NZ626702B2 - Methods of pest control in soybean - Google Patents

Abstract

The disclosure relates to a method of applying a compound of formula (III) to a crop of soybean plants, the locus thereof, or propagation material thereof, for controlling and/or preventing infestation of the soybean crop by stinkbugs. The stinkbug may be Nezara viridula, Piezodorus spp., Acrosternum spp or Euchistus heros. The compound may be applied in combination with an attractant selected from glucose, saccharose, salt, glutamate, citric acid, soybean oil, peanut oil and soybean milk. m spp or Euchistus heros. The compound may be applied in combination with an attractant selected from glucose, saccharose, salt, glutamate, citric acid, soybean oil, peanut oil and soybean milk.

Description

Divisional application out of NZ 613413 NEW ZEALAND PATENTS ACT 1953 COMPLETE SPECIFICATION Methods of pest control in soybean We, Syngenta Participations AG, of Schwarzwaldallee 215, 4058 Basel, Switzerland, and Syngenta Limited, of European Regional Centre, Priestley Road, Surrey Research Park, , Guildford, GU2 7YH, United m, 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 13) METHODS OF PEST L IN SOYBEAN The present invention, the invention ofNZ 613413 and the invention ofNZ 700056 relate to methods of pest control in soybean crops.

Stink bugs (Hemiptera Pentatomidae) are true bugs which can be significant pests when present in large numbers. The nymphs and adults have piercing mouthparts which most use to suck sap from plants. According to Stewart et al., Soybean Insects - Stink bugs, sity of Tennessee Institute of Agriculture, W200 09-0098, stink bugs are probably the most common pest m in soybean. Although they may feed on many parts of the plant, they typically target developing seed including the pods, meaning that injury to soybean seed is the primary problem associated with stink bug infestations. 0fthe 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 & , 1980). l of stinkbugs in soybean is often vital to prevent significant economic damage.

Insecticides commonly used to control stinkbugs include pyrethroids, neonicotinoids and organophosphates, although pyrethroid insecticides are usually the method of choice for controlling stink bugs in soybean. However, there are increasing ms with icide resistance, particularly in brown stink bug populations and particularly to pyrethroids. 'stus heros (F.)) can also be lt 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, nematicidally and/or moluscicidally active by antagnonism of the gamma-aminobutyric acid (GABA)—gated chloride channel, and which comprise a partially ted cycle that is substituted by a haloalkyl substituent and one or two optionally substituted aromatic or heteroaromatic rings, represent a new class of pesticides that are described for example in Ozoe et a1. Biochemical and Biophysical Research Communications, 391 (2010) 744-749.

Compounds from this class are broadly described in W0 2005/085216 (EP1’731512), W0 2007/123853, , W02009/002809, W0 2008/019760, W0 2008/122375, W0 2008/128711, W0 2009/097992, W0 2010/072781, W0 2010/072781, , W0 2007/125984, W0 2008/130651, JP 2008110971, IP2008133273, JP2009108046, /022746, WO 22746, W0 2010/032437, W02009/080250, W02010/020521, W02010/025998, /020522, W02010/084067, W02010/086225, W02010/149506 and W02010/108733.

It has now surprisingly been found that particular icides from this new class of gamma- aminobutyric acid (GABA)—gated chloride channel nists (disclosed in e.g. W0 2005/085216 (EP1731512), W02009/002809 and W02009/080250) 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 stinkbugs 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 thereof, or propagation material thereof, a nd a compound of formula I F3C O\N +1 \ F25 0H X (F28)p (I) wherein X is P1 or P2 \ HNACFB it F: l ,/’ 1¢ Fj‘\\,//’i::> T N \If 0 0 0 P1 P2 R5 is , bromo, CF3 or methyl; each R8 is ndently bromo, chloro, fluoro or trifluoromethyl; p is 1, 2 or 3; and wherein the method is for controlling and/or preventing infestation of the soybean crop by Euschistus, preferably Euschistus heros.

In a further aspect the ion provides use of a compound of formula I for control of stus, preferably Euschistus heros. The use may be for controlling stinkbugs istus) that are resistant to one or more other icides, 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 ation al thereof, a compound of formula II (11) wherein cycle A is A2a W0 2012;104331 U.) #2 \ / #1 A‘f—A5 wherein AL? and A5, are independently OH, 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 31/4#2 O,N #2 #2 #3 I #212 #1 #1 81 82 #2 O £3?O #2 N #90 \ \ B4 B5 B6 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 difluoromethyl or trifluoromethyl; each R8 is independently bromo, chloro, fluoro or trifluoromethyl; p is 2 or 3; and X is P1 or P2 \ HN CF3 H | H # N / # N \n/ N \n/ O 0 0 P1 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 , the locus thereof, or propagation al thereof, nd of formula III (III) wherein cycle A is Ala or A2a # # # 2 \ ’ 2 \ ’ # 1 1 A3—A4 , ‘ A—A5 A1 a A2a wherein A3, A4, A4“ and A5. are independently 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 ON #2 #2 o #3 / #3 / #3 / #1 #1 #1 B1 32 B3 #2 O #3>LZ we)#3 #3 N ‘50N \ \ #1 #1 #1 B4 B5 86 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 , bromo; CF3 or methyl; R7 is chlorodifluoromethyl or trifluoromethyl; each R8 is independently bromo; , fluoro or trifluoromethyl; 13 p is 2 or 3; and X is selected from P3 to P11 W0 2012I104331 U: H # N # N\/DH # H # N T S Y \Cs T The i]: v/0 O O \0 .S’ o $ P3 P4 P5 P6 8 H H 3’ # N \n/ # HVDN # N s S \n/ \\ Y P7 P8 P9 P10 P11 In a further aspect the invention es a method of controlling and/or preventing infestation of stinkbugs in soybean comprising applying to a crop of soybean plants> the locus thereof, or propagation material thereof, a compound that of a 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 ugsi 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 of the invention may exist in different geometric or optical isomers or eric forms. This invention covers all such isomers and tautomers and mixtures thereof in all proportions as well as ic forms such as deuterated compounds.The compounds of the invention may contain one or more asymmetric carbon atoms, for e, at the C(#2)#3 group, and may exist as enantiomers (or as pairs of diastereoisomers) or as es of such.

In one group of compounds of formula 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. Preferably X is Pl. Each R8 may take the same value.

A ularly preferred nd of formula I is a compound of formula IX F O‘N F \ HNACF3 o u 'X Cl 0 Another particularly preferred compound of formula I is a compound of formula Iy Preferred 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 preferably B1.

U: In one group ofcompounds cycle B is B1. In another group of compounds cycle B is B2, in another group ofcompounds cycle B is B3, in another group ofcompounds cycle B is B4, in another group of compounds cycle B is BS, in another group of compounds cycle B is B6.

Preferably cycle C is cycle Cl (R8), More preferably cycle C is 3,5-dibromo-phenyl, chloro-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 CH.

Preferably A4, is C-H or C—RS, most ably A” is OH.

Preferably 5' is OH 15 or C-RS, most preferably Aw is C-H.

Preferably no more than one of A3 and A4 is nitrogen. Preferably no more than one of A4] and AS' is nitrogen.

Preferably R5 is methyl.

Preferably R7 is romethyl.

Preferably 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, A1, A2, A4,, A5, R5, R7 and R8 in compounds of formula III are, in any combination, as set out for compounds of formula II.

In compounds of fomiula 111 ably cycle A is cycle Ala in which A3 and A4 are C-H.

In one group of compounds of formula II each R8 takes the same value. Likewise, in one group of compounds ula 111 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) n G is oxygen, R7 is trifluoromethyl, R5 is methyl, R1 is hydrogen, and cycle C and R2 have the values listed Table X below.

Table 2: Table 2 provides 176 compounds of formula (B) 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.

Table 3: Table 3 provides 176 compounds of formula (C) 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.

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

Table 52Table 5 provides 176 compounds of formula (E) n 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 Y N R l (E) N\ 1 WO 20121104331 8 2012/051638 Table 6: Table 6 es 176 compounds of formula (F) 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.

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. 3,3-dichloro—phenyl- (2,2,2-trifluoro-ethylcarbamoyl) -methyl -_1,1dioxo-thietan-Z—yl-methyl-X8 1,1-dioxo-thietan-3 -yl-methyl— X 12 3,4,5-trichloro-phenyl- (2,2,2-trifluoro—ethylcarbamoyl) -methy1 3,4,5-trichloro—phenyl- (PYfid-Z-yl)-methyl- 3,4,5-trichloro-phenyl- thietanyl- 3,4,5-trichloro-phenyl- l-oxo-thietanyl- trichloro-phenyl- l, l —dioxo—thietan—3 —yl— 3,4,5—trichloro—phenyl- thietan-Z—yl-methyl- 3,4,5-trichloro—phenyl- 1 —oxo-thietan—2~yl-methyl- W0 20121104331 9 3,4,5-tfichloro-pheny1— 1,1-dioxo-thietanyl-methyl- 3,4,5-trichloro-pheny1- thietanyl-methy1— 3,4,5—trichloro—phenyl- l-oxo-thietany1-methyl- 3,4,5-trichloro-phenyl- oxo-thietan-3 -yl-methy1- -X23 3,5dichlorofluoro-pheny1- (2,2,2-trifluoro-ethylcarbamoyl) 3,5-dichlorofluoro-pheny1- (Pyfid-Z—y1)-methy1- 3,5—dichloro—4-fluoro—phenyl- thietany1- 3,5dichloro—4-fluoro-phenyl— 1—oxo-thietanyl- 3,5 dichloro-4—fluoro-pheny1— 1, 1 —dioxo—thietan-3 —y1— hloro—ll-fluoro-phenyl- thietan-Z-yl—mefllyl- 3,5 —dichloro~4~fluoro-pheny1- 1-0X0-thietany1—methyl- 3,5-dichloro~4~fluoro-phenyl- 1,1-dioxo~thietanyl-methy1- 3,5-dich10ro-4~fluoro-phenyl- thietany1-methyl— 3,5-dichloro—4~fluoro-pheny1- 1-oxo-thietan-3—yl-methyl— 3,5 -dichlorofluoro-pheny1- 1,1—dioxo—thietan—3 -y1-methyl- -X34 3-chlorofluoro-phenyl- (2,2,2—trifluoro-ethylcarbamoyl) 3-chlorofluoro—pheny1- (pyrid-Z-yl)-methyl- 3-chlorofluoro-phenyl- 3—chloro—4-flu0ro—pheny1- 1-oxo-thietanyl- 3—chloro-4—fluoro—phenyl- 1,1-dioxo—thietan-3 —y1— 3~ch10ro-4—fluoro—phenyl- thietan-Z-yl-methyl— 3-chloro-4—fluoro-phenyl- l-oxo-thietan-Z-yl—methyl- 3-chlorofluoro-pheny1- 1, 1 dioxo—thietan-Z-y1-methy1- 3-chloro—4-fluoro-pheny1~ thietan—3-yl-methy1- 3—chlorofluoro-pheny1- l-oxo-thietan—3-y1-methy1— ro-4—fluoro-pheny1- 1, 1 dioxo-thietan—3—y1-methyl- X45 3-fluorochloro-phenyl- (2,2,2~trifluoroethylcarbamoyl) -methy1 3-fluorochloro-pheny1- (pyrid—Z-y1)-methyl- 3-fluorochloro-pheny1- thietan—3-y1— 3-fluoro-4—chloro-phenyl- 1-oxo-thietanyl- 3-fluorochloro-phenyl- 1,1-dioxo-thietan-3 -y1- 3-fluorochloro-phenyl— n-Z-yl—methyl- 3-fluorochloro—phenyl— thietan—2-y1—methy1- X52 3-fluorochloro-pheny1- 1, 1-dioxo-thietan-2—y1—methyl— 3—fluorochloro-pheny1- thietan—3 -y1-methyl- 3-fluoro-4—chloro-phenyl- l—oxo-thietanyl-mefl1yl— 3-fluorochloro-phenyl— 1,1 dioxo-thietan-3 thyl- -—X563,4-dichloro-pheny1- (2,2,2-trifluoroethylcarbamoyl) _3,4—dichloro—phenyl- 1,1-dioxo-thietanyl- —3,4—dichloro-phenyl- thietan-Z-yl-methyl- _3,4-dichloro-pheny1- l-oxo—thietan—Z-yl-methyl- 3 ,4-dichloro—phenyl- 1 1 ~dioxo-thietany1-methy1— 3,4-dichloro-phenyl- nyl—methyl- 3,4-dichloro-pheny1- l-oxo—thietan-3—yl-mefl1yl- 3,4-dichloro—pheny1- 1,1 -dioxo-thietan-3 -yl-methyl- X.67 3,5 dichloro—4—bromo-phenyl- (2,2,2-triflu0ro-ethylcarbamoyl) -methy1 3,5dichlorobromo-phenyl- (pyrid-Z-yl)-methy1- 3,5dichlorobromo-phenyl- thietan-3—yl- 3,5—dichlorobromo-phenyl- l-oxo—thietan-3—yl- 3,5 -dichloro-4—bromo-pheny1- 1,1—dioxo-thietan-3 -y1— 3,5—dichlorobromo-phenyl- thietanyl-methyl— 3,5dichloro—4-bromo-pheny1- 1—oxo—thietan—2-y1-mefl1yl- 3,5 —dichloro—4—bromo—phenyl- 1,1 ~dioxo-thietanyl—methyl- 3,5-dichlorobromo—phenyl- n-3—yl—methyl- 3,5dichlorobromo-phenyl- 1—oxo-thietan-3—yl-methyl— 3,5-dichloro-4~bromo-phenyl- 1,1—dioxo-thietanyl-methyl- -X.78 3,5dichlorofluoro—phenyl— (2,2,2-tIifluoro-ethylcarbamoyl) 3,5-dichlorofluoro-phenyl- (pyrid-Z-yI)-methyl- ch10rofluoro-phenyl- ny1- 3,5dichlorofluoro-phenyl- l-oxo-thietan-3 -yl- 3,5dichlorofluoro—phenyl— thietan-Z—yl—methyl- 3,5 dichlorofluoro-phenyl- l—oxo-thietan—Z—yl-methyl- 3,5 —dichlorofluoro—pheny1- 1,1dioxo-thietan—Z-yl-methyl— wo 2012/104331 11 -X.86 3,5—dichlorofluoro-phenyl- thietanyl~methyl- 3,5—dichloro—4—fluoro-phenyl- thietanyl-methyl— 3,5 -dichlorofluoro-phenyl- 1,1-dioxo-thietan-3 -yl-methyl- X.89 3,4,5-trifluoro-phenyl- (2,2,2-trifluoroethylcarbamoyl) —methyl 3,4,5-tn'fluoro-pheny1— (Pyfid—Z-y1)-mefl1yl- 3,4,5-trifluoro-phenyl- 3,4,5-trifluoro-phenyl- l-oxo-thietany1- 3,4,5-trifluoro—pheny1— oxo—thietan-3 ~y1— 3,4,5-trifluoro-pheny1- thietan-2~y1—methyl- 3,4,5-trifluoro-phenyl- 1-oxo—thietan—2-yl—methyl- 3,4,5-trifluoro-pheny1- 1, 1 -dioxo~thietanyl-methyl- trifluoro-pheny1- thietany1—methyl- 3,4,5—trifluoro-pheny1- 1~oxo-thietan-3—yl-mefl1y1- 3,4,5-trifluoro-phenyl- 1,1 dioxo—thietan-3 -y1-methy1— X. 100 3-chloro-5 -bromo—phenyl- (2,2,2-trifluoro-ethylcarbamoyl) 3-chlorobromo-pheny1- (PYI’id-Z-yl)-methy1- ro-5—bromo-phenyl- 3-chlor0bromo—phenyl- l—oxo—thietan—3-y1- 3-chlorobromo-pheny1— 1, 1 dioxo-thietan-3 —yl- 3—chloro-5—bromo-phenyl- thietan-Z-yl-mefllyl- 3-chlorobromo—phenyl- 1—oxo-thietan~2-yl-methyl- 1,1-dioxo-thietanyl~methyl— 3-chloro-5—bromo-phenyl- 1 1 dioxo-thietany1-methy1— -X1 1 1 3-chloro-5 -fluoro~pheny1— (2,2,2-trifluoroethylcarbamoyl) -methy1 3-chlorofluoro-phenyl- (DYfid-Z-yl)-methyl- 3-chlorofluoro-pheny1- thietany1- 3-chlorofluoro-pheny1- l-oxo-thietany1- 3-chlorofluoro-pheny1— oxo-thietan-3 -y1- 3-chloro—5-fluoro-phenyl- thietan—Z—yl-methyl— 3-ghlorofluoro-pheny1- 1-oxo-thietan—2-yl-methyl- 3-chloro—5 —fluoro-phenyl- 1, 1 dioxo-thietan—Z-y1-methyl- -X119 3-chlorofluoro~phenyl- thietan—3—yI-methyl- 3—chloro-5 —fluoro—phenyl- l—oxo-thietan-3 thyl- 3-chloro-5 -fluoro-pheny1- 1,1-dioxo-thietan-3 -yl-methyl- -X122 3-chlorotrifluoromethy1-phenyl- (2,2,2-trifluoroethylcarbamoyl) -methy1 3-chlor0trifluoromethyl—phenyl- (pyrid—Z-yl)-methy1- ro—5-trifluoromethyl-phenyl- 3—chloro—5—trifluoromethyl—phenyl- 1—0xo—thietan-3—yl— ro-5 -trifluoromethy1-pheny1- 1,1 -dioxo-thietan-3 -y1— 3-chloro-5—trifluoromethy1-pheny1- thietan-Z-yl-methyl— 3-chloro-5—trifluoromethyl-phenyl— l-oxo—thietan-Z-yl—methyl- 3-chloro-5 -trifluoromethyl-phenyl- 1, 1dioxo-thiemn-Z—yl—methyl- 3-chloro-5—trifluoromethy1-pheny1- thietany1-methyl- 3-chlorotrifluoromethyl-phenyl~ 1-oxo—thietan-3—yI-methy1- 3~chlorotrifluoromethyl—pheny1~ 1, 1 thietan-3 ~y1-methyl- -X133 3-chlorochloro—5-trifluoromethyl-pheny1- (2,2,2-trifluoro-ethylcarbamoyl) -methy1 3-chlorochlorotrifluoromethyl-phenyl— (DYIid-Z-yl)—methy1- X. 135 3-chlorochlor0-5 oromethy1-phenyl- thietan-3 -y1- 3—chlorochlorotrifluoromethyl—phenyl— 1-oxo-thietanylchlorochloro—5-trifluoromethy1-phenyl- 1, 1 dioxo—thietan-3 —yl— 3-chlorochloro—5-tfifluoromethyl-pheny1~ thietan-Z-yl-methyl- 3-chloroch10ro~5-trifluoromethy1—pheny1- l-oxo-thietan-Z-yl—methyl- 3-ch10ro-4—chloro-5—trifluoromethyl—pheny1- 1,1 dioxo-thietan-Z~yl-methy1- 3-chloro-4—chloro—5 -trifluoromethyl-phenyl — thietan-3 —yl-methyl- 3~chloro—4—ch10ro-5 ~trifluoromethy1-phenyl — 1 -oxo-thietan-3 -yl-methy1- X. 143 3-chlorochlorotrifluoromethy1-phenyl— 1, 1 —dioxo—thietan-3 ~y1-methy1~ -X 144 tfifluoromethyl~phenyl- (2,2,2-trifluoro-ethylcarbamoyl) -methy1 3,5-di-trifluoromethyl-pheny1- (pyfid—Z—yl)-methy1- 3,5di-tfifluoromethyl-phenyl- thietanyl- 3,5 di-tfifluoromethyl-pheny1- l-oxo-thietan-3 ~y1- 3,5 uoromethyl-phenyl- 1,1-dioxo—thietan-3 -yl- 3,5di-tfifluoromefllyl-phenyl- 3,5di—tfifluoromethyl—phenyl- thietan-Z-yl-mefllyl- X. 15 1 3,5 di-tfifluoromethyl-phenyl— 1: 1 dioxo-thiemn—Z-yl-mefllyl- wo 2012;104331 13 2012/051638 -X152 3,5di-tfifluoromethyl-phenyl- thietanyl—methyl- 3,5 -di-trifluoromethyl-phenyl- 1-oxo-thietan-3 thyl- 3,5 -di-trifluoromethyl-pheny1- 1,1 -dioxo-thietan-3 -yl~methyl- -X, 155 3,5 di-tfifluoromethylchloro-pheny1- (2,2,2-t1ifluoro-ethylcarbamoy1) -methy1 3,5—di-trifluoromethyl—4—chloro—phenyl- -Z—yl)-methyl— 3,5—di-trifluoromethylchloro-phenyl— 3,5—di-trifluoromethylchloro-phenyl- 1-oxo—thietan—3-yl- 3,5—di-trifluoromethylchloro-phenyl— 1,1-dioxo-thietanyl- 3,5-di—trifluoromethylchloro-phenyl- thietan-Z-yl-methyl— 3,5-di-trifluoromethy1—4—chloro-pheny1— 1-oxo~thietanyl-methyl— 1,1—dioxo—thietan~2—yl-methy1~ 3,5-di-trifluoromethylchloro-phenyl- thietan-3—yl-methyl- 3,5-di-trifluoromethylchloro~phenyl- l-oxo-thietanyl-methyl- X. 165 3 ,5 ifluoromethylchloro—phenyl- 1,1—dioxo-thietan-3 -yl-methyl— Xl 166 3-trifluoromethyl-phenyl- (2,2,2-trifluoro-ethylcarbamoyl) -methyl 1,1-dioxo-thietanyl—methyl— 1,l—dioxo-thietan—3-yl-methyl— Compounds of formula 1 include at least one chiral centre and may exist as compounds of formula 1* or compounds offormula 1* *. wo 20121104331 14 Compounds of formula II where cycle B is selected from B1 to B6 e at least one chiral centre and may exist as compounds of formula 11* (IIA*, IIB*, IIC*, HD*, IIE*, IIF*) or compounds of formula II** (ILA**, IIB**, IIC**, IID**, IIE**, IIF**).

WO 2012710431 15 2012/051638 63 ~ (R8), X X (IIE*) (R8), X X (IIF*) (HF**) Compounds of formula 111 where cycle B is selected from B1 to B6 include at least one chiral centre and may exist as compounds of formula 111* (IIIA*, IIIB*, IIIC*, IIID*, IIIE*, 111F*) or compounds ula III** (IIIA**, , IIIC**, IIID**, IIIE**, IIIF**). These generic ures correspond to the structures of formula II above.

Generally the compounds of formula I** are more biologically active than the respective compounds offormula 1*. The invention includes mixtures ofcompounds 1* and IM 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. In an enantiomerically (or epimerically) enriched mixture of formula I“, the molar proportion ofcompound I** compared to the total amount of both omers 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 enantiomerically (or epimerically) enriched mixture of formula 11*, the molar tion of the 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 es of formula I** are preferred.

Generally the compounds of formula II** are more biologically active than the respective compounds of formula 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 ntially 50:50 molar ratio. In an enantiomerically (or epimerically) enriched mixture of formula II**, the molar proportion of compound 11** compared to the total amount of both 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 of the compound of formula 11* compared to the total amount of both enantiomers (or epimerically) is for example greater than wo 2012;104331 16 50%, eg. 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 11** are preferred.

Generally the nds of formula 111** are more biologically active than the respective compounds of formula 111*. The invention es mixtures of compounds 111* and111** 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 epimerically) enriched mixture of formula 111* *, the molar tion of nd 111** compared to the total amount of both 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 omerically (or epimerically) enriched mixture of formula 111*, the molar proportion ofthe compound of formula 111* 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 III** are preferred.

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

In a further aspect the invention also provides a method comprising applying to a crop of soybean plants, the locus thereof, or propagation material thereof, a compound of formula IV G1 is oxygen; G2 is O or CH2; wo 20121104331 17 L is a bond, methylene or ethylene; one of Al and A2 is S, SO or SO; and the other is -C(R4)R4-; R3 is hydrogen; each R4 is ndently hydrogen or methyl; Y1 is C-R6, 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-C2alkyl, C1-Cghaloalkyl, C3-C5cycloalkyl, C3— Cshalocycloalkyl, C1—C2alkoxy, C1-Cghaloalkoxy; R6 together with R5 forms a -CH=CH-CH=CH- ; X2 is OK6 or nitrogen; X1, X3 and X6 are independently hydrogen, halogen or tiihalomethyl, wherein at least two of X], X3 and X6 are not hydrogen; X4 is trifluoromethyl, difluoromethyl or chlorodifluoromethyl.

In a further aspect the invention provides a method of lling and/or preventing infestation of stinkbugs in soybean comprising applying to a crop of soybean plants, the locus thereof, or propagation material thereof, a compound of a IV. Preferably the stinkbug is stus, more preferably Euschz‘stus herosi The stinkbugs may be stinkbugs that are resistant to one or more other icides, preferably pyrethroid, neonicotinoids and organophosphates, more preferably roid icides.

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 Euschz‘sz‘us, more preferably Euschistus heros. 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.

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

Preferably P is selected from P3 to P11 #THVDS kit/“fl, #\[(])/N\C\S\\O \g/ fisgo HVC/S H NVQH H\/C/ =O# N\//j H # N\/C/’/ hr” # # N r s, r P7 P8 P9 P10 P11 In one group of compounds P is selected from P4, P5 and P6. ably each R4 is hydrogen.

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

Preferably G1 is oxygen.

Preferably G2 is , Preferably L is a bond.

Preferably Al is R4—, more preferably —CH2-.

Preferably A2 is S, S0 or 80;.

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

Preferably at least two of X, X3 and X6 are , bromo or trifluoromethyl, Preferably X2 is C-Xé; Preferably X1 is chloro, X2 is CH, X3 is chloro, or X1 is chloro, x2 is C-F, X3 is hydrogen, or X1 is fluoro, X2 is C-Cl, X3 is hydrogen, or X1 is chloro, X2 is C-Cl, X3 is hydrogen, or X1 is chloro, X2 is C-Br, X3 is chloro, or X1 is , 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 tn'fluoromethyl, X2 is CH, X3 is trifluoromethyl, or X1 is trifluoromethyl, x2 is C-Cl, X3 is trifluoromethyl, or x1 is trifluoromethyl, 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 trifluoromethyl. Most preferably x1 is chloro, X2 is CH, x3 is chloro.

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

In one group of compounds 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 OK6 and R6 together with R5 forms a - CH=CH-CH=CH— bridge.

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

In one group of nds of formula IV X2 is C-XG, Y1, Y2 and Y3 are C-H, G1 is oxygen, 0.) UI G2 is oxygen, A1 is CH2, A2 is S, SO or 802, 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-Xé, Y1, Y2 and Y3 are C-H, G1 is oxygen, G2 is oxygen, Al is CH2, A2 is S, SO or S02, 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.

In another group of compounds of formula IV X2 is C-XG, Y1, Y2 and Y3 are C-H, G1 is oxygen, G2 is oxygen, Al is CH2, A2 is S, SO or $02, L is a bond, R3 and each R4 is hydrogen, R5 is , bromo, methyl or trifluoro methyl, Y1 is CH, Y2 is CH, and Y3 is CH, X4 is romethyl, X1 is chloro, X2 is CH, X3 is chloro.

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

Compounds of formula IV include at least one chiral centre and may exist as compounds of formula IV* or compounds of formula IV**. (lV*) (|V**) Compounds of formula IV** are more biologically active than compounds of a 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 l: 10, e.g. a substantially 50:50 molar ratio. Preferably the 2O compound of formula I is a racemic mixture ofthe compounds of formula IV** and IV* or is enantiomerically enriched for the compound of formula or e, when the compound of formula IV is an enantiomerically enriched mixture of a 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%. Preferably the compound of formulaI is at least 90% enriched for the compound of formula I.

Where Al or A2 is SO, the compound 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 2012/104331 20 molar ratio. For example, in trans enriched mixtures ofthe compound of formula IV, e.g. when A1 or A2 is SO, the molar proportion ofthe trans nd in the mixture 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) eg when A1 or A2 is SO, the molar proportion of the cis compound in the mixture 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%. The compound of formula IV may be enriched for the trans sulphoxide. Likewise, the nd of formula IV may be enriched for the cis sulphoxide, A selection of preferred compounds of formula IV are nds A1 to A16 shown in Table A below.

Table A: Com ounds of a IV a F3C IN Cl 0 OMGH N\L/<;.A2 (lVa) Cl 0 The symbol * indicates the location ofthe chiral centre No. at * racemic mixture SO (trans) racemic mixture VJ _ FE: racemic mixture 0 _racemic mixture O O (cis) -7 racemic mixture O mmwoooO (trans) I.racemic mixture 0 masforIV** m -10 asforIV** U‘O“OO5:3CLO- o 00m -asforIV**11 o 0[F -l2 asforIV** —13 as for IV** H -14 as for IV** -15 as for IV** _asforIV**l6 IV** refers to a compound of a IV**.

Reference to compounds of the invention also includes reference to salts and N-oxides.

The methods and uses ofthe invention are preferably for controlling and/or preventing ation ofthe n crop by stink bugs, including stink bugs that are resistant to other insecticides, e.g. pyrethroid insecticides. Stinkbugs that are "resistant" to a particular insecticide 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 exposed to the insecticide.

Application is ofthe compounds of the invention is to a crop of soybean plants, the locus thereof or propagation material thereof. Preferably application is to a crop of soybean plants or the locus thereof, more preferably to a crop of n plants. Application may be before infestation or when the pest is present. Application of the nds ofthe ion can be performed according to any ofthe usual modes of application, eg. foliar, drench, soil, in furrow 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 ofapplication. For control of Stinkbugs it can be advantageous to apply the nds ofthe invention with an attractant, particularly when the application is foliar. ugs are often located near to the ground, and application of an attractant may encourage migration up the plant towards the active ient.

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

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

An attractant may be premixed with the compound ofthe invention prior to application, eg. as a readymix or tankmix, or by simultaneous application or sequential application to the plant. Suitable rates of tants are for example 0.02kg/ha-3kg/ha.

The compounds ofthe invention are preferably used for pest control on soybean at 1:500 g/ha, preferably 10—70gi’ha.

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

The compounds ofthe 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 produce biologically active compounds that control infestation by plant pests.

In a fiirther preferred embodiment, transgenic plants and plant ars obtained by genetic ering methods, if riate 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 ble or in use are treated according to the invention. Plant cultivars are understood as meaning plants having novel ties ("traits") which have been obtained by conventional ng, by mutagenesis or by recombinant DNA techniques.

These can be cultivars, bio- or genotypes. Depending on the plant species or plant cultivars, their location and growth ions (soils, climate, vegetation period, diet), the treatment according to the invention may also result in dditive "synergistic") efiects.

Thus, for example, reduced application rates and/or a widening ofthe activity spectrum and/or an se in the activity of the substances and compositions which can be used according to the invention, better plant growth, increased tolerance to high or low temperatures, increased tolerance to drought or to water or soil salt content, increased ng 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 of the 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 invention include all plants which, by virtue ofthe genetic modification, received c 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 drought or to water or soil salt content, increased flowering performance, easier harvesting, accelerated maturation, higher harvest , higher y and/or a higher ional value ofthe ted products, better storage stability and/or processability of the 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 s, and also increased tolerance of the plants to certain herbicidally active compounds.

Traits that are emphasized in particular are the increased defence of the plants t insects, arachnids, nematodes and slugs and snails by virtue of toxins formed in the plants, in particular those formed in the plants by the genetic material from Bacillus thuringiensis (for example by the genes CrylA(a), CrylA(b), CrylA(a), CryllA, CrylllA, CrleIBZ, Cry9c, CryZAb, Cry3Bb and CrylF and also combinations thereof) (referred to herein as "Bt "). Traits that are also particularly emphasized are the increased defence of the plants against fungi, bacteria and viruses by ic acquired resistance (SAR), systemin, phytoalexins, elicitors and ance 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 or phosphinotricin (for example the "PAT" gene). The genes which impart the desired traits in question can also be present in combination with one r in the transgenic plants. es of "Bt plants" are soya bean varieties which are sold under the trade names YIELD GARD(®) Examples of herbicide-tolerant plants which may be mentioned are soya bean varieties which are sold under the trade names Roundup Ready(®) (tolerance to sate), Liberty ) (tolerance to phosphinotricin), IMT(®) (tolerance to imidazolinones) and STS(®) (tolerance to sulphonylureas).

WO 20121104331 23 Herbicide-resistant plants (plants bred in a conventional manner for herbicide tolerance) which may be mentioned include the varieties sold under the name Clearfield(®) (for example .

Ofparticular interest are soybean plants carrying trains conferring resistance to 2.4D (eg.

Enlist®), glyphosate (e.g. Roundup Ready®, Roundup Ready 2 Yield®), sulfonylurea (cg, STS®), glufosinate (eg. y Link®, lgnite®), Dicamba (Monsanto) HPPD tolerance (e.g. isoxaflutole herbicide) (Bayer CropScience, Syngenta). Double or triple stack in soybean plants of any ofthe traits described here are also of st, 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 st.

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

The compounds of the invention may be used on soybean to l, for example, Elasmopalpus Zignosellus, Diloboderus abderus, Diabrott‘ca speciosa, Sternechus subsignafus, idae, Agratis ypsz'lon, Julus ssp. , Amicarsz’a gemmatalz's, Megascelis ssp. , m’rermes ssp.

Gr32110tat‘pidae, Nezara viridula, Piezoa’orus spp. , Acrostemum spp. , Neomegalotomzzs Spp. , Cerotoma trifurcata, Papilliajaponica, Edessa spp. , Liogenysfiiscus, Euchz‘stus heros, stalk borer, Scaptocoris castcmea, phyllophaga spp. , Pseudoplusz’a includens, Spodoptera Spp., Bemz‘sz’a Iabacz‘, Agriotes spp., preferably Diloboa’erus abderus, Diabrotz'ca speciosa, Nezara vz‘rz‘dula, Piezodorus Spp. , Acrosternum sppl , Ceroz‘oma Irifiircaz‘a, z‘ajapom'ca, Euchistus heros, phyllophaga spp. , Agrioles spp..

The compounds ofthe ion are preferably used on n to control stinkbugs, Nezara spp. (cg. Nezara viridula, Nezara antennata, Nezara hilare), orus spp. (eg. Piezodorus guildz'niz’), Acrostemum spp. Euchistus spp. (eg. Euchz’stus heros, Euschz'stus servus), Halyomorpha halys, Plaufia crossol‘a, Rz'ptortus clavatus, Rhopalus msculatus, Antestz‘opsz's lus, Dichelops spp. (eg. Dichelopsfirrcatus, Dichelops melacanthus), Emygaster Spp. (eg. Eurygaster intergriceps, Emygaster maura), Oebalus Spp. (eg. Oebalus mexz’cana, Oebalus poecz'lus, Oebalus pugnase, Scotz'nophara spp. (e.g. Scott‘nophara , Scofinopham ata). Preferred targets include Antestiopsz's orbitalus, Dichelopsfurcaz‘us, ops melacanthus, Euchistus heros, Euschz’stus servus, Nezara viridula, Nezara hilare, Piezodorus guildz‘nii, orpha halys. In one ment the stinkbug target is Nezara viridula, Piezodorus 519p, Acrosternum Spp, Euchz’stus heros. The compounds ofthe invention are particularly ive against Euschistus and in particular Euchz'srus herosr stus and in particular Euchz‘sz‘us heros are the preferred targets.

In order to apply a compounds ofthe invention as an insecticide, acaricide, cide or molluscicide to a pest, a locus of pest, or to a plant susceptible to attack by a pest, compounds ofthe invention is usually formulated into a composition which includes, in addition to the compound ofthe invention, a suitable inert diluent or carrier and, optionally, a surface active agent (SFA). SFAs are chemicals which are able to modify the properties of an ace (for example, liquid/solid, /air or liquid/liquid interfaces) by lowering the interfacial tension and thereby leading to changes in other ties (for e sion, emulsification and wetting). It is preferred that all compositions (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 of the invention. The composition is generally used for the control of pests such that a compound of the 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 of the invention 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 sing a compound of the invention can be chosen from a number of formulation types, including le powders (DP), soluble powders (SP), water soluble granules (SG), water dispersible granules (WG), wettable powders (WP), granules (GR) (slow or fast release), e 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 (130)), micro-emulsions (ME), suspension concentrates (SC), aerosols, fogging/smoke formulations, capsule suspensions (CS) and seed treatment formulations. The formulation type chosen in any instance will depend upon the particular e envisaged and the al, chemical and ical properties ofthe compound ofthe invention.

Dustable powders (DP) may be prepared by mixing a compound of the 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, sulfiir, lime, flours, talc and other organic and inorganic solid carriers) and mechanically grinding the mixture to a fine powder.

Soluble powders (SP) may be prepared by mixing a nd of the invention with one or more water—soluble inorganic salts (such as sodium bicarbonate, sodium carbonate or ium sulfate) or one or more water-soluble organic solids (such as a ccharide) and, optionally, one or more wetting agents, one or more sing agents or a mixture of said agents to improve water dispersibility/solubiliw. The mixture is then ground to a fine powder. Similar compositions may also be granulated to form water soluble granules (SG).

Wettable powders (WP) may be ed 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 tate 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 of the ion and one or more powdered solid diluents or carriers, or from pre-fonned blank granules by ing a compound ofthe invention (or a solution thereof, in a suitable agent) in a porous granular al (such as pumice, lgite clays, fuller’s earth, kieselguhr, diatomaceous earths or ground corn cobs) or by adsorbing a compound ofthe invention (or a solution thereof, in a suitable agent) on to a hard wo 2012;104331 25 core material (such as sands, silicates, mineral carbonates, sulfates 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, ethers, 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 ketone, alcohol or glycol ether. These ons may contain a surface active agent (for example to improve water dilution or prevent llization in a spray tank). fiable concentrates (BC) or oil—in—water emulsions (EW) may be ed by dissolving a compound ofthe invention in an organic solvent (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 alkylnaphthalenes, exemplified by SOLVESSO 100, SOLVESSO 150 and SOLVESSO 200; SOLVESSO is a Registered Trade Mark), ketones (such as cyclohexanone or methylcyclohexanone) and alcohols (such as benzyl alcohol, furfiiryl alcohol or butanol), N—alkylpyrrolidones (such as N-methylpyrrolidone or N- octylpyrrolidone), dirnethyl amides of fatty acids (such as C8-C10 fatty acid dimethylamide) and chlorinated hydrocarbons. An EC product may spontaneously emulsify on on to water, to produce an on with sufficient 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. le solvents for use in EWs include vegetable oils, chlorinated arbons (such as benzenes), aromatic solvents (such as alkylbenzenes or aphthalenes) and other appropriate organic solvents which have a low solubility in water.

Microemulsions (ME) may be prepared by mixing water with a blend ofone or more solvents with one or more SFAs, to e spontaneously a thermodynamically stable isotropic liquid formulation. A compound ofthe invention is present initially in either the water or the solvent/SFA blend. Suitable solvents for use in MES include those 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 t may be determined by conductivity measurements) and may be suitable for mixing water-soluble and oil— soluble pesticides in the same ation. An MB is suitable for dilution into water, either remaining as a microemulsion or forming a tional oil-in-water emulsion.

Suspension concentrates (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 g the solid compound ofthe invention in a suitable medium, optionally with one or more dispersing , to produce a fine particle suspension of the compound. One or more wetting agents W0 2012(104331 26 may be included in the composition and a suspending agent may be included to reduce the rate at which the particles settle. Alternatively, a nd of the invention may be dry milled and added to water, containing agents hereinbefore described, to produce the desired end product.

Aerosol formulations comprise a compound ofthe invention and a suitable propellant (for example n-butane). A compound ofthe invention may also be dissolved or sed 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 r to the preparation of EW formulations but with an onal polymerization stage such that an aqueous dispersion of oil droplets is obtained, in which each oil droplet is ulated by a polymeric shell and contains a compound ofthe invention and, optionally, a carrier or diluent therefor. The polymeric shell may be produced by either an interfacial polycondensation reaction or by a coacervation procedure. The compositions may provide for controlled release of the compound of the invention and they may be used for seed treatment. A compound ofthe ion may also be formulated in a biodegradable polymeric matrix to provide a slow, controlled release of the compound.

A composition may include one or more additives to improve the biological mance of the composition (for example by improving wetting, retention or distribution on es; ance to rain on treated surfaces; or uptake or mobility of a compound of the invention). Such additives include surface active agents, spray additives based on oils, for example certain l 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 nd of the invention).

A compound ofthe ion 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 soluble 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 preparations of DS, SS, WS, FS and LS compositions are very similar to those of, respectively, DP, SP, WP, SC and DC compositions described above. Compositions for treating seed may include an agent for assisting the adhesion of the composition to the seed (for example a mineral oil or a rming barrier).

Wetting agents, dispersing agents and emulsifying agents may be e SFAs of the cationic, anionic, amphoteric or non—ionic type.

Suitable SFAs ofthe cationic type e quaternary ammonium compounds (for example rimethyl ammonium bromide), imidazolines and amine salts.

Suitable c SFAs include alkali metals salts of fatty acids, salts of aliphatic monoesters of sulfuric acid (for example sodium lauryl sulfate), salts of sulfonated aromatic compounds (for example sodium dodecylbenzenesulfonate, m dodecylbenzenesulfonate, butylnaphthalene sulfonate and mixtures of sodium di-z'sopropyl- and tri-isopropyl-naphthalene sulfonates), ether sulfates, alcohol wo 2012/104331 27 2012/051638 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 orus pentoxide (predominately di—esters), for example the reaction between lauryl alcohol and tetraphosphon'c acid; additionally these products may U- be ethoxylated), sulfosuccinamates, paraffin or olefine sulfonates, taurates and lignosulfonates. le SFAs ofthe amphoteric type include betaines, propionates and glycinates.

Suitable SFAs of the non-ionic type include condensation products of alkylene oxides, such as ethylene oxide, propylene oxide, butylene oxide or mixtures f, with fatty alcohols (such as oleyl alcohol or cetyl alcohol) or with alkylphenols (such as cctylphenol, 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.

Suitable suspending agents include hydrophilic 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 applying pesticidal compounds. For e, it may be applied, formulated or unformulated, to the pests or to a locus of the pests (such as a habitat of the pests, or a growing plant liable to infestation by the pests) or to any part of the plant, including the foliage, stems, es 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 onic culture systems), directly or it may be d on, dusted on, applied by dipping, applied as a cream or paste formulation, applied as a vapor or applied through distribution or incorporation of a composition (such as a granular composition or a ition packed in a 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 ques 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 of a 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 often 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 d by conventional spray equipment. Such aqueous ations may contain varying amounts of a compound ofthe invention (for example 0.0001 to 10%, by ) depending upon the purpose for which they are to be used. wo 04331 28 A compound ofthe ion 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 of the invention.

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

The compositions of this invention may contain other compounds having biological activity, for example micronutrients or compounds having fungicidal activity or which possess plant growth regulating, herbicidal, icidal, nematicidal or acaricidal ty.

The compound ofthe invention may be the sole active ient ofthe composition or it be admixed with one or more additional active ingredients such as a pesticide, fungicide, synergist, herbicide or plant growth regulator where appropriate. An additional active ingredient may: e a composition having a broader spectrum of activity or sed persistence at a locus; synergize the ty or ment the ty (for example by increasing the speed of effect or ming repellency) ofthe compound ofthe invention; or help to overcome or prevent the development of ance to individual components. The particular additional active ingredient will depend upon the intended y ofthe composition. Examples of suitable pesticides include the following: a) a roid including those selected from the group consisting of pennethrin, cypennethrin, fenvalerate, esfenvalerate, deltamethrin, cyhalothrin, lambda-cyhalothrin, gammacyhalothrin , bifenthrin, fenpropathrin, cyfluthrin (including beta cyfluthrin), tefluthnn, ethofenprox, natural pyrethrin, tetramethrin, S-bioallethrin, thrin, prallethrin and -benzylfi1rylmethy1~(l_3_)-(lR,3 S)—2,2—dimethyl— 3 -(2—oxothiolan—3 —ylidenemethyl)cyclopropane carboxylate; b) an organophosphate including those selected from the group consisting of fos, acephate, methyl parathion, azinphos—methyl, demeton-s-methyl, heptenophos, thiometon, fenamiphos, monocrotophos, profenofos, triazophos, methamidophos, dimethoate, amidon, malathion, yrifos, phosalone, terbufos, fensulfothion, fonofos, phorate, phoxim, pirimiphos—methyl, pirimiphos-ethyl, fenitrothion, fosthiazate and diazinon; c) a carbamate including those selected from the group consisting ofpiiimicarb, triazamate, cloethocarb, uran, furathiocarb, ethiofencarb, aldicarb, thiofurox, carbosulfan, bendiocarb, fenobucarb, propoxur, methomyl, thiodicarb and oxamyl; d) a benzoyl urea including those selected from the group consisting of diflubenzuron, triflumuron, hexaflumuron, flufenoxuron, lufenuron and chlorfluazuron; e) an organic tin compound selected from the group consisting 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; wo 20121104331 29 h) an chlorine compound including those ed from the group consisting of lfan (in particular alpha-endosulfan), benzene hexachloride, DDT, chlordane and dieldrin; i) an amidine including those selected from the group consisting of chlordimeform and amitraz; j) a nt agent including those selected 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, furan, thiarnethoxam, clothianidin, zine and flonicamid; 1) a diacylhydrazine including those selected from the group consisting oftebufenozide, chromafenozide and methoxyfenozide; m) a diphenyl ether including those selected from the group consisting 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 tetronic acid compound including esifen; r) a diamide including those selected from the group consisting of flubendiamide, ntraniliprole (Rynaxypyr®) and cyantraniliprole; s) sulfoxaflor; t) metaflumizone; u) fipronil and ethiprole; v) pyrifluqinazon; W) buprofezin; X) thiuron; y) 4-[(6-Chloro—pyridin-3 -ylmethyl)-(2,2-difluoro-ethyl)—amino]-5H—furanone (DE 102006015467); 2) flupyradifurone. aa) CAS: —17-7 (WO 2006129714; W02011/147953; W02011/147952) ab) CAS: 269148 (WO 2007020986) In addition to the major chemical classes of ide listed above, other pesticides having particular targets may be employed in the composition, if appropriate for the intended utility ofthe composition. For instance, selective insecticides for particular crops, for example stemborer specific insecticides (such as cartap) or hopper c insecticides (such as buprofezin) for use in rice may be employed. Alternatively insecticides or acaricides specific for particular insect s/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; W0 2012/104331 30 acaricides, such as bromopropylate or chlorobenzilate; or growth tors, such as hydramethylnon, cyromazine, methoprene, chlorfluazuron or diflubenzuron).

Examples of fimgicidal compounds which may be included in the composition of the invention are (E)—N—methyl-2~[2-(2,5-dimethylphenoxymethyl)phenyl]methoxy-iminoacetamide (SSF-129), 4-bromocyano-N,N-dimethyltrifluoromethylbenzimidazolesulfonamide, OL-[N-(3 -chloro-2,6- -xylyl)meth0xyacetamido] -y—butyrolactone, 4—chlorocyano-N,N—dimethyl-5 —p—tolylimidazole- l - sulfonamide l6, cyamidazosulfamid), 3-5 -dichloro-N-(3 -chloro—l-ethyl—l—methyl—2-oxopropyl)— 4-methy1benzamide (RH-7281, zoxamide), N—allyl—4,5,-dimethyltrlrnethylsilylthiophene carboxamide (MON65500), N-(l ~cyano-l,2-dimethylpropyl)(2,4-dichlorophenoxy)propionamide (AC3 82042), ethoxy—S ~pyridyl)-cyclopropane carboxamide, acibenzolar (CGA245704), alanycarb, aldimorph, ine, azaconazole, azoxystrobin, benalaxyl, benomyl, biloxazol, bitertanol, blasticidin S, bromuconazole, bupirimate, captafol, captan, carbendazim, carbendazim chlorhydrate, carboxin, carpropamid, carvone, 96, 97, ethionate, chlorothalonil, chlorozolinate, clozylacon, copper containing compounds such as copper oxychloride, copper oxyquinolate, copper sulfate, copper tallate and ux mixture, cymoxanil, cyproconazole, cyprodinil, debacarb, di-Z-pyridyl disulfide l,l‘~dioxide, dichlofluanid, ezine, dicloran, diethofencarb, difenoconazole, difenzoquat, diflumetorim, -z's0—propyl-S—benzyl thiophosphate, dimefluazole, dimetconazole, dimethomorph, dimethirimol, diniconazole, dinocap, dithianon, dodecyl dimethyl ammonium chloride, dodemorph, dodine, doguadine, edifenphos, epoxiconazole, ethirimol, ethyl-(Z)-N-benzyl-N-([methyl(methyl-thioethy1ideneaminooxycarbonyl)amino]thio)-B—a1aninate, etridiazole, famoxadone, done (RPA407213), fenarimol, fenbuconazole, fenfuram, fenhexamid (KBR273 8), fenpiclonil, fenpropidin, fenpropimorph, fentin acetate, fentin hydroxide, ferbam, ferimzone, fluazinam, onil, ver, fluoroimide, fluquinconazole, flusilazole, flutolanil, flutn'afol, folpet, fuberidazole, furalaxyl, tpyr, guazatine, hexaconazole, yisoxazole, zole, imazalil, imibenconazole, iminoctadine, iminoctadine triacetate, ipconazole, iprobenfos, iprodione, iprovalicarb (SZX0722), isopropanyl butyl carbamate, isoprothiolane, kasugamycin, im-methyl, LY186054, LY211795, LY248908, mancozeb, maneb, mefenoxam, mepanipyrim, mepronil, metalaxyl, metconazole, metiram, metiram-zinc, metominostrobin, myclobutanil, neoasozin, nickel dimethyldithiocarbamate, nitrothal-z‘sopropyl, nuarimol, e, mercury compounds, oxadixyl, oxasulfuron, oxolinic acid, oxpoconazole, oxycarboxin, pefurazoate, penconazole, pencycuron, phenazin oxide, yl-Al, phosphorus acids, phthalide, picoxystrobin 3), poly- oxin D, polyram, probenazole, prochloraz, procymidone, propamocarb, propiconazole, propineb, propionic acid, phos, pyrifenox, thanil, pyroquilon, pyroxyfur, pyirolnitrin, quaternary ammonium compounds, quinomethionate, quinoxyfen, quintozene, sipconazole (F-155), sodium La.) UI pentachlorophenate, spiroxamine, streptomycin, sulfur, tebuconazole, tecloftalam, tecnazene, tetraconazole, thiabendazole, thifluzamid, 2-(thiocyanomethylthio)benzothiazole, thiophanate—methyl, thiram, timibenconazole, tolclofos—methyl, tolylfluanid, triadimefon, triadimenol, triazbutil, triazoxide, tricyclazole, tridemorph, trifloxystrobin 9202), triforine, triflumizole, triticonazole, wo 2012;104331 31 validamycin A, vapam, vinclozolin, zineb, ziram; N-[9-(dichloromethylene)-1,2,3,4-tetrahydro-l,4- methanonaphthalen-S —yl] (difluoromethyl)-l -methyl-lH-pyrazolecarboxamide [107295 7-7 1- l], 1—methyl-3 romethyl-1H-pyrazole—4-carboxylic acid (2-dichloromethyleneethyl—1-methy1- indanyl)-amide, and yldifluoromethyl-4H-pyrazole—4—carboxylic acid [2-(2,4-dichlorophenyl )methoxymethyl -ethyl] -amide.

Preferred additional pesticidally active ingredients are those selected from otinoids, pyrethroids, strobilurins, triazoles and carboxamides (SDHI inhibitors). Pyrethroids are of st 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 roids, in parrticular lambda—cyhalothrin, exhibit synergistic l of stinkbugs (according to the Colby a), in particular Euschz'stus, eg. Euschz'sz‘us heros.

In a r aspect of the invention there is provided a method comprising applying to a crop of soybean plants, the locus thereof, or propagation material thereof, a combination of a compound a compound ofthe invention and lambda cyhalothrin 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 of formula I. In r embodiment the compound is a 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 compound is a compound from Table A.

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

Examples of suitable synergists for use in the itions 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 required.

An example of a rice selective herbicide 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 themselves 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 ient as a suspension (using a preparation analogous to that of an SC) but dispersing the liquid active ient as an emulsion (using a preparation analogous to that of an EW). The resultant composition is a suspoemulsion (SE) formulation.

Unless otherwise stated the weight ratio ofthe compound of I, II, III or IV with an additional active ingredient may lly be between 1000 : l and l : 1000. In other embodiments that weight ratio ofA to B may be between 500 : l to l : 500, for e between 100 : l to l : 100, for example wo 2012/104331 32 between 1 : 50 to 50: l, for e 1 :20 to 20 : 1, for example 1:10 to 10:1, for example 1:5 to 5:1, for example 1:1.

Compositions of the invention include those prepared by ing prior to application, eg. as a readymix or tankmix, or by simultaneous application or sequential ation to the plant.

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

Figures Figure 1 shows the results of a field trial to investigate control of Euschz‘sz‘us heros on soybeans with the compound offormula Ix ic es of enantiomers) i The X axis indicates 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 ted in Example 1.

Figure 2 shows the results of a field trial to investigate control ofEuschistus heros on soybeans with the compound of formula Ix (racemic mixtures of enantiomers). The X axis indicates grams of active ingredient per e 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 tes % control. Bars 1- 4 show 2O control after 2, 5, 12 and 16 days afier application respectively. 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 of enantiomers) and formula Iy (racemix mixture of enantiomers). The X axis indicates grams of active ingredient per hectare of (a) thiamethoxam + lambda cyhalothrin, (b) methamidophos, (c) formula Iy at 60 g/ha, (d) formula Iy at 120 g/ha, (e) formula Ix at 60 g/ha, (f) a 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. mental details are indicated in Example 3.

Examples Example 1 Field trial: l ofEuschz‘stus heros on soybeans, Application was Foliar application using a boomsprayer. The spray volume was 200 l/ha. Each plot size was 60m2. The soybean was at grOWth stage bbch 72. The compound offormula Ix was d as an EC formulation. The beta-cyfluthrin + imidacloprid (9.4 g/ha and 75 g/ha respectively) /thiamethoxam + -cyhalothrin (21,2 g/ha and 28.2 g/ha respectively) were applied as sion concentrate formulations. The results (% control of adults) are shown in Figure 1 and represent the average of 3 replicates.

WO 20121104331 33 Example 2 Field trial: control ofEuschz'sms heros on soybeans. Application was Foliar ation using a boomsprayer. The spray volume was 200 l/ha. Each plot size was 108m2. The soybean was at growth stage bbch 72. The compound 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 formulations. The s (% control of adults) are shown in Figure 2 and represent the average of 3 replicates.

Example 3 Field trial: control ofEuschz'stus heros on soybeans. Application was Foliar application using a boomsprayer. The spray volume was 200 Mm. Each plot size was 108m2. The soybean 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 metharnidophos was d as a soluble concentrate formulation. The results (% l of adults) are shown in Figure 3 and represent the average of 3 replicates.

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

After drying, 2 n seeds are added and plants are ed with 10 N—2 nymphs of the neotropical brown stink bug stus heros in plastic 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 efi‘ects. The results are shown in Tables El and E2 below. The data is an average oftwo replicates.

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

Table El Rate / ppm Compound 1 Compound 2 Compound 3 Compound 4 (comparative (comparative example) CI \63 O 0 \CNYO (3) (4) 0 Compounds 1-4 are disclosed in W02009/080250.

Table E2 Rate / ppm Compound 5 Compound 6 Compound 7 Compound 8 Compound 9 (comparative (comparative rative example) example) example) _--_-— -___—— WO 20121104331 35 Compounds 5-9 are compounds from W02005/085216 73 1512) and W02009/002809.

References Corréa—Perreira, B. S.; Panizzi, A. R., Percevejos da soja e seu manejo, Londrina: Embrapa-CNPSo, 1999, 45 (Circular Técnica, 24), Galileo, M.H.M., Heinrichs E.A., ao foliar em plantas de soja (glycine max (1.) merrill) resultantes da acao de Piezodorus guildiniz’ ood, 1837) (Hemz'ptera pentatomidae), em diferentes niveis e épocas de infestacao. An. Soc. Entomol. Brasil, 1978, 7, 85-98.

Panizzi, A. R, Slansky junior, F. Review of phytophagous pentatomids (Hemiptera pentatomz‘dae) associated 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 Euschz‘stus heros em armadilhas s com feromonio sexual, 2003, Comunicado Técnico 93. Brasilia, DF.

Sosa-Gomez, D.R., Silva, 1, Da, Lopes, I. O. N., Corso, 1., Almeida, A.M. R. Almeida, , g. c.p.m.; baur, m. insecticide susceptibility of ’stus heros (Heteroptera pentatomz‘dae) in Brazil, Journal of Economic logy, 2009, 102(3), 1209-1216.

Todd, J. W., Herzog, D. 0, Sampling hagous pentatomz‘dae on soybean. in: Kogan, M., Herzog, D, C. (ed). Sampling methods in soybean entomology, New York: Springer, 1980, 43 8—478.

Claims (1)

What is claimed

1. A method comprising applying to a crop of soybean plants, the locus thereof, or propagation material thereof, a compound of formula III 5 (III) wherein cycle A is Ala or A2a #2 \ / #1 #2 \ / #1 A§—A4 A‘f—A5 A1 3 A22: 10 wherein A3, A4, A4. and A5. are independently OH, or nitrogen and n #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 #3 / #3 / #3 / # # 1 # 1 1 B1 82 BS #2 O #3>E———_-Z #2#91(3)40 #2 3 VG N\ 3 N\ #1 #1 #1 B4 BS B6 wherein #1 indicates the bond to cycle A, #2 indicates the bond to R7 and #3 indicates the 15 bond to cycle C; cycle C is phenyl; R5 is chloro, bromo, CF3 or methyl; R7 is chlorodifluoromethyl or trifluoromethyl; each R8 is ndently bromo, , fluoro or trifluoromethyl; 20 p is 2 or 3; and X is selected from P3 to P11 H