquino~, chlorobenzilate, dicofol, dienochlor, cyhe~atin, hexythiazox, amitraz, propargite, tebufenpyrad and fenbutatin oxide; and biological agents such as Bacillus thuringiensis, baculovirus and avermectin B.
In certain instances, combinations with other arthropodicides having a similiar spectrum of control but a different mode of action will be particularly advantageous for resistance management.
Arthropod pests are controlled and protection of agronomic crops, animal and human health is achieved by applying one or more of the compounds of this invention, in an effective amount, to the Pnvironment of the pests including the agronomic and/or nonagronomic locus of infestation, to the area to be protected, or directly on the pests to be controlled. A preferred method of application is by spraying. Alternatively, granular formulations of these compounds can be applied to the plant foliage or the soil. Other methods of applicat.ion include direct and residual sprays, aerial sprays, systemic uptake, baits, eartags, boluses, foggers, fumigants,-aerosols, and many others. The compounds can be incorporated into baits that are consumed by the arthropods or in devices such as traps and the like.
The compounds of this invention can be applied in their pure state, but most often application will be of a formulation comprising one or more compounds with suitable carriers, diluents~ and surfactants and possibly in combination with a food depending on the contemplated end use. A preferred method of app~ication involves 2123~
WO93/10096 PCT/US9~/09337 spraying a water dispersion or refined oil solution of the compounds. Combinations with spray oils, spray oil concentrations, spreader stickers, adjuvants, and synergists and other solvents such as piperonyl butoxide often enhance compound efficacy.
The rate of application required for effective control will depend on such factors as the species of arthropod to be controlled, the pest's life cycle, life stage, its size, location, time of year, host crop or animal, feeding behaviorr mating behavior, ambient moisture, temperature, and the like. Under normal circumstances, application rates of about O.Ol to 2 kg of active ingredient per hectare are sufficsent to control pests in agronomic ecosystems, but as little as O.OOl kg/hectare may be sufficient or as much as 8 kg hectare may be required. For nonagronomic applications, effective use rates will range from about l.0 to 50 mg/square meter but as little as 0.1 mgJsquare meter may be sufficient or as much as 150 mg/square meter may be required.
The following Tests demonstrate th~ control efficacy of compounds of this invention on speciric pests. The pest control protection afforded by the compounds is not limited, however, to these species. See Index Tables A-C
for compound descriptions.

~ ;.
Fall A~yworm Test units, each consisting of a H.I.S. (high impact 30 styrene) with 16 cells. In 12 of the cells is a wet ~`
filter paper and approximatelv 8 cm2 of lima leaf, in the other 4 cells is a 0.5 cm layer of wheat germ diet.
Fifteen to twenty third instar larvae of Fall Armyworm (Spodoptera frugiperda) were placed in an 8 ounce (230 ml) plastic cup. Solutions of each of the test compounds W093/l~6 ~!l 23~1a2 PCT/US92/09337 (acetone/distilled water 75/25 solvent) were sprayed into the tray and cup. Spraying was accomplished by passing the tray and cup, on a con~eyer belt, directly beneath a flat fan hydraulic nozzle which discharged the spray at a rate of 0.5 pounds of active ingredient per acre (about 0.55 kg/ha) at 30 p.s.i. (207 kPa). The insects were transferred into the tray (one insect per cell). The trays were then covered and held at 27C and 50~ relative humidity for 48 hours, after which time readings were taken on the 12 cells with lima leaves. The 4 remaining cells were read at 7 days for a delayed toxicity reading.
Of the compounds tested, the following resulted in greater than or equal to 80% mortality: 4*.
*Tested at 0.13 kg/ha TEST B
SQuthern Corn Ro~tworm Test units, each consisting of an a-ounce (230 mL) plastic cup containing 1 sprouted corn seed, were prepared. Sets of three test units were sprayed as described in Test A with indi~idual solutions of the test compounds. After the spray on the cups had dried, five third-instar larvae of the southern coxn rootworm (Diabrotica undecimpunctata howardi) were placecl into each cup. A moistened dental wick was inserted into each cup to prevent drying and the cups were then covered. The cups were then held at 27C and 50% relative humidity for 48 hours, ~fter which time mortality readings were taken.
Of the compounds testedr the following resulted in greater than or equal to 80% mortality: l, 2, 3*, 4*, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14**, 15, 16, 17, 18, 19, ~0, 21, 22, 24, 25, 26, 27, 28, 29, 30, 31, 3~, 33, 34, 38*.
*Tested at 0.13 kg/ha. ** The listed compounds 14-38 were tested under an analogous protocol where the cups contained a soybean-wheatgerm diet, and second-instar lar~ae were used.

WO g3/10096 2 1 2 3 ~ ~ 2 PCT/US92/09337 TEST C
~er LeafhoD~er Test units were prepared from a series of 12-ounce (350 mL) cups, each containing oat (Avena sativa) seedlings in a 1-inch (2.54 cm) layer of sterilized soil and a 1/2 inch (1.27 cm) layer of sand. The test units were sprayed as described in Test A with individual solutions of the below-listed compounds. After the oats had dried from the spraying, between 10 and 15 adult aster leafhoppers (Mascrostel es fasci frons) were aspirated into each of the cups covered with vented lids. The cups were held at ~7C and 50% relative humidity for 48 hours, after which time mortality readings were taken. Of the compounds tested, the following resulted in greater than ~
or equal to 80% mortality: 1, 2, 7, 15, 16, 21, 22, 25, ~-26, 38*.
*Tested at 0.13 kg/ha Five adult boll weevils (Anthonomus grandis) were placed into each of a series of 9 ounce (260 mL) cups.
The test units were sprayed as described in Test A with ~-individual solutions of the below-listed compounds. Each cup was then covered with a vented lid and held at 27C
and 50% relative humidity for 48 hours, after which time mortality readings were taken. Of the compounds tested, the following resulted in greater than or equal to 80 mortality: 1, 15, 21, 29, 32.
TEST
Black Bean A~hid Individual nasturium leaves were infested ~ith 10 to 15 aphids ~all stages of Aphis Fabae) and sprayed with their undersides facing up as described in Test A. The leaves were then set in 3/8 inch (0.94 cm) diameter vial containing 4 ml of sugar water solution and covered with WO93/10096 2123~2 32 PCT/US92/09337 a clear plastice 1 ounce (28 ml) portion cup to prevent escape of the aphids that drop from the leaves. The test units were held at 27C and 50% relative humidity for 98 hours, after which time mortality readings were taken.
Of the compounds tested, the following resulted in greater than or equal to 80~ mortality: 19, 20, 33.

r---n le~fh-no~-Three rice (Oryza sativ~) seedlings, 1.5 leaf stage and about 10 cm tall are transplanted into a 1/2 oz (14 mL) plastic cup containing Kumiai Brown artificial soil. Seven milliliters of distilled water is then added to the cup. The test chemical is prepared by first dissolving the chemical in acetone and then adding wa~er to produce a 75:25 mixture of acetone:water. The concentration of the test chemical in the solvent mixture is 100 ppm. Four plastic cups, each cup serving as a replicate, are then placed on a spray chamber turntable.
The cups are sprayed for 45 seconds with 50 mL of the chemical solution at a pressure of 2.0 kg/cm2 with an air atomizing spray nozzel. The tu-ntable completes 7.5 rotations during the 45 second spray interval. After chemical application, treated cups are held in a vented enclosure to dry for about 2 hours. After drying, the cups are placed into concial shaped test units and the surface of the soil is covered with 2 to 3 mm of quartz sand. Eight to ten 3rd-instar nymphs of the green leafhopper (Nephotettix cincticeps) are transferred into the test units using an aspirator. The test units are 30 held at 27C and 65~ relative humidity. Counts of the number of live and dead nymphs are taken at 24 and 48 hours post-infestation. Insects which cannot walk are classified as dead. Of the compounds tested, the following gave mortality levels of 80~ or higher at 48 hours post-infestation: 1, 15, 2S, 28, 29, 30, 31, 32.

W O 93/10096 2 1 2 3 9 ~ ~ PC~r/US92/09337 TE;ST G
Brown Plantho~er Same method as described in Test F, using the brown planthopper (Nilaparv~t~ l ugens) as the test species. Of the compounds tested, the following gave mortality of 80%
or higher at 48 hours post-infestation: 1, 4, 9, 14, 15, 19, 21, 22, 24, 25, 26, 28, 29, 30, 31, 32, 33.
TE$~ H
Solution_Systemi~ Activity_A~ainst Gree~ Leafho~per Ny~h~
The test chemical is added directly into 10 mL of distilled water and dissolved completely. This chemical -~
solution is poured into a conical shaped test unit.
Three rice seedlings are then positioned in the unit by a notched sponge disk. The sponge disk allows complete immersion of the seedling root systems in the chemical solution, while the aerial portion O! the plant is isolated above the solution. The sponge also prevents --the test nymphs from accidentally contacting the test solution. A 7 to 10 mm space, between the surface of the chemical solution and the bottom of ~he sponge disk, prevents accidental chemical contamination of the sponge.
The concentration of the test chemical in the chemical solution is 100 ppm. The rice seedlings are allowed to absorb the chemical from the solution for 24 hours in a growth chamber held at 27C and 65% relative humidity.
Eight to ten 3rd-instar nymphs of the green leafhopper (~ephotettix cincticeps) are transferred into the test units using an asp-.rator. The infested units are held under the same temperature and humidity conditions described above. Counts of the number of live and dead nymphs are taken at 24 and 48 hours post-infestation.
Inse~ts which cannot walk are classified as dead. Of the compounds tested, the following gave mortality levels of 80% or higher at 48 hours post-infestation: 1, 15, 16, 21, 22, 28, 29.

WO 93/10096 PCI/l~S92/09337 D ~

TE~T I
Solution Systemic ActiYity Ag~in~t Bro~n PLanthopper Nymphs Same methods as use~ for Solution Systemic Activity against green leafhopper nymphs, except that the brown planthopper (Nilaparvata lugens) is the test species. Of the compounds tested, the following gave mortality levels - of 80% or higher at 48 hours post-infestation: 1, 9, 15, 16, ~1, 22, 26, 28, 29.

.. `:

Claims (9)

1. A compound having the formulae:

, , I II

wherein:
Q is selected from the group , , , , and ;

X is selected from the group O, S and NR6;
Y is selected from the group O and S;
Z is selected from the group H, halogen, CN, NO2, C1-C3 alkyl, C1-C3 haloalkyl, C1-C3 alkoxy, C1-C3 haloalkoxy and S(O)nR7;

R is selected from C1-C3 alkyl;
R1 is selected from the group C1-C6 alkyl, C1-C6 haloalkyl, C1-C5 alkoxy, C2-C5 alkoxyalkyl, C2-C6 alkenyl, C2-C6 haloalkenyl, C2-C6 alkynyl, C3-C6 haloalkynyl, C3-C6 cycloalkyl, C4-C7 cycloalkylalkyl, N(R4)R5, phenyl optionally substituted with 1 or 2 substituents selected from the group W; benzyl optionally substituted with 1 or 2 substitutents selected from the group W; and C1-C5 alkyl substituted with a group selected from CN, N(R4)R5 and S(O)nR7;
R2 is selected from the group H, C1-C2 alkyl, C1-C2 haloalkyl, formyl, C2-C3 alkylcarbonyl, C2-C3 alkoxycarbonyl, C3 alkenyl and C3 alkynyl; or R1 and R2 can be taken together to form -CH2CH2CH2CH2CH2-, -CH2CH2CH2CH2- or -CH2CH2OCH2CH2-;
R3 is selected from the group C1-C2 alkyl and C1-C2 haloalkyl;
R4 and R5 are independently selected from methyl and ethyl; or R4 and R5 can be taken together to form -CH2CH2CH2CH2CH2-, -CH2CH2CH2CH2- or -CH2CH2OCH2CH2-;
R6 is selected from the group H, C1-C3 alkyl and C1-C3 haloalkoxy;
R7 is from the group C1-C2 alkyl and C1-C2 haloalkyl;
W is selected from the group halogen, C1-C2 alkyl, C1-C2 alkoxy, CF3 and OCF3; and n is 0, 1 or 2.

2. A compound according to Claim 1 wherein:
R1 is selected from the group C1-C4 alkyl, C3-C5 cycloalkyl, C4-C5 cycloalkylalkyl and C1-C5 alkyl substituted with CN;

R2 is selected from the group H and CH3;
R3 is CH3;
X is selected from the group O and S; and Z is selected from the group H and halogen.

3. A compound according to Claim 2 wherein Q is selected from the group Q-1 and Q-6.

4. A compound according to Claim 3 wherein Q is Q-1.

5. A compound according to Claim 3 wherein Q is Q-6.

6. A compound according to Claim 4 selected from the group:
N-(1-methylethyl)-6-[(methylsulfonyl)oxy]-2-pyridinecarboxamide;
N-(1-methylethyl)-6-[(methylsulfonyl)oxy]-2-pyridinecarbothioamide;
N-(1-methylpropyl)-6-[(methylsulfonyl)oxy]-2-pyridinecarboxamide; and 3-chloro-N-(1-methylethyl)-6-[(methylsulfonyl)oxy]-2-pyridinecarboxamide.

7. A compound according to Claim 6 which is:
N-(1-methylpropyl)-6-[(methylsulfonyl)oxy]-2-pyridinecarboxamide.

8. An arthropodicidal composition comprising an arthropodicidally effective amount of a compound according to any one of Claims 1 to 7 and a carrier therefor.

9. A method for controlling arthropods comprising contacting the arthropods or their environment with an arthropodicidally effective amount of a compound according to any one of Claims 1 to 7.