US 20140148471 A1 (19) United States (12) Patent Application Publication (10) Pub. No.: US 2014/0148471 A1 BRETSCHINEDER et al. (43) Pub. Date: May 29, 2014

(54) HETEROCYCLIC COMPOUNDSAS (60) Provisional application No. 61/359,058, filed on Jun. PESTICIDES 28, 2010. (71) Applicant: Bayer CropScience AG, Monheim (DE) (30) Foreign Application Priority Data (72) Inventors: Thomas BRETSCHNEIDER, Lohmar Jun. 28, 2010 (EP) ...... 10167453.9 (DE); Reiner FISCHER, Monheim Mar. 24, 2011 (EP) ...... 11159576.5 (DE); Martin FULEIN, Dusseldorf (DE); Peter JESCHKE, Bergisch Gladbach (DE); Adeline KOHLER, Publication Classification Wuppertal (DE); Joachim KLUTH, (51) Int. Cl. Langenfeld (DE); Friedrich August AOIN 43/56 (2006.01) MUHLTHAU, Bad Sodenam Taunus AOIN 413/40 (2006.01) (DE); Yoshitaka SATO, Ibaraki (JP): (52) U.S. Cl. Arnd VOERSTE, Koln (DE); Eiichi CPC ...... A0IN 43/56 (2013.01); A0IN 43/40 SHIMOJO, Oyama-shi (JP) (2013.01) (73) Assignee: Bayer CropScience AG, Monheim (DE) USPC ...... 514/256; 544/322:546/256; 514/333; 546/270.4: 514/341 (21) Appl. No.: 14/169,849 (57) ABSTRACT (22) Filed: Jan. 31, 2014 The present application relates to novel heterocyclic com Related U.S. Application Data pounds, to the use thereof for controlling animal pests, which (62) Division of application No. 13/171,030, filed on Jun. include arthropods and especially insects, and to processes 28, 2011, now Pat. No. 8,686,004. for preparing the novel compounds. US 2014/0148471 A1 May 29, 2014

HETEROCYCLIC COMPOUNDSAS in which the arrow in each case marks the bond to the adjacent PESTICIDES r19,Fois) R" in the case of the heterocycles (A) and (D) is 0001. The present application relates to novel heterocyclic hydrogen, halogen, cyano, alkyl, alkoxy, amino, alky compounds, to processes for preparation thereof and to the lamino, dialkylamino, alkylthio or haloalkyl and use thereof for controlling animal pests, which include arthro I0010) R' in the case of heterocycle (C) is hydrogen, alkyl pods and especially insects, and also to intermediates for or haloalkyl, preparation of the heterocyclic compounds. 0011 B is hydrogen, halogen, cyano, nitro, alkyl, 0002 Particular thiazolyl, thiadiazolyl and pyrazolyl cycloalkyl, haloalkyl, amino, alkylamino, dialkylamino, compounds have already become known as insecticidally alkylthio or alkoxy and active ingredients (cf. WO 2010/006713 A2). (0012) G is optionally substituted heterocyclyl, optionally 0003 Modern crop protection compositions have to meet substituted heteroaryl or optionally substituted aryland many demands, for example in relation to the level, duration I0013 G' is a radical from the group of and breadth of their action and possible use. Questions of toxicity and of combinability with other active ingredients or (E) formulation auxiliaries play a role, as does the question of the X (O) expense that the synthesis of an active ingredient requires. In addition, resistances can occur. For all these reasons, the N1Ns. search for novel crop protection compositions cannot be con sidered to be complete, and there is a constant need for novel compounds having properties which, compared to the known (F) compounds, are improved at least in relation to individual aspects. 0004. It was an object of the present invention to provide compounds which widen the spectrum of the pesticides in various respects. 0005. This object, and further objects which are not stated (G) explicitly but can be discerned or derived from the connec tions discussed herein, are achieved by novel compounds of the formula (I) (I) 4 1N GS - (H) Al-- y N4 in which I0006 A' and A are each independently hydrogen, halo (I) gen, cyano, nitro, alkyl, cycloalkyl or alkoxy, 0007 G' is N or C-A' and 0008 G is a radical from the group of (A) (J)

(B) (K) (O) (C) 1NNS 1 N f and L (O), X (L)

(D) (M) US 2014/0148471 A1 May 29, 2014

0014) and in the case of the heterocycles (A), (B) and (0024) R' is hydrogen or alkyl, (C) is also the radical I0025I RandR may also form, together with the nitrogen atoms to which they are bonded, a Saturated or unsaturated and optionally substituted 4- to 8-membered ring which (N) may contain at least one further heteroatom from the group of Sulphur, oxygen (where oxygen atoms must not be immediately adjacent) and nitrogen and/or at least one carbonyl group, I0026 Rand R7 in the radical (E) may also form, together with the N—S(O), group to which they are bonded, a 0015 in which the arrow in each case marks the bond to saturated or unsaturated and optionally Substituted 4- to G, 8-membered ring which may contain one or more further 0016 X is oxygen or Sulphur, heteroatoms from the group of Sulphur, oxygen (where 0017 n is 1 or 2, oxygen atoms must not be immediately adjacent) and 0018 R is a radical from the group of hydrogen, alkyl, nitrogen and/or at least one carbonyl group, haloalkyl, cyanoalkyl, alkoxy, haloalkoxy, alkenyl, alkynyl (0027 R and R7 may also form, together with the N–S and alkoxyalkyl, in each case optionally halogen-Substi (O) group to which they are bonded, a Saturated or unsat tuted alkylcarbonyl and alkylsulphonyl, in each case urated and optionally substituted 4- to 8-membered ring optionally halogen-substituted alkoxycarbonyl, in each which may contain one or more further heteroatoms from case optionally halogen-, alkyl-, alkoxy-, haloalkyl- and the group of Sulphur, oxygen (where oxygen atoms must cyano-Substituted cycloalkylcarbonyl, or a cation, for not be immediately adjacent) and nitrogen and/or at least example a mono- or divalent metal ion or an optionally one carbonyl group, alkyl- or arylalkyl-substituted ammonium ion, 10028. RandR may also form, together with the nitrogen 0019 Rand Rare each independently a radical from the atom to which they are bonded, a saturated or unsaturated group of in each case optionally Substituted alkyl, alkenyl and optionally substituted 4- to 8-membered ring which and alkynyl, in each case optionally substituted cycloalkyl, may contain one or more further heteroatoms from the cycloalkylalkyl and cycloalkenyl, in which the rings may group of Sulphur, oxygen (where oxygenatoms must not be contain at least one heteroatom from the group of Sulphur, immediately adjacent) and nitrogen and/or at least one oxygen (where oxygen atoms must not be immediately carbonyl group, adjacent) and nitrogen, in each case optionally substituted 0029 L is oxygen or sulphur, aryl, heteroaryl, arylalkyl and heteroarylalkyl and an I0030 R and R'' are each independently an in each case optionally Substituted amino group, optionally Substituted radical from the group of alkyl, alk 0020 R and R may also form, together with the N–S enyl, alkynyl, alkoxy, alkenyloxy, alkynyloxy, cycloalkyl, (O) group to which they are bonded, a saturated or unsat cycloalkyloxy, cycloalkenyloxy, cycloalkylalkoxy, alky urated and optionally substituted 4- to 8-membered ring lthio, alkenylthio, phenoxy, phenylthio, benzyloxy, ben which may contain one or more further heteroatoms from Zylthio, heteroaryloxy, heteroarylthio, heteroarylalkoxy the group of Sulphur, oxygen (where oxygen atoms must and heteroarylalkylthio. not be immediately adjacent) and nitrogen and/or at least I0031) R' and R' may also form, together with the phos one carbonyl group, phorus atom to which they are bonded, a saturated or unsat I0021) R' is a radical from the group of in each case option urated and optionally substituted 5- to 7-membered ring ally substituted alkyl, alkoxy, alkenyl and alkynyl, in each which may contain one or two heteroatoms from the group case optionally Substituted cycloalkyl, cycloalkylalkyl and of oxygen (where oxygen atoms must not be immediately cycloalkenyl, in which the rings may contain at least one adjacent) and Sulphur, and heteroatom from the group of Sulphur, oxygen (where oxy 10032) R'' and R'' are each independently an in each case genatoms must not be immediately adjacent) and nitrogen, optionally Substituted radical from the group of alkyl, alk in each case optionally Substituted aryl, heteroaryl, aryla enyl, alkynyl, phenyl and phenylalkyl, lkyl and heteroarylalkyl and an optionally substituted 0033 Y' and Y are each independently C=O or S(O), amino group, 0034 m is 1, 2, 3 or 4, I0022 R is a radical from the group of hydrogen, in each I0035) R' is a radical from the group of hydrogen, alkyl, case optionally substituted alkyl, alkoxy, alkenyl and alky haloalkyl, cyano, cyanoalkyl, hydroxyalkyl, hydroxyl, nyl, in each case optionally Substituted cycloalkyl, alkoxy, alkoxyalkyl, alkylthioalkyl, alkenyl, haloalkenyl, cycloalkylalkyl and cycloalkenyl, in which the rings may cyanoalkenyl, alkynyl, haloalkynyl, cyanoalkynyl, alkyl contain at least one heteroatom from the group of Sulphur, carbonyl and alkoxycarbonyl, oxygen (where oxygen atoms must not be immediately 10036) Y is a radical from the group of alkoxy, haloalkoxy, adjacent) and nitrogen, in each case optionally substituted alkylthio, haloalkylthio and NR'R' where R'' and R' aryl, heteroaryl, arylalkyl and heteroarylalkyl and an are each independently radicals from the group of hydro optionally Substituted amino group, gen, alkyl, cycloalkyl, cycloalkylalkyl, haloalkyl, cyano, 0023 R and R may also form, together with the N- C cyanoalkyl, hydroxyl, alkoxy, haloalkoxy, hydroxyalkyl, (X) group to which they are bonded, a saturated or unsat alkoxyalkyl, alkylthioalkyl, alkenyl, haloalkenyl, urated and optionally substituted 4- to 8-membered ring cyanoalkenyl, alkynyl, haloalkynyl, cyanoalkynyl, alkyl which may contain one or more further heteroatoms from carbonylandalkoxycarbonyl, or R'' and R' together with the group of Sulphur, oxygen (where oxygen atoms must the nitrogen atom to which they are bonded may form an not be immediately adjacent) and nitrogen and/or at least optionally substituted saturated or unsaturated 5- to one carbonyl group, 8-membered ring optionally containing heteroatoms, US 2014/0148471 A1 May 29, 2014 3

I0037 G and G' may additionally also together form an -continued optionally substituted heterocycle which optionally con R2 tains one or more further heteroatoms from the group of M Oxygen, nitrogen and Sulphur, H-N He and salts and N-oxides of the compounds of the formula (I). \R13 , 0038. When G' is N, compounds of the formula (Ia) are thus obtained (IIIE-G, IIIM) O

(Ia) 2 2 N1 N1,N.31G3 G4 Gl N GS --- |-- Al-- A / 2 UA. 2 R13' A2AN A2 N (IE-G, IM) and, when G' is C-A", compounds of the formula (Ib) are obtained where R' is (Ib) 4 A r - (III) A 4 (O), 1N7S (III) in which the remaining Substituents are each as defined (O) above. 0039. It has additionally been found that the compounds of the formula (I) can be obtained by the processes described N1 NR. below. I0040. Depending on the Gradical, the compounds of the formula (I) can be divided into the substructures (I) to (I). L (IIIC) 0041 Compounds of the formula (I, I) can be pre O pared, for example, by reacting the carboxylic acids of the - R O formula (II) or the acid chlorides thereof with amine deriva 1N R9 (III) tives of the formula (III, III). EN O 0042 Compounds of the formula (I) can be prepared, for example, as will be explained in detail later, from the amines of the formula (II). 0043 Compounds of the formula (I) can be prepared, for example, by reacting the heterocyclic amines of the formula (II) with sulphonyl chlorides of the formula (III).

11N No.3 Al / 2 N -2'- ^N ( 1, y 9- Y2-N V

(It) US 2014/0148471 A1 May 29, 2014

0044 Compounds of the formula (I) can be prepared, for 0049. The inventive compounds may also be present as example, by reacting Sulphonyl chlorides of the formula (II) metal complexes, as described for otheramides, for example, with amines of the formula (III). in DE 2221647. 0045 Compounds of the formula (I) can be prepared, for 0050 Preferred substituents or ranges for the radicals example, by reacting Sulphonyl chlorides of the formula (II) shown in the compounds of the formula (I) are elucidated with amides of the formula (III). below.

/ (Ik)K 11N GS-SG31 \ R5 Al- (O) ÁCa N R2 X (II3) , 2 11N S-so H-N 1. I pi A U. 2 X-R5 ^s X (III) (IL)

0046 Compounds of the formula (I) can be prepared, for 10051) A" and A are each independently hydrogen, halo example, by reacting nitriles of the formula (II) or thio gen, cyano, nitro, C-C-alkyl, C-C-cycloalkyl or C-C- amides of the formula (II) with oxy, thio oramino derivatives alkoxy. of the formula (III). 0.052 G' is N or C-A'.

11N N31 H-Y Al- (III) YC2 N (R1 = H) (IL4) N Al y 2 l A2 N Gl N GS G3 NH H-Y3 (IN) at,I 2 k (III) A2 NN (IIs)

0047 Finally, it has been found that novel compounds of 0053 G’ is a radical from the group of the formula (I) have very pronounced biological properties and are Suitable in particular for controlling animal pests, (A) especially insects, arachnids and nematodes, which are encountered in agriculture, in forests, in the protection of stored products and materials and in the hygiene sector. 0048. The compounds of the general formula (I) may, where appropriate, depending on the nature of the Substitu (B) ents, be in the form of geometric and/or optically active isomers or corresponding isomer mixtures in different com positions. The invention relates both to the pure isomers and to the isomer mixtures.

US 2014/0148471 A1 May 29, 2014

-continued 0071 where the arrow in each case marks the bond to (K) the sulphur atom in the radicals (E), (F) and (J)), in each (O) case optionally halogen-, cyano- (including in the alkyl ! is moiety), nitro-, C-C-alkyl-, C-C-haloalkyl-C-C- 1NN -R cycloalkyl-, C-C-alkoxy-, C-C-haloalkoxy-, C-C, alkylthio-, C-C-haloalkylthio-, C-C-alkylsulphi k nyl-, C-C-haloalkylsulphinyl-, C-C-alkylsulpho (L) nyl-, C-C-haloalkylsulphonyl-, amino-, C-C-alky (O), X lamino-, di(C-C-alkyl)amino-, C-C- S alkylcarbonylamino-, C-C-alkoxycarbonylamino-, 11 NN R5 C-C-alkoxy-C-C-alkyl-, C-C-haloalkoxy-C-C- k alkyl-, C-C-alkenyl-, C-C-alkynyl-, C-C-cy (M) cloalkyl-C-C-alkyl-, C-C-alkylcarbonyl-, C-C- X alkoxycarbonyl- or aminocarbonyl-substituted aryl, N heteroaryl, aryl-C-C-alkyl and heteroaryl-C-C- - N e alkyl, or NR'R" in which R" and R" are each indepen dently a radical from the group of hydrogen, C-C- R2 alkyl, C-C-haloalkyl, C-C-cycloalkyl, C-C- cycloalkyl-C-C-alkyl, C-C-alkoxy, C-C- 0064 and in the case of the heterocycles (A), (B) and alkylcarbonyl and C-C-alkoxylcarbonyl. (C) is also the radical 0072 R and R may also, together with the N-S(O), group to which they are bonded, form a saturated or unsat urated and optionally halogen-, C-C-alkyl-, C-C-ha loalkyl-, C-C-alkoxy-, C-C-haloalkoxy-Substituted 5 R13 (N) to 7-membered ring which may contain one or more further heteroatoms from the group of Sulphur, oxygen (where oxygen atoms must not be immediately adjacent) and nitrogen and/or at least one carbonyl group; RandR may -- especially, together with the N S(O), group to which they 0065 in which the arrow marks the bond to G. are bonded, be a radical from the group of 006.6 X is oxygen or sulphur. 0067 n is 1 or 2. I0068 R is a radical from the group of hydrogen, C-C- (O) (O) alkyl, C-C-haloalkyl, cyano-C-C-alkyl, C-C-alkoxy, \ ^ \ ^ \ S v ), C-C-haloalkoxy, C-C-alkenyl, C-C-alkynyl, C-C- alkoxy-C-C-alkyl, in each case optionally halogen-Sub stituted C-C-alkylcarbonyl and C-C-alkylsulphonyl, U. optionally halogen-Substituted C-C-alkoxycarbonyl, K ? OK. optionally halogen-, C-C-alkyl-, C-C-alkoxy-, C-C- V O (O), V (O), haloalkyl- and cyano-Substituted C-C-cycloalkylcarbo A. 7 nyl, or a cation, for example a mono- or divalent metalion, Such as Na' and K", or an optionally C-C-alkyl- or aryl C-C-alkyl-substituted ammonium ion. N-S O 0069 Rand Rare each independently a radical from the group of in each case optionally halogen-, C-C-alkoxy-, C-C-haloalkoxy-, C-C-alkylthio-, C-C-haloalky lthio-, C-C-alkylsulphinyl-, C-C-haloalkylsulphinyl-, 0.073 (in which the arrow again in each case marks the C-C-alkylsulphonyl- and C-C-haloalkylsulphonyl bond to G). Substituted C-C-alkyl, C-C-alkenyl and C-C-alky 10074 R is a radical from the group of in each case option nyl, in each case optionally halogen-, C-C-alkyl-C-C- ally halogen-, C-C-alkoxy-, C-C-haloalkoxy-, C-C- haloalkyl-, C-C-alkoxy- or C-C-haloalkoxy alkylthio-, C-C-haloalkylthio-, C-C-alkylsulphinyl-, Substituted C-C-cycloalkyl, C-C-cycloalkyl-C-C- C-C-haloalkylsulphinyl-, C-C-alkylsulphonyl- or alkyl and C-C-cycloalkenyl, in which the rings may C-C-haloalkylsulphonyl-substituted C-C-alkyl, contain at least one heteroatom from the group of Sulphur, C-C-alkoxy, C-C-alkenyl and C-C-alkynyl, in each oxygen (where oxygen atoms must not be immediately case optionally halogen-, C-C-alkyl-, C-C-haloalkyl-, adjacent) C-C-alkoxy- or C-C-haloalkoxy-Substituted C-C- 0070 and nitrogen (and especially cycloalkyl, C-C-cycloalkyl-C-C-alkyl and C-C-cy cloalkenyl, in which the rings may contain at least one heteroatom from the group of Sulphur, oxygen (where oxy genatoms must not be immediately adjacent) and nitrogen, in each case optionally halogen-, cyano-(including in the alkyl moiety), nitro-, C-C-alkyl-, C-C-haloalkyl-, C-C-cycloalkyl-, C-C-alkoxy-, C-C-haloalkoxy-, C-C-alkylthio-, C-C-haloalkylthio-, C-C-alkylsul bec) phinyl-, C-C-haloalkylsulphinyl-, C-C-alkylsulpho nyl-, C-C-haloalkylsulphonyl-, amino-, C-C-alky US 2014/0148471 A1 May 29, 2014

lamino-, di (C-C-alkyl)amino-, C-C- (0078 R is hydrogen or C-C-alkyl. alkylcarbonylamino-, C-C-alkoxycarbonylamino-, I0079 R and R may also, together with the nitrogen C-C-alkoxy-C-C-alkyl-, C-C-haloalkoxy-C-C- atoms to which they are bonded, be a saturated or unsatur alkyl-, C-C-alkenyl-C-C-alkynyl-C-C-cycloalkyl ated and optionally halogen-, C-C-alkyl-, C-C-ha C-C-alkyl-, C-C-alkylcarbonyl-, C-C-alkoxycarbo loalkyl-, C-C-alkoxy-, C-C-haloalkoxy-Substituted 5 nyl- or aminocarbonyl-Substituted aryl, heteroaryl, aryl to 7-membered ring which may contain at least one further C-C-alkyl and heteroaryl-C-C-alkyl, or NR'R' in heteroatom from the group of Sulphur, oxygen (where oxy which R" and R" are each independently a radical from the genatoms must not be immediately adjacent) and nitrogen group of hydrogen, C-C-alkyl, C-C-haloalkyl, C-C- and/or at least one carbonyl group; R and R may espe cycloalkyl, C-C-alkoxy, C-C-alkylcarbonyl and cially, together with the N N group to which they are C-C-alkoxylcarbonyl. bonded, be a radical from the group of I0075 R is a radical from the group of hydrogen, in each case optionally halogen-, C-C-alkoxy-, C-C-ha loalkoxy-, C-C-alkylthio-, C-C-haloalkylthio-, C-C- X (O), X (O) alkylsulphinyl-, C-C-haloalkylsulphinyl-, C-C-alkyl Sulphonyl- or C-C-haloalkylsulphonyl-substituted -( X-RM -( Y-RM C-C-alkyl, C-C-alkoxy, C-C-alkenyl and C-C- N-N alkynyl, in each case optionally halogen-, C-C-alkyl-, C-C-haloalkyl-, C-C-alkoxy- or C-C-haloalkoxy O-7 O Substituted C-C-cycloalkyl, C-C-cycloalkyl-C-C- O alkyl and C-C-cycloalkenyl, in which the rings may con X (O), X (O) tain at least one heteroatom from the group of Sulphur, oxygen (where oxygen atoms must not be immediately -( Y-RM -( Y-RM adjacent) and nitrogen, in each case optionally halogen N-N N-N cyano-(including in the alkyl moiety), nitro-C-C-alkyl-, C-C-haloalkyl-, C-C-cycloalkyl-, C-C-alkoxy-, C-C-haloalkoxy-, C-C-alkylthio-, C-C-haloalky ( ) - lthio-, C-C-alkylsulphinyl-, C-C-haloalkylsulphinyl-, X (O) X (O) C-C-alkylsulphonyl-, C-C-haloalkylsulphonyl-, -( X-RA -( Y-RA amino-, C-C-alkylamino-, di(C-C-alkyl)amino-, N-N N-N C-C-alkylcarbonylamino-, C-C-alkoxycarbony lamino-, C-C-alkoxy-C-C-alkyl-, C-C haloalkoxy C-C-alkyl-, C-C-alkenyl-, C-C-alkynyl-, C-C-cy cloalkyl-C-C-alkyl-, C-C-alkylcarbonyl-, C-C- alkoxycarbonyl- or aminocarbonyl-substituted aryl heteroaryl, aryl-C-C-alkyl and heteroaryl-C-C-alkyl, (where the whole radical (F) is depicted and the arrow again or NR'R" in which R and R" are each independently a in each case marks the bond to G). radical from the group of hydrogen, C-C-alkyl, C-C- 0080 R and R7 may also, in the case that G is (E), haloalkyl, C-C-cycloalkyl, C-C-alkoxy, C-C-alkyl together with the N S(O), group to which they are carbonyl and C-C-alkoxylcarbonyl. bonded, form a saturated or unsaturated and optionally 0076 R and R may also, together with the N COX) halogen-, C-C-alkyl-, C-C-haloalkyl-, C-C-alkoxy-, group to which they are bonded, form a saturated or unsat C-C-haloalkoxy-substituted 5- to 7-membered ring urated and optionally halogen-, C-C-alkyl-, C-C-ha which may contain one or more further heteroatoms from loalkyl-, C-C-alkoxy-, C-C-haloalkoxy-substituted 5 the group of Sulphur, oxygen (where oxygen atoms must to 7-membered ring which may contain one or more further not be immediately adjacent) and nitrogen and/or at least heteroatoms from the group of Sulphur, oxygen (where one carbonyl group; R and R may especially, together oxygen atoms must not be immediately adjacent) and with the N—S(O), group to which they are bonded, be a nitrogen and/or at least one carbonyl group; RandR may radical from the group of especially, together with the N—CCX) group to which they are bonded, be a radical from the group of (O), O) O) O) A V A v MSi v M(O) cy -S N O X X OlX V O) : V O) NN /No NN N^\

X X2-/

0077 (in which the arrow in each case marks the bond (in which the arrow in each case marks the bond to the C(X) to the sulphur atom in the radical (L)). group). US 2014/0148471 A1 May 29, 2014

0081) R' and R7 may also, in the case that G is (F), loalkyl-, C-C-alkoxy-, C-C-haloalkoxy-Substituted 5 together with the N S(O), group to which they are to 7-membered ring which may contain one or two heteroa bonded, form a saturated or unsaturated and optionally toms from the group of oxygen (where oxygenatoms must halogen-, C-C-alkyl-, C-C-haloalkyl-, C-C-alkoxy-, not be immediately adjacent) and sulphur, RandR' may C-C-haloalkoxy-substituted 5- to 7-membered ring especially, together with the phosphorus atom to which which may contain one or more further heteroatoms from they are bonded, be the radical the group of Sulphur, oxygen (where oxygen atoms must not be immediately adjacent) and nitrogen and/or at least one carbonyl group; R and R may especially, together O with the N—S(O), group to which they are bonded, be a K/ radical from the group of

OO R2 R2 R2 \ (O) \ (O) \ (O) V " \ " \ " 0.087 (in which the arrow marks the bond to the nitro gen atom in the radical (G)). y N-S - I0088 R'' and R'' are each independently an in each case optionally halogen-, C-C-alkyl-, C-C-haloalkyl-, \-O C ) O-7 C-C-alkoxy-, C-C-haloalkoxy-substituted radical O R2 R2 R2 from the group of C-C-alkyl, C-C-alkenyl, C-C- M M M alkynyl, phenyl and phenyl-C-C-alkyl. -a-N (O) --N (O) --N (O), I0089. Y' and Y are each independently C=O or S(O). V A. V M V A 0090 m is 1, 2, 3 or 4. I0091) R' is a radical from the group of hydrogen, C-C- alkyl, C-C-haloalkyl, cyano, C-C-cyanoalkyl, C-C- Cy N-S O hydroxyalkyl, hydroxyl, C-C-alkoxy, C-C-alkoxy-C- Co-alkyl, C-C-alkylthio-C-C-alkyl, C-C-alkenyl, C-C-haloalkenyl, C-C-cyanoalkenyl, C-C-alkynyl, (in which the N R group is also shown and the arrow in C-C-haloalkynyl, C-C-cyanoalkynyl, C-C7-alkylcar each case marks the bond to the C(X) group). bonyl and C-C7-alkoxycarbonyl. I0082) RandR may also, together with the nitrogenatom 0092 Y is a radical from the group of C-C-alkoxy, to which they are bonded, form a saturated or unsaturated C-C-haloalkoxy, C-C-alkylthio, C-C-haloalkylthio and optionally halogen-, C-C-alkyl-, C-C-haloalkyl-, and NR'R' where R'' and Rare each independently a C-C-alkoxy-, C-C-haloalkoxy-Substituted 5- to radical from the group of hydrogen, C-C-alkyl, C-Cs 7-membered ring which may contain one or more further cycloalkyl, C-C-cycloalkyl-C-C-alkyl, C-C-ha heteroatoms from the group of Sulphur, oxygen (where loalkyl, cyano, C-C-cyanoalkyl, hydroxyl, C-C- oxygen atoms must not be immediately adjacent) and alkoxy, C-C-haloalkoxy, C-C-hydroxyalkyl, C-C- nitrogen and/or at least one carbonyl group; RandR may alkoxy-C-C-alkyl, C-C-alkylthio-C-C-alkyl, C-C- especially, together with the nitrogen atom to which they alkenyl, C-C-haloalkenyl, C-C-cyanoalkenyl, C-C- are bonded, be a radical from the group of alkynyl, C-C-haloalkynyl, C-C-cyanoalkynyl, C-C,- alkylcarbonyl and C-C,-alkoxycarbonyl, or R'' and R' together with the nitrogen atom to which they are bonded are an optionally halogen-, cyano-, C-C-alkyl-, C-C- haloalkyl-, C-C-alkoxy-, C-C-cycloalkyl- or C-C- alkylthio-substituted saturated or unsaturated 5- to 8-mem bered ring which may contain one or more further atoms OO from the group of Sulphur, oxygen (where oxygen atoms must not be immediately adjacent) and nitrogen and/or at least one carbonyl group; R'' and R' may especially, I0083 (in which the arrow in each case marks the bond together with the nitrogen atom to which they are bonded, to the sulphur atom in the radical (K)). be a radical from the group of 008.4 L is oxygen or sulphur. I0085 R and R'' are each independently an in each case optionally halogen-substituted radical from the group of C-C-alkyl, C-C-alkenyl, C-C-alkynyl, C-C- alkoxy, C-C-alkenyloxy, C-C-alkynyloxy, C-C-cy cloalkyl, C-C-cycloalkyloxy, C-C-cycloalkenyloxy, C-C-cycloalkyl-C-C-alkoxy, C-C-alkylthio. C-C- alkenylthio, phenoxy, phenylthio, benzyloxy, benzylthio. heteroaryloxy, heteroarylthio, heteroaryl-C-C-alkoxy and heteroaryl-C-C-alkylthio. 0.093 (in which the arrow in each case marks the bonds I0086) R and R' may also, together with the phosphorus to the carbon atom in the (N) radical). atom to which they are bonded, form a saturated or unsat I0094 G and G may additionally together form an urated and optionally halogen-, C-C-alkyl-, C-C-ha optionally substituted heterocycle which optionally con US 2014/0148471 A1 May 29, 2014

tains further heteroatoms from the group of oxygen, nitro cloalkyl-, C-C-haloalkyl-, hydroxyl-, C-C-alkoxy-, gen and sulphur; G and G may especially form a bicycle C-C-haloalkoxy-, C-C-alkylthio-, C-C-alkylcarbo from the group of nyl-, C-C-alkoxycarbonyl-, C-C-alkenyl- or C-C- alkynyl-substituted pyrazolyl, oxazolyl, thiazolyl, oxadia Zolyl, triazolyl pyridinyl, pyridaZinyl, pyrimidinyl, O O O V/ pyrazinyl or triazinyl: G is with emphasis an optionally N N-SV halogen-, cyano-, methyl-, methoxy-, trifluoromethyl-, N-R2 N-R2 amino- or dimethylamino-substituted radical from the 4. s/ 4. group of

/ \, O (0095 (in which the arrow marks the bond to G). 0096 Particularly preferred substituents or ranges for the radicals shown in the compounds of the formula (I) are elu cidated below. I0097 A' is hydrogen, halogen or cyano, and A' is espe cially a radical from the group of hydrogen, fluorine and chlorine. 0098. A is hydrogen. 0099 G' is N or C-A'. I0100 G’ is a radical from the group of

(A)

0105 in which the arrow in each case marks the bond to G, and G' is also shown for illustration, and additionally optionally halogen-, cyano-, nitro-, amino-, (B) C-C-alkylamino-, di-(C-C)-alkylamino-, C-C-alkyl-, C-C-cycloalkyl-, C-C-haloalkyl-, hydroxyl-, C-C- alkoxy-, C-C-haloalkoxy-, C-C-alkylthio-, C-C-alkyl carbonyl-C-C-alkoxycarbonyl-, C-C-alkenyl- or C-C- (C) alkynyl-Substituted phenyl, and when G' is one of the radicals (E) and (L), I0106 G may also be optionally halogen-, cyano-, nitro-, amino-, C-C-alkylamino-, di(C-C)-alkylamino-, C-C-alkyl-, C-C-cycloalkyl-, C-C-haloalkyl-, G and C-C-alkoxy-, C-C-haloalkoxy-, C-C-alkylthio-, C-C-alkylcarbonyl-, C-C-alkoxycarbonyl-, C-C- (D) alkenyl- or C-C-alkynyl-substituted 5-membered hetero cyclyl or 6-membered heterocyclyl from the group of

is 21 . % No.. 1 . S, Y Y N N G4 G4 A M 0101 in which the arrow marks the bond to the adjacent G4 G4 r1ng. 0102) R' is hydrogen or C-C-alkyl, and R' is especially hydrogen or methyl. 0.107 in which the arrow in each case marks the bond to (0103) B is hydrogen. G, and G' is also shown for illustration. I0104) G is in each case optionally halogen-, cyano-, I0108 G' is a radical from the group of nitro-, amino-, C-C-alkylamino-, di-C-C-alkylamino-, C-C-alkyl-, C-C-cycloalkyl-, C-C-haloalkyl-, hydroxyl-, C-C-alkoxy-, C-C-haloalkoxy-, C-C- (E) alkylthio-, C-C-alkylcarbonyl-, C-C-alkoxycarbonyl-, C-C-alkenyl- or C-C-alkynyl-Substituted 5-membered heteroaryl or 6-membered heteroaryl; G is especially optionally halogen-, cyano-, nitro-, amino-, C-C-alky lamino-, di-C-C-alkylamino-, C-C-alkyl-, C-C-cy US 2014/0148471 A1 May 29, 2014 10

-continued C-C-alkylamino-, di(C-C-alkyl)amino-, C-C- (L) alkylcarbonylamino-, C-C-alkoxycarbonylamino-, (O), X C-C-alkoxy-C-C-alkyl-, C-C-haloalkoxy-C-C- alkyl-, C-C-alkenyl-, C-C-alkynyl-, C-C-cy 11 NN R5 cloalkyl-C-C-alkyl-, C-C-alkylcarbonyl-, C-C- alkoxycarbonyl- or aminocarbonyl-substituted aryl, k heteroaryl, aryl-C-C-alkyl and heteroaryl-C-C- alkyl, or NR'R" in which R" and R" are each indepen 0109 and in the case of the heterocycles (A), (B), and dently a radical from the group of hydrogen and C-C- (C) is also the radical alkyl, and R is especially a radical from the group of methyl, ethyl, i-propyl, CF, CHF, CHF, CHCF, cyclopropyl, dimethylamino, diethylamino, phenyl and R13 (N) benzyl. 10116 R is a radical from the group of in each case option ally halogen-, C-C-alkoxy-, C-Ca-haloalkoxy-, C-C- -- alkylthio-, C-Ca-haloalkylthio-, C-C-alkylsulphinyl-, C-Ca-haloalkylsulphinyl-, C-C-alkylsulphonyl- and 0110 in which the arrow in each case marks the bond to C-Ca-haloalkylsulphonyl-substituted C-C-alkyl, G. C-C-alkenyl and C-C-alkynyl, in each case optionally 0111 X is oxygen. halogen-, C-C-alkyl-, C-Ca-haloalkyl-, C-C-alkoxy-, 0112 n is 2. C-Ca-haloalkoxy-substituted C-C-cycloalkyl, C-C- 0113 Ri1S a rad1Caldical from the groupgrOur ofO hydrogen,rOgel, C-C,C--O-- cycloalkyl-C-C-alkyl and C-C-cycloalkenyl, in which alkyl, C-C-alkynyl, cyano-C-C-alkyl and C-C- the rings may contain at least one heteroatom from the alkoxy-C-C-alkyl, optionally halogen-substituted group of Sulphur, oxygen (where oxygenatoms must not be C-C-alkylcarbonyl or C-C alkylsulphonyl, optionally immediately adjacent) and nitrogen (and especially halogen-substituted C-C-alkoxycarbonyl, optionally halogen-, C-C-alkyl-, C-C-alkoxy-, C-C-haloalkyl and cyano-substituted C-C-cycloalkylcarbonyl, or a cat ion, for example a mono- or divalent metalion oran option ally C-C-alkyl- or aryl-C-C-alkyl-substituted ammo nium ion; R is especially a radical from the group of hydrogen, methyl, ethyl, CHOCH, CHOCH2CH, COCH, COCHCH cyclopropyl, Na', K" and "N(CH) 4. I0114 R is a radical from the group of in each case option 0117 where the arrow in each case marks the bond to ally halogen-, C-C-alkoxy-, C-Ca-haloalkoxy-, C-C- the Sulphur atom in the radical (E)), in each case option alkylthio-, C-Ca-haloalkylthio-, C-C-alkylsulphinyl-, ally halogen-, cyano- (including in the alkyl moiety), C-Ca-haloalkylsulphinyl-, C-C-alkylsulphonyl- and nitro-, C-C-alkyl-, C-Ca-haloalkyl-, C-C-cy C-Ca-haloalkylsulphonyl-substituted C-C-alkyl, cloalkyl-, C-C-alkoxy-, C-Ca-haloalkoxy-, C-C- C-C-alkenyl and C-C-alkynyl, in each case optionally halogen-, C-C-alkyl-, C-Ca-haloalkyl-, C-C-alkoxy-, alkylthio-, C-Ca-haloalkylthio-, C-C-alkylsulphi C-Ca-haloalkoxy-Substituted C-C-cycloalkyl, C-C- nyl-, C-Ca-haloalkylsulphinyl-, C-C- cycloalkyl-C-C-alkyl and C-C-cycloalkenyl, in which alkylsulphonyl-, C-C-haloalkylsulphonyl-, amino-, the rings may contain at least one heteroatom from the C-C-alkylamino-, di(C-C-alkyl)amino-, C-C- group of Sulphur, oxygen (where oxygenatoms must not be alkylcarbonylamino-, C-C-alkoxycarbonylamino-, immediately adjacent) and nitrogen (and especially C-C-alkoxy-C-C-alkyl-, C-C-haloalkoxy-C-C- alkyl-, C-C-alkenyl-, Ca-Ca-alkynyl-, C-C-cy cloalkyl-C-C-alkyl-, C-C-alkylcarbonyl-, C-C- alkoxycarbonyl- or aminocarbonyl-substituted aryl, heteroaryl, aryl-C-C-alkyl and heteroaryl-C-C-alkyl or NR'R" in which R" and R" are each independently a radical from the group of hydrogen, C-C-alkyl and C-C-cycloalkyl-C-C-alkyl, and R is especially a O radical from the group of methyl, ethyl, i-propyl, CF, CHF CHF, CHCF, cyclopropyl, cyclopropylm 0115 where the arrow in each case marks the bond to ethyl, cyclopropylethyl, dimethylamino, diethylamino, the carbon atom in the radical (L)), in each case option ally halogen-, cyano- (including in the alkyl moiety), phenyl and benzyl. nitro-, C-C-alkyl-, C-C-haloalkyl-, C-C-cy I0118 G and G may additionally also forman optionally cloalkyl-, C-C-alkoxy-, C-Ca-haloalkoxy-, C-C- substituted heterocycle which optionally contains further alkylthio-, C-Ca-haloalkylthio-, C-C-alkylsulphi heteroatoms from the group of oxygen, nitrogen and Sul nyl-, C-Ca-haloalkylsulphinyl-, C-C- phur, G and G may especially form a bicycle from the alkylsulphonyl-, C-C-haloalkylsulphonyl-, amino-, group of US 2014/0148471 A1 May 29, 2014 11

-continued O O O V/ N N-SV N-R2 N-R2 4. s/ % N / \, O in which the broken line means the bond to G, I0127 G is a radical from the group of 0119 (in which the arrow marks the bond to G'). 0120) R' is a radical from the group of hydrogen, C-C- (A) alkyl, C-C-haloalkyl, cyano, C-C-cyanoalkyl, C-C- RI hydroxyalkyl, hydroxyl, C-C-alkoxy, C-C-alkoxy-C- C-alkyl, C-C-alkylthio-C-C-alkyl, C-C-alkenyl, C-Ca-haloalkenyl, C-C-cyanoalkenyl, C-C-alkynyl, - \ C-Ca-haloalkynyl, C-C-cyanoalkynyl, C-C-alkylcar bonyl and C-C-alkoxycarbonyl. (B) I0121 Y is a radical from the group of C-C-alkoxy, C-Ca-haloalkoxy, C-C-alkylthio, C-C-haloalkylthio and NR'R' where R'' and Rare each independently a (D) radical from the group of hydrogen, C-C-alkyl, C-C- RI cycloalkyl, C-C-cycloalkyl-C-C-alkyl, C-C-ha loalkyl, cyano, C-C-cyanoalkyl, hydroxyl, C-C- alkoxy, C-C-haloalkoxy, C-Ca-hydroxyalkyl, C-C- alkoxy-C-C-alkyl, C-C-alkylthio-C-C-alkyl, C-C- alkenyl, C-Ca-haloalkenyl, C-C-cyanoalkenyl, C-C- alkynyl, C-Ca-haloalkynyl, C-C-cyanoalkynyl, C-Cs alkylcarbonyl, C-Cs-alkoxycarbonyl, or R'' and R' 0.128 in which the arrow in each case marks the bond to together with the nitrogen atom to which they are bonded the adjacent ring. are an optionally halogen-, cyano-, C-C-alkyl-, C-C- haloalkyl-, C-C-alkoxy, C-C-cycloalkyl- or C-C- I0129) R' is hydrogen or methyl. alkylthio-substituted saturated or unsaturated five- to I0130 B is hydrogen. eight-membered ring which may contain a further atom I0131 G is an optionally halogen-, cyano-, methyl-, meth from the group of sulphur, oxygen and nitrogen and/or one oxy-, trifluoromethyl-, amino- or dimethylamino-Substi carbonyl group; R'' and R' may especially, together with tuted radical from the group of the nitrogen atom to which they are bonded, be a radical

from the group of

O S O

0.122 (in which the arrow in each case marks the bonds to the carbon atom in the (N) radical). 0123 Very particularly preferred substituents or ranges of the radicals shown in the compounds of the formula (I) are elucidated hereinafter. 0124 A' is a radical from the group of hydrogen, fluorine and chlorine. 0.132 in which the arrow in each case marks the bond to 0125 A is hydrogen. G, and G' is also shown for illustration. 0126 G' is NorC-A", which leads to compounds contain I0133) G is a radical from the group of ing the following structural elements: (E) US 2014/0148471 A1 May 29, 2014 12

-continued C-C-alkoxy-C-C-alkyl-, C-C-haloalkoxy-C-C- (L) alkyl-, C-C-alkenyl-, C-C-alkynyl-, C-C-cy (O), X cloalkyl-C-C-alkyl-, C-C-alkylcarbonyl-, C-C- alkoxycarbonyl- or aminocarbonyl-substituted aryl, 11 Sn R5 heteroaryl, aryl-C-C-alkyl and heteroaryl-C-C- alkyl, or NR'R" in which R" and R" are each indepen R2 dently a radical from the group of hydrogen and C-C- alkyl, and R is especially a radical from the group of I0134) and in the case of the heterocycles (A) and (B) is methyl, ethyl, i-propyl, CF, CHF, CHF, CHCF, also the radical cyclopropyl, dimethylamino, diethylamino, phenyl and benzyl. (N) I014.1) R' is a radical from the group of in each case option ally halogen-, C-C-alkoxy-, C-Ca-haloalkoxy-, C-C- alkylthio-, C-Ca-haloalkylthio-, C-C-alkylsulphinyl-, C-Ca-haloalkylsulphinyl-, C-C-alkylsulphonyl- and C-Ca-haloalkylsulphonyl-substituted C-C-alkyl, C-C-alkenyl and C-C-alkynyl, in each case optionally halogen; C-C-alkyl, C-C-haloalkyl-, C-C-alkoxy-, 0135) in which the arrow in each case marks the bond to C-Ca-haloalkoxy-Substituted C-C-cycloalkyl, C-C- G. cycloalkyl-C-C-alkyl and C-C-cycloalkenyl, in which 0136 X is oxygen. the rings may contain at least one heteroatom from the 0137 n is 2. group of Sulphur, oxygen (where oxygenatoms must not be I0138 R is a radical from the group of hydrogen, C-C- immediately adjacent) and nitrogen (and is especially alkyl, C-C-alkynyl, cyano-C-C-alkyl and C-C- alkoxy-C-C-alkyl, optionally halogen-substituted C-C-alkylcarbonyl or C-C-alkylsulfonyl, optionally halogen-substituted C-C-alkoxycarbonyl, optionally halogen-, C-C-alkyl-, C-C-alkoxy-, C-Ca-haloge nalkyl- and cyano-Substituted C-C-cycloalkylcarbonyl, or a cation, for example a mono- or divalent metalion oran 5) optionally C-C-alkyl- or aryl-C-C-alkyl-substituted ammonium ion; R is especially a radical from the group of 0.142 where the arrow in each case marks the bond to hydrogen, methyl, ethyl, CHOCH, CHOCH2CH, the Sulphur atom in the (E) radical), in each case option COCH, COCHCH, CHCN, propynyl, cyclopropyl, ally halogen-, cyano- (including in the alkyl moiety), Na', K" and "N(CH). nitro-, C-C-alkyl-, C-Ca-haloalkyl-, C-C-cy 0139 R is a radical from the group of in each case option cloalkyl-, C-C-alkoxy-, C-Ca-haloalkoxy-, C-C- ally halogen-, C-C-alkoxy-, C-Ca-haloalkoxy-, C-C- alkylthio-, C-Ca-haloalkylthio-, C-C-alkylsulphi alkylthio-, C-Ca-haloalkylthio-, C-C-alkylsulphinyl-, nyl-, C-Ca-haloalkylsulphinyl-, C-C- C-Ca-haloalkylsulphinyl-, C-C-alkylsulphonyl- and alkylsulphonyl-, C-C-haloalkylsulphonyl-, amino-, C-Ca-haloalkylsulphonyl-substituted C-C-alkyl, C-C-alkylamino-, di(C-C-alkyl)amino-, C-C- C-C-alkenyl and C-C-alkynyl, in each case optionally alkylcarbonylamino-, C-C-alkoxycarbonylamino-, halogen-, C-C-alkyl, C-C-haloalkyl-, C-C-alkoxy-, C-C-alkoxy-C-C-alkyl-, C-C-haloalkoxy-C-C- C-Ca-haloalkoxy-substituted C-C-cycloalkyl, C-C- alkyl-, C-C-alkenyl-, C-C-alkynyl-, C-C-cy cycloalkyl-C-C-alkyl and C-C-cycloalkenyl, in which cloalkyl-C-C-alkyl-, C-C-alkylcarbonyl-, C-C- the rings may contain at least one heteroatom from the alkoxycarbonyl- or aminocarbonyl-substituted aryl, group of Sulphur, oxygen (where oxygenatoms must not be heteroaryl, aryl-C-C-alkyl and heteroaryl-C-C- immediately adjacent) and nitrogen (and is especially alkyl, or NR'R" in which R" and R" are each indepen dently a radical from the group of hydrogen and C-C- alkyl, and R is especially a radical from the group of methyl, ethyl, i-propyl, CF, CHF, CHF, CHCF, cyclopropyl, dimethylamino, diethylamino, phenyl and benzyl. I0143 R' is a radical from the group of hydrogen, C-C- alkyl, C-C-haloalkyl, cyano, C-C-cyanoalkyl, C-C- hydroxyalkyl, hydroxyl, C-C-alkoxy, C-C-alkoxy-C- 0140 where the arrow in each case marks the bond to C-alkyl, C-C-alkylthio-C-C-alkyl, C-C-alkenyl, the carbon atom in the (L) radical), in each case option C-Ca-haloalkenyl, C-C-cyanoalkenyl, C-C-alkynyl, ally halogen-, cyano- (including in the alkyl moiety), C-Ca-haloalkynyl, C-C-cyanoalkynyl, C-C-alkylcar nitro-, C-C-alkyl-, C-C-haloalkyl-, C-C-cy bonyl and C-C-alkoxycarbonyl. cloalkyl-, C-C-alkoxy-, C-Ca-haloalkoxy-, C-C- 10144) Y is a radical from the group of C-C-alkoxy, alkylthio-, C-Ca-haloalkylthio-, C-C-alkylsulphi C-Ca-haloalkoxy, C-C-alkylthio, C-Ca-haloalkylthio nyl-, C-Ca-haloalkylsulphinyl-, C-C- and NR'R' where R'' and R'' an Rare each indepen alkylsulphonyl-, C-C-haloalkylsulphonyl-, amino-, dently a radical from the group of hydrogen, C-C-alkyl, C-C-alkylamino-, di(C-C-alkyl)amino-, C-C- C-C-cycloalkyl, C-C-cycloalkyl-C-C-alkyl, C-C- alkylcarbonylamino-, C-C-alkoxycarbonylamino-, haloalkyl, cyano, C-C-cyanoalkyl, hydroxyl, C-C- US 2014/0148471 A1 May 29, 2014

alkoxy, C-Ca-haloalkoxy, C-C-hydroxyalkyl, C-C- 0.148. In the very particularly preferred definitions, unless alkoxy-C-C-alkyl, C-C-alkylthio-C-C-alkyl, C-C- stated otherwise, alkenyl, C-Ca-haloalkenyl, C-C-cyanoalkenyl, C-C- aryl is phenyl and alkynyl, C-Ca-haloalkynyl, C-C-cyanoalkynyl, C-Cs hetaryl (equivalent to heteroaryl, including as part of a larger alkylcarbonyl and C-Cs-alkoxycarbonyl, or R'' and R' unit, for example hetarylalkyl) is a radical selected from the together with the nitrogen atom to which they are bonded group of pyrazolyl, oxazolyl, thiazolyl pyridyl, pyrimidinyl, may form an optionally halogen-, cyano-, C-C-alkyl-, pyridazinyl and pyrazinyl. C-Ca-haloalkyl-, C-C-alkoxy-, C-C-cycloalkyl- or 0149 Halogen-substituted radicals, for example C-C-thioalkyl-substituted saturated or unsaturated five haloalkyl, mono- or polyhalogenate, up to the maximum to six-membered ring which may contain a further atom number of possible Substituents. In the case of polyhaloge from the group of Sulphur, oxygen and nitrogen and/or a nation, the halogenatoms may be identical or different. In this carbonyl group; R'' and R' together with the nitrogen case, halogen is fluorine, chlorine, bromine or iodine, espe atom to which they are bonded may especially be a radical cially fluorine, chlorine or bromine. from the group of 0150 Saturated or unsaturated hydrocarbyl radicals, such as alkyl or alkenyl, may in each case be straight-chain or branched as far as possible, including in combination with heteroatoms, as, for example, in alkoxy. 0151 Optionally substituted radicals may be mono- or polysubstituted, where the substituents in the case of polysub stitution may be the same or different. I0152. In the radicals (A), (B), (C) and (D) that G can represent, the arrow in each case marks the bond to the adja 0145 (in which the arrow in each case marks the bond cent ring. to the carbon atom in the (N) radical). I0153. In an emphasized group of inventive compounds, G 0146 In the preferred definitions, unless stated otherwise, is the radical (A). halogen is selected from the group of fluorine, chlorine, bro 0154) In a further emphasized group of inventive com mine and iodine, preferably in turn from the group of fluorine, pounds, G is the radical (B). chlorine and bromine, 0.155. In a further emphasized group of inventive com aryl (including as part of a larger unit, for example arylalkyl) pounds, G is the radical (C). is selected from the group of phenyl, naphthyl, anthryl, 0156. In a further emphasized group of inventive com phenanthrenyl, and is preferably in turn phenyl, pounds, G is the radical (D). hetaryl (synonymous with heteroaryl, including as part of a 0157. In a further emphasized group of inventive com larger unit, for example hetarylalkyl) is selected from the pounds, X is oxygen. group of furyl, thienyl, pyrrolyl pyrazolyl, imidazolyl, 1.2, 0158. In a further emphasized group of inventive com 3-triazolyl, 1,2,4-triazolyl, oxazolyl, isoxazolyl, thiazolyl, pounds, X is Sulphur. isothiazolyl, 1.2.3-oxadiazolyl, 1,2,4-oxadiazolyl, 1,3,4-oxa 0159. In a further emphasized group of inventive com diazolyl, 1,2,5-oxadiazolyl, 1,2,3-thiadiazolyl, 1,2,4-thiadia pounds, G' is C. H. Zolyl, 1,3,4-thiadiazolyl, 1.2.5-thiadiazolyl pyridyl, pyrim 0160. In a further emphasized group of inventive com idinyl, pyridazinyl, pyrazinyl, 1,2,3-triazinyl, 1,2,4-triazinyl, pounds, G' is C F. 1,3,5-triazinyl, benzofuryl, benzisofuryl, benzothienyl, ben 0.161. In a further emphasized group of inventive com Zisothienyl, indolyl, isoindolyl, indaZoyl, benzothiazolyl, pounds, G' is N (nitrogen). benzisothiazolyl, benzoxazolyl, benzisoxazolyl, benzimida 0162. In a further emphasized group of inventive com Zolyl. 2, 1,3-benzoxadiazole, quinolinyl, isoquinolinyl, cin pounds, A' is hydrogen. nolinyl, phthalazinyl, quinazolinyl, quinoxalinyl, naphthy 0163. In a further emphasized group of inventive com ridinyl, benzotriazinyl, purinyl, pteridinyl and indolizinyl, pounds, A is hydrogen. 5-membered heterocyclyl is apartially saturated 5-membered 0164. In a further emphasized group of inventive com ring which contains 1 or 2 nitrogenatoms and/or one oxygen pounds, n is 2. atom and/or one Sulphur atom, 0.165. In a further emphasized group of inventive com 6-membered heterocyclyl is apartially saturated 6-membered pounds, R' is hydrogen. ring which contains 1 or 2 nitrogenatoms and/or one oxygen 0166 In a further emphasized group of inventive com atom and/or one Sulphur atom. pounds, R' is methyl. 0147 In the particularly preferred definitions, unless 0167. In a further emphasized group of inventive com stated otherwise, pounds, R is fluorine. halogen is selected from the group of fluorine, chlorine, bro 0.168. In a further emphasized group of inventive com mine and iodine, preferably in turn from the group of fluorine, pounds, G' is the radical (E). chlorine and bromine, 0169. In a further emphasized group of inventive com aryl (including as part of a larger unit, for example arylalkyl) pounds, G' is the radical (I). is selected from the group of phenyl, naphthyl, anthryl, 0170 In a further emphasized group of inventive com phenanthrenyl, and is preferably in turn phenyl, pounds, G is the radical (L). hetaryl (including as part of a larger unit, for example hetary 0171 In a further emphasized group of inventive com lalkyl) is selected from the group of pyridyl, pyrimidyl, oxa pounds, G is the radical (N). diazolyl, oxazolyl, pyrazinyl, imidazolyl, thiazolyl, thiadiaz 0172. In a further emphasized group of inventive com olyl and furanyl. pounds, G is a pyrazolyl radical. US 2014/0148471 A1 May 29, 2014

0173. In a further emphasized group of inventive com 0183. A further emphasized embodiment of the invention pounds, G is a thiazolyl radical. relates to compounds of the formula (ID) 0.174. In a further emphasized group of inventive com (ID) pounds, G is a triazolyl radical. RI 0.175. In a further emphasized group of inventive com pounds, G is a pyridinyl radical. N2 0176). In a further emphasized group of inventive com s pounds, G is a pyrimidinyl radical. 0177. An emphasized embodiment of the invention relates 1s-1 \ to compounds of the formula (IA) Cr. (LA) in which G' is C H, C F. C C1 or N, 0184) R' is hydrogen or methyl, B is hydrogen and G' is one of the (E) and (L) radicals. 0185. The substituents in the (E), (L) and (N) radicals in in which the compounds of the formulae (IA), (IB), (IC) and (ID) may each assume the definitions specified in the description G' is C H, C F. C. Clor N, above. (0178) R' is hydrogen or methyl and 0186 The radical definitions or illustrations given above G' is one of the (E), (L)and (N) radicals and especially the (E) in general terms or within areas of preference apply to the end radical. products of the formula (I) (and hence to the compounds of A group of compounds preferred among the compounds of the formulae (Ia), (Ib), (IA), (IB), (IC) and (ID)) and corre the formula (IA) are those in which G' is C F. R' is hydro spondingly to starting materials and intermediates. These gen and G' is the (E) radical. radical definitions can be combined with one another as 0179 A further emphasized embodiment of the invention desired, i.e. including combinations between the respective relates to compounds of the formula (IB) preferred ranges. 0187 Preference is given in accordance with the invention (IB) to compounds of the formula (I) in which a combination of the N definitions listed above as preferred is present. y-/s 0188 Particular preference is given in accordance with the invention to compounds of the formula (I) in which a combi nation of the definitions listed above as particularly preferred is present. 0189 Very particular preference is given in accordance in which with the invention to compounds of the formula (I) in which a combination of the definitions listed above as very particu G' is C H, C F. C. Clor N and larly preferred is present. 0190. The preparation of the inventive compounds is 0180 G' is one of the (E), (L) and (N) radicals. explained in detail hereinafter. 0181. A further emphasized embodiment of the invention 0191 The compounds of the formula (II), (II), (II), (II) relates to compounds of the formula (IC) and (II) in which G' represents the radicals (A), (B) and (C), which are required as starting materials, can be prepared (IC) analogously to the methods described in WO 2010/006713 A2. (II) O

1N1 G3N3 ls OH Alt YsC2 in which (II) 1N s G' is C H, C F. C C1 or N, Al 0182 R is hydrogen or methyl, ye NH2 B is hydrogen and A2 G' is one of the (E), (L) and (N) radicals. US 2014/0148471 A1 May 29, 2014 15

-continued 0193 For example, reaction of a bromide of the formula (II) (IV) with a pyrazole of the formula (V) in the presence of a capper catalyst and of a base Such as potassium carbonate gives the compounds of the formula (VI). See, for example, for 3-(4-bromopyrazol-1-yl)pyridine: Journal of Heterocy clic Chemistry 1981, 18, 9-14: European Journal of Organic Chemistry, 2004, 695. These pyrazoles of the formula (VI) are used to obtain, by reaction with bromine or N-bromosuc (II4) cinimide, the bromides of the formula (VII). See, for CN example, for 3-(4-bromopyrazol-1-yl)pyridine: Journal of Heterocyclic Chemistry 18, 1981, 9-14. The bromides of the formula (VII) are used to obtain, by reaction with, for example, bis(pinacolato)diborane in the presence of a palla (IIs) dium catalyst and of base, the boronic esters of the formula (VIII). The starting compounds of the formula (II) required can be obtained from the bromides of the formula (VII) by reaction with a compound of the formula (X), which consti tutes an H-G-R unit which contains an N-H, for example a pyrazole, in the presence of a copper catalyst and of a base, or according to the same process by reaction of the bromides of the formula (IV) with a suitable pyrazole of the formula (IX). 0.192 The starting compounds of the formula (II), (II), (II), (II) and (IIs) in which G' represents the radical (D), 0194 In addition, inventive compounds of the formula (I) which are required as starting materials, can be prepared can be obtained by reaction of the boronic esters of the for analogously to the methods described in the literature, as mula (VIII) with a halide of the formula (XI) in the presence follows. of a palladium catalyst and of a base (Suzuki reaction).

Reaction scheme 1

R1 RI Br2 e Pod cat OR 14 O N Na- A. Bir Diborane B G11n Bro0 NBs G11n N his - G|1n N wOR 15 1. 2- 1- ye B |--As a B A3N A3N A3N (IV) (VII) (VIII)

Cu cat. Base H-G V R (X)

R1

Na G3 N V Gl n R Al- y 4 B (II) US 2014/0148471 A1 May 29, 2014

0.195. When R is a protected carboxylic acid, for example (0200. The further radicals mentioned for R' can be pre an ester, the carboxylic acid (II) can be prepared easily by pared from the acids of the formula (II) or the acid chlorides known methods. thereof by means of literature methods, or analogously to 0196. When R is a protected amine, the amine (II) can be these methods, for example reacted with compounds of the prepared easily by known methods. formula (III) according to Chem. Letters 36, 1370 (2007) or 0.197 When R is halogen, for example bromine, (analo J. Med. Chem. 29, 1299 (1986) to give the inventive com gously to WO2007/45588A1 and US2008/318941), the halo pounds of the formula (I), or, for example, with compounds gen can be exchanged for a metal, for example lithium. The of the formula (III) according to J. Org. Chem. 72, 465 metal compound reacts with Sulphur dioxide and then with a (2007) or Phosphorus & Sulfur 20, 93 (1984) to give the chlorinating reagent Such as Sulphuryl chloride or N-chloro inventive compounds of the formula (I) and, for example, Succinimide to give the starting compound (II). with cyanamines of the formula (III) according to WO2006/ 002099 A2 to give the inventive compounds of the formula Reaction scheme 2 (I). O G2 ls R2 Reaction scheme 3 N No.3 OH H-Y O at, 2 -- Yis He A2 NN (IIIE-G, IIIM) N1 silsN31 No (II) Al--y 2 -3- As N O (II) 11N GS --- 2 Al--I R11 y 2 R13 o=y A: N G3 o N No.3 R12 (IE-G, IM) |-- Ae(YN Y- - I - where R' is A. NH2 (IIH) (O), (O), i R10 R11 1Ns. N1 NR, 11 O EN Y-R 1. V in III A. (in IIIE) R6 R9 (in III) N (in IIIE) (in III) G3 1. Al---N-Norso 0198 The amine derivatives of the formula (III, III) y 2 required as starting materials are known or can be prepared by As N methods known in principle. (IIH) (0199 The acids of the formula (II) can be reacted, after activation, for example to give the acid chloride (see, for example, Bioorg & MedChem Letters 15, 4354 (2005)), or by 0201 Compounds of the formula (I) can be prepared, for means of activating reagents such as CDI (carbonyldiimida example, by reacting the carboxamides of the formula (II) Zole; see, for example, Bioorg & MedChem 9, 1543 (2001), with sulphoxides of the formula (III) by means of literature EDC (1-ethyl-3-3-dimethylaminopropylcarbodiimide methods or analogous methods; see, for example, WO 2008/ hydrochloride) in the presence of DMAP (dimethylaminopy 154528 A2. ridine; see, for example, J. Med. Chem. 50,3101 (2007)), or 0202 The carboxamides of the formula (II) required as DCC (dicyclohexylcarbodiimide) in the presence of HOBT starting materials can be prepared from the acids (II) or the (1-hydroxybenzotriazole; see, for example, J. Med. Chem. acid chlorides by means of literature methods or analogous 50, 3101 (2007)), with sulphonamides of the formula (III), optionally in the presence of a base Such as a metal hydride methods, for example as described in WO 2007/103755A2 or (especially sodium hydride) or DBU (diazabicycloun US 2009f2O3657 A1. decene), to give the inventive compounds of the formula (I) 0203 The sulphoxides of the formula (III) are com in which X is oxygen. pounds known from the literature. US 2014/0148471 A1 May 29, 2014 17

Reaction scheme 4 R2 RO Hal O O O (III)III c. 11 n s

A. a O -->O AlA2 N ( iii. Y (III12) N O R2 (IF) 11N s Al- H AsAa N 2 (II) 1 ?ci- R3 G|1N Gris- Nse (On w Al- 3 (O), 44 R (III) A2 2) base, (I) R2-X

0204 Compounds of the formula (I) can be prepared, for 0206 Compounds of the formula (I) can be prepared, for example, by reacting the amines of the formula (II) with example, by reacting, heterocyclic amines of the formula (II) compounds of the formula (III) or (III), analogously to the with sulphonyl chlorides of the formula (III) in the presence methods described in WO2007/132475 A1 or WO2006/ of a base, for example pyridine or Sodium hydroxide; cf., for O19831 A1. example, WO 2007/114532 A1 and US 2006/211603 A1. 0207. The chlorosulphinyl or chlorosulphonyl derivatives 0205 The compounds of the formula (III) and (III) are of the formula (III) required as starting materials are known known or can be prepared by methods known in principle. or can be prepared by methods known in principle.

Reaction scheme 5 R2 R8

R2 G3 s S H-X Al---n-Nar So, R8 y 2 (IIIk) As N (IK) R5 R2 X R2 G2 S H \ N1 Nc31so R5 at, N 2 (IL) US 2014/0148471 A1 May 29, 2014

0208 Compounds of the formula (I) can be prepared, for “Scheeren's reagent'), or more preferably 2.4-bis(4-methox example, by reacting the Sulphonyl chlorides of the formula yphenyl)-2,4-dithioxo-1,3,2,4-dithiadiphosphetane "Lawes (II) with amines of the formula (III), optionally in the son's Reagent (LR), 2.4-bis(4-phenoxyphenyl)-2,4- presence of a base, for example pyridine or triethylamine, dithioxo-1,3,2,4-dithiadiphosphetane “Belleau's reagent analogously to the methods described in U.S. Pat. No. 6,265, (BR) or 2.4-bis(4-phenylthiophenyl)-2,4-dithioxo-1,3,2,4- 411, WO 2007/114532 A1 or U.S. Pat. No. 6,673,817. dithiadiphosphetane. 0209. The amines of the formula (III) required as starting 0215 N-Oxides can be obtained, for example, by reacting materials are known or can be prepared by methods known in compounds of the formula (I) with mCPBA (meta-chlorop principle. erbenzoic acid). Salts of compounds of the formula (I) are 0210 Compounds of the formula (I) in which X is oxy obtainable by reacting compounds of the formula (I) with gen can be prepared, for example, by reacting Sulphonyl compounds of the formula RX in which X is, for example, chlorides of the formula (II) with amides of the formula halogen Such as chlorine or bromine and Ris, for example, an (III) in the presence of a base, for example sodium hydride or in each case optionally Substituted alkyl, alkenyl or alkynyl n-butyllithium, analogously to the methods described in radical. US2004/006143 or Org. Let. 3458-3461 (2009). 0216. The intermediates of the formulae (XII), (XIII), 0211. The amides of the formula (III) required as starting (XIV), (XV), (XVI), (XVII) and (XVIII) which follow are materials are known or can be prepared by methods known in novel and also form part of the subject-matter of the inven principle. tion.

Reaction scheme 6 11N1 G3N31 CN H-Y3 Al- (III) R13 Aa A2 N is U S A N 11N is is H-Y3 Al-HUya 2 R13 (III) 3 N (IIs)

0212 Compounds of the formula (I) can be prepared, for 0217 Compounds of the formula (XII) example, by reaction of nitriles of the formula (II) or thio amides of the formula (II) with oxy, thio oramino derivatives of the formula (III). Oxy derivatives can be used, for (XII) example, by the methods described in European Journal of N i Medicinal Chemistry 2009, 44(6), 2497-2505; thio deriva (1N 4 N-R7 tives can be used, for example, by the methods described in MV Journal of the America Chemical Society 1985, 107(28), & O O 5745-5754. Amino derivatives can be used, for example, by the methods described in Bioorganic & Medicinal Chemistry Letter 2010, 20(1), 299-301, WO2007/083239 A1 or Euro in which pean Journal of Medicinal Chemistry 2010, 45(3), 902-908. R" is fluorine, chlorine, bromine or iodine (especially chlo 0213. The compounds of the formula (III) required as rine, bromine or iodine) and starting materials are known or can be prepared by methods X, R and Rare each as defined above. known in principle. 0218 Particular mention should be made of the following 0214 Compounds of the formula (I), (I) and (I) in compounds of the formula (XII). which X is Sulphur can be prepared from the corresponding compounds of the formula (I), (I) and (I) in which X is oxygen by reaction with a thionating reagent. The Sulphiding N agents (thionating reagents) used are preferably phosphorus reagents, for example diphosphorus pentasulphide (PSs). l l is diphosphorus pentasulphide/pyridine (PSs/Py), diphospho C N ns1 rus pentasulphide/triethylamine (PS/NEt), diphosphorus /\, pentasulphide/sodium hydrogencarbonate (PSs/NaHCO US 2014/0148471 A1 May 29, 2014 19

-continued -continued N N l l is 2 -N R5 Br N Ns 1 N S O / \, OMV O r8 N H l l is 2 -N R5 I N n S 1. I ulN S O / \, OM \,O r8 where R' is methyl, ethyl, cyclopropyl, CF, CHCF, dim ethylamino, diethylamino, phenyl or benzyl. where R is a radical from the group of methyl, ethyl, i-pro 0219 Compounds of the formula (XIII) pyl, CF, CHF, CHF, CHCF, cyclopropyl, dimethy lamino, diethylamino, phenyl and benzyl. (XIII) 0223 Compounds of the formula (XV) y (XV) S R2 Gl N S -(N N-R N - in which G' is nitrogen, C-halogen, C-cyano, C-nitro, /\, C-alkyl, C-cycloalkyl or C-alkoxy, preferably nitrogen, C-halogen, C-cyano, C-nitro, C-C-C-alkyl, C-C-C- in which cycloalkyl or C-C-C-alkoxy. R' is fluorine, chlorine, bromine or iodine (especially chlo 0220 Particular mention should be made of the following rine, bromine or iodine) and compounds of the formula (XIII). X, RandR are each as defined above. 0224 Particular mention should be made of the following u -u compounds of the formula (XV): C. c. -s,S \ N1 N N1 N O /\, S -S, \ N-R 4. 4 MV 3 O O 0221 Compounds of the formula (XIV) S (XIV) N R2 -S, \ N-R O /\, 1N 4 7& r R5 4\, . where R is methyl, ethyl, cyclopropyl, CF, CHCF, dim ethylamino, diethylamino, phenyl or benzyl. in which 0225 Compounds of the formula (XVI) R" is fluorine, chlorine, bromine or iodine (especially chlo rine, bromine or iodine) and (XVI) X, Rand Rare each as defined above. 0222 Particular mention should be made of the following 7 compounds of the formula (XIV): R 16 ( %y Ns- R X / \, H

-N R5 in which C ul S le MV R' is fluorine, chlorine, bromine or iodine (especially chlo O O rine, bromine or iodine) and X, R and Rare each as defined above. US 2014/0148471 A1 May 29, 2014 20

0226 Particular mention should be made of the following 0231 Compounds of the formula (XVIII) compounds of the formula (XVI): S - > -ss (XVIII) C % 4\,5 S - S N-N-R Br % 4\,5 S S | in which 0232 G' is nitrogen, C-halogen, C-cyano, C-nitro, I - %> -ss5 { C-alkyl, C-cycloalkyl or C-alkoxy, preferably nitrogen, C-halogen, C-cyano, C-nitro, C-C-C-alkyl, C-C-C- 4\, cycloalkyl or C-C-C-alkoxy and where R is as defined above and is especially methyl, ethyl, 0233 R’ is as defined above. cyclopropyl. CF, CHCF, dimethylamino, diethylamino, 0234 Particular mention should be made of the following phenyl or benzyl. compounds of the formula (XVIII): 0227 Compounds of the formula (XVII) (XVII) N2 s N N A / le S-N o%i \R? in which 0228 G' is nitrogen, C-halogen, C-cyano, C-nitro, C-alkyl, C-cycloalkyl or C-alkoxy, preferably nitrogen, C-halogen, C-cyano, C-nitro, C-C-C-alkyl, C-C-C- cycloalkyl or C-C-C-alkoxy and 0229 R is as defined above. 0230 Particular mention should be made of the following compounds of the formula (XVII). Na s N

2 N o-i-Nil 0235. The inventive active ingredients, given good plant O tolerance, favourable homeotherm toxicity and good environ mental compatibility, are Suitable for protecting plants and fy /s plant organs, for increasing harvest yields, for improving the quality of the harvested material and for controlling animal pests, especially insects, arachnids, helminths, nematodes Crs -eS-NH2 and molluscs, which are encountered in agriculture, in horti le culture, in animal husbandry, inforests, in gardens and leisure O facilities, in the protection of stored products and of materials, N2 and in the hygiene sector. They can preferably be used as crop s protection compositions. They are active against normally N sensitive and resistant species and against all or some stages of development. The abovementioned pests include: se 0236. From the order of the Anoplura (Phthiraptera), for N O-I-i-Nil example, Damalinia spp., Haematopinus spp., Linognathus O spp., Pediculus spp., Trichodectes spp. 0237 From the class of the Arachnida, for example, Acarus Siro, Aceria Sheldoni, Aculops spp., Aculus spp., US 2014/0148471 A1 May 29, 2014

Amblyomma spp., Argas spp., Boophilus spp., Brevipalpus monchus spp., Heterakis spp., Hymenolepis nana, Hvostron spp., Bryobia praetiosa, Chorioptes spp., Dermanyssus galli gulus spp., Loa Loa, Nematodirus spp., Oesophagostomum nae, Eotetranychus spp., Epitrimerus pyri, Eutetranychus spp., Opisthorchis spp., Onchocerca volvulus, Ostertagia spp., Eriophyes spp., Hemitarisonemus spp., Hyalomma spp., spp., Paragoninus spp., Schistosomen spp., Strongyloides Ixodes spp., Latrodectus mactans, Metatetranychus spp., Oli fielleborni, Strongyloides Stercoralis, Stronyloides spp., Tae gonychus spp., Ornithodoros spp., Panonychus spp., Phyllo nia saginata, Taenia solium, Trichinella spiralis, Trichinella coptruta oleivora, Polyphagotarisonemus latus, Psoroptes nativa, Trichinella britovi, Trichinella nelsoni, Trichinella spp., Rhipicephalus spp., Rhizoglyphus spp., Sarcoptes spp., pseudopsiralis, Tricho strongulus spp., Trichuris trichuria, Scorpio maurus, Stenotarisonemus spp., Tarsonemus spp., Wuchereria bancrofti. Tetranychus spp., Vasates lycopersici. 0247. It is also possible to control protozoa, such as Eime 0238 From the class of the Bivalva, for example, Dreis ria. Sena spp. 0239 From the order of the Chilopoda, for example, Geo 0248 From the order of the Heteroptera, for example, philus spp., Scutigera spp. Anasa tristis, Antestiopsis spp., Blissus spp., Calocoris spp., 0240 From the order of the Coleoptera, for example, Campylomma livida, Cavelerius spp., Cimex spp., Creontia Acanthoscelides Obtectus, Adoretus spp., Agelastica alni, des dilutus, Dasynus piperis, Dichelops fircatus, Diconocoris Agriotes spp., Amphimallon solstitialis, Anobium punctatum, hewetti, Dysdercus spp., Euschistus spp., Eurygaster spp., Anoplophora spp., Anthonomus spp., Anthrenus spp., Apogo Heliopeltis spp., Horcias nobilellus, Leptocorisa spp., Lep nia spp., Atomaria spp., Attagenus spp., Bruchidius Obtectus, toglossus phyllopus, Lygus spp., Macropes excavatus, Miri Bruchus spp., Ceuthorhynchus spp., Cleonus mendicus, Con dae, Nezara spp., Oebalus spp., Pentomidae, Piesma oderus spp., Cosmopolites spp., Costelytra zealandica, Cur quadrata, Piezodorus spp., Psalus seriatus, Pseudacy.sta culio spp., Cryptorhynchus lapathi, Dermestes spp., persea, Rhodnius spp., Sahlbergella singularis, Scotino Diabrotica spp., Epillachna spp., Faustinus cubae, Gibbium phora spp., Stephanitis nashi, Tibraca spp., Triatoma spp. psylloides, Heteronychus arator, Hylamorpha elegans, 0249 From the order of the Homoptera, for example, Hylotrupes bajulus, Hypera postica, Hypothenemus spp., Acyrthosipon spp., Aeneolamia spp., Agonoscena spp., Aleu Lachnosterna consanguinea, Leptinotarsa decemlineata, rodes spp., Aleurolobus barodensis, Aleurothrixus spp., Lissorhoptrus Oryzophilus, Lixus spp., Lyctus spp., Amrasca spp., Anuraphis cardui, Aonidiella spp., Apha Melligethes aeneus, Melolontha melolontha, Migdolus spp., nostigma piri, Aphis spp., Arboridia apicalis, Aspidiella spp., Monochamus spp., Naupactus xanthographus, Niptus holo Aspidiotus spp., Atanus spp., Aulacorthum Solani, Bemisia leucus, Oryctes rhinoceros, Oryzaephilus surinamensis, spp., Brachycaudus helichrysii, Brachycolus spp., Brevico Otiorrhynchus sulcatus, Oxycetonia jucunda, Phaedon ryne brassicae, Calligpona marginata, Carneocephala cochleariae, Phyllophaga spp., Popillia japonica, Preminot fiulgida, Ceratovacuna lanigera, Cercopidae, Ceroplastes rypes spp., Psylliodes chrysocephala, Ptinus spp., Rhizobius spp., Chatosiphon fragaefolii, Chionaspis tegalensis, Chlo ventralis, Rhizopertha dominica, Sitophilus spp., Spheno rita Onuki, Chromaphis juglandicola, Chrysomphalus ficus, phorus spp., Sternechus spp., Symphyletes spp., Tenebrio Cicadulina mbila, Coccomytilus halli, Coccus spp., Crypto molitor; Tribolium spp., Trogoderma spp., Tichius spp., myzus ribis, Dalbulus spp., Dialeurodes spp., Diaphorina Xylotrechus spp., Zabrus spp. spp., Diaspis spp., Doralis spp., Drosicha spp., Dysaphis 0241. From the order of the Collembola, for example, spp., Dysmicoccus spp., Emposca spp., Eriosoma spp., Eryth Onychiurus armatus. roneura spp., Euscelis bilobatus, Geococcus coffeae, Homa 0242. From the order of the Dermaptera, for example, lodisca coagulata, Hyalopterus arundinis, Icerya spp., Idi Forficula auricularia. ocerus spp., Idioscopus spp., Laodelphax striatellus, 0243 From the order of the Diplopoda, for example, Bla Lecanium spp., Lepidosaphes spp., Lipaphis erysimi, Macro niulus guttulatus. siphum spp., Mahanarva fimbriolata, Melanaphis sacchari, Metcalfiella spp., Metopolophium dirhodium, Monelia cos 0244. From the order of the Diptera, for example, Aedes talis, Monelliopsis pecanis, Myzus spp., Nasonovia ribisini spp., Anopheles spp., Bibio hortulanus, Caliphora erythro gri, Nephotettix spp., Nilaparvata lugens, Oncometopia spp., cepha, Ceratitis capitata, Chrysomyia spp., Cochliomyia Orthezia praelonga, Parabemisia myricae, Paratrioza spp., spp., Cordylobia anthropophaga, Culex spp., Cuterebra spp., Parlatoria spp., Pemphigus spp., Peregrinus maidis, Phen Dacus oleae, Dermatobia hominis, Drosophila spp., Fannia acoccus spp., Phioeomyzus passerinii, Phorodon humuli, spp., Gastrophilus spp., Hyllemyia spp., Hyppobosca spp., Phylloxera spp., Pinnaspis aspidistrae, Planococcus spp., Hypoderma spp., Liriomyza spp. Lucilia spp., Musca spp., Protopulvinaria pyriformis, Pseudaulacaspis pentagona, Nezars spp., Oestrus spp., Oscinella frit, Pegomyia hyos Pseudococcus spp., Psylla spp., Pteromalus spp., Pyrilla cyani, Phorbia spp., Stomoxys spp., Tabanus spp., Tannia spp., Quadraspidiotus spp., Quesada gigas, RastrucOccus spp., Tipula paludosa, Wohlfahrtia spp. spp., Rhopalosiphum spp., Saissetia spp., Scaphoides titanus, 0245. From the class of the Gastropoda, for example, Schizaphis graminum, Selenaspidus articulatus, Sogata spp., Arion spp., Biomphalaria spp., Bulinus spp., Deroceras spp., Sogatella furcifera, Sogatodes spp., Stictocephala festina, Galba spp., Lynnaea spp., Oncomelania spp., Succinea spp. Tenalaphara malayensis, Tinocallis caryaefoliae, Tomaspis 0246. From the class of the helminths, for example, Ancy spp., Toxoptera spp., Trialeurodes vaporariorum, Trioza lostoma duodenale, Ancylostoma ceylanicum, Acylostoma spp., Tiphlocyba spp., Unaspis spp., Viteus vitifolii. braziliensis, Ancylostoma spp., Ascaris lubricoides, Ascaris spp., Brugia malayi, Brugia timori, Bunostomum spp., Chab 0250 From the order of the Hymenoptera, for example, ertia spp., Clonorchis spp., Cooperia spp., Dicrocoelium Diprion spp., Hoplocampa spp., Lasius spp., Monomorium spp., Dictyocaulus filaria, Diphyllobothrium latum, Dracun pharaonis and Vespa spp. culus medimensis, Echinococcus granulosus, Echinococcus 0251 From the order of the Isopoda, for example, Arma multilocularis, Enterobius vermicularis, Faciola spp., Hae dilidium vulgare, Oniscus asellus and Porcellio scaber: US 2014/0148471 A1 May 29, 2014 22

0252 From the order of the Isoptera, for example, Reticu with the use of Surfactants, that is to say emulsifiers and/or litermes spp. and Odontotermes spp. dispersants and/or foam-formers. The formulations are pre 0253 From the order of the Lepidoptera, for example, pared either in suitable facilities or else before or during Acronicta major, Aedia leucomelas, Agrotis spp., Alabama application. argillacea, Anticarsia spp. Barathra brassicae, Bucculatrix 0263. The auxiliaries used may be those substances which thurberiella, Bupalus piniarius, Cacoecia podana, Capua are Suitable for imparting particular properties to the compo reticulana, Carpocapsa pomonella, Chematobia brumata, sition itself and/or to preparations derived therefrom (for Chilo spp., Choristoneura filmiferana, Clysia ambiguella, example spray liquors, seed dressings). Such as certain tech Cnaphalocerus spp., Earias insulana, Ephestia kuehniella, nical properties and/or also particular biological properties. Euproctis chrysorrhoea, Euxoa spp., Feltia spp., Galleria Typical auxiliaries include: extenders, solvents and carriers. mellonella, Helicoverpa spp., Heliothis spp., Hofinannophila 0264 Suitable extenders are, for example, water, polar and pseudospretella, Homona magnanima, Hyponomeuta nonpolar organic chemical liquids, for example from the padella, Laphygma spp., Lithocolletis blancardella, Litho classes of the aromatic and nonaromatic hydrocarbons (such phane antennata, Loxagrotis albicosta, Lymantria spp., as paraffins, alkylbenzenes, alkylnaphthalenes, chloroben Malacosoma neustria, Mamestra brassicae, Mocis repanda, Zenes), the alcohols and polyols (which may optionally also Mythinna separata, Oria spp., Oulema Oryzae, Panolis flam be substituted, etherified and/or esterified), the ketones (such mea, Pectinophora gossypiella, Phyllocnistis citrella, Pieris as acetone, cyclohexanone), esters (including fats and oils) spp., Plutella xylostella, Prodenia spp., Pseudaletia spp., and (poly)ethers, the unsubstituted and Substituted amines, Pseudoplusia includens, Pyrausta nubilalis, Spodoptera amides, lactams (such as N-alkylpyrrolidones) and lactones, spp., Thermesia gemmatalis, Tinea pellionella, Tineola bis the Sulphones and Sulphoxides (such as dimethyl SulphoX selliella, Tortrix viridana, Trichoplusia spp. ide). 0254. From the order of the Orthoptera, for example, 0265. If the extender utilized is water, it is also possible to Acheta domesticus, Blatta Orientalis, Blattella germanica, use, for example, organic solvents as auxiliary solvents. Use Gryllotalpa spp., Leucophaea maderac, Locusta spp., Mel ful liquid solvents essentially include: aromatics Such as anoplus spp., Periplaneta americana, Schistocerca gregaria. Xylene, toluene or alkylnaphthalenes, chlorinated aromatics 0255 From the order of the Siphonaptera, for example, and chlorinated aliphatic hydrocarbons such as chloroben Ceratophyllus spp. and Xenopsylla cheopis. Zenes, chloroethylenes or methylene chloride, aliphatic 0256 From the order of the Symphyla, for example, Scuti hydrocarbons such as cyclohexane or paraffins, for example gerella immaculata. petroleum fractions, mineral and vegetable oils, alcohols 0257. From the order of the Thysanoptera, for example, Such as butanol or glycol and also their ethers and esters, Baliothrips biformis, Enneothrips flavens, Frankliniella spp., ketones such as acetone, methyl ethylketone, methyl isobutyl Heliothrips spp., Hercinothrips femoralis, Kakothrips spp., ketone or cyclohexanone, strongly polar solvents such as Rhipiphorothrips cruentatus, Scirtothrips spp., Taeniothrips dimethyl Sulphoxide, and also water. cardamomi and Thrips spp. 0266 Useful solid carriers include: 0258 From the order of the Thysanura, for example, Lepi for example ammonium salts and natural rock flours, such as sma saccharina. kaolins, clays, talc, chalk, quartz, attapulgite, montmorillo 0259. The phytoparasitic nematodes include, for example, nite or diatomaceous earth, and synthetic rock flours, such as Anguina spp., Aphelenchoides spp., Belonoaimus spp., Bur finely divided silica, alumina and silicates; useful solid car Saphelenchus spp., Dity lenchus dipsaci, Globodera spp., riers for granules include: for example, crushed and fraction Heliocotylenchus spp., Heterodera spp., Longidorus spp., ated natural rocks such as calcite, marble, pumice, Sepiolite Meloidogyne spp., Pratylenchus spp., Radopholus similis, and dolomite, and also synthetic granules of inorganic and Rotylenchus spp., Trichodorus spp., Tilenchorhynchus spp., organic flours, and granules of organic material Such as paper, Tvlenchulus spp., Tilenchulus semipenetrans and Xiphinema sawdust, coconut shells, maize cobs and tobacco stalks; use spp. ful emulsifiers and/or foam-formers include: for example 0260 The inventive compounds can, at certain concentra nonionic and anionic emulsifiers, such as polyoxyethylene tions or application rates, also be used as herbicides, safeners, fatty acid esters, polyoxyethylene fatty alcohol ethers, for growth regulators or agents to improve plant properties, or as example alkylaryl polyglycol ethers, alkylsulphonates, alkyl microbicides, for example as fungicides, antimycotics, bac Sulphates, arylsulphonates and also protein hydrolysates; tericides, viricides (including agents against Viroids) or as Suitable dispersants are nonionic and/or ionic Substances, for agents against MLO (mycoplasma-like organisms) and RLO example from the classes of the alcohol-POE and/or -POP (rickettsia-like organisms). They can also be used as interme ethers, acid and/or POP POE esters, alkylaryl and/or POP diates or precursors for the synthesis of further active ingre POE ethers, fat and/or POPPOE adducts, POE- and/or POP dients. polyol derivatives, POE- and/or POP-sorbitan or -sugar 0261 The active ingredients can be converted to the cus adducts, alkyl or aryl Sulphates, alkyl- orarylsulphonates and tomary formulations, such as solutions, emulsions, wettable alkyl or aryl phosphates or the corresponding PO-ether powders, water- and oil-based suspensions, powders, dusts, adducts. Additionally Suitable are oligo- or polymers, for pastes, soluble powders, soluble granules, granules for broad example those derived from vinylic monomers, from acrylic casting, Suspoemulsion concentrates, natural compounds acid, from EO and/or PO alone or in combination with, for impregnated with active ingredient, synthetic Substances example, (poly)alcohols or (poly)amines. It is also possible to impregnated with active ingredient, fertilizers and also use lignin and its Sulphonic acid derivatives, unmodified and microencapsulations in polymeric Substances. modified celluloses, aromatic and/or aliphatic Sulphonic 0262 These formulations are produced in a known man acids and also their adducts with formaldehyde. ner, for example by mixing the active ingredients with extend 0267 In the formulations it is possible to use tackifiers ers, that is, liquid solvents and/or solid carriers, optionally Such as carboxymethylcellulose, natural and synthetic poly US 2014/0148471 A1 May 29, 2014 mers in the form of powders, granules or lattices, such as gum fenamiphos, fenitrothion, fenthion, fosthiazate, heptenophos, arabic, polyvinyl alcohol and polyvinyl acetate, or else natu imicyafos, isofenphos, isopropyl O-(methoxyaminothio ral phospholipids such as cephalins and lecithins and Syn phosphoryl)salicylate, isoxathion, malathion, mecarbam, thetic phospholipids. methamidophos, methidathion, mevinphos, monocrotophos, 0268. It is possible to use dyes Such as inorganic pigments, naled, omethoate, oxydemeton-methyl, parathion, parathion for example iron oxide, titanium oxide and Prussian Blue, and methyl, phenthoate, phorate, phosalone, phosmet, phospha organic dyes such as alizarin dyes, azo dyes and metal phtha midon, phoxim, pirimiphos-methyl, profenofos, propetam locyanine dyes, and trace nutrients such as salts of iron, phos, prothiofos, pyraclofos, pyridaphenthion, quinalphos, manganese, boron, copper, cobalt, molybdenum and zinc. sulfotep, tebupirimfos, temephos, terbufos, tetrachlorvin 0269. Further additives may be perfumes, mineral or veg phos, thiometon, triaZophos, triclorfon and vamidothion. etable, optionally modified oils, waxes and nutrients (includ 0276 (2) GABA-gated chloride channel antagonists, for ing trace nutrients). Such as salts of iron, manganese, boron, example copper, cobalt, molybdenum and zinc. cyclodieno-organochlorines, for example chlordane and 0270 Additional components may be stabilizers, such as endosulfan; or cold stabilizers, preservatives, antioxidants, light stabilizers, phenylpyrazoles (fiproles), for example ethiprole and or other agents which improve chemical and/or physical sta fipronil. bility. 0277 (3) Sodium channel modulators/voltage-dependent 0271 The formulations contain generally between 0.01 Sodium channel blockers, for example and 98 percent by weight of active ingredient, preferably pyrethroids, for example acrinathrin, allethrin, d-cis-trans between 0.5 and 90%. allethrin, d-trans allethrin, bifenthrin, bioallethrin, bioal 0272. The inventive active ingredients may also be lethrin S-cyclopentenyl isomer, bioresmethrin, cyclopro present, as such or in their formulations, in a mixture with one thrin, cyfluthrin, beta-cyfluthrin, cyhalothrin, lambda-cyha or more Suitable fungicides, bactericides, acaricides, nemati lothrin, gamma-cyhalothrin, cypermethrin, alpha cides, insecticides, microbicides, fertilizers, attractants, ster cypermethrin, beta-cypermethrin, theta-cypermethrin, Zeta ilants, synergists, safeners, semiochemicals and/or plant cypermethrin, cyphenothrin (R)-trans-isomers. growth regulators, in order thus to broaden the spectrum of deltamethrin, empenthrin (EZ)-(1R)-isomers, esfenvaler activity, to prolong the duration of action, to increase the ate, etofenproX, fempropathrin, fenvalerate, flucythrinate, flu speed of action, to prevent repellency or to preclude the methrin, tau-fluvalinate, halfenproX, imiprothrin, kadethrin, development of resistance. In addition, such combinations permethrin, phenothrin (1R)-trans-isomer, prallethrin, can improve plant growth, increase tolerance to high or low pyrethrins (pyrethrum), resmethrin, silafluofen, tefluthrin, temperatures, to drought or to water content or soil salinity, tetramethrin, tetramethrin (1R)-isomers, tralomethrin and enhance flowering performance, facilitate harvesting and transfluthrin; or increase yields, accelerate ripening, increase quality and/or DDT; or methoxychlor. the nutritional value of the harvested products, prolong Stor 0278 (4) Nicotinergic acetylcholine receptor (nAChR) age life and/or improve the processability of the harvested agonists, for example products. In general, combination of the inventive active neonicotinoids, for example acetamiprid, clothianidin, ingredients and mixing partners gives synergistic effects, dinotefuran, imidacloprid, niteupyram, thiacloprid and thia which means that the efficacy of the particular mixture is methoxam; or greater than the efficacy of the individual components. It is nicotine. generally possible to use the combinations either as seed 0279 (5) Nicotinergic acetylcholine receptor (nAChR) applications or in premixes, tankmixes or readymixes. allosteric activators, for example 0273 Particularly favourable mixing partners are, for spinosins, for example spinetoram and spinosad. example, the following: 0280 (6) Chloride channel activators, for example avermectinS/milbemycins, for example abamectin, emamec Insecticides/Acaricides/Nematicides: tin benzoate, lepimectin and milbemectin. 0274 The active ingredients identified here by their com 0281 (7) Juvenile hormone imitators, for example mon name are known and are described, for example, in the Juvenile hormone analogues, for example hydroprene, kino pesticide handbook (“The Pesticide Manual 14th Ed., Brit prene and methoprene; or fenoxycarb or pyriproxyfen. ish Crop Protection Council 2006) or can be found on the 0282 (8) Active ingredients with unknown or nonspecific Internet (e.g. http://www.alanwood.net/pesticides). mechanisms of action, for example (0275 (1) Acetylcholinesterase (AChE) inhibitors, for alkyl halides, for example methyl bromide and other alkyl example halides; or carbamates, for example alanycarb, aldicarb, bendiocarb, chloropicrin; or sulphuryl fluoride; or borax; or tartar emetic. benfuracarb, butocarboxim, butoxycarboxim, carbaryl, car 0283 (9) Selective antifeedants, for example bofuran, carbosulfan, ethiofencarb, fenobucarb, formetanate, pymetrozine; or flonicamid. furathiocarb, isoprocarb, methiocarb, methomyl, metolcarb, 0284 (10) Mite growth inhibitors, for example clofentez oxamyl, pirimicarb, propoXur, thiodicarb, thiofanox, triaz ine, hexythiazox and diflovidazin; or etoxazole. amate, trimethacarb. XMC and xylylcarb; or 0285 (11) Microbial disruptors of the insect gut mem organophosphates, for example acephate, azamethiphos, brane, for example Bacillus thuringiensis Subspecies israe azinphos-ethyl, azinphos-methyl, cadusafos, chlorethoxyfos, lensis, Bacillus sphaericus, Bacillus thuringiensis subspecies chlorfenvinphos, chlormephos, chlorpyrifos, chlorpyrifos alzawai, Bacillus thuringiensis subspecies kurstaki, Bacillus methyl, coumaphos, cyanophos, demeton-S-methyl, diazi thuringiensis Subspecies tenebrionis and BT plant proteins: non, dichlorvos/DDVP, dicrotophos, dimethoate, dimeth Cry1Ab, Cry1Ac, Cry1 Fa, Cry2Ab, mCry3A, Cry3 Ab, ylvinphos, disulfoton, EPN, ethion, ethoprophos, famphur, Cry3Bb, Cry34/35Ab1. US 2014/0148471 A1 May 29, 2014 24

0286 (12) Oxidative phosphorylation inhibitors, ATP dis aminofuran-2(5H)-one (known from WO 2007/115643), ruptors, for example diafenthiuron; or 4-(5,6-dichloropyrid-3-yl)methyl(2-fluoroethyl) organotin compounds, for example azocyclotin, cyhexatin aminofuran-2(5H)-one (known from WO 2007/115646), and fenbutatin oxide; or 4-(6-chloro-5-fluoropyrid-3-yl)methyl (cyclopropyl) propargite, or tetradifon. aminofuran-2(5H)-one (known from WO 2007/115643), 0287 (13) Oxidative phosphorylation decouplers acting 4-(6-chloropyrid-3-yl)methyl (cyclopropyl)aminofuran by interrupting the H proton gradient, for example chlor 2(5H)-one (known from EP-A-0539.588), 4-(6-chloropy fenapyr, DNOC and sulfluramid. 0288 (14) Nicotinergic acetylcholine receptor antago rid-3-yl)methyl(methyl)aminofuran-2(5H)-one (known nists, for example benSultap, cartap-hydrochloride, thiocy from EP-A-0539.588), 1-(6-chloropyridin-3-yl)ethyl(me clam and thiosultap-sodium. thyl)oxido- '-sulphanylidene}cyanamide (known from WO 0289 (15) Chitin biosynthesis inhibitors, type 0, for 2007/149134), and its diastereomers (1R)-1-(6-chloropyri example bistrifluoron, chlorfluaZuron, diflubenzuron, flucy din-3-yl)ethyl(methyl)oxido-...- cloXuron, flufenoXuron, hexaflumuron, lufenuron, novalu sulphanylidene cyanamide (A) and (1S)-1-(6-chloropyri ron, noviflumuron, teflubenzuron and triflumuron. din-3-yl)ethyl(methyl)oxido-...- 0290 (16) Chitin biosynthesis inhibitors, type 1, for sulphanylidene}cyanamide (B) (likewise known from example buprofezin; WO2007/149134) and sulfoxaflor(likewise known from WO 2007/149134), and its diastereomers (R)-methyl(oxido) 0291 (17) Moulting disruptors, dipteran, for example (1R)-1-6-(trifluoromethyl)pyridin-3-yl)ethyl-N'-sulpha cyromazine; nylidenelcyanamide (A1) and (S)-methyl(oxido)-(1S)-1-(6- 0292 (18) Ecdysone receptor agonists, for example chro (trifluoromethyl)pyridin-3-yl)ethyl-N'-sulphanylidene mafenozide, halofenozide, methoxyfenozide and cyanamide (A2), designated as diastereomer group A (known tebufenozide. from WO 2010/074747, WO 2010/074751), (R)-methyl 0293 (19) Octopaminergic agonists, for example amitraz: (oxido){(1S)-1-6-(trifluoromethyl)pyridin-3-ylethyl-N'- 0294 (20) Complex-III electron transport inhibitors, for sulphanylidenelcyanamide (B1) and (S)-methyl(oxido) example hydramethylnone; or acequinocyl; or fluacrypyrim, (1R)-1-6-(trifluoromethyl)pyridin-3-yl)ethyl-N'- 0295 (21) Complex-I electron transport inhibitors, for Sulphanylidenelcyanamide (B2), designated as diastereomer example METI acaricides, for example fenaZaquin, fenpy group B (likewise known from WO 2010/074747, WO 2010/ roximate, pyrimidifen, pyridaben, tebufenpyrad and tolfen 074751) and 11-(4-chloro-2,6-dimethylphenyl)-12-hydroxy pyrad; or 1,4-dioxa-9-azadispiro4.2.4.2tetradec-11-en-10-one rotenone (Derris). (known from WO 2006/089633), 3-(4-fluoro-2,4-dimethyl 0296 (22) Voltage-dependent sodium channel blockers, biphenyl-3-yl)-4-hydroxy-8-oxa-1-azaspiro4.5 dec-3-en-2- for example indoxacarb; or metaflumizone. one (known from WO 2008/067911), 1-2-fluoro-4-methyl 0297 (23) Inhibitors of acetyl-CoA carboxylase, for 5-(2.2.2-trifluoroethyl)sulphinylphenyl-3- example tetronic and tetramic acid derivatives, for example (trifluoromethyl)-1H-1,2,4-triazole-5-amine (known from spirodiclofen, spiromesifen and spirotetramat. WO 2006/043635), (3S,4aR,12R,12aS.12bS)-3-cyclopro 0298 (24) Complex-IV electron transport inhibitors, for pylcarbonyl)oxy-6,12-dihydroxy-4,12b-dimethyl-11-oxo example phosphines, for example aluminium phosphide, cal 9-(pyridin-3-yl)-1,3,4,4a,5,6,6a, 12.12a, 12b-decahydro-2H, cium phosphide, phosphine and Zinc phosphide; or cyanide. 11H-benzof pyrano.4.3-bchromen-4-yl)methyl 0299 (25) Complex-II electron transport inhibitors, for cyclopropanecarboxylate (known from WO 2008/066153), example cyenopyrafen. 2-cyano-3-(difluoromethoxy)-N,N-dimethylbenzenesulpho 0300 (28) Ryanodine receptor effectors, for example dia namide (known from WO2006/056433), 2-cyano-3-(difluo mides, for example chlorantraniliprole and flubendiamide. romethoxy)-N-methylbenzenesulphonamide (known from 0301 Further active ingredients with unknown mecha WO2006/100288), 2-cyano-3-(difluoromethoxy)-N-ethyl nism of action, for example amidoflumet, azadirachtin, ben benzenesulphonamide (known from WO2005/035486), clothiaz, benzoximate, bifenazate, bromopropylate, chi 4-(difluoromethoxy)-N-ethyl-N-methyl-1,2-benzothiazole nomethionat, cryolite, cyantraniliprole (Cyazypyr), 3-amine 1,1-dioxide (known from WO2007/057407), N-1- cyflumetofen, dicofol, diflovidazine, fluensulfone, flufen (2,3-dimethylphenyl)-2-(3,5-dimethylphenyl)ethyl-4,5-di erim, flufiprole, fluopyram, flufenozide, imidaclothiz, iprodi hydro-1,3-thiazole-2-amine (known from WO2008/104503), one, pyridalyl pyrifluquinazon and iodomethane; and also {1'-(2E)-3-(4-chlorophenyl)prop-2-en-1-yl)-5-fluorospiro products based on Bacillus firmus (1-1582, BioNeem, Votivo) indole-3,4'-piperidine-1 (2H)-y1}(2-chloropyridin-4-yl) and the following known active ingredients: methanone (known from WO2003/106457), 3-(2,5-dimeth 3-bromo-N-(2-bromo-4-chloro-6-(1-cyclopropylethyl)car ylphenyl)-4-hydroxy-8-methoxy-1,8-diazaspiro4.5 dec-3- bamoylphenyl)-1-(3-chloropyridin-2-yl)-1H-pyrazole-5- en-2-one (known from WO2009/049851), 3-(2,5- carboxamide (known from WO2005/077934), 4-(6-bro dimethylphenyl)-8-methoxy-2-oxo-1,8-diazaspiro4.5 dec mopyrid-3-yl)methyl(2-fluoroethyl)aminofuran-2(5H)- 3-en-4-yl-ethyl carbonate (known from WO2009/049851), one (known from WO 2007/115644), 4-(6-fluoropyrid-3- 4-(but-2-yn-1-yloxy)-6-(3,5-dimethylpiperidin-1-yl)-5-fluo yl)methyl(2,2-difluoroethyl)aminofuran-2(5H)-one ropyrimidine (known from WO2004/099160), (2,2,3,3,4,4,5, (known from WO 2007/115644), 4-(2-chloro-1,3-thiazol 5-octafluoropentyl)(3,3,3-trifluoropropyl)malononitrile 5-yl)methyl(2-fluoroethyl)aminofuran-2(5H)-one (known (known from WO2005/063094), (2,2,3,3,4,4,5,5-octafluoro from WO 2007/115644), 4-(6-chloropyrid-3-yl)methyl(2- pentyl)(3.3.4.4.4-pentafluorobutyl)malononitrile (known fluoroethyl)aminofuran-2(5H)-one (known from WO 2007/ from WO2005/063094), 8-2-(cyclopropylmethoxy)-4-(trif 115644), 4-(6-chloropyrid-3-yl)methyl(2,2-difluoroet luoromethyl)phenoxy-3-6-(trifluoromethyl)pyridazin-3- hyl)aminofuran-2(5H)-one (known from WO 2007/ yl)-3-azabicyclo[3.2.1]octane (known from WO2007/ 115644), 4-(6-chloro-5-fluoropyrid-3-yl)methyl(methyl) 040280), 2-ethyl-7-methoxy-3-methyl-6-(2,2,3,3- US 2014/0148471 A1 May 29, 2014 tetrafluoro-2,3-dihydro-1,4-benzodioxin-6-yl)oxy include, for example, mineral and vegetable oils. Useful oils quinolin-4-ylmethyl carbonate (known from JP2008/ include all mineral or vegetable oils—modified or other 110953), 2-ethyl-7-methoxy-3-methyl-6-(2,2,3,3- wise—which are typically usable in agrochemical composi tetrafluoro-2,3-dihydro-1,4-benzodioxin-6-yl)oxyquinolin tions. Examples include Sunflower oil, rapeseed oil, olive oil, 4-yl acetate (known from JP2008/110953), PF1364 (CAS castor oil, colza oil, cornseed oil, cottonseed oil and Soybean Reg. No. 1204776.60-2) (known from JP2010/018586), 5-5- oil or the esters of the oils mentioned. Preference is given to (3,5-dichlorophenyl)-5-(trifluoromethyl)-4,5-dihydro-1,2- rapeseed oil, sunflower oil and their methyl or ethyl esters, oxazol-3-yl)-2-(1H-1,2,4-triazol-1-yl)benzo-nitrile (known especially rapeseed oil methyl ester. from WO2007/075459), 5-5-(2-chloropyridin-4-yl)-5-(trif 0303. The concentration of penetrant in the inventive com luoromethyl)-4,5-dihydro-1,2-oxazol-3-yl)-2-(1H-1,2,4- positions can be varied within a wide range. In the case of a triazol-1-yl)benzonitrile (known from WO2007/075459), formulated crop protection composition, it is generally 1 to 4-5-(3,5-dichlorophenyl)-5-(trifluoromethyl)-4,5-dihydro 95% by weight, preferably 1 to 55% by weight, more prefer 1.2-oxazol-3-yl)-2-methyl-N-(2-oxo-2-(2.2.2-trifluoroet ably 15-40% by weight. In the ready-to-use compositions hyl)aminoethylbenzamide (known from WO2005/ (spray liquors), the concentrations are generally between 0.1 085216), 4-(6-chloropyridin-3-yl)methyl (cyclopropyl) and 10 g/l, preferably between 0.5 and 5 g/l. amino-1,3-oxazol-2(5H)-one, 4-(6-chloropyridin-3-yl) 0304. When used as insecticides, the inventive active methyl(2,2-difluoroethyl)amino-1,3-oxazol-2(5H)-one, ingredients may also be present in their commercially avail 4-(6-chloropyridin-3-yl)methyl-(ethyl)amino-1,3-ox able formulations and in the use forms, prepared from these azol-2(5H)-one, 4-(6-chloropyridin-3-yl)methyl(methyl) formulations, as a mixture with Synergists. Synergists are amino-1,3-oxazol-2(5H)-one (all known from WO2010/ compounds which enhance the action of the active ingredi 005692), NNI-0711 (known from WO2002096882), ents, without any need for the synergist added to be active 1-acetyl-N-4-(1,1,1,3,3,3-hexafluoro-2-methoxypropan-2- itself. yl)-3-isobutylphenyl-N-isobutyryl-3,5-dimethyl-1H-pyra 0305. When used as insecticides, the inventive active Zole-4-carboxamide (known from WO2002096882), methyl ingredients may also be present in their commercially avail 2-2-(3-bromo-1-(3-chloropyridin-2-yl)-1H-pyrazol-5-yl) able formulations and in the use forms, prepared from these carbonyl)amino)-5-chloro-3-methylbenzoyl-2-methyl-hy formulations, as a mixture with inhibitors which reduce deg drazinecarboxylate (known from WO2005/085216), methyl radation of the active ingredient after use in the environment 2-2-(3-bromo-1-(3-chloropyridin-2-yl)-1H-pyrazol-5-yl) of the plant, on the Surface of parts of plants or in plant tissues. carbonyl)amino)-5-cyano-3-methylbenzoyl-2-ethylhydra (0306 The active ingredient content of the use forms pre zinecarboxylate (known from WO2005/085216), methyl pared from the commercially available formulations may 2-2-(3-bromo-1-(3-chloropyridin-2-yl)-1H-pyrazol-5-yl) vary within wide limits. The active ingredient concentration carbonyl)amino)-5-cyano-3-methylbenzoyl-2-methylhy of the application forms may be from 0.00000001 to 95% by drazinecarboxylate (known from WO2005/085216), methyl weight of active ingredient, preferably between 0.00001 and 2-3,5-dibromo-2-({3-bromo-1-(3-chloropyridin-2-yl)-1H 1% by weight. pyrazol-5-yl)carbonyl)amino)benzoyl-1,2-diethylhydrazi 0307 The compounds are applied in a customary manner necarboxylate (known from WO2005/085214) methyl 2-3, appropriate for the use forms. 5-dibromo-2-(3-bromo-1-(3-chloropyridin-2-yl)-1H 0308 The good plant compatibility of the active ingredi pyrazol-5-yl)carbonyl)amino)-benzoyl-2- ents in the concentrations needed for control of plant diseases ethylhydrazinecarboxylate (known from WO2005/085216), allows treatment of above-ground plant parts, of plants and (5RS,7RS:5RS,7SR)-1-(6-chloro-3-pyridylmethyl)-1,2,3,5, seed, and of the soil. 6,7-hexahydro-7-methyl-8-nitro-5-propoxyimidazo 1,2-a 0309 The inventive treatment of the plants and plant parts pyridine (known from WO2007/101369), 2-6-2-(5-fluoro with the active ingredients is effected directly or by allowing pyridin-3-yl)-1,3-thiazol-5-ylpyridin-2-yl)pyrimidine them to act on the Surroundings, habitat or storage space by (known from WO2010/006713), 2-6-2-(pyridin-3-yl)-1,3- the customary treatment methods, for example by dipping, thiazol-5-ylpyridin-2-yl)pyrimidine (known from spraying, evaporating, fogging, Scattering, painting on, WO2010/006713), 1-(3-chloropyridin-2-yl)-N-4-cyano-2- injecting, and, in the case of propagation material, especially methyl-6-(methylcarbamoyl)phenyl-3-((5-(trifluorom in the case of seeds, also by applying one or more coats. ethyl)-1H-tetrazol-1-yl)methyl)-1H-pyrazole-5-carboxam 0310 All plants and plant parts can be treated in accor ide (known from WO2010/069502), 1-(3-chloropyridin-2- dance with the invention. Plants are understood here to mean yl)-N-4-cyano-2-methyl-6-(methylcarbamoyl)phenyl-3- all plants and plant populations, such as desired and undesired 5-(trifluoromethyl)-2H-tetrazol-2-yl)methyl)-1H-pyrazole wild plants or crop plants (including naturally occurring crop 5-carboxamide (known from WO2010/069502), N-(2-(tert plants). Crop plants may be plants which can be obtained by butylcarbamoyl)-4-cyano-6-methylphenyl)-1-(3- conventional breeding and optimization methods or by bio chloropyridin-2-yl)-3-(5-(trifluoromethyl)-1H-tetrazol-1- technological and genetic engineering methods or combina yl)methyl)-1H-pyrazole-5-carboxamide (known from tions of these methods, including the transgenic plants and WO2010/069502) and N-(2-(tert-butylcarbamoyl)-4-cyano including the plant varieties which are protectable and non 6-methylphenyl)-1-(3-chloropyridin-2-yl)-3-(5-(trifluo protectable by plant breeders’ rights. Parts of plants shall be romethyl)-2H-tetrazol-2-yl)methyl)-1H-pyrazole-5-car understood to mean all above-ground and below-ground parts boxamide (known from WO2010/069502). and organs of plants, such as shoot, leaf flower and root, 0302) In a preferred embodiment of the invention, a pen examples including leaves, needles, stems, trunks, flowers, etrant is additionally added to the crop protection composi fruit bodies, fruits and seeds, and also roots, tubers and rhi tions to enhance the action. Useful penetrants also include, Zomes. The plant parts also include harvested material and for example, substances which promote the availability of the Vegetative and generative propagation material, for example compounds of the formula (I) in the spray coating. These cuttings, tubers, rhizomes, slips and seeds. US 2014/0148471 A1 May 29, 2014 26

0311 Plants which can be treated in accordance with the tion period, diet), the treatment according to the invention invention include the following: cotton, flax, grapevine, fruit, may also result in superadditive (“synergistic) effects. For Vegetables, such as Rosaceae sp. (for example pome fruits example, the following effects exceeding the effects actually Such as apples and pears, but also stone fruits such as apricots, to be expected are possible: reduced application rates and/or cherries, almonds and peaches, and Soft fruits such as Straw a widening of the activity spectrum and/or an increase in the berries), Ribesioidae sp., Juglandaceae sp., Betulaceae sp. activity of the active ingredients and compositions which can Anacardceae sp., Fagaceae sp., Moraceae sp., Oleaceae sp., be used according to the invention, better plant growth, Actinidaceae sp., Lauraceae sp., Musaceae sp. (for example increased tolerance to high or low temperatures, increased banana plants and banana plantations), Rubiaceae sp. (for tolerance to drought or to water or soil salt content, increased example coffee), Theaceae sp., Sterculiceae sp., Rutaceae sp. flowering performance, easier harvesting, accelerated matu (for example lemons, oranges and grapefruit); Solanaceae sp. ration, higher harvest yields, bigger fruits, larger plant height, (for example tomatoes), Lilaceae sp., Asteraceae sp. (for greener leaf colour, earlier flowering, higher quality and/or a example lettuce), Umbelliferae sp., Cruciferae sp., Chenopo higher nutritional value of the harvested products, higher diaceae sp., Cucurbitaceae sp. (for example cucumber), Alli Sugar concentration within the fruits, better storage stability aceae sp. (for example leeks, onions), Papilionaceae sp. (for and/or processability of the harvested products. example peas); major crop plants such as Gramineae sp (for 0315. At certain application rates, the inventive active example maize, turf cereals such as wheat, rye, rice, barley, ingredients may also have a fortifying effect on plants. They oats, millet and triticale), Poaceae sp (for example Sugar are therefore suitable for mobilizing the defence system of the cane), AsterOceae sp. (for example Sunflower), Brasicaceae plant against attack by unwanted phytopathogenic fungi and/ sp. (for example white cabbage, red cabbage, broccoli, cau or microorganisms and/or viruses. This may be one of the liflower, Brussels sprouts, pak choi, kohlrabi, radishes, and reasons for the enhanced activity of the inventive combina also oilseed rape, mustard, horseradish and cress), Fabacae tions, for example against fungi. Plant-fortifying (resistance sp. (for example beans, peanuts), Papillonaceae sp. (for inducing) Substances shall be understood to mean, in the example Soya beans), Solanaceae sp. (for example potatoes), present context, also those Substances or combinations of Chenopodiaceae sp. (for example Sugar beet, fodder beet Substances which are capable of stimulating the defence sys Swiss chard, beetroot); useful plants and ornamental plants in tem of plants in Such a way that, when Subsequently inocu gardens and forests; and genetically modified types of each of lated with unwanted phytopathogenic fungi, the plants treated these plants. display a Substantial degree of resistance to these unwanted 0312. As already mentioned above, it is possible to treat all phytopathogenic fungi. The inventive substances can there plants and their parts according to the invention. In a preferred fore be used for protection of plants from attack by the patho embodiment, wild plant species and plant cultivars, or those gens mentioned within a certain period of time after the obtained by conventional biological breeding methods, Such treatment. The period within which protection is achieved as crossing or protoplast fusion, and also parts thereof, are generally extends for from 1 to 10 days, preferably 1 to 7 days, treated. In a further preferred embodiment, transgenic plants after the treatment of the plants with the active ingredients. and plant cultivars obtained by genetic engineering, if appro 0316 Plants and plant varieties which are preferably priate in combination with conventional methods (Geneti treated in accordance with the invention include all plants cally Modified Organisms), and parts thereofare treated. The which have genetic material which imparts particularly term “pats' or “parts of plants' or “plant parts” has been advantageous, useful traits to these plants (whether obtained explained above. More preferably, plants of the plant cultivars by breeding and/or biotechnological means). which are each commercially available or in use are treated in 0317 Plants and plant varieties which are likewise prefer accordance with the invention. Plant cultivars are understood ably treated in accordance with the invention are resistant to to mean plants which have new properties (“traits') and have one or more biotic stress factors, i.e. said plants have a better been obtained by conventional breeding, by mutagenesis or defence against animal and microbial pests, such as against by recombinant DNA techniques. They can be cultivars, vari nematodes, insects, mites, phytopathogenic fungi, bacteria, eties, bio- or genotypes. viruses and/or viroids. 0313. The inventive treatment method can be used for the 0318. Plants and plant varieties which may also be treated treatment of genetically modified organisms (GMOs), for according to the invention are those plants which are resistant example plants or seeds. Genetically modified plants (or to one or more abiotic stress factors. Abiotic stress conditions transgenic plants) are plants in which a heterologous gene has may include, for example, drought, cold temperature expo been integrated Stably into the genome. The expression "het Sure, heat exposure, osmotic stress, waterlogging increased erologous gene' essentially means a gene which is provided soil salinity, increased exposure to minerals, exposure to or assembled outside the plant and when introduced in the oZone, exposure to strong light, limited availability of nitro nuclear, chloroplastic or mitochondrial genome gives the gen nutrients, limited availability of phosphorus nutrients or transformed plant new or improved agronomic or other prop shade avoidance. erties by expressing a protein or polypeptide of interest or by 0319 Plants and plant varieties which can likewise be downregulating or silencing other gene(s) which are present treated in accordance with the invention are those plants in the plant (using for example antisense technology, coSup which are characterized by enhanced yield characteristics. pression technology or RNAi technology RNA interfer Enhanced yield in these plants may be the result of for ence). A heterologous gene present in the genome is also example, improved plant physiology, improved plant growth called a transgene. A transgene that is defined by its specific and development, such as water use efficiency, water reten presence in the plant genome is called a transformation or tion efficiency, improved nitrogen use, enhanced carbon transgenic event. assimilation, improved photosynthesis, increased germina 0314 Depending on the plant species or plant varieties, tion efficiency and accelerated maturation. Yield can also be their location and growth conditions (soils, climate, vegeta affected by improved plant architecture (under stress and US 2014/0148471 A1 May 29, 2014 27 non-stress conditions), including early flowering, flowering acetyltransferase enzyme. Glyphosate-tolerant plants can control for hybrid seed production, seedling vigour, plant also be obtained by selecting plants containing naturally size, internode number and distance, root growth, seed size, occurring mutations of the abovementioned genes. fruit size, pod size, pod or ear number, seed number per pod 0323. Other herbicide-resistant plants are for example or ear, seed mass, enhanced seed filling, reduced seed dis plants that have been made tolerant to herbicides inhibiting persal, reduced pod dehiscence and lodging resistance. Fur the enzyme glutamine synthase, Such as bialaphos, phosphi ther yield traits include seed composition, such as carbohy nothricin or glufosinate. Such plants can be obtained by drate content, protein content, oil content and composition, expressing an enzyme detoxifying the herbicide or a mutant nutritional value, reduction in anti-nutritional compounds, glutamine synthase enzyme that is resistant to inhibition. One improved processibility and better storage stability. Such efficient detoxifying enzyme is, for example, an enzyme 0320 Plants that may be treated according to the invention encoding a phosphinothricin acetyltransferase (such a the bar are hybrid plants that already express the characteristics of or pat protein from Streptomyces species). Plants expressing heterosis, or hybrid effect, which results in generally higher an exogenous phosphinothricin acetyltransferase have been yield, vigour, health and resistance towards biotic and abiotic described. stress factors. Such plants are typically produced by crossing 0324 Further herbicide-tolerant plants are also plants that an inbred male-sterile parent line (the female parent) with have been made tolerant to the herbicides inhibiting the another inbred male-fertile parent line (the male parent). The enzyme hydroxyphenylpyruvatedioxygenase (HPPD). hybrid seed is typically harvested from the male-sterile plants Hydroxyphenylpyruvatedioxygenases are enzymes that and sold to growers. Male-sterile plants can sometimes (for catalyse the reaction in which para-hydroxyphenylpyruvate example in maize) be produced by detasseling (i.e. mechani (HPP) is converted to homogentisate. Plants tolerant to HPPD cal removal of the male reproductive organs or male flowers); inhibitors can be transformed with a gene encoding a natu however, it is more typical for malesterility to be the result of rally occurring resistant HPPD enzyme, or a gene encoding a genetic determinants in the plant genome. In that case, and mutated HPPD enzyme. Tolerance to HPPD inhibitors can especially when seed is the desired product to be harvested also be obtained by transforming plants with genes encoding from the hybrid plants, it is typically beneficial to ensure that certain enzymes enabling the formation of homogentisate male fertility in hybrid plants, which contain the genetic despite the inhibition of the native HPPD enzyme by the determinants responsible for male sterility, is fully restored. HPPD inhibitor. Tolerance of plants to HPPD inhibitors can This can be accomplished by ensuring that the male parents also be improved by transforming plants with a gene encod have appropriate fertility restorer genes which are capable of ing an enzyme prephenate dehydrogenase in addition to a restoring the male fertility in hybrid plants that contain the gene encoding an HPPD-tolerant enzyme. genetic determinants responsible for male sterility. Genetic 0325 Further herbicide-resistant plants are plants that determinants for male sterility may be located in the cyto have been made tolerant to acetolactate synthase (ALS) plasm. Examples of cytoplasmic male sterility (CMS) were inhibitors. The known ALS inhibitors include, for example, for instance described for Brassica species. However, genetic Sulphonylurea, imidazolinone, trizalopyrimidines, pyrimidi determinants for male sterility can also be located in the nyl oxy(thio)benzoates and/or Sulphonylaminocarbonyltria nuclear genome. Male-sterile plants can also be obtained by olinone herbicides. Different mutations in the ALS enzyme plant biotechnology methods such as genetic engineering. A (also known as acetohydroxy acid synthase, AHAS) are particularly useful means of obtaining male-sterile plants is known to confer tolerance to different herbicides and groups described in WO 89/10396, in which, for example, a ribonu of herbicides. The production of sulphonylurea-tolerant clease Such as a barnase is selectively expressed in the tape plants and imidazolinone-tolerant plants has been described tum cells in the stamens. Fertility can then be restored by in the international publication WO 1996/033270. Further expression in the tapetum cells of a ribonuclease inhibitor Sulphonylurea- and imidazolinone-tolerant plants have also Such as barstar. been described, for example in WO 2007/024782. 0321 Plants or plant varieties (obtained by plant biotech 0326. Other plants tolerant to imidazolinone and/or sul nology methods such as genetic engineering) which may be phonylurea can be obtained by induced mutagenesis, by treated according to the invention are herbicide-tolerant selection in cell cultures in the presence of the herbicide or by plants, i.e. plants made tolerant to one or more given herbi mutation breeding. cides. Such plants can be obtained either by genetic transfor 0327 Plants or plant cultivars (obtained by plant biotech mation, or by selection of plants containing a mutation nology methods such as genetic engineering) which may also imparting Such herbicide tolerance. be treated according to the invention are insect-resistant 0322. Herbicide-tolerant plants are, for example, glypho transgenic plants, i.e. plants made resistant to attack by cer sate-tolerant plants, i.e. plants which have been made tolerant tain target insects. Such plants can be obtained by genetic to the herbicide glyphosate or salts thereof. For example, transformation, or by selection of plants containing a muta glyphosate-tolerant plants can be obtained by transforming tion which imports such insect resistance. the plant with a gene which encodes the enzyme 5-enolpyru 0328. In the present context, the term “insect-resistant vylshikimate-3-phosphate synthase (EPSPS). Examples of transgenic plant includes any plant containing at least one such EPSPS genes are the AroA gene (mutant CT7) of the transgene comprising a coding sequence encoding: bacterium Salmonella typhimurium, the CP4 gene of the bac 0329. 1) an insecticidal crystal protein from Bacillus thu terium Agrobacterium sp., the genes encoding a petunia ringiensis or an insecticidal portion thereof Such as the EPSPS, a tomato EPSPS, or an Eleusine EPSPS. It can also be insecticidal crystal proteins compiled online at http:// a mutated EPSPS. Glyphosate-tolerant plants can also be www.lifesci. Sussex.ac.uk/Home/Neil Crickmore/Bt/, or obtained by expressing a gene that encodes a glyphosate insecticidal portions thereof, for example proteins of the oxidoreductase enzyme. Glyphosate-tolerant plants can also Cry protein classes Cry1Ab, Cry1Ac, Cry 1F, Cry2Ab, be obtained by expressing a gene that encodes a glyphosate Cry3Ae or Cry3Bb or insecticidal portions thereof; or US 2014/0148471 A1 May 29, 2014 28

0330 2) a crystal protein from Bacillus thuringiensis or a 0339 a. plants which contain a transgene capable of portion thereof which is insecticidal in the presence of a reducing the expression and/or the activity of the poly second other crystal protein than Bacillus thuringiensis or (ADP-ribose)polymerase (PARP) gene in the plant cells or a portion thereof. Such as the binary toxin made up of the plants; Cy34 and Cy35 crystal proteins; or 0340 b. plants which contain a stress tolerance-enhancing 0331 3) a hybrid insecticidal protein comprising parts of transgene capable of reducing the expression and/or the two different insecticidal crystal proteins from Bacillus activity of the PARG-encoding genes of the plants or plant thuringiensis, such as a hybrid of the proteins of 1) above or cells; a hybrid of the proteins of2) above, for example the Cry1A. 0341 c. plants which contain a stress tolerance-enhancing 105 protein produced by maize event MON98034 (WO transgene coding for a plant-functional enzyme of the nico 2007/027777); or tinamide adenine dinucleotide Salvage biosynthesis path way, including nicotinamidase, nicatinate phosphoribosyl 0332 4) a protein of any one of points 1) to 3) above transferase nicotinic acid mononucleotide wherein some, particularly 1 to 10, amino acids have been adenyltransferase nicotinamide adenine dinucleotide syn replaced by another amino acid to obtain a higher insecti thetase or nicotinamide phosphoribosyltransferase. cidal activity to a target insect species, and/or to expand the 0342 Plants or plant cultivars (obtained by plant biotech range of target insect species affected, and/or because of nology methods such as genetic engineering) which may also changes induced in the encoding DNA during cloning or be treated according to the invention show altered quantity, transformation, such as the Cry3Bb1 protein in maize quality and/or storage stability of the harvested product and/ events MON863 or MON88017, or the Cry3A protein in or altered properties of specific ingredients of the harvested maize event MIR604; or product Such as: 0333 5) an insecticidal secreted protein from Bacillus 0343 1) Transgenic plants which synthesize a modified thuringiensis or Bacillus cereus, or an insecticidal portion starch which is altered with respect to its chemophysical thereof such as the vegetative insecticidal proteins (VIP) traits, in particular the amylose content or the amylose/ listed at: http://www.lifesci.sussex.ac.uk/Home/Neil amylopectin ratio, the degree of branching, the average Crickmore/Bt/vip.html, for example proteins from the chain length, the distribution of the side chains, the Viscos VIP3Aa protein class; or ity behaviour, the gel resistance, the grain size and/or grain 0334 6) a secreted protein from Bacillus thuringiensis or morphology of the starch in comparison to the synthesized Bacillus cereus which is insecticidal in the presence of a starch in wild-type plant cells or plants, such that this second secreted protein from Bacillus thuringiensis or B. modified starch is better suited for certain applications. cereus, such as the binary toxin made up of the VIP1A and 0344) 2) Transgenic plants which synthesize non-starch VIP2A proteins; carbohydrate polymers or which synthesize non-starch carbohydrate polymers with altered properties in compari 0335 7) a hybrid insecticidal protein comprising parts son to wild-type plants without genetic modification. from different secreted proteins from Bacillus thuringien Examples are plants which produce polyfructose, espe sis or Bacillus cereus, Such as a hybrid of the proteins in 1) cially of the inulin and levan type, plants which produce above or a hybrid of the proteins in 2) above; or alpha-1,4-glucans, plants which produce alpha-1,6- 0336 8) a protein of any one of points 1) to 3) above branched alpha-1,4-glucans, and plants producing alter wherein some, particularly 1 to 10, amino acids have been a. replaced by another amino acid to obtain a higher insecti 0345 3) Transgenic plants which produce hyaluronan. cidal activity to a target insect species, and/or to expand the 0346 Plants or plant cultivars (obtained by plant biotech range of target insect species affected, and/or because of nology methods such as genetic engineering) which may also changes induced in the encoding DNA during cloning or be treated according to the invention are plants. Such as cotton transformation (while still encoding an insecticidal pro plants, with altered fibre characteristics. Such plants can be tein), such as the VIP3Aa protein in cotton event COT 102. obtained by genetic transformation, or by selection of plants 0337 Of course, insect-resistant transgenic plants, as used containing a mutation imparting Such altered fibre character herein, also include any plant comprising a combination of istics and include: genes encoding the proteins of any one of the abovemen 0347 a) plants, such as cotton plants, which contain an tioned classes 1 to 8. In one embodiment, an insect-resistant altered form of cellulose synthase genes; plant contains more than one transgene encoding a protein of 0348 b) plants, such as cotton plants, which contain an any one of the abovementioned classes 1 to 8, to expand the altered form of rSw2 or rSw3 homologous nucleic acids; range of target insect species affected or to delay insect resis 0349 c) plants, such as cotton plants, with an increased tance development to the plants, by using different proteins expression of Sucrose phosphate synthase, insecticidal to the same target insect species but having a 0350 d) plants, such as cotton plants, with an increased different mode of action, such as binding to different receptor expression of Sucrose synthase; binding sites in the insect. 0351 e) plants, such as cotton plants, wherein the timing 0338 Plants or plant cultivars (obtained by plant biotech of the plasmodesmatal gating at the basis of the fibre cell is nology methods such as genetic engineering) which may also altered, for example through downregulation of fibre-se be treated according to the invention are tolerant to abiotic lective f3-1,3-glucanase; stress factors. Such plants can be obtained by genetic trans 0352 f) plants, such as cotton plants, which have fibres formation, or by selection of plants containing a mutation with altered reactivity, for example through the expression imparting such stress resistance. Particularly useful stress of the N-acetylglucosaminetransferase gene including tolerant plants include the following: nodC and chitin Synthase genes. US 2014/0148471 A1 May 29, 2014 29

0353 Plants or plant cultivars (obtained by plant biotech Anopheles spp., Culex spp., Simulium spp., Eusimulium spp., nology methods such as genetic engineering) which may also Phlebotomus spp., Lutzomyia spp., Culicoides spp., be treated according to the invention are plants, such as oil Chrysops spp., Hybomitra spp., Atylotus spp., Tabanus spp., seed rape or related Brassica plants, with altered oil profile Haematopota spp., Philipomyia spp., Braula spp., Musca characteristics. Such plants can be obtained by genetic trans spp., Hydrotaea spp., Stomoxys spp., Haematobia spp., formation, or by selection of plants containing a mutation Morelia spp., Fannia spp., Glossina spp., Caliphora spp., imparting Such altered oil characteristics and include: Lucilia spp., Chrysomyia spp., Wohlfahrtia spp., Sarcophaga 0354) a) plants, such as oilseed rape plants, which produce spp., Ocstrus spp., Hypoderma spp., Gasterophilus spp., Hip oil having a high oleic acid content; pobosca spp., Lipoptena spp. and Mellophagus spp. 0355 b) plants, such as oilseed rape plants, which produce 0364. From the order of the Siphonapterida, for example oil having a low linolenic acid content; Pulex spp., Ctenocephalides spp. (Ctenocephalides canis, 0356 c) plants, such as oilseed rape plants, which produce Ctenocephalides felis), Xenopsylla spp. and Ceratophyllus oil having a low level of saturated fatty acids. spp. 0357 Particularly useful transgenic plants which may be 0365. From the order of the Heteropterida, for example, treated according to the invention are plants which comprise Cimex spp., Triatoma spp., Rhodnius spp. and Panstrongylus one or more genes which encode one or more toxins are the spp. transgenic plants which are sold under the following trade 0366. From the order of the Blattarida, for example Blatta names: YIELD GARDR) (for example maize, cotton, soya Orientalis, Periplaneta americana, Blattella germanica and beans), KnockCut(R) (for example maize), BiteCard R. (for Supella spp. example maize), BT-Xtra.R. (for example maize), StarLink R. (for example maize), Bolgard(R) (cotton), Nucotnir (cotton), 0367 From the subclass of the Acari (Acarina) and the Nucotn 33B(R) (cotton), NatureGard(R) (for example maize), orders of the Meta- and Mesostigmata, for example, Argas ProtectaR) and New Leaf R (potato). Examples of herbicide spp., Ornithodorus spp., Otobius spp., Ixodes spp., Amblvo tolerant plants which should be mentioned are maiz varieties, mma spp., Boophilus spp., Dermacentor spp., Haemophysa cotton varieties and soya been varieties which are available lis spp., Hyalomma spp., Rhipicephalus spp., Dermanyssus under the following trade names: Roundup Ready(R) (toler spp., Raillietia spp., Pneumonyssus spp., Sternostoma spp. ance to glyphosate, for example maize, cotton, Soya beans), and Varroa spp. Liberty Link. R (tolerance to phosphinothricin, for example 0368 From the order of the Actinedida (Prostigmata) and oilseed rape), IMIR (tolerance to imidazolinone) and SCS(R) Acaridida (Astigmata), for example, Acarapis spp., Cheyle (tolerance to Sulphonylurea, for example maize). Herbicide tiella spp., Ornithochevletia spp., Myobia spp., Psorergates resistant plants (plants bred in a conventional manner for spp., Demodex spp., Trombicula spp., Listrophorus spp., herbicide tolerance) which should be mentioned include the Acarus spp., Tvrophagus spp., Caloglyphus spp., Hypodectes varieties sold under the Clearfield name (for example maize). spp., Pterolichus spp., Psoroptes spp., Chorioptes spp., Oto 0358 Particularly useful transgenic plants which may be dectes spp., Sarcoptes spp., Notoedres spp., Knemidocoptes treated according to the invention are plants containing trans spp., Cytodites spp. and Laminosioptes spp. formation events, or a combination of transformation events, 0369. The inventive active ingredients of the formula (I) and that are listed for example in the databases for various are also suitable for controlling arthropods which attack agri national or regional regulatory agencies (see for example cultural livestock, for example cattle, sheep, goats, horses, http://gmoinfo.jrc.it/gmp browse.aspx and http://www.ag pigs, donkeys, camels, buffaloes, rabbits, chickens, turkeys, bios.com/dbase.php). ducks, geese, honey-bees, other domestic animals such as, for 0359 The plants listed can be treated in accordance with example, dogs, cats, caged birds, aquarium fish, and experi the invention in a particularly advantageous manner with the mental animals, for example hamsters, guinea pigs, rats and compounds of the general formula (I) and/or the active ingre mice. The control of these arthropods is intended to reduce dient mixtures according to the invention. The preferred cases of death and reduced productivity (of meat, milk, wool, ranges stated above for the active ingredients or mixtures also hides, eggs, honey etc.), and so more economic and easier apply to the treatment of these plants. Particular emphasis is animal husbandry is possible by use of the inventive active given to the treatment of plants with the compounds or mix ingredients. tures specifically mentioned in the present text. 0370. The inventive active ingredients are used in the vet 0360. The inventive active ingredients act not only against erinary sector and in animal husbandry in a known manner, by plant, hygiene and stored product pests, but also in the vet enteral administration in the form of, for example, tablets, erinary medicine sector against animal parasites (ecto- and capsules, potions, drenches, granules, pastes, boluses, the endoperasites). Such as hard ticks, soft ticks, mange mites, feed-through process and Suppositories, by parenteral admin leaf mites, flies (biting and licking), parasitic fly larvae, lice, istration, Such as, for example, by injection (intramuscular, hair lice, feather lice and fleas. These parasites include: Subcutaneous, intravenous, intraperitoneal and the like), 0361 From the order of the Anoplurida, for example, Hae implants, by nasal administration, by dermal use in the form, matopinus spp., Linognathus spp., Pediculus spp., Phtirus for example, of dipping or bathing, spraying, pouring on and spp. and Solenopotes app. spotting on, washing and powdering, and also with the aid of 0362. From the order of the Mallophagida and the subor moulded articles containing the active ingredient, such as ders Amblycerina and Ischnocerina, for example, Trime collars, ear marks, tail marks, limb bands, halters, marking nopon spp., Menopon spp., Trinoton spp., Bovicola spp., Wer devices and the like. neckiella spp., Lepikentron spp., Damalina spp., 0371. When used for livestock, poultry, domestic animals Trichodectes spp., and Felicola spp. and the like, the active ingredients of the formula (I) can be 0363 From the order of the Diptera and the suborders used as formulations (for example powders, emulsions, flow Nematocerina and Brachycerina, for example, Aedes spp., ables) comprising the active ingredients in an amount of 1 to US 2014/0148471 A1 May 29, 2014 30

80% by weight, either directly or after 100 to 10 000-fold 0384 From the order of the Isopoda, for example, Oniscus dilution, or they may be used as a chemical bath. asellus, Porcellio Scaber: 0372. It has also been found that the inventive compounds 0385 From the order of the Diplopoda, for example, Bla have strong insecticidal action against insects which destroy niulus guttulatus, Polydesmus spp. industrial materials. 0386 From the order of the Chilopoda, for example, Geo 0373) Preferred but nonlimiting examples include the fol philus spp. lowing insects: 0387 From the order of the Zygentoma, for example, beetles, such as Hylotrupes bajulus, Chlorophorus pilosis, Ctenolepisma spp., Lepisma saccharina, Lepismodes inquili Anobium punctatum, Xestobium rufovillosum, Ptilinus pecti S. cornis, Dendrobium pertinex, Emobius mollis, Priobium car 0388. From the order of the Blattaria, for example, Blatta pini, Lyctus brunnrmeus, Lyctus africanus, Lyctus planicol Orientalies, Blattella germanica, Blattella asahinai, Leu lis, Lyctus linearis, Lyctus pubescens, Trogoxylon aequale, cophaea maderae, Panchlora spp., Parcoblattas spp., Minthes rugicollis, Xvleborus spec. Tryptodendron spec. Periplaneta australasiae, Periplaneta americana, Periplan Apate monachus, Bostrychus capucins, Heterobostrychus eta brunnea, Periplaneta fuliginosa, Supella longipalpa. brunneus, Sinoxylon spec. Dinoderus minutus, (0389. From the order of the Saltatoria, for example, dermapterans, such as Sirex juvencus, Urocerus gigas, Uro Acheta domesticus. Cerus gigas taignus, Urocerus augur, termites, such as Kalotermes flavicollis, Cryptotermes brevis, 0390 From the order of the Dermaptera, for example, Heterotermes indicola, Reticulitermes flavipes, Reticuliter Forficula auricularia. mes Santonensis, Reticulitermes lucifigus, Mastotermes dar 0391 From the order of the Isoptera, for example, Kalo winiensis, Zootermopsis nevadensis, Coptotermes formosa termes spp., Reticulitermes spp. fati.S. 0392. From the order of the Psocoptera, for example, Lepi bristletails, such as Lepisma saccarina. natus spp., LipOscelis spp. 0374 Industrial materials in the present connection are 0393. From the order of the Coleoptera, for example, understood to mean inanimate materials, such as preferably Anthrenus spp., Attagenus spp., Dermestes spp., Latheticus plastics, adhesives, sizes, papers and cards, leather, wood, Oryzae, Necrobia spp., Ptinus spp., Rhizopertha dominica, processed wood products and coating compositions. Sitophilus granarius, Sitophilus Oryzae, Sitophilus zeanais, 0375. The ready-to-use compositions may optionally also Stegobium paniceum. comprise other insecticides, and optionally one or more fun 0394 From the order of the Diptera, for example, Aedes gicides. aegypti, Aedes albopictus, Aedes taeniorhynchus, Anopheles 0376. With respect to possible additional mixing partners, spp., Caliphora erythrocephala, Chrysozona pluvialis, reference is made to the insecticides and fungicides men Culex quinquefasciatus, Culex pipiens, Culex tarsalis, tioned above. Drosophila spp., Fannia canicularis, Musca domestica, Phle 0377. At the same time, the inventive compounds can be botomus spp., Sarcophaga Camaria, Simulium spp., Stomoxys employed for protection of objects which come into contact calcitrans, Tipula paludosa. with saltwater or brackish water, especially hulls, Screens, 0395. From the order of the Lepidoptera, for example, nets, buildings, moorings and signalling systems, against Achroia grisella, Galleria mellonella, Plodia interpunctella, fouling. Tinea cloacella, Tinea pellionella, Tineola bisselliella. 0378. In addition, the inventive compounds can be used as 0396 From the order of the Siphonaptera, for example, antifouling compositions, alone or in combinations with Ctenocephalides canis, Ctenocephalides felis, Pulex irritans, other active ingredients. Tungs penetrans, Xenopsylla cheopis. 0379 The active ingredients are also suitable for control 0397. From the order of the Hymenoptera, for example, ling animal pests in the domestic sector, in the hygiene sector Camponotus herculeanus, Lasius fuliginosus, Lasius niger, and in the protection of Stored products, especially insects, Lasius umbratus, Monomorium pharaonis, Paravespula spp., arachnids and mites, which are found in enclosed spaces, for Tetramorium cacspitum. example homes, factory halls, offices, vehicle cabins and the 0398. From the order of the Anoplura, for example, like. They can be used to control these pests alone or in Pediculus humanus capitis, Pediculus humanus corporis, combination with other active ingredients and auxiliaries in Pemphigus spp., Phylloera vastatrix, Phthirus pubis. domestic insecticide products. They are effective against sen 0399. From the order of the Heteroptera, for example, sitive and resistant species, and against all developmental Cimex hemipterus, Cimex lectularius, Rhodinus prolixus, Tri stages. These pests include: atoma infestans. 0380 From the order of the Scorpionidea, for example, 0400. In the field of domestic insecticides, they are used Buthus Occitanus. alone or in combination with other Suitable active ingredients, 0381 From the order of the Acarina, for example, Argas Such as phosphoric esters, carbamates, pyrethroids, neonico persicus, Argas reflexus, Bryobia spp., Dermanyssus gallina, tinoids, growth regulators or active ingredients from other Glyciphagus domesticus, Ornithodorus moubat, Rhipiceph known classes of insecticides. alus sanguineus, Trombicula alfreddugesi, Neutrombicula 04.01 They are employed in aerosols, unpressurized spray autumnalis, Dernatophagoides pteronissimus, Dermatopha products, for example pump and atomizer sprays, automatic goides forinae. fogging Systems, foggers, foams, gels, evaporator products 0382 From the order of the Araneae, for example, Avicu with evaporator tablets made of cellulose or plastic, liquid lariidae, Araneidae. evaporators, gel and membrane evaporators, propeller-driven 0383. From the order of the Opiliones, for example, Pseu evaporators, energy-free or passive evaporation systems, doscorpiones chelifer, Pseudoscorpiones cheiridium, Opil moth papers, moth bags and moth gels, as granules or dusts, iones phalangium. in baits for spreading or in bait stations. US 2014/0148471 A1 May 29, 2014

PREPARATION EXAMPLES extracted with dichloromethane and the organic phase was dried over magnesium Sulphate. The solvent was removed on Example A a rotary evaporator under reduced pressure and the residue was chromatographed (ethyl acetate, cyclohexane). N-(6-1-(Pyridin-3-yl)-1H-pyrazol-4-ylpyridin-2-yl) (0408. Yield: 680 mg (55% of theory), log P (HCOOH) methaneSulphonamide 2.19, M+1272.2 (0409 H NMR (d-DMSO): 1.30 (s, 12H), 7.51 (m. 1H), Stage 1: 3-(4-Bromopyrazol-1-yl)pyridine 7.90 (s, 1H), 8.25 (m, 1H),8.51 (m, 1H), 8.73 (s, 1H),9.12 (m, 0402 1H). Stage 3: 6-1-(Pyridin-3-yl)-1H-pyrazol-4-ylpyri Na Na dine-2-amine 0410

2 2 C/N o?N B -- 0403 3-Pyrazol-1-ylpyridine (500 mg, 3.44 mmol) was dissolved in acetonitrile (15 ml), and ammonium cerium(IV) nitrate (944 mg, 1.72 mmol) was added (slightly exothermic). Or2 Yo N-Bromosuccinimide (736 mg, 4.13 mmol) was added in N portions (slightly exothermic) and the mixture was stirred at N room temperature for 30 minutes (min) and then heated under reflux for 3 hours (h). After the mixture had cooled, ethyl 2 Her acetate was added. The organic phase was washed with water, Br N NH2 Na washed with a sodium sulphate solution and then dried over Ns magnesium Sulphate. The solvent was removed on a rotary N evaporator under reduced pressure. 04.04 Yield: 750 mg (93% of theory), log P (HCOOH) 1.56, M+1 224.0 2 04.05 H NMR (d-DMSO): 7.54 (m, 1H), 7.90 (s, 1H), N NH2 8.20 (m. 1H), 8.55 (m, 1H), 8.79 (s, 1H), 9.06 (m, 1H). 0411 Under argon, 3.17 g (11.7 mmol) of 3-4-(4.4.5.5- Stage 2: 3-4-(4,4,5,5-Tetramethyl-1,3,2dioxaboro tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-pyrazol-1-ylpyri lan-2-yl)pyrazol-1-ylpyridine dine, 2.02 g (11.7 mmol) of 6-bromopyridine-2-amine and 945 mg (817 umol) of tetrakis(triphenylphosphine)palladium 0406 were added to a mixture, degassed by means of argon, of 23.3 ml of 2 M sodium carbonate solution in water and 63.3 ml of acetonitrile. The reaction mixture was heated to 75° C. for 18 N2 hours, diluted with acetonitrile after cooling, dried over NU/ Br MgSO, filtered and concentrated. The crude product thus obtained was purified by chromatography (acetonitrile/ac etone). r2 N 0412 Yield 1.76 g (71% of theory) 0413 HPLC-MS: log P (HCOOH): 0.30; mass (m/z): Na y 238.1 (M+H)" 0414 H NMR (d6-DMSO): 5.88 (s. 2H), 6.35 (d. 1H), R 6.93 (d. 1H), 7.42 (t, 1H), 7.58 (dd. 1H),8.22 (s, 1H), 8.28 (m, 1H), 8.54 (dd. 1H), 8.97 (s, 1H), 9.15 ppm (d. 1H). C2 N O N Stage 4: N-(6-1-(Pyridin-3-yl)-1H-pyrazol-4-yl) pyridin-2-yl)methanesulphonamide 0407 Under argon, 3-(4-bromopyrazol-1-yl)pyridine 0415 (1.00 g, 4.46 mmol), 1,1'-bis(diphenylphosphino)-ferrocene (dppf) (74 mg., 0.13 mmol), palladium dichloride-dppf (109 mg, 0.13 mmol), potassium acetate (1.31 g, 13.3 mmol) and N2 pinacolatodiborane (1.19 g, 4.68 mmol) were added to diox s ane (11 ml). The mixture was heated under reflux for 24 hand N N \ -- sa He then cooled. The solvent was removed on a rotary evaporator c1 N. under reduced pressure, dichloromethane (100 ml) and water (100 ml) were added to the residue, and the solids formed 4. NH2 were filtered off with suction and discarded. The filtrate was US 2014/0148471 A1 May 29, 2014 32

-continued Stage 2: Methyl 6-2-(5-fluoropyridin-3-yl)-1,3-thia N2 Zol-5-ylpyridine-2-carboxylate / NS N \ 0425 N N-Z O 4. N-429 iss y \ F N S -- 2 0416) 146 mg (585umol) of 6-1-(pyridin-3-yl)-1H-pyra N Zol-4-ylpyridine-2-amine and 54.0 ul (701 umol) of N-me thylmorpholine were initially charged in 10 ml of dichlo N romethane, and methaneSulphonyl chloride was added at 2 O room temperature. The mixture was stirred overnight and the Br N N -- reaction mixture was filtered through silica gel (eluent: ethyl acetate). After concentration, the crude product was purified O by chromatography (dichloromethane/methanol). 0417. Yield: 50 mg (27% of theory); HPLC-MS: log P F Y-N/ \ (HCOOH): 1.26; mass (m/z): 316.0 (M+H)"; N S Ns 0418 H NMR (d6-DMSO): 6.82 (d. 1H), 7.45 (d. 1H), 2 7.59 (dd. 1H), 7.78 (t, 1H), 8.30 (m, 2H), 8.57 (dd. 1H), 9.09 N O (s, 1H), 9.17 (d. 1H), 10.55 ppm (s, 1H). or \ Example B 0426 748 mg (4.15 mmol) of the fluoropyridylthiazole, 897 mg (4.15 mmol) of the bromopyridine, 62 mg (0.13 6-2-(5-Fluoropyridin-3-yl)-1,3-thiazol-5-yl)-N-(tri mmol) of dihydrogen dichlorobis(di-t-butylphosphinito-kP) fluoromethyl)sulphonyl-pyridine-2-carboxamide palladate(2-) (dichlorobisdi-tert-butyl (hydroxy)phospho ranyl)palladium, POPd, from CombiPhos, USA) and 1.147 Stage 1: 3-Fluoro-5-(1,3-thiazol-2-yl)pyridine g (8.3 mmol) of potassium carbonate were stirred in 10 ml of dimethylformamide under argon at 120° C. for 16 h. 0419 0427 For workup, the mixture was concentrated and puri fied by means of column chromatography on silica gel (elu ent: cyclohexane/ethyl acetate). 0428 Yield: 615 mg (47% of theory) 0429 HPLC-MS: log P (HCOOH): 2.37; mass (m/z): 316.0 (M+H)"; F N B-No - C - 0430 "H NMR (d6-DMSO): 3.93 (s, 3H), 8.03 (m, 1H), 8.14 (m. 1H), 8.36 (m, 2H), 8.73 (m. 1H), 8.80 (m. 1H), 9.12 2 (m. 1H) ppm. N Stage 3: 6-2-(5-Fluoropyridin-3-yl)-1,3-thiazol-5- y ylpyridine-2-carboxylic acid F S 0431 2 N

0420 2.0 g (8.97 mmol) of the pyridyl boric ester, 1.47g X-Y (8.97 mmol) of the 2-bromothiazole, 197 mg (0.27 mmol) of r S NS bis(diphenylphosphino)ferrocenepalladium(II) chloride and 2 3.72 g (26.9 mmol) of potassium carbonate were stirred under N O -> argon in 40 ml of dimethoxyethane at 80°C. for 16 h. or \ 0421 For workup, the mixture was concentrated and puri fied by means of column chromatography on silica gel (elu N ent: cyclohexane/ethyl acetate). F ()--/ 0422 Yield: 778 mg (48% of theory) N S Ns. 0423 HPLC-MS: log P (HCOOH): 1.48; mass (m/z): 4. OH 180.9 (M+H)"; O 0424 H NMR (d6-DMSO): 7.95 (m, 1H), 8.04 (m, 1H), 8.24 (m. 1H), 8.69 (m. 1H), 9.04 (m. 1H) ppm. US 2014/0148471 A1 May 29, 2014

0432 570 mg (1.81 mmol) of the methyl pyridylcarboxy Example C late were dissolved in a mixture of 25 ml of tetrahydrofuran and 8ml of water, a solution of 152 mg (3.62 mmol) of lithium 6-5-(5-Fluoropyridin-3-yl)-1,3,4-thiadiazol-2-yl)-N- hydroxide monohydrate in 17 ml of water was added and the (methylsulphonyl)pyridine-2-carboxamide mixture was stirred at room temperature for 16 h. 0443 0433 For workup, the mixture was concentrated and par titioned between water and methyl t-butyl ether, the aqueous -N phase was acidified with 1N hydrochloric acid, and the pre y-/s F \ cipitated solid was filtered off with suction and dried. N S NZ 0434 Yield: 556 mg (91% of theory) -- 2 0435 HPLC-MS: log P (HCOOH): 1.72; mass (m/z): N O 302.1 (M+H): O \ Li 0436 H NMR (d6-DMSO): 8.00 (m, 1H), 8.10 (m, 1H), O 832 (m, 2H), 8.72 (m, 1H), 8.78 (m, 1H), 9.10 (m, 1H), 13.5 (br) ppm. HNll O Stage 4: 6-2-(5-Fluoropyridin-3-yl)-1,3-thiazol-5- e N yl-N-(trifluoromethyl)sulphonylpyridine-2-car y-/s boxamide F \ N S N-Z 0437 4. H N O O \2 Y-N/ % s F S \ N Ns -- 0444, 200 mg (0.64 mmol) of the lithium salt and 1.01 g (7.78 mmol) of diisopropylethylamine were initially charged 2 N OH in 5 ml of acetonitrile, 198 mg (0.77 mmol) of bis(2-oxo-3- O oxazolidinyl)-phosphinyl chloride (BOP-CI) were added, the O mixture was stirred for 20 min, 185 mg (1.94 mmol) of methanesulphonamide and 99 mg (0.64 mmol) of diazabicy Os! cloundecene (DBU) were added and the mixture was stirred F>r YNH, s at room temperature for 16 h. F 0445 For workup, the mixture was concentrated and par titioned between water and ethyl acetate, and the organic Y-N/\ F phase was dried and concentrated. The further purification was effected by means of column chromatography on silica F N S Ns \ NY O gel (eluent: dichloromethane/methanol) and then on RP 18 l/ silica gel (eluent: waterfacetonitrile). N / \,, 0446. Yield: 37 mg (15% of theory) O H 0447. HPLC-MS: log P (HCOOH): 1.79; mass (m/z): 380.1 (M+H): 0438 100 mg (0.33 mmol) of the pyridylcarboxylic acid 0448 1H NMR (d6-DMSO): 3.40 (s, 3H), 8.22 (m, 1H), were initially charged in 5 ml of tetrahydrofuran, 81 mg (0.50 8.30 (m. 1H), 8.48 (m, 1H), 8.59 (m. 1H), 8.82 (m. 1H), 9.18 mmol) of carbonyldiimidazole were added and the mixture (m. 1H), 12.1 (br) ppm. was boiled at reflux for 1 h. After cooling to room tempera Example D ture, 74 mg (0.50 mmol) of trifluoromethanesulphonamide were added, the mixture was stirred for 10 min, then 76 mg 6-1-(5-Fluoropyridin-3-yl)-1H-pyrazol-4-yl)-N- (0.50 mmol) of diazabicycloundecene (DBU) were added and (methylsulphonyl)pyridine-2-carboxamide the mixture was stirred at room temperature for 16 h. 0439 For workup, the mixture was concentrated and puri Stage 1: fied by means of column chromatography on silica gel (elu 6-Bromo-N-(methylsulphonyl)pyridine-2-carboxamide ent: dichloromethane/methanol). 0449) 0440 Yield: 28 mg (20% of theory) N 0441 HPLC-MS: log P (HCOOH): 1.86; mass (m/z): Hy 433.0 (M+H)"; O + leO 0442 H NMR (d6-DMSO): 7.60 (m, 1H), 7.88 (m, 1H), Br 4. o 7.96 (m. 1H), 8.12 (m, 1H), 8.30 (m, 1H), 8.70 (m. 1H), 8.89 (m. 1H), 9.10 (m. 1H) ppm. US 2014/0148471 A1 May 29, 2014 34

-continued Stage 3: 6-1-(5-Fluoropyridin-3-yl)-1H-pyrazol-4- N yl-N-(methylsulphonyl)pyridine-2-carboxamide H O 0460) Br N 2 N n iII 1.

O O F

0450 5.40 g (26.7 mmol) of 6-bromo-2-pyridinecarboxy lic acid were initially charged in 150 ml of tetrahydrofuran, 6.51 g (40.0 mmol) of carbonyldiimidazole were added and the mixture was boiled at reflux for 1 h. After cooling to room temperature, 3.81 g (40.0 mmol) of methanesulphonamide were added, the mixture was stirred for 10 min, then 6.10 g (40 mmol) of diazabicycloundecene (DBU) were added and the mixture was stirred at room temperature for 16 h. 0451. For workup, the mixture was concentrated and puri fied by means of column chromatography on silica gel (elu ent: dichloromethane/methanol). 0452. Yield: 5.10 g (69% of theory) H 0453 HPLC-MS: log P (HCOOH): 1.21; mass (m/z): N O 281.0 (M+H)"; O \/ 0454 H NMR (d6-DMSO): 3.37 (s, 3H), 7.95 (m, 2H), % s 8.06 (m. 1H) ppm. Stage 2: N-(Methylsulphonyl)-6-(1H-pyrazol-4-yl) 0461) 43 mg (0.37 mmol) of 3,5-difluoropyridine, 99 mg pyridine-2-carboxamide (0.37 mg) of the pyrazolylpyridine, 6 mg (0.01 mmol) of dihydrogen dichloro bis(di-t-butylphosphinito-kP)palladate 0455 (2-) (POPd, from CombiPhos, USA) and 102 mg (0.74 mmol) of potassium carbonate were stirred in 5 ml of dim ethylformamide under argon at 120° C. for 12 h. N 0462 For workup, the mixture was concentrated and puri ? O fied by means of column chromatography on silica gel (elu HN 21 1. ent: dichloromethane/methanol). R -- 0463 Yield: 35 mg (26% of theory) O 0464 HPLC-MS: log P (HCOOH): 1.98; mass (m/z): 362.1 (M+H)*: N 0465 H NMR (d6-DMSO): 3.40 (s, 3H), 7.98 (m, 1H), 8.08 (m, 2H), 8.2 (m, 1H), 8.58 (m, 1H), 8.70 (m, 1H), 9.08 Br N 2 NNg1 - - - (m. 1H), 9.40 (m. 1H) ppm. Example E N-(6-2-(Pyridin-3-yl)-1,3-thiazol-5-ylpyridin-2- y1}Sulphonyl)acetamide Stage 1: N-(6-Bromopyridin-2-yl)sulphonyl)acetamide 0466 0456 285 mg (1.47 mmol) of the 4-pyrazoleboronic ester, 410 mg (1.47 mmol) of the bromopyridine, 32 mg (0.04 N mmol) of bis(diphenylphosphino) ferrocenepalladium(II) O chloride and 467 mg (4.41 mmol) of potassium carbonate were stirred in 10 ml of dimethoxyethane under argon at 80° Br 4. 4. C. for 16 h. / YNH, 0457 For workup, the mixture was concentrated and puri N fied by means of column chromatography on silica gel (elu O O ent: cyclohexane/ethyl acetate). B 4. 4. ls 0458 Yield: 145 mg (37% of theory) / SN CH 0459 HPLC-MS: log P (HCOOH): 0.91; mass (m/z): 267.0 (M+H)" US 2014/0148471 A1 May 29, 2014

0467 6-Bromopyridine-2-sulphonamide (0.5 g, 2.11 0473 H NMR (d6-DMSO): 2.03 (s, 3H), 7.61 (m, 1H), mmol, prepared by the methods described in WO2005/ 8.02 (m. 1H), 8.13 (m. 1H), 830 (m, 1H), 8.41 (m, 1H), 8.71 058299) and potassium carbonate (2.92 g, 21.1 mmol) were (m. 1H), 8.91 (m. 1H), 9.20 (m. 1H) ppm. initially charged in acetonitrile (10 ml). While cooling with ice, acetylchloride (1.16 g. 14.8 mmol) was added dropwise Example F and the reaction mixture was stirred at room temperature for 16 h. The solvent was removed under reduced pressure, and N-(6-1-(Pyridin-3-yl)-1H-pyrazol-4-ylpyridin-2- the residue was taken up in water and acidified with dilute y1}Sulphonyl)acetamide hydrochloric acid solution. It was extracted with ethylacetate and the solvent was removed under reduced pressure. This Stage 1: 6-(Pyridin-3-yl)-1H-pyrazol-4-yl)pyridine gave 0.54 g (85% of theory) of N-(6-bromopyridin-2-yl) 2-Sulphonamide Sulphonyl-acetamide. 0468 HPLC-MS: Log P (HCOOH): 0.95; mass (m/z): 0474) 278.9 (M+H)"; 0469 H NMR (d6-DMSO): 1.99 (s.3H), 799-8.01 (m, CH3 1H), 8.08 (t, 1H), 8.11-8.13 (m. 1H), 12.48 (s, 1H) ppm. B Stage 2: N-(6-2-(Pyridin-3-yl)-1,3-thiazol-5-yl) s- O-CIY CHs it pyridin-2-yl)sulphonyl)acetamide CH3 2 0470 N

N O 2N / -e- Br N n / NH2

N N/

0475 Under argon, 3-4-(4.4.5.5-tetramethyl-1,3,2-diox aborolan-2-yl)-1H-pyrazol-1-yl)pyridine (0.2g, 0.74 mmol. prepared by the methods described in WO 2011/045224), 6-bromopyridin-2-sulphonamide (0.175 g, 0.74 mmol) and tetrakis(triphenylphosphine)palladium (0.025 g, 0.022 mmol) were added to a mixture, degassed by means of argon, 0471 N-(6-Bromopyridin-2-yl)sulphonyl)acetamide of sodium carbonate solution in water (2.9 ml, 2 M/L) and (0.112 g, 0.4 mmol), 3-(1,3-thiazol-2-yl)pyridine (0.065 g, acetonitrile (4 ml). The reaction mixture was stirred at 70° C. 0.4 mmol, prepared by the methods described in WO 2010/ for 18 h. After cooling, the reaction mixture was poured onto 006713), dichlorobisdi-tert-butyl(hydroxy)phosphoranyl water and the precipitated crystals were filtered off with suc tion. They were subsequently stirred with diethyl ether and palladium (0.006 g., 0.012 mmol) and caesium carbonate filtered off with suction. This gave 0.23 g (97% of theory) of (0.26g, 0.8 mmol) were stirred in 10 ml of N,N-dimethylfor 6-1-(pyridin-3-yl)-1H-pyrazol-4-ylpyridine-2-sulphona mamide at 120° C. under argon for 16 h. After cooling, the Solvent was removed under reduced pressure and the residue mide. was chromatographed (silica gel, dichloromethane/methanol 0476 HPLC-MS: Log P (HCOOH): 0.99; mass (m/z): eluent). This gave 0.024 g (15% of theory) of N-(6-2- 302.1 (M+H)" (pyridin-3-yl)-1,3-thiazol-5-ylpyridin-2-ylsulphonyl)ac 0477 H NMR (d6-DMSO): 7.43 (s. 2H), 7.60-7.63 (m, etamide. 1H), 7.76 (d. 1H), 8.00 (d. 1H), 8.11 (t, 1H), 8.28-8.31 (m, 0472 HPLC-MS: Log P (HCOOH): 1.30; mass (m/z): 1H), 8.53 (s, 1H), 8.58-8.60 (m, 1H), 9.16-9.17 (m, 1H), 9.33 361.0 (M+H): (S, 1H) ppm US 2014/0148471 A1 May 29, 2014 36

Stage 2: N-(6-1-(Pyridin-3-yl)-1H-pyrazol-4-yl) pyridin-2-yl)sulphonyl)acetamide -continued 0478

29 N V O) O CH S

0483 2-Bromo-1,3-thiazole-4-carboxylic acid (0.8 g. 3.85 mmol) was initially charged in tetrahydrofuran (10 ml). N,N'-Carbonyldiimidazole (0.94 g. 5.77 mmol) was added and the reaction mixture was heated under reflux for 1 h. Methanesulphonamide (0.55 g, 5.77 mmol) was added and, after 10 min, 1.8-diazabicyclo5.4.0]undec-7-ene (0.88 g. 5.77 mmol). The reaction mixture was stirred at room tem perature for 16 h and then the solvent was removed under reduced pressure. The residue was taken up in water and acidified with hydrochloric acid. The precipitated product was filtered off with suction. The aqueous phase was extracted with dichloromethane; the organic phase was dried over sodium sulphate and filtered, and the solvent was removed under reduced pressure. This gave a total of 1.0 g (89% of theory) of 2-bromo-N-(methylsulphonyl)-1,3-thiaz 0479. 6-1-(Pyridin-3-yl)-1H-pyrazol-4-ylpyridin-2-sul ole-4-carboxamide. phonamide (0.15 g., 0.44 mmol) was initially charged in 0484 HPLC-MS: Log P (HCOOH): 0.83; mass (m/z): acetonitrile (1.5 ml) under argon, and sodium hydride (0.026 284.9 (M+H)"; g, 0.66 mmol. 60%) was added in portions. The reaction mixture was stirred at room temperature for 1 h, then acetyl 0485 H NMR (d6-DMSO): 3.33 (s, 3H), 8.61 (s, 1H), chloride (0.052 g, 0.66 mmol) was added dropwise. The 12.00 (s, 1H) reaction mixture was stirred at 82° C. for 33 hand, after cooling, the solvent was removed under reduced pressure. Stage 2: N-(Methylsulphonyl)-2-1-(pyridin-3-yl)- The residue was taken up in Saturated sodium hydrogencar 1H-pyrazol-4-yl-1,3-thiazole-4-carboxamide bonate Solution, dichloromethane was added and the precipi tated solid was filtered off. The phases of the filtrate were 0486 separated; the aqueous phase was adjusted to pH 3 with hydrochloric acid and left to stand for 16 h. The precipitated crystals were filtered off with suction. Yield 0.02 g (12% of CH3 theory) of N-(6-1-(pyridin-3-yl)-1H-pyrazol-4-yl-pyridin 2-yl)sulphonyl)acetamide. O- B/ CH3 0480 HPLC-MS: Log P (HCOOH): 1.17; mass (m/z): s- Y CHs it 344.1 (M+H)" CH3 0481 'H NMR (d6-DMSO): 2.03 (s, 3H), 7.60-7.64 (m, 2 1H), 7.92-7.94 (m. 1H), 8.08-8.10 (m. 1H), 8.17-8.20 (m, N 1H), 8.29-8.31 (m, 1H), 8.37 (s, 1H), 8.59-8.60 (m, 1H), O 9.16-9.17 (m. 1H), 9.26 (s, 1H), 12.31 (s, 1H) ppm H N O Example G Jyry,N O2, N-(Methylsulphonyl)-2-1-(pyridin-3-yl)-1H-pyra Br S Zol-4-yl-1,3-thiazole-4-carboxamide O Stage 1: 2-Bromo-N-(methylsulphonyl)-1,3-thiazole s Y (NH 4-carboxamide ^ 's ( 0482 Y M So HC

OH O V -NH2 -e- N N/

0487 Under argon, 3-4-(4.4.5.5-tetramethyl-1,3,2-diox aborolan-2-yl)-1H-pyrazol-1-yl)pyridine (0.1 g, 0.37 mmol), US 2014/0148471 A1 May 29, 2014 37

2-bromo-N-(methylsulphonyl-1,3-thiazole-4-carboxamide Stage 2: 4-1-(5-Fluoropyridin-3-yl)-1H-pyrazol-4- (0.105 g, 0.37 mmol) and tetrakis(triphenylphosphine)palla yl-N-(methylsulphonyl)-1,3-thiazole-2-carboxamide dium (0.013 g, 0.011 mmol) were added to a mixture, degassed by means of argon, of sodium carbonate Solution in 0494 water (1.5 ml, 2 M/L) and acetonitrile (3.8 ml). The reaction mixture was stirred at 70° C. for 16 h. After cooling, the reaction mixture was poured onto water and extracted with CH3 dichloromethane. The organic phase was dried over sodium Sulphate and the solvent was removed under reduced pres B sure. The residue was subsequently stirred with diethyl ether F s- O-CICY CHs it and filtered off with suction. This gave 0.23 g (97% of theory) CH3 2 of 6-1-(pyridin-3-yl)-1H-pyrazol-4-ylpyridine-2-sulpho N namide. 0488 HPLC-MS: Log P (HCOOH): 1.25; mass (m/z): 350.1 (M+H)" O 0489 H NMR (d6-DMSO): 3.38 (S. 3H), 7.48-749 (m, H 1H), 8.32-8.35 (m. 1H), 8.45 (s, 1H), 8.56 (s, 1H), 8.59-8.60 NY2 O (m. 1H), 9.19-9.20 (m. 1H), 9.34 (s, 1H) ppm N2\ a V Example H S. Br us/ " 4-1-(5-Fluoropyridin-3-yl)-1H-pyrazol-4-yl)-N- (methylsulphonyl)-1,3-thiazole-2-carboxamide Stage 1: 4-Bromo-N-(methylsulphonyl)-1,3-thiazole S O 2-carboxamide X-( 0490 / N 's (NH Y. /So, H3C O OH O -- \-NH. -as Na S HC1 V N

Br -N/ O 0495 Under argon, 3-fluoro-5-4-(4.4.5.5-tetramethyl-1, O 3.2-dioxaborolan-2-yl)-1H-pyrazol-1-yl)pyridine (0.2 g, H 0.69 mmol, prepared by the methods described in WO 2011/ Nye 045224), 2-bromo-N-(methylsulphonyl)-1,3-thiazole-4-car N2N cav boxamide (0.2 g, 0.69 mmol) and tetrakis-(triphenylphos CH3 phine)palladium (0.024 g., 0.021 mmol) were added to a mixture, degassed by means of argon, of Sodium carbonate solution in water (2.8 ml, 2 M/L) and acetonitrile (9.4 ml). 0491 4-Bromo-1,3-thiazole-2-carboxylic acid (1.0 g, 4.8 The reaction mixture was stirred at 70° C. for 16 h. After mmol) were initially charged in tetrahydrofuran (10 ml). cooling, the reaction mixture was poured onto water and N,N'-Carbonyldiimidazole (1.17 g, 7.2 mmol) was added and extracted with dichloromethane. The aqueous phase was the reaction mixture was heated under reflux for 1 h. Meth acidified with hydrochloric acid and the precipitated solid anesulphonamide (0.69 g, 7.2 mmol) was added and, after 10 was filtered off with suction. The crude product was chro min, 1.8-diazabicyclo[5.4.0]undec-7-ene (1.10g, 7.2 mmol). matographed with ethyl acetate/2-propenol on silica gel. This The reaction mixture was stirred at room temperature for 16 gave 0.21 g (8% of theory) of 4-1-(5-fluoropyridin-3-yl)- hand then the solvent was removed under reduced pressure. 1H-pyrazol-4-yl)-N-(methylsulphonyl)-1,3-thiazole-2-car The residue was taken up in water and acidified with hydro boxamide. chloric acid. The precipitated product was filtered off with suction. This gave 1.18 g (84% of theory) of 4-bromo-N- 0496 HPLC-MS: Log P (HCOOH): 1.68; mass (m/z): (methylsulphonyl)-1,3-thiazole-2-carboxamide. 368.1 (M+H)" 0492 HPLC-MS: Log P (HCOOH): 0.63; mass (m/z): 0497 H NMR (d6-DMSO): 2.99 (s.3H), 7.96 (s, 1H), 284.9 (M+H): 8.33 (s, 1H), 8.34 (s, 1H), 8.55-8.57 (m, 1H), 9.10 (s, 1H), 0493 H NMR (d6-DMSO): 3.31 (s, 3H), 8.31 (s, 1H) 9.12 (s, 1H) ppm US 2014/0148471 A1 May 29, 2014 38

Example I Stage 2: Ethyl 3-2-(5-fluoropyridin-3-yl)-4-methyl 1,3-thiazol-5-yl)-1-methyl-1H-pyrazole-5-carboxy 3-2-(5-Fluoropyridin-3-yl)-4-methyl-1,3-thiazol-5- late yl)-1-methyl-N-(methyl-sulphonyl)-1H-pyrazole-5- 0502 carboxamide

Stage 1: Ethyl 4-2-(5-fluoropyridin-3-yl)-4-methyl O 1,3-thiazol-5-yl)-2,4-dioxobutanoate CH3 O N \-ch, 0498 F N O N S O CH3 N N CH3

F -- S O

2 N

O H3 1. O O N- CH3 -

O

O CH3 O 0503 Ethyl 4-2-(5-fluoropyridin-3-yl)-4-methyl-1,3- N \-ch, thiazol-5-yl)-2,4-dioxobutanoate (6.9 g, 20.5 mmol) and methylhydrazine (0.65g, 20.5 mmol) were heated in ethanol F Y O (250 ml) under reflux for 2b. The product formed was filtered off with suction and the solvent of the filtrate was removed under reduced pressure. The residue was chromatographed rns2 on silica gel (cyclohexane/ethyl acetate eluent). This gave a N total of 1.24 g (17% of theory) of ethyl 3-2-(5-fluoropyridin 3-yl)-4-methyl-1,3-thiazol-5-yl)-1-methyl-1H-pyrazole-5- carboxylate. As a by-product, 4.8 g. (67% of theory) of ethyl 0499 Under argon, lithium bis(trimethylsilyl)amide (21 5-2-(5-fluoropyridin-3-yl)-4-methyl-1,3-thiazol-5-yl)-1- ml. 1 M/L in tetrahydrofuran) was initially charged intetrahy methyl-1H-pyrazole-3-carboxylate were obtained. drofuran (150 ml). At -78°C., 1-2-(5-fluoropyridin-3-yl)-4- 0504 HPLC-MS: Log P (HCOOH): 3.70; mass (m/z): methyl-1,3-thiazol-5-yl)ethanone (5.0g, 21 mmol, prepared 347.0 (M+H)" analogously to Biorg. & Med. Chem. Lett 1056 (2007) and 0505 H NMR (d6-DMSO): 1.35 (t, 3H), 2.63 (s, 3H), 2828 (2010)) dissolved in diethyl ether was slowly added 4.15 (s, 3H), 4.35 (q, 2H), 7.17 (s, 1H), 8.19-8.22 (m. 1H), dropwise and the reaction mixture was stirred for 2 h. Diethyl 8.68-8.69 (m. 1H), 9.00-9.01 (m, 1H) ppm oxalate (3.1 g, 21 mmol) dissolved in ether was added drop Stage 3: 3-2-(5-Fluoropyridin-3-yl)-4-methyl-1,3- wise and the reaction mixture was stirred at room temperature thiazol-5-yl)-1-methyl-1H-pyrazole-5-carboxylic for 16 h. Subsequently, potassium hydrogensulphate Solution acid (5%) was added and the mixture was extracted repeatedly with ethyl acetate. The combined organic phases were dried 0506 and the solvent was removed under reduced pressure. This gave 7.1 g (99% of theory) of ethyl 4-2-(5-fluoropyridin-3- yl)-4-methyl-1,3-thiazol-5-yl)-2,4-dioxobutanoate. (0500 HPLC-MS: Log P (HCOOH): 3.37; mass (m/z): 337.1 (M+H)" 0501 H NMR (d6-DMSO): 1.31 (t, 3H), 2.79 (s.3H), 4.31-4.32 (m, 2H), 6.71 (bs, 2H), 8.33 (d. 1H), 8.77 (s, 1H), 9.10 (s, 1H) ppm US 2014/0148471 A1 May 29, 2014 39

-continued 3-2-(5-fluoropyridin-3-yl)-4-methyl-1,3-thiazol-5-yl)-1- methyl-N-(methylsulphonyl)-1H-pyrazole-5-carboxamide. 0512 HPLC-MS: Log P (HCOOH): 2.04; mass (m/z): 396.0 (M+H)" 0513 H NMR (d6-DMSO): 2.55 (s, 3H), 3.40 (s, 3H), 4.12 (s.3H), 7.68 (m. 1H), 8.12 (m, 1H), 8.69 (m, 1H), 9.01 (m. 1H) ppm 0507 Ethyl 3-2-(5-fluoropyridin-3-yl)-4-methyl-1,3- Example J thiazol-5-yl)-1-methyl-1H-pyrazole-5-carboxylate (1.1 g. 3.1 mmol) was dissolved in tetrahydrofuran (200 ml) and Methyl 6-2-(5-Fluoropyridin-3-yl)-1,3-thiazol-5-yl) water (100 ml), and lithium hydroxide monohydrate (0.26 g. pyridine-2-carboximidoate 6.2 mmol) dissolved in water (100 ml) was added. The reac tion mixture was stirred at room temperature for 16 h, then neutralized with hydrochloric acid, and the solvent was Stage 1: 6-2-(5-Fluoropyridin-3-yl)-1,3-thiazol-5- removed under reduced pressure. The precipitated solid was ylpyridine-2-carbonitrile filtered off with suction. This gave 0.96 g (94% of theory) of 3-2-(5-fluoropyridin-3-yl)-4-methyl-1,3-thiazol-5-yl)-1- 0514 methyl-1H-pyrazole-5-carboxylic acid. 0508 HPLC-MS: Log P (HCOOH): 2.05; mass (m/z): 319.0 (M+H)" F N1 yN N 0509 H NMR (d6-DMSO): 2.62 (s, 3H), 4.14 (s, 3H), N S -- -e- 7.13 (s, 1H), 8.18-8.22 (m, 1H),8.68-8.69 (m, 1H), 9.00-9.01 2 2 Br N CN (m. 1H) ppm N Stage 4: 3-2-(5-Fluoropyridin-3-yl)-4-methyl-1,3- 21 thiazol-5-yl)-1-methyl-N-(methylsulphonyl)-1H N pyrazole-5-carboxamide S N CN N 0510) N -S

F N N/

0515 Under argon, 3-fluoro-5-(1,3-thiazol-2-yl)pyridine (0.99 g, 5.47 mmol) and 6-bromopyridin-2-carbonitrile (1.0 g, 5.47 mmol) were initially charged in DMF (15 ml). After 10 min, at room temperature, tris(2-methylphenyl)phosphine (0.13 g. 0.23 mmol) and palladium(II) chloride (0.1 g, 0.55 mmol) were added. The reaction mixture was stirred at 130° C. for 14 h. After cooling, water and ethyl acetate were added and the precipitated product was filtered off with suction. The organic phase of the filtrate was removed and the aqueous phase was extracted three times with ethyl acetate. The com bined organic phases were dried over magnesium Sulphate 0511 3-2-(5-Fluoropyridin-3-yl)-4-methyl-1,3-thiazol and the solvent was removed under reduced pressure. The 5-yl)-1-methyl-1H-pyrazole-5-carboxylic acid (0.08 g., 0.25 residue was stirred with dichloromethane and filtered off with mmol) and methanesulphonamide (0.024g, 0.25 mmol) were suction. This gave a total of 0.94 g (61% of theory) of 6-2- initially charged in ice-cooled dichloromethane (10 ml). (5-fluoropyridin-3-yl)-1,3-thiazol-5-yl)pyridine-2-carboni 4-Dimethylaminopyridine (0.006 g., 0.05 mmol) and N-(3- trile. dimethylaminopropyl)-N'-ethylcarbodiimide hydrochloride (0.053 g. 0.275 mmol) were added. The reaction mixture was 0516 HPLC-MS: Log P(HCOOH): 2.51; mass (m/z): 283 stirred at 0°C. for 2 hand then at room temperature for 16 h. (M+H)" The solvent was removed under reduced pressure and the 0517 H NMR (d6-DMSO): 8.02 (d. 1H), 8.20 (t, 1H), residue was chromatographed on silica gel (dichloromethane/ 8.32-8.46 (m, 1H), 8.44 (d. 1H), 8.75 (d. 1H), 8.84 (s, 1H), ethyl acetate eluent). This gave 0.074 g (72% of theory) of 9.12 (s, 1H) ppm US 2014/0148471 A1 May 29, 2014 40

Stage 2: Methyl 6-2-(5-fluoropyridin-3-yl)-1,3-thia Example K Zol-5-ylpyridine-2-carboximidoate 6-2-(5-Fluoropyridin-3-yl)-1,3-thiazol-5-ylpyri dine-2-carboximide amide hydrochloride (1:1) 0518 0522

21 21

N Sa NH s N CN s N N N N -S -e- N -s O -as YCH, F N / F N N N/

21 21 N NH s N N NH N S N N -S NH2 CH N N -S O NCH, F / F \ { N N/ 0523 Methyl 6-2-(5-fluoropyridin-3-yl)-1,3-thiazol-5- ylpyridine-2-carboximidoate (0.1 g, 0.32 mmol) and ammo 0519) 6-2-(5-Fluoropyridin-3-yl)-1,3-thiazol-5-ylpyri nium chloride (0.016g, 0.3 mmol) were stirred in methanol (3 dine-2-carbonitrile (0.33 g, 1.17 mmol) and sodium methox ml) and dichloromethane (2 ml) at room temperature for 2 ide (0.13 g, 0.23 mmol) were stirred in methanol (10 ml) and days. The solvent was removed under reduced pressure, and dichloromethane (10 ml) at room temperature for 3 d. The the residue was taken up in methanol and filtered through precipitated solid was filtered off and the solvent of the filtrate Celite. The solvent of the filtrate was removed under reduced was removed under reduced pressure. The residue was dis pressure, and the residue was stirred with t-butyl methyl ether solved in dichloromethane and filtered through Celite. The and filtered off with suction. This gave 0.07 g (65% of theory) solvent of the filtrate was removed under reduced pressure. of 6-2-(5-fluoropyridin-3-yl)-1,3-thiazol-5-ylpyridine-2- This gave 0.32 g (83% of theory) of methyl 6-2-(5-fluoro carboximide amide hydrochloride (1:1). pyridin-3-yl)-1,3-thiazol-5-ylpyridine-2-carboximidoate. 0524 HPLC-MS: Log P(HCOOH): 0.71; mass (m/z): 300 (M+H)" 0520 HPLC-MS: Log P(HCOOH): 0.90; mass (m/z): 315 0525 H NMR (d6-DMSO): 8.19-8.22 (m, 1H), 8.26-8.31 (M+H)" (m. 2H), 839-8.41 (m, 1H), 8.74-8.75 (m. 1H), 8.93 (s, 1H), 9.07-9.08 (m. 1H) ppm 0521 'H NMR (d6-DMSO): 4.05 (s, 3H), 7.79-7.81 (m, 0526. The following compounds of the formula (I) were 2H), 7.87-7.91 (m. 1H), 8.05-8.07 (m, 1H), 8.38 (s, 1H), 8.56 obtained analogously to or according to the preparation pro (s, 1H), 9.06 (s, 1H), 9.24 (s, 1H) ppm cesses described above:

logP Mass Number Compound (HCOOH) NMR data M + 1

1 O 1.26 1H NMR (d6-DMSO): 6.82 (d. 316.0 (PEA) N 4. 1H), 7.45 (d. 1H), 7.59 (dd, 1H), N 7.78 (t, 1H), 8.30 (m, 2H), 8.57 (dd, /So, n 1H), 9.09 (s, 1H), 9.17 (d. 1H), HN 10.55 ppm (s, 1H). N N 2

US 2014/0148471 A1 May 29, 2014 56

-continued logP Number Compound (HCOOH) NMR data

XIII-4 N 1.34 1H NMR (DMSO): 8.00 (m, 1H), 8.08 (m, 1H), y 8.83 (m, 1H) 9.12 (m, 1H), 9.40 (m, 1) NC N S

2 N

0529. The preparation processes described above were used to obtain the following intermediates of the formula (XIV):

logP Number Compound (HCOOH) NMR data XIV-1 N 1.32 1H NMR (d6-DMSO): 0.92 (t, 3H), 2.28 (q, 2H), 7.99 (m, 1H), 8.06-8.13 (m, O O 2H), 12.39 (br, 1H) 2 Br N s2 --- O N XIV-2 N O.95 1H NMR (d6-DMSO): 1.98 (s, 3H), 7.98-8.12 (m, 3H), 12.4 (br. 1H) ppm O

B r 4. M 4.r NH / -- O

0530. The preparation processes described above were used to obtain the following intermediates of the formula (XV): logP Number Compound (HCOOH) NMR data logP Number Compound (HCOOH) NMR data XVI-1 "Ny. O.63 .N.t XV-1 Br S O.82 1H NMR (d6- o (s, 3H), 8.31 DMSO): 3.33 (s, N (s, 1H) \ f 3H), 8.61 (s, N H 1H), 12.00 (s, V NN^ O 1H) O /\SO & 6 N 0531. The preparation processes described above were 0532. The preparation processes described above were used to obtain the following intermediates of the formula used to obtain the following intermediates of the formula (XVI): (XVII):

logP Number Compound (HCOOH) NMR data

XVII-1 Na o O.99 1H NMR (d6-DMSO): 7.43 (s. 2H), 7.60 7.63 (m, 1H), 7.76 (d. 1H), 8.00 (d. 1H), 8.11 (t, 1H), 8.28-8.31 (m, 1H), 8.53 (s, 1H), 8.58 NU/ 8.60 (m, 1H), 9.16-9.17 (m, 1H), 9.33 (s, 1H)

r 2 N US 2014/0148471 A1 May 29, 2014 57

-continued logP Number Compound (HCOOH) NMR data

XVII-2 Na o 1.44 1H NMR (d6-DMSO): 7.78 (s, 2H), 7.77 7.79 (m, 1H), 7.99-8.01 (m, 1H), 8.12 8.14 (m, 1H), 8.29-8.32 (m, 1H), 8.57 (s, 1H), F N 2 QN / 8.62-8.63 (m, 1H), 9.09 (s, 1H), 9.41 (s, 1H) 2 2 o21\ N NH2

XVII-3 Na o O.89 1H NMR (d6-DMSO): 7.48 (s. 2H), 7.78 7.80 (m, 1H), 7.99-7.80 (m, 1H), 8.12 8.16 (m, 1H), 8.60 (s, 1H), 9.21 (s, 1H), N1 N N/ \N A O 9.38 (s, 2H), 9.41 (s, 1H) sa 2 o2\ N NH2

1) Description of Method for Determination of the log P 0544 Discs of Chinese cabbage (Brassica pekinensis) Values (Formic Aid Method) infested by all stages of the green peach aphid (Myzus persi cae) are sprayed with an active ingredient preparation of the 0533. The log Pvalues given in the table were determined desired concentration. in accordance with EEC Directive 79/831 Annex V.A8 by (0545. After the desired time, the efficacy in % is deter HPLC (High Performance Liquid Chromatography) using a mined. 100% means that all of the aphids have been killed; reverse-phase column (C18). Temperature: 55° C. 0% means that none of the aphids have been killed. 0534 Eluents for determination in the acidic range (pH 0546. In this test, for example, the following compounds 3.4): of the Preparation Examples showed, at an application rate of 0535 Eluent A:acetonitrile+1 ml of formic acid/litre. Elu 500 g/ha, an efficacy of 80%. 1, 10, 15, 21, 28, 62, 63 ent B: water+0.9 ml of formic acid/litre. 0547. In this test, for example, the following compounds 0536 Gradient: from 10% eluent A/90% eluent B to 95% of the Preparation Examples showed, at an application rate of eluent A/5% eluent B in 4.25 min. 500 g/ha, an efficacy of 90%. 5, 14, 23, 32,34, 37,38, 45,47, 0537. The calibration was effected with unbranched 48, 65, 74 alkan-2-ones (having 3 to 16 carbonatoms) with known log P 0548. In this test, for example, the following compounds values (log P values determined on the basis of the retention of the Preparation Examples showed, at an application rate of times by linear interpolation between two successive 500 g/ha, an efficacy of 100%: 2,3,4,6,7,8,9,11, 12, 13, 16, alkanones). The lambda max values were determined in the 17, 18, 19, 20, 22, 24, 25, 26, 27, 29, 30, 31,33,35, 36,39, 40, maxima of the chromatographic signals using the UV spectra 41, 42,43,44, 46, 51, 52,53,54, 55,56, 57,58, 59, 60, 61, 64, from 200 nm to 400 nm. 66, 67,68, 69, 70, 71, 72, 73, 75, 76, 77, 78. 21 Measurement of the NMR Spectra Tetranychus Test, OP-Resistant (Spray Treatment) 0549 Solvent: 78.0 parts by weight of acetone 0538. The NMR spectra were determined with a Bruker 0550 1.5 parts by weight of dimethylformamide Avance 400 fitted with a flow probe head (volume 60 ul). The 0551 Emulsifier: 0.5 part by weight of alkylaryl polygly solvent used was CDCN or de-DMSO, with tetramethylsi col ether lane (0.00 ppm) used as a reference. In particular cases, the 0552. To prepare an appropriate active ingredient prepa NMR spectra were determined with a Bruker Avance II 600. ration, 1 part by weight of active ingredient is mixed with the The solvent used was CDCN or d-DMSO, with tetrameth stated amounts of solvent and emulsifier, and the concentrate ylsilane (0.00 ppm) used as a reference. is diluted with emulsifier-containing water to the desired con 0539. The splitting of the signals was described as follows: centration. Discs ofbean leaves (Phaseolus vulgaris) infested S (singlet), d(doublet), t(triplet), q(quartet), quin (quintet), m by all stages of the red spider mite (Tetranychus urticae) are (multiplet). sprayed with an active ingredient preparation of the desired concentration. Biological Examples 0553. After the desired time, the efficacy in % is deter mined. 100% means that all of the spider mites have been Myzus Test (Spray Treatment) killed: 0% means that none of the spider mites have been killed. 0540 Solvent 78 parts by weight of acetone 0554. In this test, for example, the following compound of (0541 1.5 parts by weight of dimethylformamide the Preparation Examples showed, at an application rate of 0542 Emulsifier: 0.5 part by weight of alkylaryl polygly col ether 500 g/ha, an efficacy of 100%: 5. 0543. To prepare an appropriate active ingredient prepa Meloidogyne Incognita Test ration, 1 part by weight of active ingredient is mixed with the stated amounts of solvent and emulsifier, and the concentrate 0555 Solvent: 80.0 parts by weight of acetone is diluted with emulsifier-containing water to the desired con 0556. To prepare an appropriate active ingredient prepa centration. ration, 1 part by weight of active ingredient is mixed with the US 2014/0148471 A1 May 29, 2014

stated amounts of solvent, and the concentrate is diluted with -continued water to the desired concentration. (C) 0557 Vessels are filled with sand, active ingredient solu R1 tion, Meloidogyne incognita egg/larvae Suspension and let ? tuce seeds. The lettuce seeds germinate and the plants develop. Galls develop on the roots. - and 0558 After the desired time, the nematicidal action is 4\s determined by the gall formation in %. 100% means that no galls were found: 0% means that the number of galls on the B treated plants corresponds to the untreated control. (D) 0559. In this test, for example, the following compounds RI of the preparation examples showed, at an application rate of NS 20 ppm, an efficacy of 100%:56, 70, 75, 78. f 11 N 21 G3 Myzus Spray Test 0560 Preliminary mixture solvent: Sorpol R SD: Sorpol R. B BDB: dimethylformamide=3:3:14 in which the arrow in each case marks the bond to the 0561. To prepare an appropriate active ingredient prepa adjacent ring, ration, 10 mg of active ingredient are mixed with 0.05 ml of R" in the case of the heterocycles (A) and (D) is hydrogen, solvent and the concentrate is diluted with water to the desired halogen, cyano, alkyl, alkoxy, amino, alkylamino, concentration. The solution in each case contains 1000 ppm dialkylamino, alkylthio or haloalkyl and of RME (rapeseed oil methyl ester) and AMS (ammonium R" in the case of heterocycle (C) is hydrogen, alkyl or Sulphate). haloalkyl, 0562 Aubergine plants (Solanum melongena var. Senryo 2gou) infested by all stages of the green peach aphid (Myzus B is hydrogen, halogen, cyano, nitro, alkyl, cycloalkyl, persicae organophosphate/carbamate resistant strain) are haloalkyl, amino, alkylamino, dialkylamino, alkylthio sprayed with an active ingredient preparation of the desired or alkoxy and concentration. G is optionally substituted heterocyclyl, optionally sub 0563. After 6 days, the efficacy in % is determined: stituted heteroaryl or optionally substituted aryland 100%: all insects killed, G' is a radical from the group of 98%: 1-4 insects survive, (E) 95%: 5-20 insects survive, X (O), 60%: fewer insects survive than in the untreated control and 0%; no difference from the untreated control. N1Ns. 0564. In this test, for example, the following compounds of the preparation examples showed, at an application rate of 100 ppm, an efficacy of 100%. 49, 50. (F) 1. Compounds of the formula (I)

(I) (G)

in which (H) A' and A are each independently hydrogen, halogen, cyano, nitro, alkyl, cycloalkyl or alkoxy, G' is N or C-A" and G is a radical from the group of (I)

RI (A)

N (J) - S G3 N-N (B) US 2014/0148471 A1 May 29, 2014 59

-continued R is a radical from the group of hydrogen, in each case (K) optionally Substituted alkyl, alkoxy, alkenyl and alky (O), nyl, in each case optionally Substituted cycloalkyl, cycloalkylalkyl and cycloalkenyl, in which the rings may contain at least one heteroatom from the group of 11 S Sulphur, oxygen (where oxygen atoms must not be R2 immediately adjacent) and nitrogen, in each case option L ally substituted aryl, heteroaryl, arylalkyl and heteroary (O) X (L) lalkyl and an optionally substituted amino group, RandR may also form, together with the N C(X) group to which they are bonded, a Saturated or unsaturated and optionally substituted 4- to 8-membered ring which may contain one or more further heteroatoms from the group of Sulphur, oxygen (where oxygen atoms must not be (M) immediately adjacent) and nitrogen and/or at least one carbonyl group, R is hydrogen or alkyl, RandR may also form, together with the nitrogenatoms to which they are bonded, a Saturated or unsaturated and optionally substituted 4- to 8-membered ring which may contain at least one further heteroatom from the group of and in the case of the heterocycles (A), (B) and (C) is also Sulphur, oxygen (where oxygen atoms must not be the radical immediately adjacent) and nitrogen and/or at least one carbonyl group, RandR in the radical (E) may also form, together with (N) the N S(O), group to which they are bonded, a satu rated or unsaturated and optionally substituted 4- to 8-membered ring which may contain one or more fur ther heteroatoms from the group of Sulphur, oxygen (where oxygenatoms must not be immediately adjacent) and nitrogen and/or at least one carbonyl group, R and R may also form, together with the N S(O), in which the arrow in each case marks the bond to G, group to which they are bonded, a Saturated or unsatur X is oxygen or Sulphur, ated and optionally substituted 4- to 8-membered ring n is 1 or 2, which may contain one or more further heteroatoms R is a radical from the group of hydrogen, alkyl, haloalkyl, from the group of Sulphur, oxygen (where oxygenatoms cyanoalkyl, alkoxy, haloalkoxy, alkenyl, alkynyl and must not be immediately adjacent) and nitrogen and/or alkoxyalkyl, in each case optionally halogen-substituted at least one carbonyl group, alkylcarbonyl and alkylsulphonyl, in each case option R° and R may also form, together with the nitrogenatom ally halogen-substituted alkoxycarbonyl, in each case to which they are bonded, a Saturated or unsaturated and optionally halogen-, alkyl-, alkoxy-, haloalkyl- and optionally substituted 4- to 8-membered ring which may cyano-Substituted cycloalkylcarbonyl, or a cation, for contain one or more further heteroatoms from the group example a mono- or divalent metalion or an optionally of Sulphur, oxygen (where oxygen atoms must not be alkyl- or arylalkyl-substituted ammonium ion, immediately adjacent) and nitrogen and/or at least one RandR are each independently a radical from the group carbonyl group, of in each case optionally substituted alkyl, alkenyl and L is oxygen or Sulphur, alkynyl, in each case optionally Substituted cycloalkyl, RandR'' are each independently an in each case option cycloalkylalkyl and cycloalkenyl, in which the rings ally Substituted radical from the group of alkyl, alkenyl, may contain at least one heteroatom from the group of alkynyl, alkoxy, alkenyloxy, alkynyloxy, cycloalkyl, Sulphur, oxygen (where oxygen atoms must not be cycloalkyloxy, cycloalkenyloxy, cycloalkylalkoxy, immediately adjacent) and nitrogen, in each case option alkylthio, alkenylthio, phenoxy, phenylthio, benzyloxy, ally substituted aryl, heteroaryl, arylalkyl and heteroary benzylthio, heteroaryloxy, heteroarylthio, heteroaryla lalkyl and an optionally substituted amino group, lkoxy and heteroarylalkylthio. R and R may also form, together with the N-S(O), R and R' may also form, together with the phosphorus group to which they are bonded, a saturated or unsatur atom to which they are bonded, a saturated or unsatur ated and optionally substituted 4- to 8-membered ring ated and optionally substituted 5- to 7-membered ring which may contain one or more further heteroatoms which may contain one or two heteroatoms from the from the group of Sulphur, oxygen (where oxygenatoms group of oxygen (where oxygen atoms must not be must not be immediately adjacent) and nitrogen and/or immediately adjacent) and Sulphur, at least one carbonyl group, R'' and R'' are each independently an in each case option R is a radical from the group of in each case optionally ally Substituted radical from the group of alkyl, alkenyl, Substituted alkyl, alkoxy, alkenyl and alkynyl, in each alkynyl, phenyl and phenylalkyl, case optionally substituted cycloalkyl, cycloalkylalkyl Y' and Y are each independently C=O or S(O), and cycloalkenyl, in which the rings may contain at least m is 1, 2, 3 or 4. one heteroatom from the group of Sulphur, oxygen R" is a radical from the group of hydrogen, alkyl, (where oxygenatoms must not be immediately adjacent) haloalkyl, cyano, cyanoalkyl, hydroxyalkyl, hydroxyl, and nitrogen, in each case optionally Substituted aryl, alkoxy, alkoxyalkyl, alkylthioalkyl, alkenyl, haloalk heteroaryl, arylalkyl and heteroarylalkyl and an option enyl, cyanoalkenyl, alkynyl, haloalkynyl, cyanoalkynyl, ally Substituted amino group, alkylcarbonyl and alkoxycarbonyl, US 2014/0148471 A1 May 29, 2014 60

Y is a radical from the group of alkoxy, haloalkoxy, alky 5. Compounds of the formula (ID) lthio, haloalkylthio and NR'R' where RandR'' are each independently radicals from the group of hydro gen, alkyl, cycloalkyl, cycloalkylalkyl, haloalkyl, (ID) cyano, cyanoalkyl, hydroxyl, alkoxy, haloalkoxy, RI hydroxyalkyl, alkoxyalkyl, alkylthioalkyl, alkenyl, haloalkenyl, cyanoalkenyl, alkynyl, haloalkynyl, N2 o cyanoalkynyl, alkylcarbonylandalkoxycarbonyl, or R' and R' together with the nitrogen atom to which they 1 N N \ / are bonded may forman optionally Substituted Saturated or unsaturated 5- to 8-membered ring optionally con taining heteroatoms, 2 a Gand G' may additionally also together forman option N ally substituted heterocycle which optionally contains one or more further heteroatoms from the group of oxy in which gen, nitrogen and Sulphur, G' is C H, C F. C. C1 or N, and salts and N-oxides of the compounds of the formula R" is hydrogen or methyl, (I). B is hydrogen and 2. Compounds of the formula (IA) G' is one of the (E) and (L) radicals specified in claim 1. 6. Composition characterized by a content of at least one compound of the formula (I) according to claims 1 to 5. (LA) 7. Method for controlling pests, characterized in that a compound of the formula (I) according to claims 1 to 5 or a composition according to claim 6 is allowed to act on the pests and/or their habitat. 8. Compounds of the formula (XII)

(XII) in which N i G' is C H, C F. C. C1 or N, 7 R" is hydrogen or methyl and 1N 4 N-R G' is one of the (E), (L) and (N) radicals specified in claim M \, 1 & O O 3. Compounds of the formula (IB) in which R" is fluorine, chlorine, bromine or iodine and (IB) X, Rand R7 are each as defined in claim 1. N-V o 9. Compounds of the formula (XIII) 1N S \ / le G4 (XIII) N in which G' is C H, C F. C C1 or N and G' is one of the (E), (L) and (N) radicals specified in claim 1. 4. Compounds of the formula (IC) in which G' is nitrogen, C-halogen, C-cyano, C-nitro, (IC) C-alkyl, C-cycloalkyl or C-alkoxy. 10. Compounds of the formula (XIV)

(XIV)

-N R5 R I6|CU 4. S in which 1 G' is C H, C F. C. C1 or N, O O X R" is hydrogen or methyl, B is hydrogen and in which G' is one of the (E), (L) and (N) radicals specified in claim R" is fluorine, chlorine, bromine or iodine and 1. X, R and Rare each as defined in claim 1. US 2014/0148471 A1 May 29, 2014

11. Compounds of the formula (XV) 13. Compounds of the formula (XVII) (XVII) (XV) S \ RI -S, Na S 1 R7 X / \, in which G' is nitrogen, C-halogen, C-cyano, C-nitro, C-alkyl, in which C-cycloalkyl or C-alkoxy, and R' is fluorine, chlorine, bromine or iodine and R’ is as defined in claim 1. X, Rand R7 are each as defined in claim 1. 14. Compounds of the formula (XVIII) 12. Compounds of the formula (XVI)

(XVIII)

(XVI)

in which G' is nitrogen, C-halogen, C-cyano, C-nitro, C-alkyl, C-cycloalkyl or C-alkoxy, in which and R" is fluorine, chlorine, bromine or iodine and R’ is as defined in claim 1. X, R and R7 are each as defined in claim 1. k k k k k