NZ700056B2 - Methods of pest control in soybean - Google Patents

Abstract

The disclosure relates to a compound selected from compounds of formula (A) wherein G is oxygen, R7 is trifluoromethyl, R5 is methyl, R1 is hydrogen, and cycle C and R2 have the values listed Table X in the specification. Cycle C may be 3,4,5-trichloro-phenyl- or 3,5 -dichloro-4-fluoro-phenyl- and R2 may include thietan-3-yl-, 1-oxo-thietan-3-yl-, 1,1-dioxo-thietan-3-yl-, 1,1-dioxo-thietan-2-yl-methyl-, 1,1-dioxo-thietan-3-yl-methyl- and thietan-3-yl-methyl-. R2 may include thietan-3-yl-, 1-oxo-thietan-3-yl-, 1,1-dioxo-thietan-3-yl-, 1,1-dioxo-thietan-2-yl-methyl-, 1,1-dioxo-thietan-3-yl-methyl- and thietan-3-yl-methyl-.

Description

PATENTS FORM N0. 5 Our ref: FlP236200NZPR Divisional application out of NZ 626702 In turn a divisional application out of NZ 613413 NEW ZEALAND PATENTS ACT 1953 COMPLETE SPECIFICATION Methods of pest control in soybean We, ta ipations AG, of zwaldallee 215, 4058 Basel, Switzerland; and Syngenta Limited, of European Regional Centre, Priestley Road, Surrey Research Park, Surrey, Guildford, GU2 7YH, United Kingdom hereby declare the invention, for which we pray that a patent may be granted to us and the method by which it is to be performed, to be particularly described in and by the following statement: (followed by page 1a) METHODS OF PEST CONTROL IN SOYBEAN The present invention, the invention ofNZ 613413 and the invention ofNZ 626702 relate to methods of pest control in soybean crops.

Stink bugs tera Pentatomidae) are true bugs which can be significant pests when present in large numbers. The nymphs and adults have ng mouthparts which most use to suck sap from plants. According to Stewart et al., Soybean s - Stink bugs, University of Tennessee Institute of Agriculture, W200 8, stink bugs are probably the most common pest problem in soybean. Although they may feed on many parts of the plant, they lly target developing seed including the pods, meaning that injury to soybean seed is the primary problem associated with stink bug infestations.

Of the complex of sucking bugs that occur in cultivation, the brown stinkbug Euschistus heros is currently considered to be the most abundant species in northern Parana to Central Brazil (Corréa- Ferreira & Panizzi, 1999), and is a significant problem in soybean (Schmidt et al., 2003). The bugs occur in soybeans from the vegetative stage and are harmful from the beginning ofpod formation until grain maturity. They cause damage to the seed (Galileo & Heinrichs 1978a, Panizzi & Slansky Jr., 1985) and can also open the way to fungal diseases and cause physiological disorders, such as soybean leaf retention (Galileo & Heinrichs 1978, Todd & Herzog, 1980).

Control of stinkbugs in soybean is often vital to prevent cant economic damage.

Insecticides commonly used to control stinkbugs include pyrethroids, neonicotinoids and organophosphates, although pyrethroid insecticides are y the method of choice for controlling stink bugs in soybean. r, there are increasing problems with insecticide resistance, particularly in brown stink bug populations and particularly to roids. Euschistus heros (F.)) can also be difficult to manage using organophosphates or endosulfan (Sosa-Gomez et al., 2009). There is therefore a need for effective alternative methods of controlling stinkbugs in soybean.

Compounds that are insecticidally, acaricidally, cidally and/or moluscicidally active by antagnonism of the gamma-aminobutyric acid (GABA)—gated de channel, and which comprise a partially saturated heterocycle that is substituted by a haloalkyl substituent and one or two ally substituted aromatic or heteroaromatic rings, represent a new class ofpesticides that are described for example in Ozoe et al. Biochemical and Biophysical ch Communications, 391 (2010) 744-749.

Compounds from this class are broadly described in (EP1731512), WO 2007/123853, , W02009/002809, , , WO 2008/128711, , , , , WC 2007/125984, , JP 2008110971, JP2008133273, JP2009108046, /022746, , , W02009/080250, WO2010/020521, W02010/025998, W02010/020522, W02010/084067, /O86225, WO2010/149506 and W02010/108733.

It has now singly been found that particular insecticides from this new class of gamma- aminobutyric acid (GABA)-gated chloride channel antagonists (disclosed in e.g. 1512), W02009/002809 and WO2009/080250) are highly effective at controlling stinkbugs, (followed by page 2) and in some cases provide greater control than the current market standard. It has also surprisingly been found that these compounds exhibit significantly higher activity against ugs than structurally similar compounds. These compounds therefore represent an important new solution for safeguarding soybean crops from stinkbugs, particularly where stink bugs are resistant to current methods.

In a first aspect the invention provides a method comprising applying to a crop of soybean plants, the locus f, or propagation material thereof, a compound a compound of formula I F3C O\N H \ R5 0 H O X (R8)p (I) wherein X is P1 or P2 \ HN/\CF3 H l H #\n/N N/ #YN\/KO 0 0 P1 P2 R5 is chloro, bromo, CF3 or methyl; each R8 is independently bromo, chloro, fluoro or trifluoromethyl; p is l, 2 or 3; and wherein the method is for controlling and/or preventing ation of the soybean crop by Euschistus, ably Euschistus heros.

In a further aspect the invention provides use of a compound of formula I for control of Euschistus, preferably Euschistus heros. The use may be for lling stinkbugs (Euschistus) that are resistant to one or more other insecticides, preferably pyrethroid, neonicotinoids and organophosphates, more preferably roid insecticides.

In a r aspect the invention provides a method sing applying to a crop of soybean plants, the locus thereof, or propagation material thereof, a compound of formula II (11) wherein cycle A is A2a #2 \41'5. #1 wherein A4‘ and A5' are ndently C-H, or nitrogen and wherein #1 indicates the bond to X and #2 indicates the bond to cycle B; cycle B is selected from B1 to B6 #2 O\N #2 #2 O N _ #3 / #3 / #3 / # # B1 32 ‘_ #2 O ArO #2 N #90N \ \ B4 B5 BS wherein #1 indicates the bond to cycle A, #2 indicates the bond to R7 and #3 indicates the bond to cycle C; cycle C is phenyl; R7 is chlorodifluoromethyl or trifluoromethyl; each R8 is independently bromo, , fluoro or romethyl; p is 2 or 3; and X is P1 or P2 \ HN CF3 H l H # N / # N T N \n/ O P1 0 . P2 and wherein the method is for controlling and/or preventing infestation ofthe soybean crop by stinkbugs.

The stinkbugs may be stinkbugs that are resistant to one or more other insecticides, preferably pyrethroid, neonicotinoids and organophosphates, more preferably pyrethroid insecticides.

In a further aspect the invention provides a method comprising applying to a crop of soybean plants, the locus thereof, or propagation material thereof, compound of formula III W0 2012/104331 4 G a x (R )p (III) wherein cycle A is Ala or A2a #24”#1 #2 \ ’ #1 ALA4 ALAS A1a A2a wherein A3, A4, A“ and A5' are independently OH, or nitrogen and n #1 tes the bond to X and #2 indicates the bond to cycle B ; cycle B is selected from B1 to B6 #2 0‘N #2 #2 o #3 / #3 / #3 / 4:1 1:1 4¢1 B1 82 B3 #2 O #2 0740 #2 #1 \#1 \ B4 BS BS wherein #1 indicates the bond to cycle A, #2 indicates the bond to R7 and #3 indicates the bond to cycle C; cycle C is phenyl; R5 is chloro, bromo, CF3 or methyl; R7 is chlorodifluoromethyl or trifluoromethyl; each R8 is independently bromo, chloro, fluoro or trifluoromethyl; p is 2 or 3; and X is selected from P3 to P11 WW 2:: :fi: 221: *‘r n r n, =5“dZ 0 ”ix o O o 0 ('5 P3 P4 P5 P6 H\/C/s g? o H H 3’ #TN\/DS = H H # N # N i #\n/N \n’ \n/ I] \\ #-\n/N\/C/ S‘b O O o 0 0 o 0 P7 P8 P9 P10 P11 In a further aspect the invention provides a method of controlling and/or preventing infestation of stinkbugs in soybean comprising ng to a crop of soybean plants, the locus thereof, propagation material thereof, a compound that of formula III. The stinkbugs may be stinkbugs that are resistant to one or more other insecticides, preferably pyrethroid, neonicotinoids and organophosphates, more preferably pyrethroid insecticides.

In a further aspect the invention provides use of a compound of formula III for control of stinkbugs. The use may be for controlling stinkbugs that are resistant to one or more other insecticides, preferably pyrethroid, neonicotinoids and organophosphates, more preferably pyrethroid insecticides.

The compounds ofthe ion may exist in different geometric or optical isomers or tautomeric forms. This invention covers all such isomers and tautomers and mixtures thereof in all tions as well as isotopic forms such as deuterated compoundsThe compounds of the invention may contain one or more asymmetric carbon atoms, for example, at the C(#2)#3 group, and may exist as enantiomers (or as pairs of diastereoisomers) or as es of such.

In one group ofcompounds of a I X is P1 or P2, R5 is chloro, bromo, CF3 or methyl; each R8 is indepedently bromo, chloro, fluoro or trifluoromethyl; p is 2 or 3. ably X is P1. Each R8 may take the same value.

A particularly preferred compound of formula I is a nd of formula Ix Another particularly preferred compound of al is a nd of formula Iy F 0‘ F l or O WO 04331 6 red values of cycle A, cycle B, cycle C,X, p, A1, A2, A4, A5, R5, R7 and R8 in compounds of formula II are, in any ation, as set out below.

Preferably cycle B is a cycle selected from cycle B1, B2 and B3, more ably B1, In one group ofcompounds cycle B is B1. In another group of compounds cycle B is B2, in another group of compounds cycle B is B3, in another group ofcompounds cycle B is B4, in another group of compounds cycle B is BS, in another group ofcompounds cycle B is B6.

Preferably cycle C is cycle Cl (RB), More preferably cycle C is 3,5-dibromo-phenyl, 3,5-dichloro-phenyl, 3,4-dichloro-phenyl, 3,5-dichloro—4- fluoro-phenyl or 3,4,5 -trichloro-phenyl.

Preferably A3 is C-H or C-RS, most preferably A3 is C-H.

Preferably A4 is OH or C-Rs, most preferably A4 is C-H.

Preferably A4' is C-H or C-RS, most preferably A4' is C-H. ably 5' is OH 15 or C-Rs, most preferably A4' is C-H.

Preferably no more than one ofA3 and A4 is nitrogen. Preferably no more than one of A4' and A5. is nitrogen.

Preferably R5 is methyl.

Preferably R7 is trifluoromethyl. ably each R8 is independently bromo or chloro.

Preferably p is 2.

Preferably X is P4, P5 or P6.

Preferred values of cycle B, cycle C, X, p, Al, A2, A4,, A5, R5, R7 and R8 in compounds of formula III are, in any ation, as set out for compounds of formula II.

In compounds offormula III preferably cycle A is cycle Ala in which A3 and A4 are C—H.

In one group of compounds offormula II each R8 takes the same value. Likewise, in one group of compounds offormula III each R8 takes the same value.

The following tables illustrate specific compounds of the invention: Table 1: Table 1 provides 176 compounds of formula (A) wherein G is oxygen, R7 is trifluoromethyl, R5 is methyl, R1 is hydrogen, and cycle C and R2 have the values listed Table X below.

II; (A) Table 2: Table 2 provides 176 compounds offonnula (B) wherein G is oxygen, R7 is romethyl, R5 is methyl, R1 is hydrogen, and cycle C and R2 have the values listed Table X below.

Table 3: Table 3 provides 176 compounds of formula (C) wherein G is oxygen, R7 is romethyl, R5 is methyl, R1 is hydrogen, and cycle C and R2 have the values listed Table X below.

Table 4: Table 4 provides 176 compounds of formula (D) wherein G is oxygen, R7 is romethyl, R5 is methyl, R1 is hydrogen, and cycle C and R2 have the values listed Table X below.

Table 52Table 5 provides 176 compounds of formula (E) wherein G is oxygen, R7 is trifluoromethyl, R5 is methyl, R1 is hydrogen, and cycle C and R2 have the values listed Table X below.

R7 \[// N R l (E) N\ 1 W0 2012/104331 8 Table 6: Table 6 provides 176 compounds of formula (F) wherein G is oxygen, R7 is romethyl, R5 is methyl, R1 is hydrogen, and cycle C and R2 have the values listed Table X below.

Table 7 Table 7 provides 176 compounds of formula (G) wherein G is oxygen, R7 is trifluoromethyl, R1 is hydrogen, and cycle C and R2 have the values listed Table X below.

-X. 1 3,5 -dichloro-pheny1— (2,2,2-trifluoro-ethylcarbamoyl) —methyl oxo-thietan-Z-yl-methyl- 3,5-dichloro-phenyl- thietanyl-methy1- 1,1-dioxo-thietan-3 -y1-methy1- -X. 12 3,4,5-t1ichloro-phenyl- (2,2,2-trifluoro-ethylcarbamoyl) -methy1 trichloro-phenyl- (pyridyl)-methy1- 3,4,5-trichloro-phenyl- 3,4,5-trichloro-phenyl- l-oxo-thietany1- 3,4,5-trichloro-phenyl- 1,1-dioxo-thietanyl- 3,4,5-trichloro-phenyl- thietanyl-methyl- 3,4,5-trichloro-phenyl- l-oxo-thietany1-methy1- wo 2012/104331 9 3,4,5-trichloro-pheny1- oxo-thietan-2—yl-methyl— 3,4,5-trichloro-phenyl- thietanyl-methyl- 3,4,5-trichloro-pheny1— l-oxo-thietan-3 -y1-methy1- 3,4,5-trichloro—phenyl— 1,1-dioxo-thietanyl-methyl- -X.23 3,5 -dichlorofluoro-phenyl- -trifluoro-ethylcarbamoy1) -methy1 chlorofluoro-pheny1- (pyn'd-Z-yl)-methyl- 3,5-dichlorofluoro-pheny1- 3,5-dichloro-4—fluoro-pheny1- thietany1- 3,5 -dichlorofluoro—pheny1- 1, l -dioxo-thietan-3 -y1- 3,5-dichlorofluoro-pheny1- thietan-Z-yl-methyl- 3,5 -dichlorofluoro-phenyl- 1-oxo-thietanyl-methyl- 3,5 -dichlorofluoro-phenyl- 1, 1 ~dioxo-thietan—2-yl-mefl1y1- 3,5-dichloro-4—fluoro—phenyl- thietanyl'-methyl- 3,5-dichlorofluoro-pheny1- 1-oxo-thietanyl—methyl- 3 ,5 -dichloro-4—fluoro-phenyl - 1, 1 -dioxo-thietan-3 -y1-methy1- -X34 3-chloro—4-fluoro-phenyl- (2,2,2-tn'fluoro-ethylcarbamoyl) -methy1 3-chlorofluoro-phenyl- (pyridyl)—methyl- 3-chloro—4-fluoro-pheny1— rofluoro-phenyl- 1-oxo—thietanyl- 3-chlorofluoro-phenyl- 1, 1 -dioxo-thietan—3 -yl- 3—chlorofluoro-phenyl- thietan-Z-yl-methyl- 3-chlorofluoro-phenyl- l-oxo-thie’ran-Z-yl—methyl- 3-chlorofluoro-phenyl- 1,1 -dioxo-thietan-2 -y1-methy1- 3-chloro—4—fluoro-pheny1- thietanyl-methyl- 3-chlorofluoro-pheny1- 1-oxo-thietanyl-methyl- X45 3-fluorochloro-phenyl- (2,2,2-tIifluoro-ethylcarbamoyl) —methy1 3-fluorochloro-pheny1— (pyrid-Z-yl)-methyl- ochloro-phenyl- ochloro-phenyl- l-oxo-thietanyl- 3—fluorochloro-phenyl- 1, 1 dioxo-thietan-3 -yl - 3—fluorochloro-phenyl- thietan-Z-yl-methyl- 3-fluorochloro-phenyl- l-oxo-thietan-Z—yl-methyl- 3—fluorochloro-pheny1— 1, 1 -dioxo-thietan—2-y1-methyl- wo 2012/104331 10 2012/051638 3-fluorochloro-pheny1— thietanyl—methyl- 3-fluorochloro—pheny1- thietany1-methyl- 3-fluoro-4—chloro-phenyl- 1 l —dioxo-thietan-3 -yl-methy1- X56 3,4-dichloro-phenyl- (2,2,2-trifluoro-ethylcarbamoy1) -methy1 3,4—dichloro-phenyl- (pyrid-Z-yl)-methyl- chloro-phenyl- 1-oxo-thietanyl- 3,4-dichloro-phenyl- ‘ 1,1-dioxo-thietanyl- 3,4—dichloro-phenyl- thietan-Z-yl-methyl- 3,4-dichloro-phenyl- l-oxo—thietan-Z-yl-methyl- 3 ,4 —dichloro-phenyl- 1 1 -dioxo-thietany1-methy1— chloro-phenyl- thietan-3—yl-methy1- 3,4-dichloro-phenyl- thietany1-methyl- 1,1—dioxo-thietanyl-methy1— -X67 3,5-dichlorobromo-phenyl- (2,2,2-tn'fluoro-ethylca.rbamoy1) -methyl 3,5-dichlorobromo-phenyl- (pyrid-Z-yl)-methyl- 3,5 -dichlorobromo-phenyl- 3 ,5 -dichlorobromo-pheny1oxo-thietan-3 -y1- 3 ,5 -dichlorobromo-phenyl - 1, 1 -dioxo-thietan-3 -y1- 3,5 -dichlorobromo-phenyl- thietan-Z-yl-methyl- 3,5-dichlorobromo-phenyl- 1-0xo-thietan-2—yl-mefl1y1- 3,5 -dichlorobromo-phenyl- 1,1-dioxo-thietanyl—methyl- 3,5 —dichloro-4~bromo-phenyl- thietan—3—yl-methyl- 3,5-dichlorobromo-pheny1- l-oxo-thietanyI-methyl- 3,5 —dichlorobromo-phenyl- 1,1 -dioxo-thietan-3 -y1—methy1- .X78 3,5 —dichlorofluoro-phenyl- (2,2,2-trifluoroethylcarbamoyl) 3,5—dichloro-4—fluoro-pheny1- (pyrid-Z-yl)-methyl- 3,5-dichlorofluoro-phenyl- 3,5 -dichlorofluoro-phenyl- 1-oxo—thietanyl- 3 ,5 -dichlorofluoro-phenyl - 1, 1 -dioxo-thietan-3 -y1- 3,5-dichlorofluoro-phenyl- thietan-Z—yl-methyl- 3,5-dichlorofluoro-pheny1- l-oxo—thietan-Z-yl-methyl- 3 ,5 -dichlorofluoro-pheny1- 1, 1 dioxo-thietan-Z-y1—methyl— 3,5-dichlorofluoro-pheny1- thietanyl-methyl- 3,5-dichlorofluoro-pheny1- l-oxo-thietanyl-methyl- 3,5—dichlorofluoro-phenyl- 1,1-dioxo-thietany1-mefl1y1- X.89 3,4,5-trifluoro-phenyl- (2,2,2-trifluoro-ethylcarbamoyl) - -methy1 3,4,5-trifluoro-phenyl- (PYIid-Z-yl)-methyl- 3,4,5-trifluoro-phenyl- 3,4,5-trifluoro-phenyl- l-oxo-thietanyl- 3,4,5-trifluoro-pheny1- 1, 1 -dioxo-thietan-3 -y1- 3,4,5-trifluoro-phenyl- thietan-Z-yl-methyl- 3,4,5-trifluoro-pheny1- l-oxo-thietan-Z-yl-methyl- 3,4,5-trifluoro-phenyl- 1,1 -dioxo—thietanyl-methyl- 3,4,5-trifluoro-phenyl— thietanyl-methyl— 3,4,5—trifluoro-phenyl- l-oxo-thietanyl-methyl- 3,4,5-trifluoro-phenyl- 1, 1 dioxo-thietan-3 —y1-methy1- -X.100 robromo-pheny1- (2,2,2-trifluoro-ethylcarbamoyl) -methy1 3-chlorobromo-phenyl- (pyfid-Z-yl)-methyl- 3-chlorobromo-pheny1- 3-chlorobromo-phenyl- l-oxo-thietany1chloro-S-bromo-pheny1- 1,1 dioxo—thietanyl- 3-chlorobromo-phenyl- thietan-Z-yl-methyl- 3-chloro-5 —bromo-phenyl- l-oxo-thietan-Z-yl-mefllyl- robromo-pheny1- 1,1dioxo-thietan-Z-yl—methyl— 3-chloro-5—bromo~pheny1- thietanyl-methyl- 3-chlorobromo-phenyl- l-oxo-thietan-3 -y1-methyl- 3-chlorobromo-phenyl- 1, 1 -dioxo—thietanyl-methyl- -X. 1 1 1 3-chloro-5 -fluoro-pheny1- (2,2,2-tfifluoro-ethylcarbamoyl) -methy1 3-chloro—5-fluoro-phenyl- -Z-yl)-methyl- 3-chlorofluoro-phenyl- n-3—y1- 3—chloro—5-fluoro-phenyl- l-oxo-thietan-3—yl- 3-chlorofluoro-phenyl- 1, l -dioxo-thietan-3 -yl - rofluoro-phenyl- thietan-Z-yl-methyl- 3-chlorofluoro-phenyl- thietan-Z-yl-methyl- I,l-dioxo-thietan-Z-yl-methyl- W0 2012/104331 12 X. l 19 3-chlorofluoro-pheny1— thietany1-methy1- X. 120 3 -chlorofluoro-phenyl- 1-oxo-thietan-3 thy1- 3-chlorofluoro-pheny1- 1,1-dioxo-thietanyl-methyl- -X.122 3-chlorotrifluoromethyl-pheny1- -trifluoro—ethylcarbamoyl) X. 126 3-chlorotrifluoromethyl-phenyl- 1,1-dioxo-thietanyl- 3-chlorotrifluoromethyl-phenyl- thietan-Z-yl-methyl- 3-chlorotrifluoromethy1-phenyl- l-oxo-thictan-Z-yl-methyl- 3-chlorotrifluoromethyl-phenyl- 1, 1 -dioxo-thietanyl-methyl- 3-chloro—5-trifluoromethyl-phenyl- thietanyl-methyl- 3-chlorotrifluoromethyl-phenyl- thietany1-methyl- 3-chlorotrifluoromethyl-phenyl— 1, 1-dioxo-thietan-3 -y1-methy1- -X.133 3—chlorochlorotn'fluoromethyl-phenyl- (2,2,2-trifluoroethylcarbamoyl) -methy1 3-chlorochlorotrifluoromethyl—phenyl- (pyrid-Z-yl)-methy1- 3—chlorochlorotrifluoromethyl-pheny1- 3-chloro-4—chlorotrifluoromethyl-phenyl- l-oxo-thietan-3 -yl- 3-chlorochloro—5-trifluoromethy1-pheny1— 1, 1 —dioxo-thietan—3 -y1- 3-chlorochlorotn'fluoromethyl-phenyl- thietan-Z-yl-methyl— 3-chloro-4—chlorot1ifluoromethyl-phenyl- l-oxo-thietan-Z-yl—methyl- 3-chlorochlorotrifluoromethyl-pheny1 — l 1 dioxo-thietan-Z-yl-methyl- 3-chloro-4—chlorotn'fluoromethyl-phenyl- thietan-3—yl—methyl- 3-chlorochloro-5~trifluoromethyl-phenyl- l-oxo-thietanyl-mefl1yl- 3-chlorochlorotrifluoromethyl-phenyl — l 1 —dioxo-thietan-3 -y1-methy1- -X.144 3,5di—tfifluoromethyl—phenyl- (2,2,2-trifluoro-ethylcarbamoyl) -methy1 3,5di-tfifluoromethyl—phenyl- (pyrid-Z-yl)-methyl- 3,5di-tfifluoromethyl-phenyl— 3,5di-tfifluoromefllyl-phenyl- 1—oxo-thietany1- 3 ,5 -di—trifluoromefl1yl—phenyl— 1 ,1 —dioxo-thietan-3 -yl- 3,5di-tfifluoromethyl-phenyl- n-Z-yl-methyl- 3,5di-tfifluoromethyl-phenyl- l-oxo-thietan-Z-yl-methyl- X. 15 1 3,5 uoromethyl-phenyl- 1,1 dioxo-thiefan—Z-yl-methyl— wo 2012/104331 13 -Cycle C I2 3,5-di-trifluoromethyl-phenyl- nyl-methyl— 3,5—di-trifluoromethyl-phenyl- 1-oxo-thietanyl-methyl- 3 ,5 -di-trifluoromethyl-phenyl- l, 1 -dioxo-thietan-3 -yl-methyl- .X.155 3,5-di-trifluoromethylchloro-phenyl- (2,2,2-trifluoro-ethylcarbamoyl) - -methyl 3,5-di—trifluoromethylchloro-phenyl- (pyfid-Z-yl)-methyl- 3,5-di—trifluoromethylchloro-phenyl- X. 158 3,5 —di—tr1fluoromethylchloro-phenyl- 1-oxo-thietan-3 -yl- X. 159 3,5 -di—trifluoromethylchloro—phenyl- 1,1-dioxo-thietan-3 -yl- X. 160 3,5 -di-trifluoromethylchloro-phenyl- thietan-Z-yl-methyl- X. 161 3,5 -di-trifluoromethylchloro-phenyl- 1-oxo-thietany1-methyl- X. 162 3,5 —di-trifluoromethyl-4~chloro—phenyl- 1,1 -dioxo—thietanyl-methyl- X. 163 3,5 -di-trifluoromethyl—4—chloro—phenyl- nyl-methyl- X. 164 3,5 -di-trifluoromethyl—4-chloro—phenyl- 1-oxo-thietan-3 -yl-methyl- X. 165 3,5-di-trifluoromethy1—4-chloro—phenyl- 1,1-dioxo-thietan-3 thyl— X. 166 3-trifluoromethyl-phenyl— (2,2,2-trifluoro-ethylcarbamoyl) -methyl X. 167 3-trifluoromethy1-phenyl- (pyrid~2-yl)-methyl- X. 168 3-trifluoromethyl-phenyl- thietanyl- X. 169 3-trifluoromethyl-phenyl— l -oxo—thietan-3 -yl- X. 170 3-trifluoromethy1-phenyl- 1, l -dioxo-thietan—3 -yl— X. l 7 1 3-trifluoromethyl-phenyl - thietan-Z-yl-methyl- X. 172 3-trifluoromethyl-phenyl- l-oxo—thietan-Z-yl-methyl- X. 173 3-trifluoromethyl-phenyl- 1,1-dioxo-thietanyl-methyl- 3-trifluoromethyl—pheny1- thietanyl-methyltrifluoromethyl-pheny1 oxo-thietan-3 -y1-methyl- X. 176 uoromethyl-phenyl- oxo-thietan-3 -yl-methyl- Compounds of formula I include at least one chiral centre and may exist as compounds of formula 1* or nds offormula I**.

(R‘s)p (|*) wo 2012/104331 14 2012/051638 Compounds of formula II where cycle B is selected from B1 to B6 include at least one chiral centre and may exist as compounds of formula II* (IIA*, IIB*, IIC*, IID*, IIB*, IIF*) or compounds of formula II** (IIA**, IIB**, IIC**, IID**, I[E**, IIF**). (l|D*) (||D**) wo 2012/104331 15 (||F*) (||F**) Compounds of formula III Where cycle B is ed from B1 to B6 include at least one chiral centre and may exist as compounds of formula 111* (IIIA*, IIIE*, IIIC*, IIID*, IIIE*, IIIF*) compounds offormula 111* * (111A* * , IIIE* * , IIIC* * , IIID* *, IIIE* * , IIIF* *). These generic structures correspond to the ures of formula II above.

Generally the compounds of formula I** are more biologically active than the respective compounds of formula 1*. The invention includes mixtures ofcompounds 1* and 1** in any ratio eg. in a molar ratio of 1:99 to 99:1, e.g. 10:1 to 1:10, e.g. a substantially 50:50 molar ratio. In enantiomerically (or epimerically) enriched mixture of formula I**, the molar proportion ofcompound I** compared to the total amount of both enantiomers is for example greater than 50%, 6g. at least 55, 60, 65, 70, 75, 80, 85, 90, 95, 96, 97, 98, or at least 99%. Likewise, in enantiomerically (or epimerically) enriched mixture of formula 11*, the molar proportion ofthe compound of formula 11* compared to the total amount of both enantiomers (or epimerically) is for e greater than 50%, e.g. at least 55, 60, 65, 70, 75, 80, 85, 90, 95, 96, 97, 98, or at least 99%. Enantiomerically (or ically) enriched mixtures of formula I** are preferred.

Generally the compounds of a II** are more biologically active than the respective compounds of a 11*. The invention includes mixtures of compounds 11* and II** in any ratio e.g. in amolar ratio of 1:99 to 99:1, e.g. 10:1 to 1:10, e.g. a substantially 50:50 molar ratio. In an enantiomerically (or ically) enriched mixture of formula II**, the molar proportion of compound II** compared to the total amount ofboth enantiomers is for example r than 50%, e.g. at least 55, 60, 65, 70, 75, 80, 85, 90, 95, 96, 97, 98, or at least 99%. Likewise, in enantiomerically (or epimerically) enriched mixture of formula 11*, the molar proportion ofthe compound of formula 11* compared to the total amount of both enantiomers (or epimerically) is for example greater than 50%, e.g. at least 55, 60, 65, 70, 75, 80, 85, 90, 95, 96, 97, 98, or at least 99%. Enantiomerically (or epimerically) enriched mixtures of formula II** are preferred. lly the compounds of formula III** are more biologically active than the respective compounds of formula III*. The invention includes mixtures of compounds 111* and III** in any ratio e.g. in amolar ratio of 1:99 to 99:1, e.g. 10:1 to 1:10, e.g. a substantially 50:50 molar ratio. In an enantiomerically (or ically) enriched mixture of formula III**, the molar proportion of compound III** compared to the total amount of both enantiomers is for example greater than 50%, 6g. at least 55, 60, 65, 70, 75, 80, 85, 90, 95, 96, 97, 98, or at least 99%. Likewise, in enantiomerically (or ically) enriched mixture of formula 111*, the molar proportion ofthe compound of formula 111* compared to the total amount ofboth enantiomers (or epimerically) is for example greater than 50%, e.g. at least 55, 60, 65, 70, 75, 80, 85, 90, 95, 96, 97, 98, or at least 99%. Enantiomerically (or epimerically) enriched mixtures of formula III** are preferred.

A preferred compound of the invention is a compound of formula Ix* * (IX**) The compounds of the invention can be made according to the methods described in the patent applications listed above. Additional s can be found in .

In a further aspect the invention also provides a method sing ng to a crop of soybean plants, the locus thereof, or propagation material thereof, a nd of formula IV G1 is oxygen; G2 is O or CH2; W0 2012/104331 17 L is a bond, ene or ethylene; one ofA1 and A2 is S, SO or 802 and the other is -C(R4)R4-; R3 is hydrogen; each R4 is ndently hydrogen or methyl; Y1 is C-Rs, CH or nitrogen; Y2 and Y3 are independently CH or nitrogen; wherein no more than two ofY1, Y2 and Y3 are nitrogen and wherein Y2 and Y3 are not both nitrogen; R5 is hydrogen, halogen, cyano, nitro, NH2, C1-C2alky1, C1-C2haloalky1, ycloalkyl, C3- Cshalocycloalkyl, C1—C2alkoxy, C1-C2haloalkoxy; R6 together with R5 forms a -CH=CH-CH=CH— bridge; X2 is C-X6 or nitrogen; X, X3 and X5 are independently hydrogen, halogen or trihalomethyl, wherein at least two ofX1, X3 and X6 are not en; X4 is trifluoromethyl, omethyl or chlorodifluoromethyl.

In a further aspect the invention provides a method of controlling and/or ting infestation of stinkbugs in soybean comprising applying to a crop of soybean plants, the locus thereof, propagation material thereof, a nd of formula IV. Preferably the stinkbug is Euschistus, more preferably Euschz'stus heros. The stinkbugs may be stinkbugs that are resistant to one or more other insecticides, preferably pyrethroid, neonicotinoids and organophosphates, more preferably pyrethroid insecticides.

In a further aspect the invention provides use of a compound of formula IV for control of stinkbugs e.g. in soybean crops. Preferably the stinkbug is Euschisrus, more preferably Euschz'stus heros. The use may be for controlling ugs that are ant to one or more other insecticides, preferably pyrethroid, neonicotinoids and organophosphates, more preferably pyrethroid insecticides.

Preferred values of P, G1, G2, A1, A2, R3, R4, X1, X2, X3 and X4 in compounds of formula IV are, in any combination, as set out below.

Preferably P is selected from P3 to P11 # N # fir S Y v T \C T v,o o o 3s 0 o 0 n P3 P4 P5 P6 H 3 H H s30 - # # N # NVC/ H NHfl \n/ , Mp , N Y T \[r ,s/\\ o O o o 0 0 o 0 P7 P8 P9 P10 P11 In one group ofcompounds P is selected from P4, P5 and P6.

Preferably each R4 is hydrogen.

Preferably R5 is hydrogen, chloro, bromo, fluoro, trifluoromethyl, methyl, ethyl, methoxy, nitro, trifluoromethOxy, cyano, cyclopropyl, more preferably R5 is hydrogen, , bromo, fluoro, trifluoromethyl, methyl, ethyl, nitro, cyano, cyclopropyl, even more preferably R5 is chloro, bromo, fluoro, methyl, trifluoromethyl, most preferably methyl. ably G1 is oxygen.

Preferably G2 is oxygen.

Preferably L is a bond.

Preferably Al is -C(R4)R4—, more preferably -CH2-.

Preferably A2 is S, SO or S02.

Preferably Y1 is CH, Y2 is CH, Y3 is CH, or Y1 is N, Y2 is CH, Y3 is CH, or Y1 is N, Y2 is N, Y3 is CH, orYl is CH, Y2 is N, Y3 is CH, orYl is CH, Y2 is CH, Y3 is N. Preferably Y1 is CH, Y2 is CH, and Y3 is CH.

Preferably X, X3 and X6 are independently hydrogen, n or trifluoromethyl, wherein at least two of X1, X3 and X6 are not hydrogen. More preferably XI, X3 and X6 are ndently hydrogen, chloro, bromo or trifluoromethyl, wherein at least two of X1, X3 and X6 are not hydrogen.

Preferably at least two of X1, X3 and X6 are chloro, bromo or romethyl.

Preferably X2 is C-X"; Preferably X1 is chloro, X2 is CH, X3 is chloro, or X1 is chloro, X2 is C-F, X3 is en, or X1 is fluoro, X2 is C-Cl, X3 is hydrogen, or X1 is , X2 is C-Cl, X3 is hydrogen, or X1 is chloro, X2 is C-Br, X3 is chloro, or X1 is chloro, X2 is C-F, X3 is chloro, or X1 is chloro, X2 is C-Cl, X3 is chloro, or X1 is chloro, X2 is C-I, X3 is chloro, or X1 is fluoro, X2 is C—F, X3 is fluoro, oer is chloro, X2 is CH, X3 is bromo, or X1 is chloro, X2 is CH, X3 is fluoro, oer is chloro, X2 is CH, X3 is trifluoromethyl, or X1 is chloro, X2 is C-Cl, X3 is trifluoromethyl, or X1 is trifluoromethyl, X2 is CH, X3 is trifluoromethyl, or X1 is trifluoromethyl, X2 is C-Cl, X3 is trifluoromethyl, or X1 is romethyl, X2 is CH, X3 is hydrogen, or X1 is chloro, X2 is N, X3 is chloro, or X1 is trifluoromethyl, X2 is N, X3 is romethyl. Most preferably X1 is chloro, X2 is CH, X3 is chloro.

Preferably X4 is romethyl, or chlorodifluoromethyl, more preferably trifluoromethyl.

In one group ofcompounds of formula IV G2 is oxygen.

In one group of compounds of formula IV G2 is CH2.

In one group of compounds of formula IV Y1 is C-R6 and R6 together with R5 forms CH=CH—CH=CH— .

In one group of compounds of formula IV X2 is C—Xé, Y1, Y2 and Y3 are OH, and R5 is chloro, bromo, methyl or trifluoromethyl.

In one group of compounds of formula IV X2 is C—XG, Y1, Y2 and Y3 are C-H, G1 is oxygen, G2 is oxygen, A1 is CH2, A2 is S, S0 or S02, L is a bond, R3 and each R4 is hydrogen, R5 is chloro, bromo, methyl or trifluoromethyl. wo 2012/104331 . 19 In another group of compounds of formula IV X2 is C-XS, Y1, Y2 and Y3 are C-H, G1 is oxygen, G2 is oxygen, A1 is CH2, A2 is S, SO or 802, L is a bond, R3 and each R4 is en, R5 is chloro, bromo, methyl or trifluoro methyl, Y1 is CH, Y2 is CH, and Y3 is CH, X4 is trifluoromethyl.

In r group of compounds offormula IV X2 is C-Xs, Y1, Y2 and Y3 are C-H, G1 is oxygen, G2 is oxygen, A1 is CH2, A2 is S, S0 or 802, L is a bond, R3 and each R4 is hydrogen, R5 is chloro, bromo, methyl or trifluoro methyl, Y1 is CH, Y2 is CH, and Y3 is CH, X4 is trifluoromethyl, X1 is chloro, X2 is CH, X3 is chloro.

In one group ofcompounds one offormula IV A1 and A2 is S, SO or 802 and the other is CH2, L is a direct bond ormethylene, Y2 and Y3 are C-H or one ofY2 and Y3 is C-H and the other is N; R3 is hydrogen or methyl; x1 is Br, x2 is CH and x3 is Br, or x1 is (:1, x2 is C-H and x3 is C1, or x1 is c1 X2 is C-Cl and X3 is C-H, or X1 is C1, X2 is C—Cl and X3 is C1; X4 is chlorodifluoromethyl trifluoromethyl; R5 is methyl, Y1 is C-Ré, R6 is hydrogen, or R5 and R6 together form a bridging 1,3- butadiene group; each R4 is hydrogen; G1 is ; G2 is oxygen.

Compounds of formula IV include at least one chiral centre and may exist as compounds of formula IV* or compounds offormula IV**.

(IV*) (IV**) nds of a IV** are more biologically active than compounds of formula IV*.

The compound offormula IV may be a mixture of compounds IV* and IV** in any ratio e.g. in a molar ratio of 1:99 to 99:1, e.g. 10:1 to 1:10, e.g. a substantially 50:50 molar ratio. Preferably the compound of formula I is a racemic mixture ofthe compounds of formula IV** and IV* or is enantiomerically enriched for the compound of formula IV**.For example, when the compound of formula IV is an enantiomerically enriched mixture of formula IV**, the molar proportion of compound IV** compared to the total amount of both enantiomers is for example greater than 50%, e.g. at least 55, 60, 65, 70, 75, 80, 85, 90, 95, 96, 97, 98, or at least 99%. ably the nd of formula I is at least 90% enriched for the compound of a I.

Where Al or A2 is SO, the nd of formula IV may be a mixture of the cis and trans isomer in any ratio, e.g. in a molar ratio of 1:99 to 99:1, e.g. 10:1 to 1:10, e.g. a substantially 50:50 wo 04331 20 molar ratio. For example, in trans ed es ofthe compound of formula IV, e.g. when A1 or A2 is SO, the molar proportion ofthe trans compound in the e compared to the total amount of both cis and trans is for example greater than 50%, e.g. at least 55, 60, 65, 70, 75, 80, 85, 90, 95, 96, 97, 98, or at least 99%. Likewise, in cis enriched mixtures ofthe compound of a IV (preferred), e.g. when A1 or A2 is SO, the molar proportion of the cis compound in the mixture compared to the total amount ofboth cis and trans is for example greater than 50%, e.g. at least 55, 60, 65, 70, 75, 80, 85, 90, 95, 96, 97, 98, or at least 99%. The compound of formula IV may be enriched for the trans sulphoxide. Likewise, the compound of formula IV may be enriched for the cis sulphoxide.

A ion of preferred compounds of formula IV are compounds Al to A16 shown in Table A below.

Table A: Com ounds offormula IV a F30 IN Cl 0 OMeH N\L/<;1.A2 (lVa) Cl 0 The symbol * indicates the location ofthe chiral centre Comp Stereochemistry L A2 l N0. at * -—IM_ O -—IM_i(DU)A wv 0 fiflflflfifllflflIIIl fiMflflflfllflmllIlii0mm EIIEMMMMEIEEIIIIican EIIEMMflflEIflEIIII IEIIEMMEfiflIEEIIIIEi _—bond III S ' noommmmooEEEQOOE"*3in& 00 CDC/lg: ,8N ioh—I. (I) V O (/3 (trans) O m.9 IV** refers to a compound of formula IV**.

Reference to compounds ofthe invention also includes reference to salts and es.

The methods and uses ofthe invention are preferably for controlling and/or preventing infestation ofthe soybean crop by stink bugs, including stink bugs that are resistant to other insecticides, cg. pyrethroid insecticides. Stinkbugs that are "resistant" to a particular icide refers e.g. to strains of stinkbugs that are less sensitive to that insecticide compared to the expected wo 2012/104331 21 sensitivity ofthe same species of stinkbug. The expected sensitivity can be measured using e.g. a strain that has not previously been d to the insecticide.

Application is ofthe compounds ofthe ion is to a crop of soybean , the locus thereof or propagation material thereof. ably application is to a crop of n plants or the locus thereof, more preferably to a crop of soybean plants. Application may be before infestation or when the pest is present. Application ofthe compounds ofthe invention can be performed according to any ofthe usual modes ofapplication, e.g. , drench, soil, in leI‘I‘OW etc. However, control of stinkbugs is usually achieved by foliar application, which is the preferred mode of application according to the invention.

The compounds ofthe invention may be applied in combination with an attractant. An attractant is a chemical that causes the insect to migrate towards the location of application. For control of stinkbugs it can be advantageous to apply the compounds ofthe invention with an attractant, particularly when the application is . Stinkbugs are often located near to the ground, and application of an attractant may encourage migration up the plant towards the active ingredient.

Suitable attractants include glucose, sacchrose, salt, glutamate (e.g. Aji-no-motoTM), citric acid (e.g.

Orobor TM), soybean oil, peanut oil and soybean milk. Glutamate and citric acid are of particular interest, with citric acid being preferred.

An attractant may be ed with the compound ofthe invention prior to application, e.g. as a readymix or tankmix, or by simultaneous application or sequential application to the plant. Suitable rates of attractants are for example 0.02kg/ha—3kg/ha.

The compounds ofthe invention are preferably used for pest l on n at 1:500 g/ha, preferably 10-70g/ha.

The compounds of the invention are suitable for use on any soybean plant, including those that have been genetically modified to be resistant to active ingredients such as herbicides, or to produce biologically active compounds that control infestation by plant pests.

The compounds of the invention are preferably used for pest control on soybean at 1:500 g/ha, preferably 10-70g/ha.

The compounds ofthe invention are suitable for use on any soybean plant, including those that have been genetically modified to be resistant to active ingredients such as herbicides, or to e biologically active compounds that control ation by plant pests.

In a further red ment, transgenic plants and plant cultivars obtained by genetic engineering methods, if appropriate in combination with conventional methods (Genetically Modified Organisms), and parts thereof, are treated. Particularly preferably, plants ofthe plant cultivars which are in each case commercially available or in use are d according to the invention. Plant cultivars are tood as meaning plants having novel properties ("traits") which have been obtained by conventional breeding, by mutagenesis or by recombinant DNA techniques.

These can be ars, bio- or pes. Depending on the plant species or plant ars, their location and growth conditions (soils, climate, vegetation period, diet), the treatment ing to the invention may also result in superadditive "synergistic") effects.

Thus, for e, reduced application rates and/or a widening ofthe activity spectrum and/or an increase in the ty ofthe substances and compositions which can be used according to the ion, better plant growth, increased tolerance to high or low temperatures, increased tolerance to drought or to water or soil salt content, inereased flowering performance, easier harvesting, accelerated maturation, higher harvest yields, higher quality and/or a higher nutritional value ofthe harvested products, better storage stability and/or processability ofthe harvested products are possible, which exceed the effects which were actually to be expected.

The preferred transgenic plants or plant cultivars (obtained by genetic engineering) which are to be treated according to the ion include all plants which, by virtue of the genetic modification, received genetic material which imparts particularly advantageous, useful traits to these .

Examples of such traits are better plant growth, increased tolerance to high or low temperatures, increased tolerance to t or to water or soil salt content, increased flowering performance, easier harvesting, accelerated maturation, higher harvest yields, higher quality and/or a higher nutritional value ofthe ted products, better storage ity and/or processability ofthe harvested products.

Further and particularly emphasized examples of such traits are a better defence ofthe plants against animal and microbial pests, such as against insects, mites, phytopathogenic fungi, bacteria and/or viruses, and also increased tolerance ofthe plants to certain herbicidally active compounds.

Traits that are emphasized in particular are the increased e ofthe plants against insects, arachnids, nematodes and slugs and snails by virtue oftoxins formed in the plants, in particular those formed in the plants by the genetic material from Bacillus thuringiensis (for example by the genes Cry1A(a), Cry1A(b), CrylA(c), CryllA, CrylllA, CryIIIB2, Cry9c, , Cry3Bb and CrylF and also combinations thereof) (referred to herein as "Bt plants"). Traits that are also particularly emphasized are the sed defence ofthe plants against fungi, bacteria and viruses by systemic acquired resistance (SAR), systemin, phytoalexins, ors and resistance genes and correspondingly expressed proteins and toxins.

Traits that are furthermore particularly emphasized are the sed tolerance of the plants to certain herbicidally active compounds, for example imidazolinones, sulphonylureas, glyphosate phosphinotricin (for example the "PAT" gene). The genes which impart the desired traits in question can also be present in combination with one another in the transgenic plants.

Examples of "Bt plants" are soya bean varieties which are sold under the trade names YIELD GARD(®) es of herbicide-tolerant plants which may be mentioned are soya bean varieties which are sold under the trade names Roundup Ready(®) (tolerance to glyphosate), Liberty Link(®) (tolerance to phosphinotricin), IMI(®) (tolerance to olinones) and STS(®) (tolerance to sulphonylureas). wo 2012/104331 23 ide-resistant plants (plants bred in a tional manner for herbicide tolerance) which may be mentioned include the varieties sold under the name Clearfield(®) (for example maize). icular interest are soybean plants carrying trains conferring resistance to 2.4D (e.

Enlist®), glyphosate (e.g. Roundup Ready®, Roundup Ready 2 Yield®), sulfonylurea (e.g. STS®), glufosinate (e.g. Liberty Link®, Ignite®), Dicamba (Monsanto) HPPD nce (e .g. isoxaflutole herbicide) (Bayer CropScience, Syngenta). Double or triple stack in soybean plants of any ofthe traits described here are also of interest, including glyphosate and sulfonyl-urea tolerance (e.g. Optimum GAT®, plants stacked with STS® and Roundup Ready® or Roundup Ready 2 Yield®), dicamba and glyphosate tolerance (Monsanto). Soybean Cyst Nematode resistance soybean (SCN® - Syngenta) and soybean with Aphid resistant trait (AMT® - Syngneta) are also of interest.

These statements also apply to plant cultivars having these genetic traits or genetic traits still to be ped, which plant cultivars will be developed and/or marketed in the .

The compounds ofthe invention may be used on soybean to control, for example, Elasmopalpus Zignosellus, Diloboderus abderus, Diabron'ca speciosa, Sternechus subsignatus, Formicidae, Agrotis ypsz'lon, Julus ssp. , Anticarsz'a gemmatalz’s, Megascelz's ssp.

, Procorm'z‘ermes ssp. , Gwllotalpz‘dae, Nezara viridula, Piezodorus spp., Acrosternum spp.

, Neomegalotomus spp., Cerotoma rcata, Popile‘ajaponz'ca, Edessa spp., ysflscus, Euchistus heros, stalk borer, Scaptocorz's castanea, phyllophaga spp., Pseudoplusia includens, Spodoptera spp., Bemz'sia tabacz', Agrioz‘es spp., preferably derus abderus, Diabrolica speciosa, Nezara viridula, Piezodorus spp.

, Acrostemum spp., Ceroz‘oma trifirrcata, Papilliajaponica, Euchz'stus heros, phyllophaga spp. , es spp..

The compounds ofthe invention are preferably used on n to control stinkbugs, e.g.

Nezara Spp. (e.g. Nezara la, Nezara antennata, Nezara hilare), Piezodorus spp. (e .g. Piezodorus guildz'nz'z'), Acrostemum spp. Euchz'stus spp. (e.g. Euchz'stus heros, Euschz'stus servus), Halyomorpha halys, Plautz'a crossol‘a, Riptortus clavatus, Rhopalus msculatus, Antestz'opsz's orbitalus, Dichelops spp. (e.g. Dichelopsfirrcatus, Dichelops melacanthus), Eurygaster spp. (e.g. Eurygaster intergrz'ceps, Eurygaster maura), Oebalus spp. (e.g. Oebalus ana, s poecilus, Oebalus pugnase, Scotinophara spp. (e.g. Scofinophara , Scotinophara ata). Preferred targets include Antesrz'opsis orbitalus, Dichelopsflrcatus, Dichelops melacanthus, Euchz‘stus heros, Euschz‘stus servus, Nezara la, Nezara hilare, Piezodorus guildz'nz'z’, Halyomorpha halys. In one embodiment the stinkbug target is Nezara viridula, orus spp. Acrosternum spp, , Euchz'stus heros. The nds ofthe invention are particularly effective against Euschz‘stus and in particular Euchz'sz‘us heros. Euschz'stus and in particular stus heros are the preferred s.

In order to apply a compounds ofthe invention as an insecticide, acaricide, nematicide molluscicide to a pest, a locus of pest, or to a plant susceptible to attack by a pest, compounds ofthe invention is usually ated into a composition which es, in addition to the compound ofthe invention, a suitable inert diluent or carrier and, optionally, a surface active agent (SFA). SFAs are als which are able to modify the properties of an interface (for example, liquid/solid, liquid/air or liquid/liquid interfaces) by lowering the interfacial tension and thereby leading to changes in other properties (for e dispersion, fication and wetting). It is preferred that all itions (both solid and liquid formulations) comprise, by weight, 0.0001 to 95%, more preferably 1 to 85%, for example 5 to 60%, of a compound ofthe invention. The composition is lly used for the control of pests such that a compound ofthe invention is applied at a rate of from 0. lg tolOkg hectare, preferably from lg to 6kg per hectare, more preferably from lg to 1kg per hectare.

When used in a seed dressing, a compound ofthe ion is used at a rate of 0.0001g to 10g (for example 0.001g or 0.05g), preferably 0.005g to 10g, more preferably 0.005g to 4g, per kilogram of seed.

Compositions comprising a compound ofthe ion can be chosen from a number of formulation types, including dustable powders (DP), soluble powders (SP), water soluble granules (SG), water dispersible granules (WG), wettable powders (WP), granules (GR) (slow or fast release), soluble concentrates (SL), oil miscible liquids (0L), ultra low volume liquids (UL), emulsifiable concentrates (EC), dispersible concentrates (DC), emulsions (both oil in water (EW) and water in oil (EO)), micro-emulsions (ME), suspension concentrates (SC), aerosols, fogging/smoke formulations, capsule suspensions (CS) and seed ent formulations. The formulation hosen in any instance will depend upon the particular e envisaged and the physical, chemical and biological properties ofthe compound ofthe ion.

Dustable powders (DP) may be prepared by mixing a compound ofthe invention with one or more solid diluents (for example natural clays, kaolin, pyrophyllite, bentonite, alumina, montmorillonite, kieselguhr, chalk, diatomaceous earths, calcium phosphates, calcium and magnesium carbonates, sulfur, lime, flours, talc and other c and inorganic solid carriers) and mechanically grinding the mixture to a fine powder.

Soluble powders (SP) may be prepared by mixing a compound ofthe invention with one or more water-soluble nic salts (such as sodium bicarbonate, sodium carbonate or magnesium sulfate) or one or more water-soluble organic solids (such as a polysaccharide) and, optionally, one or more wetting agents, one or more dispersing agents or a mixture of said agents to improve water dispersibility/solubility. The mixture is then ground to a fine powder. Similar compositions may also be granulated to form water soluble granules (SG).

Wettable s (WP) may be prepared by mixing a compound ofthe invention with one or more solid diluents or carriers, one or more wetting agents and, preferably, one or more dispersing agents and, optionally, one or more suspending agents to facilitate the dispersion in liquids. The mixture is then ground to a fine powder. Similar compositions may also be granulated to form water dispersible granules (WG).

Granules (GR) may be formed either by granulating a mixture of a compound ofthe ion and one or more powdered solid diluents or carriers, or from pre-formed blank granules by ing compound ofthe invention (or a solution thereof, in a suitable agent) in a porous granular material (such as , attapulgite clays, fiiller’s earth, kieselguhr, diatomaceous earths or ground corn cobs) or by adsorbing a compound ofthe invention (or a on thereof, in a suitable agent) on to a hard wo 2012/104331 25 core material (such as sands, silicates, mineral carbonates, es or phosphates) and drying if necessary. Agents which are commonly used to aid absorption or adsorption include solvents_(such as aliphatic and ic petroleum solvents, alcohols, , ketones and esters) and sticking agents (such as polyvinyl acetates, polyvinyl alcohols, dextrins, sugars and vegetable oils). One or more other additives may also be included in granules (for example an emulsifying agent, wetting agent or dispersing agent).

Dispersible Concentrates (DC) may be prepared by dissolving a compound ofthe invention in water or an organic solvent, such as a , alcohol or glycol ether. These ons may contain a surface active agent (for example to improve water dilution or prevent crystallization in a spray tank).

Emulsifiable concentrates (EC) or oil-in-water emulsions (EW) may be prepared by dissolving a compound ofthe invention in an c t (optionally containing one or more wetting agents, one or more emulsifying agents or a mixture of said agents). Suitable organic solvents for use in ECs include aromatic hydrocarbons (such as alkylbenzenes or aphthalenes, exemplified by SOLVESSO 100, SOLVESSO 150 and SOLVESSO 200; SOLVESSO is a Registered Trade Mark), ketones (such as cyclohexanone or cyclohexanone) and alcohols (such as benzyl alcohol, furfuryl alcohol or butanol), N—alkylpyrrolidones (such as N—methylpyrrolidone or N- octylpyrrolidone), dimethyl amides of fatty acids (such as C3-Cm fatty acid dimethylamide) and chlorinated hydrocarbons. An EC product may spontaneously emulsify on addition to water, to produce an emulsion with ent stability to allow spray application through appropriate equipment. Preparation of an EW involves obtaining a compound of the invention either as a liquid (if it is not a liquid at room temperature, it may be melted at a reasonable temperature, typically below 70°C) or in solution (by dissolving it in an appropriate solvent) and then emulsifiying the resultant liquid or solution into water containing one or more SFAs, under high shear, to produce an emulsion.

Suitable solvents for use in EWs include vegetable oils, chlorinated hydrocarbons (such as benzenes), ic solvents (such as enzenes or alkylnaphthalenes) and other appropriate organic solvents which have a low solubility in water.

Microemulsions (ME) may be ed by mixing water with a blend ofone or more solvents with one or more SFAs, to produce spontaneously a thermodynamically stable isotropic liquid formulation. A compound of the invention is present initially in either the water or the solvent/SPA blend. le solvents for use in MEs e fliose hereinbefore described for use in ECs or in EWs.

An ME may be either an oil-in-water or a water-in-oil system (which system is present may be determined by conductivity measurements) and may be suitable for mixing water-soluble and oil- soluble pesticides in the same formulation. An MB is suitable for dilution into water, either ing as a microemulsion or forming a conventional oil—in-water emulsion.

Suspension trates (SC) may comprise aqueous or non-aqueous suspensions of finely divided insoluble solid particles of a compound ofthe invention. SCs may be ed by ball or bead milling the solid compound ofthe invention in a suitable medium, optionally with one or more sing agents, to produce a fine particle suspension ofthe compound. One or more wetting agents WO 04331 26 may be included in the composition and a ding agent may be included to reduce the rate at which the particles settle. Alternatively, a compound ofthe invention may be dry milled and added to water, containing agents hereinbefore described, to e the desired end product.

Aerosol formulations comprise a compound ofthe invention and a suitable propellant (for example ne). A compound ofthe invention may also be dissolved or dispersed in a suitable medium (for example water or a water miscible liquid, such as n-propanol) to provide compositions for use in non-pressurized, hand-actuated spray pumps.

A compound ofthe invention may be mixed in the dry state with a pyrotechnic mixture to form a composition suitable for generating, in an enclosed space, a smoke containing the compound.

Capsule suspensions (CS) may be prepared in a manner similar to the preparation ofEW formulations but with an additional polymerization stage such that an aqueous dispersion of oil droplets is obtained, in which each oil droplet is encapsulated by a polymeric shell and contains a compound ofthe invention and, ally, a carrier or t therefor. The polymeric shell may be produced by either an interfacial polycondensation reaction or by a coacervation procedure. The compositions may provide for controlled e of the compound ofthe invention and they may be used for seed treatment. A compound ofthe invention may also be formulated in a biodegradable polymeric matrix to provide a slow, controlled release ofthe compound.

A composition may include one or more additives to improve the biological performance of the composition (for example by improving wetting, ion or distribution on surfaces; resistance to rain on treated surfaces; or uptake or ty ofa compound ofthe invention). Such additives include e active agents, spray additives based on oils, for e certain mineral oils or natural plant oils (such as soy bean and rape seed oil), and blends ofthese with other bio-enhancing adjuvants (ingredients which may aid or modify the action of a compound ofthe invention).

A compound ofthe invention may also be formulated for use as a seed treatment, for example as a powder composition, including a powder for dry seed treatment (DS), a water e powder (SS) or a water dispersible powder for slurry treatment (WS), or as a liquid composition, including a flowable concentrate (FS), a solution (LS) or a capsule suspension (CS). The ations of DS, SS, WS, FS and LS compositions are very similarto those of, respectively, DP, SP, WP, SC and DC compositions described above. Compositions for treating seed may include an agent for ing the adhesion ofthe composition to the seed (for example a mineral oil or a film-forming barrier).

Wetting agents, dispersing agents and emulsifying agents may be surface SFAs ofthe cationic, anionic, amphoteric or non-ionic type.

Suitable SFAs ofthe cationic type include quaternary ammonium compounds (for example cetyltrimethyl ammonium bromide), imidazolines and amine salts. le anionic SFAs include alkali metals salts of fatty acids, salts of aliphatic ters of sulfuric acid (for example sodium lauryl sulfate), salts of sulfonated aromatic compounds (for example sodium dodecylbenzenesulfonate, calcium dodecylbenzenesulfonate, aphthalene ate and mixtures of sodium opropyl- and tri-z‘sopropyl-naphthalene sulfonates), ether es, alcohol W0 04331 27 ether sulfates (for example sodium laureth—3 -sulfate), ether carboxylates (for example sodium laureth- 3-carboxylate), phosphate esters (products from the on between one or more fatty alcohols and phosphoric acid (predominately mono-esters) or phosphorus pentoxide (predominately di—esters), for example the reaction n lauryl l and tetraphosphoric acid; additionally these products may be ethoxylated), sulfosuccinamates, paraffm or olefme sulfonates, taurates and lignosulfonates.

Suitable SFAs ofthe amphoteric type include betaines, propionates and glycinates.

Suitable SFAs ofthe non-ionic type include condensation products of alkylene oxides, such ethylene oxide, ene oxide, butylene oxide or mixtures thereof, with fatty alcohols (such as oleyl alcohol or cetyl alcohol) or with alkylphenols (such as henol, nonylphenol or octylcresol); partial esters derived from long chain fatty acids or hexitol anhydrides; condensation products of said partial esters with ethylene oxide; block polymers (comprising ethylene oxide and propylene ; alkanolamides; simple esters (for example fatty acid polyethylene glycol esters); amine oxides (for example lauryl dimethyl amine oxide); and lecithins. le suspending agents include hilic colloids (such as polysaccharides, polyvinylpyrrolidone or sodium carboxymethylcellulose) and swelling clays (such as bentonite or attapulgite).

A compound ofthe invention may be applied by any of the known means of ng pesticidal compounds. For example, it may be d, formulated or unformulated, to the pests or to a locus of the pests (such as a habitat ofthe pests, or a growing plant liable to infestation by the pests) to any part ofthe plant, including the foliage, stems, branches or roots, to the seed before it is planted or to other media in which plants are growing or are to be planted (such as soil surrounding the roots, the soil generally, paddy water or hydroponic e systems), directly or it may be sprayed on, dusted on, applied by dipping, applied as a cream or paste formulation, d as a vapor or applied through distribution or incorporation of a ition (such as a granular composition or a composition packed in a water-soluble bag) in soil or an aqueous environment.

A compound ofthe invention may also be injected into plants or sprayed onto vegetation using electrodynamic spraying techniques or other low volume methods, or applied by land or aerial irrigation systems.

Compositions for use as aqueous preparations (aqueous solutions or dispersions) are generally supplied in the form ofa concentrate containing a high proportion ofthe active ingredient, the concentrate being added to water before use. These concentrates, which may include DCs, SCs, ECs, EWs, MEs, SGs, SPS, WPs, WGs and CSs, are ofien required to withstand storage for prolonged periods and, after such storage, to be capable of addition to water to form aqueous preparations which remain homogeneous for a ient time to enable them to be applied by conventional spray equipment. Such aqueous ations may contain varying amounts ofa compound ofthe ion (for example 0.0001 to 10%, by weight) depending upon the purpose for which they are to be used.

A compound ofthe invention may be used in mixtures with fertilizers (for example nitrogen-, potassium- or phosphorus—containing fertilizers). Suitable formulation types include granules of izer. The mixtures preferably contain up to 25% by weight of the compound ofthe invention.

The invention therefore also provides a fertilizer composition comprising a izer and a compound ofthe invention.

The compositions ofthis invention may contain other nds having biological activity, for example micronutrients or compounds having fungicidal activity or which possess plant growth regulating, herbicidal, insecticidal, cidal or acaricidal activity.

The compound ofthe invention may be the sole active ingredient ofthe composition or it be admixed with one or more additional active ingredients such as a pesticide, fungicide, synergist, ide or plant growth regulator where appropriate. An additional active ingredient may: e a composition having a broader spectrum of activity or increased persistence at a locus; synergize the activity or complement the activity (for example by increasing the speed of effect or overcoming repellency) ofthe compound ofthe invention; or help to overcome or prevent the development of resistance to individual components. The particular additional active ient will depend upon the ed utility of the composition. Examples of suitable pesticides include the following: a) a pyrethroid ing those selected from the group consisting of permethrin, cypermethrin, fenvalerate, esfenvalerate, deltamethrin, cyhalothrin, lambda-cyhalothrin, gamma- cyhalothrin, bifenthrin, fenpropathrin, cyfluthrin (including beta cyfluthrin), tefluthrin, ethofenprox, l pyrethrin, ethrin, S—bioallethrin, fenfluthrin, prallethrin and -benzylfiirylmethyl-(E)-(1R,3S)-2,2-dimethyl- 3-(2-oxothiolan-3 -ylidenemethyl)cyclopropane carboxylate; b) an organophosphate including those ed from the group consisting of sulprofos, te, methyl parathion, azinphos-methyl, demeton—s-methyl, ophos, thiometon, fenamiphos, monocrotophos, profenofos, triazophos, methamidophos, dimethoate, amidon, malathion, chlorpyrifos, one, terbufos, fensulfothion, fonofos, phorate, phoxim, pirimiphos-methyl, pirimiphos-ethyl, fenitrothion, fosthiazate and diazinon; c) a carbamate including those selected from the group consisting ofpirimicarb, triazamate, ocarb, carbofuran, furathiocarb, ethiofencarb, aldicarb, thiofurox, carbosulfan, bendiocarb, fenobucarb, propoxur, methomyl, thiodicarb and oxamyl; d) a benzoyl urea including those ed from the group consisting of diflubenzuron, uron, hexaflumuron, flufenoxuron, lufenuron and chlorfluazuron; e) an organic tin compound selected from the group ting of cyhexatin, fenbutatin oxide and azocyclotin; f) a pyrazole including those selected from the group consisting of tebufenpyrad and fenpyroximate; g) a macrolide including those selected from the group consisting of abamectin, emamectin (e.g. emamectin benzoate), ivermectin, milbemycin, spinosad, azadirachtin and spinetoram; 2012/051638 h) an organochlorine compound including those selected from the group consisting of endosulfan (in particular alpha-endosulfan), benzene hexachloride, DDT, chlordane and dieldrin; i) an amidine including those selected from the group consisting of chlordimefonn and amitraz; j) a fumigant agent including those ed from the group consisting of chloropicrin, dichloropropane, methyl bromide and metam; k) a neonicotinoid compound including those selected from the group consisting of imidacloprid, thiacloprid, acetamiprid, nitenpyram, dinotefuran, thiamethoxam, clothianidin, nithiazine and flonicamid; 1) a diacylhydrazine including those selected from the group consisting fenozide, chromafenozide and methoxyfenozide; m) a diphenyl ether including those selected from the group ting of diofenolan and pyriproxyfen; n) indoxacarb; o) chlorfenapyr; p) pymetrozine; q) a tetramic acid compound including those selected from the group consisting of spirotetramat and spirodiclofen, or a ic acid compound including spiromesifen; r) a diamide ing those selected from the group consisting of flubendiamide, chlorantraniliprole (Rynaxypyr®) and cyantraniliprole; s) sulfoxaflor; t) metaflumizone; u) fipronil and ethiprole; v) pyrifluqinazon; W) buprofezin; x) diafenthiuron; y) 4-[(6-Chloro-pyridin-3 -ylmethyl),-(2,2-difluoro-ethyl)-amino]-5H-furan—2-one (DE 015467); 2) flupyradifurone. aa) CAS: 915972—17-7 (WO 2006129714; W02011/147953; /147952) ab) CAS: 269148 (WO 2007020986) In addition to the major chemical classes icide listed above, other pesticides having particular targets may be employed in the composition, ifappropriate for the intended utility ofthe ition. For instance, ive insecticides for particular crops, for example stemborer specific insecticides (such as cartap) or hopper specific insecticides (such as buprofezin) for use in rice may be employed. Alternatively icides or acaricides specific for particular insect species/stages may also be included in the compositions (for example acaricidal ovo-larvicides, such as clofentezine, flubenzimine, hexythiazox or tetradifon; acaricidal motilicides, such as dicofol or propargite; wo 2012/104331 30 ides, such as bromopropylate or chlorobenzilate; or growth regulators, such as hydramethylnon, cyromazine, methoprene, chlorfluazuron or diflubenzuron).

Examples of fungicidal compounds which may be included in the composition ofthe invention are (_E_)—N-methyl[2-(2,5-dimethylphenoxymethyl)phenyl]methoxy-iminoacetamide (SSF-129), 4-bromocyano-N,N-dimethyltrifluoromefl1ylbenzimidazole-l -sulfonamide, (3 —chloro-2,6— -xylyl)methoxyacetamido] -y-butyrolactone, 4-chlorocyano—N,N-dimethy1-5 -p-tolylimidazole sulfonamide (IKF-916, azosulfamid), chloro-N—(3-chloro-l-ethyl-l-methyloxopropyl)— 4—methylbenzamide (RH—7281, zoxamide), N-allyl-4,5,~dimethyltrimethylsilylthiophene-3— carboxamide (MON65500), N—(l—cyano-l,2-dimethylpropyl)(2,4—dichlorophenoxy)propionamide (AC382042), N—(2-methoxypyridyl) -cyclopropane carboxamide, acibenzolar (CGA245704), alanycarb, aldimorph, anilazine, azaconazole, azoxystrobin, benalaxyl, benomyl, biloxazol, anol, blasticidin S, bromuconazole, bupirimate, captafol, captan, carbendazim, carbendazim chlorhydrate, in, carpropamid, carvone, CGA41396, CGA41397, chinomethionate, chlorothalonil, chlorozolinate, clozylacon, copper containing compounds such as copper oxychloride, copper nolate, copper sulfate, copper tallate and Bordeaux mixture, cymoxanil, cyproconazole, cyprodinil, debacarb, dipyridy1 disulfide 1,l'—dioxide, dichlofluanid, ezine, dicloran, diethofencarb, difenoconazole, difenzoquat, torim, 0,0-di-iS0-propy1-S-benzyl thiophosphate, dimefluazole, dimetconazole, dimethomorph, dimethirimol, diniconazole, dinocap, dithianon, dodecyl dimethyl um chloride, dodemorph, dodine, doguadine, edifenphos, onazole, ethirimol, (Z)-N-benzyl-N-([methyl(methyl-thioethylideneaminooxycarbonyl)amino]thio)—B-alaninate, etn'diazole, famoxadone, fenamidone (RPA407213), fenarimol, fenbuconazole, am, fenhexamid (KBR273 8), fenpiclonil, fenpropidin, pimorph, fentin acetate, fentin hydroxide, , ferimzone, am, fludioxonil, flumetover, fluoroimide, fluquinconazole, flusilazole, flutolanil, flutriafol, folpet, fuberidazole, furalaxyl, furametpyr, guazatine, hexaconazole, yisoxazole, hymexazole, imazalil, imibenconazole, tadine, iminoctadine triacetate, ipconazole, iprobenfos, iprodione, iprovalicarb (SZXO722), isopropanyl butyl ate, isoprothiolane, kasugamycin, kresoxim-methyl, LY186054, LY211795, LY248908, mancozeb, maneb, mefenoxam, mepanipyrim, mepronil, metalaxyl, metconazole, m, metiram—zinc, metominostrobin, myclobutanil, neoasozin, nickel dimethyldithiocarbamate, nitrothal-z'sopropyl, nuarimol, ofurace, mercury compounds, oxadixyl, oxasulfiiron, oxolinic acid, oxpoconazole, boxin, pefurazoate, penconazole, pencycuron, phenazin oxide, phosetyl-Al, phosphorus acids, phthalide, picoxystrobin (ZA1963), poly- oxin D, polyram, probenazole, prochloraz, procymidone, propamocarb, propiconazole, propineb, propionic acid, pyrazophos, pyIifenox, pyrimethanil, pyroquilon, pyroxyfur, pyrrolnitrin, quaternary ammonium compounds, quinomethionate, quinoxyfen, quintozene, sipconazole (F—155), sodium pentachlorophenate, spiroxamine, streptomycin, sulfur, tebuconazole, tecloftalam, tecnazene, tetraconazole, thiabendazole, thifluzamid, 2-(thiocyanomethylthio)benzothiazole, thiophanate-methyl, thiram, timibenconazole, tolclofos-methyl, tolylfluanid, triadimefon, menol, triazbutil, xide, tricyclazole, tfidemorph, trifloxystrobin (CGA279202), triforine, triflumizole, triticonazole, wo 2012/104331 31 validamycin A, vapam, vinclozolin, zineb, ziram; N-[9-(dichloromethylene)-l,2,3,4-tetrahydro-1,4- methanonaphthalen-S -y1] (difluoromethyl)-1 -methyl-lH—pyrazolecarboxamide 57-7 1 - 1], 1-methyl-3 -difluoromethyl-lH—pyrazolecarboxylic acid (2-dichloromethylene-3 -ethyl-l-methy1- indanyl)-amide, and l-methy1-3 -difluoromethyl—4H—pyrazolecarboxylic acid [2-(2,4-dichloro- phenyl)~2-methoxymethyl -ethyl] -amide.

Preferred additional pesticidally active ingredients are those ed from neonicotinoids, pyrethroids, strobilurins, triazoles and amides (SDI-II inhibitors). Pyrethroids are of interest of which lambda-cyhalothrin is of particular interest. Combinations of compounds ofthe invention, particularly compounds from Table A, and particularly when X is P3, P4 or P5 and pyrethroids, in parrticular lambda-cyhalothrin, exhibit synergistic control of stinkbugs (according to the Colby formula), in particular Euschistus, e.g. Euschistus heros.

In a further aspect ofthe invention there is provided a method comprising ng to a crop of soybean plants, the locus thereof, or propagation material thereof, a combination of a compound compound ofthe invention and lambda thrin in a synergistically effective amount, wherein the method is for control and/or prevention of stinkbugs, preferably Euschistus, e.g. Euschz‘stus heros. In one embodiment the compound is a compound offormula I. In another embodiment the compound is compound offormula II. In another embodiment the compound is a compound of formula III. In another embodiment the compound is a compound of formula IV. Preferably the nd is compound from Table A.

The compounds ofthe invention may be mixed with soil, peat or other g media for the protection of plants against seed-borne, soil-borne or foliar fungal es.

Examples of suitable synergists for use in the compositions include piperonyl butoxide, sesamex, safroxan and dodecyl imidazole.

Suitable herbicides and plant-growth regulators for inclusion in the compositions will depend upon the intended target and the effect ed.

An example of a rice ive ide which may be included is propanil. An e of a plant growth regulator for use in cotton is PIXTM.

Some mixtures may comprise active ingredients which have significantly different physical, chemical or biological properties such that they do not easily lend lves to the same conventional formulation type. In these circumstances other formulation types may be prepared. For example, where one active ingredient is a water insoluble solid and the other a water insoluble liquid, it may nevertheless be possible to disperse each active ingredient in the same continuous aqueous phase by dispersing the solid active ingredient as a suspension (using a preparation analogous to that of an SC) but dispersing the liquid active ingredient as an on (using a preparation analogous to that of an EW). The resultant ition is a suspoemulsion (SE) formulation.

Unless ise stated the weight ratio ofthe compound of I, II, III or IV With an additional active ingredient may lly be between 1000 : 1 and l : 1000. In other embodiments that weight ratio ofA to B may be between 500 : l to l : 500, for example between 100 : l to l : 100, for example between 1 :50 to 50: 1, for example 1 :20 to 20: 1, for example 1:10 to 10:1, for example 1:5 to 5:1, for example 1: 1. itions ofthe invention include those ed by premixing prior to application, eg. as a readymix or tankrnix, or by simultaneous application or sequential application to the plant.

The invention will now be illustrated by the following non-limiting Examples. All citations incorporated by nce.

Figures Figure 1 shows the results of a field trial to investigate l ofEuschz'stus heros on soybeans with the compound of formula Ix (racemic mixtures of enantiomers) . The X axis tes grams of active ingredient per hectare of (a) beta-cyfluthrin + imidacloprid, (b) thiamethoxam + lambda cyhalothrin, (c) formula Ix at 35 g/ha, (d) formula Ix at 53 g/ha. The Y axis indicates % control. Bars 1-5 show control after 1, 3, 5, 8 and 15 days after application respectively. Experimental details are indicated in Example 1.

Figure 2 shows the results of a field trial to investigate control ofEuschz'stus heros on soybeans with the compound of formula Ix (racemic mixtures of omers). The X axis tes grams of active ient per hectare of (a) beta-cyfluthrin + imidacloprid, (b) thiamethoxam + lambda cyhalothrin, (c) a Ix at 35 g/ha, (d) formula Ix at 53 g/ha. The Y axis indicates % control. Bars 1- 4 show control afier 2, 5, 12 and 16 days after application tively. Experimental details are indicated in Example 2.

Figure 3 shows the results of a field trial to investigate control ofEuschz‘stus heros on soybeans with the compound of formula Ix (racemic mixtures ofenantiomers) and formula Iy (racemix mixture of enantiomers). Tire X axis indicates grams of active ingredient per hectare of (a) thiamethoxam + lambda thrin, (b) methamidophos, (c) formula Iy at 60 g/ha, (d) formula Iy at 120 g/ha, (e) formula Ix at 60 g/ha, (f) formula Ix at 120 g/ha. The Y axis indicates % control. Bars 1-5 show control after 2, 5, 7, 10 and 13 days after application respectively. Experimental details are indicated in Example 3.

Examples Example 1 Field trial: control ofEuschz'stus heros on soybeans. Application was Foliar application using rayer. The spray volume was 200 l/ha. Each plot size was 60m2. The soybean was at growth stage bbch 72. The nd of formula Ix was applied as an EC formulation. The beta—cyfluthrin + imidacloprid (9.4 g/ha and 75 g/ha respectively) /thiamethoxam + lambda-cyhalothrin (21.2 g/ha and 28.2 g/ha respectively) were applied as suspension concentrate ations. The results (% control of adults) are shown in Figure l and represent the average of 3 replicates. wo 2012/104331 33 Example 2 Field trial: control ofEuschz'stus heros on soybeans. Application was Foliar application using a boomsprayer. The spray volume was 200 1/ha. Each plot size was 108m2. The soybean was at growth stage bbch 72. The compound offormula Ix was applied as an EC formulation. The beta-cyfluthrin + imidacloprid (9.4 g/ha and 75 g/ha respectively) ethoxam + lambda-cyhalothrin (21.2 g/ha and 28.2 g/ha respectively) were applied as suspension concentrate ations. The results (% control of ) are shown in Figure 2 and represent the average of 3 replicates. e 3 Field trial: control ofEuschz'stus heros on soybeans. Application was Foliar application using a boomsprayer. The spray volume was 200 l/ha. Each plot size was 108m2. The n was at growth stage bbch 75. The compounds offormula Ix and Iy were applied as an EC formulation. The thiamethoxam + lambda-cyhalothrin (21.2 g/ha and 28,2 g/ha respectively) was applied as a suspension concentrate formulation. The methamidophos was d as a soluble concentrate ation. The results (% control of adults) are shown in Figure 3 and represent the average of 3 replicates.

Example 4 Euschz'stus heros (Neotropical brown stink bug) (contact/feeding activity) 2 week old soybean plants are sprayed in a turn table spray chamber with the diluted spray solutions.

After drying, 2 soybean seeds are added and plants are infested with 10 N-2 nymphs ofthe neotropical brown stink bug Euschistus heros in c test boxes. Boxes are incubated in a climate chamber at °C and 60 % RH. Evaluation is done 5 days after infestation on mortality and growth effects. The results are shown in Tables E1 and E2 below. The data is an average oftwo replicates.

The results show that the compounds of the invention are significantly more active against stinkbugs than structurally similar compounds, particularly at low rates of application.

Table El Rate / ppm Compound 1 Compound 2 nd 3 Compound 4 rative (comparative example) wo 2012/104331 34 (3) (4) 1? nds 1-4 are disclosed in W02009/080250.

Table E2 Rate / ppm Compound 6 Compound 7 Compound 8 Compound 9 (comparative (comparative (comparative example) example) (7) ° W0 2012/104331 35 Compounds 5-9 are nds from W02005/085216 (EP1731512) and WO2009/002809.

References Corréa—Perreira, B. S.; Panizzi, A. R., Percevejos da soja e seu manejo, Londrina: Embrapa—CNPSo, 1999, 45 (Circular Te'cnica, 24). o, M.H.M., Heinrichs E.A., Retencao foliar em plantas de soja (glycine max (1.) merrill) resultantes da acfio de Piezodorus guildinii (Westwood, 1837) (Hemz'ptera pentatomz'dae), em diferentes niveis e e’pocas de infestagao. An. Soc. Entomol. Brasil, 1978, 7, 85-98.

Panizzi, A. R., Slansky junior, F. Review of phytophagous omids (Hemiptera pentatomz‘dae) ated with soybean in the Americas, Florida Entomologist, Gainesville, 1985, 68(1), 184-214.

Schmidt, F. G. V., Pires, C. S. S., Sujii, E. R,., Borges, M,., Pantaleao, D. C., Lacerda, A. L., Azevedo, C. R., Comportamento e captura das fémeas de Euschistus heros em annadilhas iscadas com nio sexual, 2003, Comunicado Técnico 93. Brasilia, DF.

Sosa-Gomez, D.R., Silva, J. Da., Lopes, I. O. N., Corso, I., Almeida, A.M. R. Almeida, moraes, g. c.p.m.; baur, m. insecticide susceptibility of Euschz'stus heros (Heteroptera pentatomz'dae) in Brazil, Journal of Economic Entomology, 2009, 102(3), 1209-1216.

Todd, J. W., Herzog, D. 0, ng hagous omz‘dae on soybean. in: Kogan, M., Herzog, D. C. (ed). ng methods in soybean entomology, New York: Springer, 1980, 438-478.

Claims (1)

Claims:

1. A compound selected from compounds of formula (A) n G is oxygen, R7 is trifluoromethyl, R5 is methyl, R1 is hydrogen, and cycle C and R2 have the values listed Table X 5 below. |Cycle C X. 14 3,4,5-trichloro-phenyl- IIthietanyl- X. l 5 3,4,5-trichloro-phenyl- l-oxo-thietan—3-yl- ‘ X. 1 6 3,4,5-trichloro-phenyl- l,1-dioxo—thietan—3 -y1- X.l7 3,4,5-trichloro-phenyl- thietan—Z-yl-methyl- X. l 8 3 ,4,5 -trichloro-phenyl0X0-thietanyl-methyl- X. 1 9 3 richloro—phenyl- l 1 -dioxo-thietanyl-methyl- X.20 trichloro-phenyl- thietan—3 -y1-methyl- X2 1 3 ,4,5 -trichloro-phenyl- l -oxo-thietanyl-methy1- X.22 3,4,5-trichloro-phenyl- l,l-dioxo-thietanyl-methyl- X25 3,5-dichlorofluoro-phenyl- thietan-3 -y1- X26 3 ,5-dichlorofluoro-phenyl- l hietanyl- 3,5-dichlorofluoro-phenyl- l ,1-dioxo-thietan-3 -yl- 3,5-dichlorofluoro-pheny1- thietan-2~yl-methyl- X29 chlorofluoro-pheny1- l-oxo-thietanyl-methyl- 3 ,5-dichlorofluoro-pheny1- 1 1 -dioxo—thietan—2-yl-methyl- X.31 3,5-dichlorofluoro—phenyl- thietan—3 -yl-methyl- X.32 3,5-dichlorofluoro-phenyl- l-oxo-thietan-3 —yl-methyl- X33 3,5-dichlorofluoro-phenyl- l,l-dioxo-thietan-3 -yl-methyl- wo