WO2014053401A2

WO2014053401A2 - Method of improving plant health

Info

Publication number: WO2014053401A2
Application number: PCT/EP2013/070154
Authority: WO
Inventors: Karsten KÖRBER; Jean-Yves WACH; Florian Kaiser; Matthias Pohlman; Prashant Deshmukh; Deborah L. Culbertson; W. David ROGERS; Koshi Gunjima; Michael David; Franz Josef Braun
Original assignee: Basf Se
Priority date: 2012-10-01
Filing date: 2013-09-27
Publication date: 2014-04-10
Also published as: WO2014053401A3

Abstract

The present invention relates to methods of improving plant health, and to methods for reducing nitrous oxide emission from soils, using anthranilamide compounds of formula (I), wherein R¹, R², R³, R⁴, R⁵, R⁶, R⁷ and k are as defined in the description; and their mixtures and compositions.

Description

Method of improving plant health Description The present invention relates to a composition comprising an anthranilamide compound of formula (I), the use of this composition for improving plant health and a method for improving plant health by treating a plant, its propagules or the locus where the plant is growing or is to grow with the above composition.

The invention relates to to the use of the compounds of formula (I) itself and their stereoiso- mers, salts, tautomers or N-oxides, especially their salts, and their mixtures, for increasing the health of plants, for increasing the yield, the resistance against fungi or animal pests or external factors like heat, cold or drought, and for increasing the quality of the crops and other parameters. This also includes the use or method of reducing nitrous oxide emission from soils. In crop protection, there is a continuous need for compositions that improve the health of plants. Healthier plants are desirable since they result in better crop yields and/or a better quality of the plants or crops. Healthier plants also better resist to biotic and/or abiotic stress. A high resistance against biotic stresses in turn allows the person skilled in the art to reduce the quantity of pesticides applied and consequently to slow down the development of resistances against the respective pesticides.

It was therefore an object of the present invention to provide a pesticidal composition which solves the problems outlined above. In particular, the composition should improve plant health.

The present invention is based on the surprising finding that a compound selected from the chemical class of N-thio-anthranilamides can be successfully used to improve plant health. Thus in the first aspect of the invention there is provided a method of improving plant health, which method comprises applying at least one pesticidally active anthranilamide compound of formula (I):

wherein

R¹ is selected from the group consisting of halogen, methyl and halomethyl; R² is selected from the group consisting of hydrogen, halogen, halomethyl and cy- ano; is selected from hydrogen, C1-C6 alkyl, C1-C6 haloalkyl, C2-C6-alkenyl, C2-C6- haloalkenyl, C2-C6-alkinyl, C2-C6-haloalkinyl, Cs-Cs-cycloalkyl, Cs-Cs-halocycloalkyl, Ci-C4-alkoxy-Ci-C4-alkyl, Ci-C4-haloalkoxy-Ci-C4-alkyl,

C(=0)R^a, C(=0)OR^b and C(=0)NR^cR^d; is hydrogen or halogen;

R⁶ are selected independently of one another from the group consisting of hydrogen, Ci-Cio-alkyl, Cs-Cs-cycloalkyl, C2-Cio-alkenyl, C2-Cio-alkynyl, wherein the aforementioned aliphatic and cycloaliphatic radicals may be substituted with 1 to 10 substituents R^e, and phenyl, which is unsubstituted or carries 1 to 5 substituents R^f; or

R⁵ and R⁶ together represent a C2-C7-alkylene, C2-C7-alkenylene or

C6-Cg-alkynylene chain forming together with the sulfur atom to which they are attached a 3-, 4-, 5-, 6-, 7-, 8-, 9- or 10-membered saturated, partially unsaturated or fully unsaturated ring, wherein 1 to 4 of the CH2 groups in the C2-C7-alkylene chain or 1 to 4 of any of the CH2 or CH groups in the C2-C7-alkenylene chain or 1 to 4 of any of the CH2 groups in the C6-Cg-alkynylene chain may be replaced by 1 to 4 groups independently selected from the group consisting of C=0, C=S, O, S, N, NO, SO, SO2 and NH , and wherein the carbon and/or nitrogen atoms in the C2- C7-alkylene, C2-C7-alkenylene or Ce-Cg-alkynylene chain may be substituted with 1 to 5 substituents independently selected from the group consisting of halogen, cy- ano, Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy, Ci-C6-haloalkoxy, Ci-C6-alkylthio, Ci-C6-haloalkylthio, Cs-Cs-cycloalkyl, Cs-Cs-halocycloalkyl, C2-C6-alkenyl, C2-C6- haloalkenyl, C2-C6-alkynyl and C2-C6-haloalkynyl; said substituents being identical or different from one another if more than one substituent is present; is selected from the group consisting of bromo, chloro, difluoromethyl, trifluorome- thyl, nitro, cyano, OCH₃, OCHF₂, OCH₂F, OCH2CF3, S(=0)_nCH₃, and S(=0)_nCF₃; is selected from the group consisting of Ci-C6-alkyl, C2-C6-alkenyl, C2-C6-alkinyl, Cs- Cs-cycloalkyl, Ci-C6-alkoxy, Ci-C6-alkylthio, Ci-C6-alkylsulfinyl, Ci-C6-alkylsulfonyl, wherein one or more CH2 groups of the aforementioned radicals may be replaced by a C=0 group, and/or the aliphatic and cycloaliphatic moieties of the aforementioned radicals may be unsubstituted, partially or fully halogenated and/or may carry 1 or 2 substituents selected from C1-C4 alkoxy;

phenyl, benzyl, pyridyl and phenoxy, wherein the last four radicals may be unsubstituted, partially or fully halogenated and/or carry 1 , 2 or 3 substituents selected from Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy, Ci-C6-haloalkoxy, (Ci-C6-alkoxy)carbonyl, Ci-C6-alkylamino and di-(Ci-C6-alkyl)amino, R^b is selected from the group consisting of Ci-C6-alkyl, C2-C6-alkenyl, C2-C6-alkinyl, Cs- Cs-cycloalkyl, Ci-C6-alkoxy, Ci-C6-alkylthio, Ci-C6-alkylsulfinyl, Ci-C6-alkylsulfonyl, wherein one or more CH2 groups of the aforementioned radicals may be replaced by a C=0 group, and/or the aliphatic and cycloaliphatic moieties of the aforementioned radicals may be unsubstituted, partially or fully halogenated and/or may carry 1 or 2 substituents selected from Ci-C4-alkoxy;

phenyl, benzyl, pyridyl and phenoxy, wherein the last four radicals may be unsubstituted, partially or fully halogenated and/or carry 1 , 2 or 3 substituents selected from Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy, Ci-C6-haloalkoxy and (C1-C6- alkoxy)carbonyl;

R^c, R^d are, independently from one another and independently of each occurrence, selected from the group consisting of hydrogen, cyano, Ci-C6-alkyl, C2-C6-alkenyl, C2- C6-alkinyl, Cs-Cs-cycloalkyl, wherein one or more CH2 groups of the aforementioned radicals may be replaced by a C=0 group, and/or the aliphatic and cycloaliphatic moieties of the aforementioned radicals may be unsubstituted, partially or fully halogenated and/or may carry 1 or 2 radicals selected from Ci-C4-alkoxy;

Ci-C6-alkoxy, Ci-C6-haloalkoxy, Ci-C6-alkylthio, Ci-C6-alkylsulfinyl, C1-C6- alkylsulfonyl, Ci-C6-haloalkylthio, phenyl, benzyl, pyridyl and phenoxy, wherein the four last mentioned radicals may be unsubstituted, partially or fully halogenated and/or carry 1 , 2 or 3 substituents selected from Ci-C6-alkyl, Ci-C6-haloalkyl, C1-C6- alkoxy, C1-C6 haloalkoxy and (Ci-C6-alkoxy)carbonyl; or

R^c and R^d, together with the nitrogen atom to which they are bound, may form a 3-, 4-, 5-, 6- or 7-membered saturated, partially unsaturated or fully unsaturated hetero- cyclic ring which may additionally contain 1 or 2 further heteroatoms or heteroatom groups selected from N, O, S, NO, SO and SO2, as ring members, where the heterocyclic ring may optionally be substituted with halogen, Ci-C4-haloalkyl, C1-C4- alkoxy or Ci-C4-haloalkoxy; R^e is independently selected from the group consisting of halogen, cyano, nitro, -OH, -

SH, -SCN, Ci-C6-alkyl, C2-C6-alkenyl, C2-C6-alkinyl, Cs-Cs-cycloalkyl, wherein one or more CH2 groups of the aforementioned radicals may be replaced by a C=0 group, and/or the aliphatic and cycloaliphatic moieties of the aforementioned radicals may be unsubstituted, partially or fully halogenated and/or may carry 1 or 2 radicals se- lected from C1-C4 alkoxy;

Ci-C6-alkoxy, Ci-C6-haloalkoxy, Ci-C6-alkylthio, Ci-C6-alkylsulfinyl, C1-C6- alkylsulfonyl, Ci-C₆-haloalkylthio, -OR^a, -NR^cR^d, -S(0)_nR^a, -S(0)_nNR^cR^d,

-C(=0)R^a, -C(=0)NR^cR^d, -C(=0)OR^b, -C(=S)R^a, -C(=S)NR^cR^d, -C(=S)OR^b,

-C(=S)SR^b, -C(=NR^c)R^b, -C(=NR^c)NR^cR^d, phenyl, benzyl, pyridyl and phenoxy, wherein the last four radicals may be unsubstituted, partially or fully halogenated and/or carry 1 , 2 or 3 substituents selected from Ci-C6-alkyl, Ci-C6-haloalkyl, C1-C6- alkoxy and Ci-C6-haloalkoxy; or

two vicinal radicals R^e together form a group =0, =CH(Ci-C4-alkyl), =C(Ci-C₄- alkyl)Ci-C₄-alkyl, =N(Ci-C₆-alkyl) or =NO(Ci-C₆-alkyl); is independently selected from the group consisting of halogen, cyano, nitro, -OH, - SH, -SCN, Ci-C6-alkyl, C2-C6-alkenyl, C2-C6-alkinyl, Cs-Cs-cycloalkyl, wherein one or more CH2 groups of the aforementioned radicals may be replaced by a C=0 group, and/or the aliphatic and cycloaliphatic moieties of the aforementioned radicals may be unsubstituted, partially or fully halogenated and/or may carry 1 or 2 radicals selected from C1-C4 alkoxy;

Ci-C6-alkoxy, Ci-C6-haloalkoxy, Ci-C6-alkylthio, Ci-C6-alkylsulfinyl, C1-C6- alkylsulfonyl, Ci-C₆-haloalkylthio, -OR^a, -NR^cR^d, -S(0)_nR^a, -S(0)_nNR^cR^d, -C(=0)R^a, -C(=0)NR^cR^d, -C(=0)OR^b, -C(=S)R^a, -C(=S)NR^cR^d, -C(=S)OR^b, -C(=S)SR^b, -C(=NR^c)R , and -C(=NR^c)NR^cR^d; k is 0 or 1 ; n is 0, 1 or 2; or a stereoisomer, salt, tautomer or N-oxide, or a polymorphic crystalline form, a co-crystal or a solvate of a compound or a stereoisomer, salt, tautomer or N-oxide thereof.

Accordingly, the present invention relates to the use of a compound of formula (I) as defined herein, or a stereoisomer, salt, tautomer or N-oxide thereof, or a composition comprising it, for improving the plant health of at least one plant variety.

Compounds of formula I WO 2007/006670, describes N-thio-anthranilamide compounds with a sulfilimine or sulfoximine group and their use as pesticides. PCT/EP2012/065650, PCT/EP2012/065651 , and the unpublished applications US 61/578267, US 61/593897 and US 61/651050 describe certain N- Thio-anthranilamide compounds and their use as pesticides.

PCT/EP2012/065648, PCT/EP2012/065649 and EP1 1 189973.8 describe processes for the syn- thesis of N-Thio-anthranilamide compounds.

However, although the anthranilamide compounds of formula (I) themselves and their combined application with other insecticides are known to have shown activity against certain crop damaging insect pests, the compounds of formula I and some of their selected mixtures with pesticidal- ly active compounds (II) have not yet been described for solving discussed problems as mentioned above.

The compounds of formula I as well as the terms "compounds for methods according to the (present) invention", "compounds according to the (present) invention" or "compounds of formu- la (I)" or "compound(s) II", which all compound(s) are applied in methods and uses according to the present invention comprise the compound(s) as defined herein as well as a known stereoisomer, salt, tautomer or N-oxide thereof. The term "composition(s) according to the invention" or "composition(s) of the present invention" encompasses composition(s) comprising at least one compound of formula I or mixtures of the compounds of formula I with other pesticidally active compound(s) II for being used and/or applied in methods according to the invention as defined above.

Depending on the substitution pattern, the compounds of the formula (I) may have one or more centers of chirality, in which case they are present as mixtures of enantiomers or diastereomers. The invention provides both the pure enantiomers or pure diastereomers of the compounds of formula (I), and their mixtures and the use according to the invention of the pure enantiomers or pure diastereomers of the compound of formula (I) or its mixtures. Suitable compounds of the formula (I) also include all possible geometrical stereoisomers (cis/trans isomers) and mixtures thereof. Cis/trans isomers may be present with respect to an alkene, carbon-nitrogen double- bond, nitrogen-sulfur double bond or amide group. The term "stereoisomer(s)" encompasses both optical isomers, such as enantiomers or diastereomers, the latter existing due to more than one center of chirality in the molecule, as well as geometrical isomers (cis/trans isomers).

Salts of the compounds of the present invention are preferably agriculturally and veterinarily acceptable salts. They can be formed in a customary method, e.g. by reacting the compound with an acid if the compound of the present invention has a basic functionality or by reacting the compound with a suitable base if the compound of the present invention has an acidic functionality.

In general, suitable "agriculturally useful salts" or "agriculturally acceptable salts" are especially the salts of those cations or the acid addition salts of those acids whose cations and anions, respectively, do not have any adverse effect on the action of the compounds according to the present invention. Suitable cations are in particular the ions of the alkali metals, preferably lithium, sodium and potassium, of the alkaline earth metals, preferably calcium, magnesium and barium, and of the transition metals, preferably manganese, copper, zinc and iron, and also ammonium (NhV) and substituted ammonium in which one to four of the hydrogen atoms are replaced by Ci-C4-alkyl, Ci-C4-hydroxyalkyl, Ci-C4-alkoxy, Ci-C4-alkoxy-Ci-C4-alkyl, hydroxy-Ci- C4-alkoxy-Ci-C4-alkyl, phenyl or benzyl. Examples of substituted ammonium ions comprise me- thylammonium, isopropylammonium, dimethylammonium, diisopropylammonium, trime- thylammonium, tetramethylammonium, tetraethylammonium, tetrabutylammonium, 2- hydroxyethylammonium, 2-(2-hydroxyethoxy)ethyl-ammonium, bis(2-hydroxyethyl)ammonium, benzyltrimethylammonium and benzyltriethylammonium, furthermore phosphonium ions, sul- fonium ions, preferably tri(Ci-C4-alkyl)sulfonium, and sulfoxonium ions, preferably tri(Ci-C4- alkyl)sulfoxonium.

Anions of useful acid addition salts are primarily chloride, bromide, fluoride, hydrogen sulfate, sulfate, dihydrogen phosphate, hydrogen phosphate, phosphate, nitrate, hydrogen carbonate, carbonate, hexafluorosilicate, hexafluorophosphate, benzoate, and the anions of Ci-C4-alkanoic acids, preferably formate, acetate, propionate and butyrate. They can be formed by reacting the compounds of the formulae I with an acid of the corresponding anion, preferably of hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid or nitric acid.

The compounds of the formula (I) may be present in the form of their N-oxides. The term "N- oxide" includes any compound of the present invention which has at least one tertiary nitrogen atom that is oxidized to an N-oxide moiety. N-oxides of compounds (I) can in particular be prepared by oxidizing the ring nitrogen atom(s) of the pyridine ring and/or the pyrazole ring with a suitable oxidizing agent, such as peroxo carboxylic acids or other peroxides. The person skilled in the art knows if and in which positions compounds of the formula (I) of the present invention may form N-oxides.

The compounds of the present invention may be amorphous or may exist in one ore more different crystalline states (polymorphs) which may have different macroscopic properties such as stability or show different biological properties such as activities. The present invention includes both amorphous and crystalline compounds of formula (I), their enantiomers or diastereomers, mixtures of different crystalline states of the respective compound of formula (I), its enantiomers or diastereomers, as well as amorphous or crystalline salts thereof. The term "co-crystal" denotes a complex of the compounds according to the invention or a stereoisomer, salt, tautomer or N-oxide thereof, with one or more other molecules (preferably one molecule type), wherein usually the ratio of the compound according to the invention and the other molecule is a stoichiometric ratio.

The term "solvate" denotes a co-complex of the compounds according to the invention, or a stereoisomer, salt, tautomer or N-oxide thereof, with solvent molecules. The solvent is usually liquid. Examples of solvents are methanol, ethanol, toluol, xylol. A preferred solvent which forms solvates is water, which solvates are referred to as "hydrates". A solvate or hydrate is usually characterized by the presence of a fixed number of n molecules solvent per m molecules compound according to the invention

The organic moieties mentioned in the above definitions of the variables are - like the term halogen - collective terms for individual listings of the individual group members. The prefix C_n-C_m indicates in each case the possible number of carbon atoms in the group.

The term halogen denotes in each case fluorine, bromine, chlorine or iodine, in particular fluo- rine, chlorine or bromine.

The term "partially or fully halogenated" will be taken to mean that 1 or more, e.g. 1 , 2, 3, 4 or 5 or all of the hydrogen atoms of a given radical have been replaced by a halogen atom, in particular by fluorine or chlorine. A partially or fully halogenated radical is termed below also "halo- radical". For example, partially or fully halogenated alkyl is also termed haloalkyl.

The term "alkyl" as used herein (and in the alkyl moieties of other groups comprising an alkyl group, e.g. alkoxy, alkylcarbonyl, alkylthio, alkylsulfinyl, alkylsulfonyl and alkoxyalkyl) denotes in each case a straight-chain or branched alkyl group having usually from 1 to 12 or 1 to 10 carbon atoms, frequently from 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms and in particular from 1 to 3 carbon atoms. Examples of Ci-C4-alkyl are methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-butyl (sec-butyl), isobutyl and tert-butyl. Examples for Ci-C6-alkyl are, apart those mentioned for Ci-C4-alkyl, n-pentyl, 1 -methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1 -ethylpropyl, n-hexyl, 1 ,1 -dimethylpropyl, 1 ,2-dimethylpropyl, 1 -methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1 ,1 -dimethylbutyl, 1 ,2-dimethylbutyl, 1 ,3-dimethylbutyl, 2,2- dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1 -ethylbutyl, 2-ethylbutyl, 1 ,1 ,2- trimethylpropyl, 1 ,2,2-trimethylpropyl, 1 -ethyl-1 -methylpropyl and 1 -ethyl-2-methylpropyl. Examples for Ci-Cio-alkyl are, apart those mentioned for Ci-C6-alkyl, n-heptyl, 1 -methylhexyl, 2- methylhexyl, 3-methylhexyl, 4-methylhexyl, 5-methylhexyl, 1 -ethylpentyl, 2-ethylpentyl, 3- ethylpentyl, n-octyl, 1 -methyloctyl, 2-methylheptyl, 1 -ethylhexyl, 2-ethylhexyl, 1 ,2-dimethylhexyl, 1 -propylpentyl, 2-propylpentyl, nonyl, decyl, 2-propylheptyl and 3-propylheptyl.

The term "alkylene" (or alkanediyl) as used herein in each case denotes an alkyl radical as defined above, wherein one hydrogen atom at any position of the carbon backbone is replaced by one further binding site, thus forming a bivalent moiety.

The term "haloalkyl" as used herein (and in the haloalkyl moieties of other groups comprising a haloalkyl group, e.g. haloalkoxy, haloalkylthio, haloalkylcarbonyl, haloalkylsulfonyl and haloal- kylsulfinyl) denotes in each case a straight-chain or branched alkyl group having usually from 1 to 10 carbon atoms ("Ci-Cio-haloalkyl"), frequently from 1 to 6 carbon atoms ("Ci-C6-haloalkyl"), more frequently 1 to 4 carbon atoms ("Ci-Cio-haloalkyl"), wherein the hydrogen atoms of this group are partially or totally replaced with halogen atoms. Preferred haloalkyl moieties are se- lected from Ci-C4-haloalkyl, more preferably from Ci-C2-haloalkyl, more preferably from halome- thyl, in particular from Ci-C2-fluoroalkyl. Halomethyl is methyl in which 1 , 2 or 3 of the hydrogen atoms are replaced by halogen atoms. Examples are bromomethyl, chloromethyl, dichlorome- thyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichloro- fluoromethyl, chlorodifluoromethyl and the like. Examples for Ci-C2-fluoroalkyl are fluoromethyl, difluoromethyl, trifluoromethyl, 1 -fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, pentafluoroethyl, and the like. Examples for Ci-C2-haloalkyl are, apart those mentioned for Ci- C2-fluoroalkyl, chloromethyl, dichloromethyl, trichloromethyl, bromomethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 1 -chloroethyl, 2-chloroethyl, 2,2,-dichloroethyl, 2,2,2- trichloroethyl, 2-chloro-2-fluoroethyl, 2-chloro-2,2-difluoroethyl, 2,2-dichloro-2-fluoroethyl, 1 - bromoethyl, and the like. Examples for Ci-C4-haloalkyl are, apart those mentioned for C1-C2- haloalkyl, 1 -fluoropropyl, 2-fluoropropyl, 3-fluoropropyl, 3,3-difluoropropyl, 3,3,3-trifluoropropyl, heptafluoropropyl, 1 ,1 ,1 -trif I uoroprop-2-yl , 3-chloropropyl, 4-chlorobutyl and the like.

The term "cycloalkyi" as used herein (and in the cycloalkyi moieties of other groups comprising a cycloalkyi group, e.g. cycloalkoxy and cycloalkylalkyl) denotes in each case a mono- or bicy- die cycloaliphatic radical having usually from 3 to 10 carbon atoms ("C3-Cio-cycloalkyl"), preferably 3 to 8 carbon atoms ("Cs-Cs-cycloalkyl") or in particular 3 to 6 carbon atoms ("C3-C6- cycloalkyl"). Examples of monocyclic radicals having 3 to 6 carbon atoms comprise cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl. Examples of monocyclic radicals having 3 to 8 carbon atoms comprise cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl. Ex- amples of bicydic radicals having 7 or 8 carbon atoms comprise bicyclo[2.1 .1]hexyl, bicy- clo[2.2.1]heptyl, bicyclo[3.1 .1 ]heptyl, bicyclo[2.2.1]heptyl, bicyclo[2.2.2]octyl and bicy- clo[3.2.1 ]octyl.

The term "cycloalkylene" (or cycloalkanediyl) as used herein in each case denotes an cycloalkyi radical as defined above, wherein one hydrogen atom at any position of the carbon backbone is replaced by one further binding site, thus forming a bivalent moiety.

The term "halocycloalkyi" as used herein (and in the halocycloalkyi moieties of other groups comprising an halocycloalkyi group, e.g. halocycloalkylmethyl) denotes in each case a mono- or bicydic cycloaliphatic radical having usually from 3 to 10 carbon atoms, preferably 3 to 8 carbon atoms or in particular 3 to 6 carbon atoms, wherein at least one, e.g. 1 , 2, 3, 4 or 5 of the hydro- gen atoms are replaced by halogen, in particular by fluorine or chlorine. Examples are 1 - and 2- fluorocyclopropyl, 1 ,2-, 2,2- and 2,3-difluorocyclopropyl, 1 ,2,2-trifluorocyclopropyl, 2,2,3,3- tetrafluorocyclpropyl, 1 - and 2-chlorocyclopropyl, 1 ,2-, 2,2- and 2,3-dichlorocyclopropyl, 1 ,2,2- trichlorocyclopropyl, 2,2,3,3-tetrachlorocyclpropyl, 1 -,2- and 3-fluorocyclopentyl, 1 ,2-, 2,2-, 2,3-, 3,3-, 3,4-, 2,5-difluorocyclopentyl, 1 -,2- and 3-chlorocyclopentyl, 1 ,2-, 2,2-, 2,3-, 3,3-, 3,4-, 2,5- dichlorocyclopentyl and the like.

The term "cycloalkyl-alkyl" used herein denotes a cycloalkyl group, as defined above, which is bound to the remainder of the molecule via an alkylene group. The term "Cs-Cs-cycloalkyl-Ci- C4-alkyl" refers to a Cs-Cs-cycloalkyl group as defined above which is bound to the remainder of the molecule via a Ci-C4-alkyl group, as defined above. Examples are cyclopropylmethyl, cyclo- propylethyl, cyclopropylpropyl, cyclobutylmethyl, cyclobutylethyl, cyclobutylpropyl, cyclopen- tylmethyl, cyclopentylethyl, cyclopentylpropyl, cyclohexylmethyl, cyclohexylethyl, cyclohexylpro- pyl, and the like.

The term "alkenyl" as used herein denotes in each case a monounsaturated straight-chain or branched hydrocarbon radical having usually 2 to 10 ("C2-Cio-alkenyl"), preferably 2 to 6 carbon atoms ("C2-C6-alkenyl"), in particular 2 to 4 carbon atoms ("C2-C4-alkenyl"), and a double bond in any position, for example C2-C4-alkenyl, such as ethenyl, 1 -propenyl, 2-propenyl, 1 - methylethenyl, 1 -butenyl, 2-butenyl, 3-butenyl, 1 -methyl-1 -propenyl, 2-methyl-1 -propenyl, 1 - methyl-2-propenyl or 2-methyl-2-propenyl; C2-C6-alkenyl, such as ethenyl, 1 -propenyl, 2- propenyl, 1 -methylethenyl, 1 -butenyl, 2-butenyl, 3-butenyl, 1 -methyl-1 -propenyl, 2-methyl-1 - propenyl, 1 -methyl-2-propenyl, 2-methyl-2-propenyl, 1 -pentenyl, 2-pentenyl, 3-pentenyl, 4- pentenyl, 1 -methyl-1 -butenyl, 2-methyl-1 -butenyl, 3-methyl-1 -butenyl, 1 -methyl-2-butenyl, 2-methyl-2-butenyl, 3-methyl-2-butenyl, 1 -methyl-3-butenyl, 2-methyl-3-butenyl, 3-methyl-3- butenyl, 1 ,1 -dimethyl-2-propenyl, 1 ,2-dimethyl-1 -propenyl, 1 ,2-dimethyl-2-propenyl, 1 -ethyl-1 - propenyl, 1 -ethyl-2-propenyl, 1 -hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, 1 -methyl-

1 - pentenyl, 2-methyl-1 -pentenyl, 3-methyl-1 -pentenyl, 4-methyl-1 -pentenyl, 1 -methyl-2- pentenyl, 2-methyl-2-pentenyl, 3-methyl-2-pentenyl, 4-methyl-2-pentenyl, 1 -methyl-3-pentenyl,

2- methyl-3-pentenyl, 3-methyl-3-pentenyl, 4-methyl-3-pentenyl, 1 -methyl-4-pentenyl, 2-methyl- 4-pentenyl, 3-methyl-4-pentenyl, 4-methyl-4-pentenyl, 1 ,1 -dimethyl-2-butenyl, 1 ,1 -dimethyl-3- butenyl, 1 ,2-dimethyl-1 -butenyl, 1 ,2-dimethyl-2-butenyl, 1 ,2-dimethyl-3-butenyl, 1 ,3-dimethyl-1 - butenyl, 1 ,3-dimethyl-2-butenyl, 1 ,3-dimethyl-3-butenyl, 2,2-dimethyl-3-butenyl, 2,3-dimethyl-1 - butenyl, 2,3-dimethyl-2-butenyl, 2,3-dimethyl-3-butenyl, 3, 3-dimethyl-1 -butenyl, 3,3-dimethyl-2- butenyl, 1 -ethyl-1 -butenyl, 1 -ethyl-2-butenyl, 1 -ethyl-3-butenyl, 2-ethyl-1 -butenyl,

2-ethyl-2-butenyl, 2-ethyl-3-butenyl, 1 ,1 ,2-trimethyl-2-propenyl, 1 -ethyl-1 -methyl-2-propenyl, 1 - ethyl-2-methyl-1 -propenyl, 1 -ethyl-2-methyl-2-propenyl and the like, or C2-Cio-alkenyl, such as the radicals mentioned for C2-C6-alkenyl and additionally 1 -heptenyl, 2-heptenyl, 3-heptenyl, 1 - octenyl, 2-octenyl, 3-octenyl, 4-octenyl, 1 -nonenyl, 2-nonenyl, 3-nonenyl, 4-nonenyl, 1 -decenyl, 2-decenyl, 3-decenyl, 4-decenyl, 5-decenyl and the positional isomers thereof.

The term "alkenylene" (or alkenediyl) as used herein in each case denotes an alkenyl radical as defined above, wherein one hydrogen atom at any position of the carbon backbone is replaced by one further binding site, thus forming a bivalent moiety.

The term "haloalkenyl" as used herein, which may also be expressed as "alkenyl which may be substituted by halogen", and the haloalkenyl moieties in haloalkenyloxy, haloalkenylcarbonyl and the like refers to unsaturated straight-chain or branched hydrocarbon radicals having 2 to 10 ("C₂-Cio-haloalkenyl") or 2 to 6 ("C₂-C₆-haloalkenyl") or 2 to 4 ("C₂-C₄-haloalkenyl") carbon atoms and a double bond in any position, where some or all of the hydrogen atoms in these groups are replaced by halogen atoms as mentioned above, in particular fluorine, chlorine and bromine, for example chlorovinyl, chloroallyl and the like.

The term "alkynyl" as used herein denotes unsaturated straight-chain or branched hydrocarbon radicals having usually 2 to 10 ("C2-Cio-alkynyl"), frequently 2 to 6 ("C2-C6-alkynyl"), preferably 2 to 4 carbon atoms ("C2-C₄-alkynyl") and one or two triple bonds in any position, for example C2- C₄-alkynyl, such as ethynyl, 1 -propynyl, 2-propynyl, 1 -butynyl, 2-butynyl, 3-butynyl, 1 -methyl-2- propynyl and the like, C2-C6-alkynyl, such as ethynyl, 1 -propynyl, 2-propynyl, 1 -butynyl, 2- butynyl, 3-butynyl, 1 -methyl-2-propynyl, 1 -pentynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, 1 - methyl-2-butynyl, 1 -methyl-3-butynyl, 2-methyl-3-butynyl, 3-methyl-1 -butynyl, 1 ,1 -dimethyl-2- propynyl, 1 -ethyl-2-propynyl, 1 -hexynyl, 2-hexynyl, 3-hexynyl, 4-hexynyl, 5-hexynyl, 1 -methyl-2- pentynyl, 1 -methyl-3-pentynyl, 1 -methyl-4-pentynyl, 2-methyl-3-pentynyl, 2-methyl-4-pentynyl, 3- methyl-1 -pentynyl, 3-methyl-4-pentynyl, 4-methyl-1 -pentynyl, 4-methyl-2-pentynyl, 1 ,1 -dimethyl- 2-butynyl, 1 ,1 -dimethyl-3-butynyl, 1 ,2-dimethyl-3-butynyl, 2,2-dimethyl-3-butynyl, 3,3-dimethyl-1 - butynyl, 1 -ethyl-2-butynyl, 1 -ethyl-3-butynyl, 2-ethyl-3-butynyl, 1 -ethyl-1 -methyl-2-propynyl and the like.

The term "alkynylene" (or alkynediyl) as used herein in each case denotes an alkynyl radical as defined above, wherein one hydrogen atom at any position of the carbon backbone is replaced by one further binding site, thus forming a bivalent moiety.

The term "haloalkynyl" as used herein, which is also expressed as "alkynyl which may be substituted by halogen", refers to unsaturated straight-chain or branched hydrocarbon radicals having iusually 3 to 10 carbon atoms ("C2-Cio-haloalkynyl"), frequently 2 to 6 ("C2-C6-haloalkynyl"), preferabyl 2 to 4 carbon atoms ("C2-C₄-haloalkynyl"), and one or two triple bonds in any position (as mentioned above), where some or all of the hydrogen atoms in these groups are replaced by halogen atoms as mentioned above, in particular fluorine, chlorine and bromine.

The term "alkoxy" as used herein denotes in each case a straight-chain or branched alkyl group usually having from 1 to 10 carbon atoms ("Ci-Cio-alkoxy"), frequently from 1 to 6 carbon atoms ("Ci-C6-alkoxy"), preferably 1 to 4 carbon atoms ("Ci-C₄-alkoxy"), which is bound to the remain- der of the molecule via an oxygen atom. Ci-C2-Alkoxy is methoxy or ethoxy. Ci-C₄-Alkoxy is additionally, for example, n-propoxy, 1 -methylethoxy (isopropoxy), butoxy, 1 -methylpropoxy (sec-butoxy), 2-methylpropoxy (isobutoxy) or 1 ,1 -dimethylethoxy (tert-butoxy). Ci-C6-Alkoxy is additionally, for example, pentoxy, 1 -methylbutoxy, 2-methylbutoxy, 3-methylbutoxy, 1 ,1 - dimethylpropoxy, 1 ,2-dimethylpropoxy, 2,2-dimethylpropoxy, 1 -ethylpropoxy, hexoxy, 1 - methylpentoxy, 2-methylpentoxy, 3-methylpentoxy, 4-methylpentoxy, 1 ,1 -dimethylbutoxy, 1 ,2- dimethylbutoxy, 1 ,3-dimethylbutoxy, 2,2-dimethylbutoxy, 2,3-dimethylbutoxy,

3,3-dimethylbutoxy, 1 -ethylbutoxy, 2-ethylbutoxy, 1 ,1 ,2-trimethylpropoxy, 1 ,2,2- trimethylpropoxy, 1 -ethyl-1 -methylpropoxy or 1 -ethyl-2-methylpropoxy. Ci-Cs-Alkoxy is additionally, for example, heptyloxy, octyloxy, 2-ethylhexyloxy and positional isomers thereof. C1-C10- Alkoxy is additionally, for example, nonyloxy, decyloxy and positional isomers thereof.

The term "haloalkoxy" as used herein denotes in each case a straight-chain or branched alkoxy group, as defined above, having from 1 to 10 carbon atoms ("Ci-Cio-haloalkoxy"), frequently from 1 to 6 carbon atoms ("Ci-C6-haloalkoxy"), preferably 1 to 4 carbon atoms ("C1-C4- haloalkoxy"), more preferably 1 to 3 carbon atoms ("Ci-C3-haloalkoxy"), wherein the hydrogen atoms of this group are partially or totally replaced with halogen atoms, in particular fluorine atoms. Ci-C₂-Haloalkoxy is, for example, OCH₂F, OCHF₂, OCF₃, OCH₂CI, OCHC , OCCI₃, chlorofluoromethoxy, dichlorofluoromethoxy, chlorodifluoromethoxy, 2-fluoroethoxy, 2- chloroethoxy, 2-bromoethoxy, 2-iodoethoxy, 2,2-difluoroethoxy, 2,2,2-trifluoroethoxy, 2-chloro-2- fluoroethoxy, 2-chloro-2,2-difluoroethoxy, 2,2-dichloro-2-fluoroethoxy, 2,2,2-trichloroethoxy or OC2F5. Ci-C4-Haloalkoxy is additionally, for example, 2-fluoropropoxy, 3-fluoropropoxy, 2,2- difluoropropoxy, 2,3-difluoropropoxy, 2-chloropropoxy, 3-chloropropoxy, 2,3-dichloropropoxy, 2- bromopropoxy, 3-bromopropoxy, 3,3,3-trifluoropropoxy, 3,3,3-trichloropropoxy, OCH2-C2F5, OCF2-C2F5, 1 -(CH₂F)-2-fluoroethoxy, 1 -(CH₂CI)-2-chloroethoxy, 1 -(CH₂Br)-2-bromoethoxy, 4-fluorobutoxy, 4-chlorobutoxy, 4-bromobutoxy or nonafluorobutoxy. Ci-C6-Haloalkoxy is additionally, for example, 5-fluoropentoxy, 5-chloropentoxy, 5-brompentoxy, 5-iodopentoxy, unde- cafluoropentoxy, 6-fluorohexoxy, 6-chlorohexoxy, 6-bromohexoxy, 6-iodohexoxy or dodecafluo- rohexoxy.

The term "alkoxyalkyl" as used herein denotes in each case alkyl usually comprising 1 to 6 car- bon atoms, preferably 1 to 4 carbon atoms, wherein 1 carbon atom carries an alkoxy radical usually comprising 1 to 10, frequently 1 to 6, in particular 1 to 4, carbon atoms as defined above. "Ci-C6-Alkoxy-Ci-C6-alkyl" is a Ci-C6-alkyl group, as defined above, in which one hydrogen atom is replaced by a Ci-C6-alkoxy group, as defined above. Examples are CH2OCH3, CH2- OC2H5, n-propoxymethyl, CH2-OCH(CH3)2, n-butoxymethyl, (l -methylpropoxy)-methyl, (2- methylpropoxy)methyl, CH2-OC(CH3)3, 2-(methoxy)ethyl, 2-(ethoxy)ethyl, 2-(n-propoxy)-ethyl, 2- (1 -methylethoxy)-ethyl, 2-(n-butoxy)ethyl, 2-(1 -methylpropoxy)-ethyl, 2-(2-methylpropoxy)-ethyl, 2-(1 ,1 -dimethylethoxy)-ethyl, 2-(methoxy)-propyl, 2-(ethoxy)-propyl, 2-(n-propoxy)-propyl, 2-(1 - methylethoxy)-propyl, 2-(n-butoxy)-propyl, 2-(1 -methylpropoxy)-propyl, 2-(2-methylpropoxy)- propyl, 2-(1 ,1 -dimethylethoxy)-propyl, 3-(methoxy)-propyl, 3-(ethoxy)-propyl, 3-(n-propoxy)- propyl, 3-(1 -methylethoxy)-propyl, 3-(n-butoxy)-propyl, 3-(1 -methylpropoxy)-propyl, 3-(2- methylpropoxy)-propyl, 3-(1 ,1 -dimethylethoxy)-propyl, 2-(methoxy)-butyl, 2-(ethoxy)-butyl, 2-(n- propoxy)-butyl, 2-(1 -methylethoxy)-butyl, 2-(n-butoxy)-butyl, 2-(1 -methylpropoxy)-butyl, 2-(2- methyl-propoxy)-butyl, 2-(1 ,1 -dimethylethoxy)-butyl, 3-(methoxy)-butyl, 3-(ethoxy)-butyl, 3-(n- propoxy)-butyl, 3-(1 -methylethoxy)-butyl, 3-(n-butoxy)-butyl, 3-(1 -methylpropoxy)-butyl, 3-(2- methylpropoxy)-butyl, 3-(1 ,1 -dimethylethoxy)-butyl, 4-(methoxy)-butyl, 4-(ethoxy)-butyl, 4-(n- propoxy)-butyl, 4-(1 -methylethoxy)-butyl, 4-(n-butoxy)-butyl, 4-(1 -methylpropoxy)-butyl, 4-(2- methylpropoxy)-butyl, 4-(1 ,1 -dimethylethoxy)-butyl and the like.

The term "haloalkoxy-alkyl" as used herein denotes in each case alkyl as defined above, usually comprising 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, wherein 1 carbon atom carries an haloalkoxy radical as defined above, usually comprising 1 to 10, frequently 1 to 6, in particular 1 to 4, carbon atoms as defined above. Examples are fluoromethoxymethyl, difluoromethox- ymethyl, trifluoromethoxymethyl, 1 -fluoroethoxymethyl, 2-fluoroethoxymethyl, 1 ,1 - difluoroethoxymethyl, 1 ,2-difluoroethoxymethyl, 2,2-difluoroethoxymethyl, 1 ,1 ,2- trifluoroethoxymethyl, 1 ,2,2-trifluoroethoxymethyl, 2,2,2-trifluoroethoxymethyl, pentafluoroethox- ymethyl, 1 -fluoroethoxy-1 -ethyl, 2-fluoroethoxy-1 -ethyl, 1 ,1 -difluoroethoxy-1 -ethyl, 1 ,2- difluoroethoxy-1 -ethyl, 2,2-difluoroethoxy-1 -ethyl, 1 ,1 ,2-trifluoroethoxy-1 -ethyl, 1 ,2,2- trifluoroethoxy-1 -ethyl, 2,2,2-trifluoroethoxy-1 -ethyl, pentafluoroethoxy-1 -ethyl, 1 -fluoroethoxy-2- ethyl, 2-fluoroethoxy-2-ethyl, 1 ,1 -difluoroethoxy-2 -ethyl, 1 ,2-difluoroethoxy-2-ethyl, 2,2- difluoroethoxy-2-ethyl, 1 ,1 ,2-trifluoroethoxy-2-ethyl, 1 ,2,2-trifluoroethoxy-2-ethyl, 2,2,2- trifluoroethoxy-2-ethyl, pentafluoroethoxy-2-ethyl, and the like.

The term "alkylthio"(also alkylsulfanyl or alkyl-S-)" as used herein denotes in each case a straight-chain or branched saturated alkyl group as defined above, usually comprising 1 to 10 carbon atoms ("Ci-Cio-alkylthio"), frequently comprising 1 to 6 carbon atoms ("Ci-C6-alkylthio"), preferably 1 to 4 carbon atoms ("Ci-C4-alkylthio"), which is attached via a sulfur atom at any position in the alkyl group. Ci-C2-Alkylthio is methylthio or ethylthio. Ci-C4-Alkylthio is additionally, for example, n-propylthio, 1 -methylethylthio (isopropylthio), butylthio, 1 -methylpropylthio (sec- butylthio), 2-methylpropylthio (isobutylthio) or 1 ,1 -dimethylethylthio (tert-butylthio). C1-C6- Alkylthio is additionally, for example, pentylthio, 1 -methylbutylthio, 2-methylbutylthio, 3- methylbutylthio, 1 ,1 -dimethylpropylthio, 1 ,2-dimethylpropylthio, 2,2-dimethylpropylthio, 1 - ethylpropylthio, hexylthio, 1 -methylpentylthio, 2-methylpentylthio, 3-methylpentylthio, 4- methylpentylthio, 1 ,1 -dimethylbutylthio, 1 ,2-dimethylbutylthio, 1 ,3-dimethylbutylthio, 2,2- dimethylbutylthio, 2,3-dimethylbutylthio, 3,3-dimethylbutylthio, 1 -ethylbutylthio, 2-ethylbutylthio, 1 ,1 ,2-trimethylpropylthio, 1 ,2,2-trimethylpropylthio, 1 -ethyl-1 -methylpropylthio or 1 -ethyl-2- methylpropylthio. Ci-Cs-Alkylthio is additionally, for example, heptylthio, octylthio, 2- ethylhexylthio and positional isomers thereof. Ci-Cio-Alkylthio is additionally, for example, nonyl- thio, decylthio and positional isomers thereof.

The term "haloalkylthio" as used herein refers to an alkylthio group as defined above wherein the hydrogen atoms are partially or fully substituted by fluorine, chlorine, bromine and/or iodine. Ci-C₂-Haloalkylthio is, for example, SCH₂F, SCHF₂, SCF₃, SCH₂CI, SCHCI₂, SCCI₃, chlorofluo- romethylthio, dichlorofluoromethylthio, chlorodifluoromethylthio, 2-fluoroethylthio, 2- chloroethylthio, 2-bromoethylthio, 2-iodoethylthio, 2,2-difluoroethylthio, 2,2,2-trifluoroethylthio, 2- chloro-2-fluoroethylthio, 2-chloro-2,2-difluoroethylthio, 2,2-dichloro-2-fluoroethylthio,

2,2,2-trichloroethylthio or SC₂F₅. Ci-C4-Haloalkylthio is additionally, for example,

2-fluoropropylthio, 3-fluoropropylthio, 2,2-difluoropropylthio, 2,3-difluoropropylthio,

2- chloropropylthio, 3-chloropropylthio, 2,3-dichloropropylthio, 2-bromopropylthio,

3- bromopropylthio, 3,3,3-trifluoropropylthio, 3,3,3-trichloropropylthio, SCH₂-C₂F₅, SCF₂-C₂F₅, 1 - (CH₂F)-2-fluoroethylthio, 1 -(CH₂CI)-2-chloroethylthio, 1 -(CH₂Br)-2-bromoethylthio,

4-fluorobutylthio, 4-chlorobutylthio, 4-bromobutylthio or nonafluorobutylthio. Ci-C6-Haloalkylthio is additionally, for example, 5-fluoropentylthio, 5-chloropentylthio, 5-brompentylthio,

5- iodopentylthio, undecafluoropentylthio, 6-fluorohexylthio, 6-chlorohexylthio, 6-bromohexylthio,

6- iodohexylthio or dodecafluorohexylthio.

The terms "alkylsulfinyl" and "S(0)_n-alkyl" (wherein n is 1 ) are equivalent and, as used herein, denote an alkyl group, as defined above, attached via a sulfinyl [S(O)] group. For example, the term "Ci-C₂-alkylsulfinyl" refers to a Ci-C₂-alkyl group, as defined above, attached via a sulfinyl [S(O)] group. The term "Ci-C4-alkylsulfinyl" refers to a Ci-C4-alkyl group, as defined above, attached via a sulfinyl [S(O)] group. The term "Ci-C6-alkylsulfinyl" refers to a Ci-C6-alkyl group, as defined above, attached via a sulfinyl [S(O)] group. Ci-C₂-alkylsulfinyl is methylsulfinyl or ethyl- sulfinyl. Ci-C4-alkylsulfinyl is additionally, for example, n-propylsulfinyl, 1 -methylethylsulfinyl (isopropylsulfinyl), butylsulfinyl, 1 -methylpropylsulfinyl (sec-butylsulfinyl), 2-methylpropylsulfinyl (isobutylsulfinyl) or 1 ,1 -dimethylethylsulfinyl (tert-butylsulfinyl). Ci-C6-alkylsulfinyl is additionally, for example, pentylsulfinyl, 1 -methylbutylsulfinyl, 2-methylbutylsulfinyl, 3-methylbutylsulfinyl, 1 ,1 -dimethylpropylsulfinyl, 1 ,2-dimethylpropylsulfinyl, 2,2-dimethylpropylsulfinyl, 1 -ethylpropylsulfinyl, hexylsulfinyl, 1 -methylpentylsulfinyl, 2-methylpentylsulfinyl, 3-methylpentylsulfinyl, 4-methylpentylsulfinyl, 1 ,1 -dimethylbutylsulfinyl, 1 ,2-dimethylbutylsulfinyl, 1 , 3-d imethyl butylsulfi nyl , 2,2-dimethylbutylsulfinyl, 2,3-dimethylbutylsulfinyl, 3,3- dimethylbutylsulfinyl, 1 -ethylbutylsulf inyl , 2-ethylbutylsulfinyl, 1 ,1 ,2-trimethylpropylsulfinyl, 1 ,2,2- trimethylpropylsulfinyl, 1 -ethyl-1 -methylpropylsulfinyl or 1 -ethyl-2-methylpropylsulfinyl.

The terms "alkylsulfonyl" and "S(0)_n-alkyl" (wherein n is 2) are equivalent and, as used herein, denote an alkyl group, as defined above, attached via a sulfonyl [S(0)2] group. The term "C1-C2- alkylsulfonyl" refers to a Ci-C2-alkyl group, as defined above, attached via a sulfonyl [S(0)2] group. The term "Ci-C4-alkylsulfonyl" refers to a Ci-C4-alkyl group, as defined above, attached via a sulfonyl [S(0)2] group. The term "Ci-C6-alkylsulfonyl" refers to a Ci-C6-alkyl group, as defined above, attached via a sulfonyl [S(0)2] group. Ci-C2-alkylsulfonyl is methylsulfonyl or ethyl- sulfonyl. Ci-C4-alkylsulfonyl is additionally, for example, n-propylsulfonyl, 1 -methylethylsulfonyl (isopropylsulfonyl), butylsulfonyl, 1 -methylpropylsulfonyl (sec-butylsulfonyl), 2- methylpropylsulfonyl (isobutylsulfonyl) or 1 ,1 -dimethylethylsulfonyl (tert-butylsulfonyl). C1-C6- alkylsulfonyl is additionally, for example, pentylsulfonyl, 1 -methylbutylsulfonyl, 2- methylbutylsulfonyl, 3-methylbutylsulfonyl, 1 ,1 -dimethylpropylsulfonyl, 1 ,2- dimethylpropylsulfonyl, 2,2-dimethylpropylsulfonyl, 1 -ethylpropylsulfonyl, hexylsulfonyl, 1 - methylpentylsulfonyl, 2-methylpentylsulfonyl, 3-methylpentylsulfonyl, 4-methylpentylsulfonyl, 1 ,1 -dimethylbutylsulfonyl, 1 ,2-dimethylbutylsulfonyl, 1 ,3-dimethylbutylsulfonyl,

2,2-dimethylbutylsulfonyl, 2,3-dimethylbutylsulfonyl, 3,3-dimethylbutylsulfonyl,

1 -ethylbutylsulfonyl, 2-ethylbutylsulfonyl, 1 ,1 ,2-trimethylpropylsulfonyl,

1 ,2,2-trimethylpropylsulfonyl, 1 -ethyl-1 -methylpropylsulfonyl or 1 -ethyl-2-methylpropylsulfonyl. The term "alkylamino" as used herein denotes in each case a group -NHR, wherein R is a straight-chain or branched alkyl group usually having from 1 to 6 carbon atoms ("C1-C6- alkylamino"), preferably 1 to 4 carbon atoms("Ci-C4-alkylamino"). Examples of Ci-C6-alkylamino are methylamino, ethylamino, n-propylamino, isopropylamino, n-butylamino, 2-butylamino, iso- butylamino, tert-butylamino, and the like.

The term "dialkylamino" as used herein denotes in each case a group-NRR', wherein R and R', independently of each other, are a straight-chain or branched alkyl group each usually having from 1 to 6 carbon atoms ("di-(Ci-C6-alkyl)-amino"), preferably 1 to 4 carbon atoms ("di-(Ci-C4- alkyl)-amino"). Examples of a di-(Ci-C6-alkyl)-amino group are dimethylamino, diethylamino, dipropylamino, dibutylamino, methyl-ethyl-amino, methyl-propyl-amino, methyl-isopropylamino, methyl-butyl-amino, methyl-isobutyl-amino, ethyl-propyl-amino, ethyl-isopropylamino, ethyl- butyl-amino, ethyl-isobutyl-amino, and the like.

The term "cycloalkylamino" as used herein denotes in each case a group -NHR, wherein R is a cycloalkyi group usually having from 3 to 8 carbon atoms ("Cs-Cs-cycloalkylamino"), preferably 3 to 6 carbon atoms("C3-C6-cycloalkylamino"). Examples of Cs-Cs-cycloalkylamino are cycloprop- ylamino, cyclobutylamino, cyclopentylamino, cyclohexylamino, and the like.

The term "alkylaminosulfonyl" as used herein denotes in each case a straight-chain or branched alkylamino group as defined above, which is bound to the remainder of the molecule via a sulfonyl [S(0)2] group. Examples of an alkylaminosulfonyl group are methylaminosulfonyl, ethyla- minosulfonyl, n-propylaminosulfonyl, isopropylaminosulfonyl, n-butylaminosulfonyl, 2- butylaminosulfonyl, iso-butylaminosulfonyl, tert-butylaminosulfonyl, and the like.

The term "dialkylaminosulfonyl" as used herein denotes in each case a straight-chain or branched alkylamino group as defined above, which is bound to the remainder of the molecule via a sulfonyl [S(0)2] group. Examples of an dialkylaminosulfonyl group are dimethylaminosul- fonyl, diethylaminosulfonyl, dipropylaminosulfonyl, dibutylaminosulfonyl, methyl-ethyl- aminosulfonyl, methyl-propyl-aminosulfonyl, methyl-isopropylaminosulfonyl, methyl-butyl- aminosulfonyl, methyl-isobutyl-aminosulfonyl, ethyl-propyl-aminosulfonyl, ethyl- isopropylaminosulfonyl, ethyl-butyl-aminosulfonyl, ethyl-isobutyl-aminosulfonyl, and the like. The suffix ,,-carbonyl" in a group denotes in each case that the group is bound to the remainder of the molecule via a carbonyl C=0 group. This is the case e.g. in alkylcarbonyl, haloalkylcar- bonyl, aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, alkoxycarbonyl, haloal- koxycarbonyl.

The term "aryl" as used herein refers to a mono-, bi- or tricyclic aromatic hydrocarbon radical such as phenyl or naphthyl, in particular phenyl.

The term "het(ero)aryl" as used herein refers to a mono-, bi- or tricyclic heteroaromatic hydrocarbon radical, preferably to a monocyclic heteroaromatic radical, such as pyridyl, pyrimidyl and the like.

A saturated, partially unsaturated or unsaturated 3- to 8-membered ring system which contains 1 to 4 heteroatoms selected from oxygen, nitrogen, sulfur, is a ring system wherein two oxygen atoms must not be in adjacent positions and wherein at least 1 carbon atom must be in the ring system e.g. thiophene, furan, pyrrole, thiazole, oxazole, imidazole, isothiazole, isoxa- zole, pyrazole, 1 ,3,4-oxadiazole, 1 ,3,4-thiadiazole, 1 ,3,4-triazole, 1 ,2,4-oxadiazole, 1 ,2,4- thiadiazole, 1 ,2,4-triazole, 1 ,2,3-triazole, 1 ,2,3,4-tetrazole, benzo[b]thiophene, benzo[b]furan, indole, benzo[c]thiophene, benzo[c]furan, isoindole, benzoxazole, benzthiazole, benzimidazole, benzisoxazole, benzisothiazole, benzopyrazole, benzothiadiazole, benztriazole, dibenzofuran, dibenzothiophene, carbazole, pyridine, pyrazine, pyrimidine, pyridazine, 1 ,3,5-triazine, 1 ,2,4- triazine, 1 ,2,4,5-tetrazine, quinoline, isoquinoline, quinoxaline, quinazoline, cinnoline, 1 ,8- naphthyridine, 1 ,5-naphthyridine, 1 ,6-naphthyridine, 1 ,7-naphthyridine, phthalazine, pyri- dopyrimidine, purine, pteridine, 4H-quinolizine, piperidine, pyrrolidine, oxazoline, tetrahydrofu- ran, tetrahydropyran, isoxazolidine or thiazolidine, oxirane or oxetane.

A saturated, partially unsaturated or unsaturated 3- to 8-membered ring system which contains 1 to 4 heteroatoms selected from oxygen, nitrogen, sulfur also is e.g.

a saturated, partially unsaturated or unsaturated 5-or 6-membered heterocycle which contains 1 to 4 heteroatoms selected from oxygen, nitrogen and sulfur, such as pyridine, pyrimidine, (1 ,2,4)-oxadiazole, (1 ,3,4)-oxadiazole, pyrrole, furan, thiophene, oxazole, thiazole, imidazole, pyrazole, isoxazole, 1 ,2,4-triazole, tetrazole, pyrazine, pyridazine, oxazoline, thiazoline, tetrahy- drofuran, tetrahydropyran, morpholine, piperidine, piperazine, pyrroline, pyrrolidine, oxazolidine, thiazolidine; or

a saturated, partially unsaturated or unsaturated 5-or 6-membered heterocycle which contains 1 nitrogen atom and 0 to 2 further heteroatoms selected from oxygen, nitrogen and sulfur, preferably from oxygen and nitrogen, such as piperidine, piperazin and morpholine.

Preferably, this ring system is a saturated, partially unsaturated or unsaturated 3- to 6- membered ring system which contains 1 to 4 heteroatoms selected from oxygen, nitrogen, sulfur, wherein two oxygen atoms must not be in adjacent positions and wherein at least 1 carbon atom must be in the ring system. Most preferably, this ring system is a radical of pyridine, pyrimidine, (1 ,2,4)-oxadiazole, 1 ,3,4-oxadiazole, pyrrole, furan, thiophene, oxazole, thiazole, imidazole, pyrazole, isoxazole, 1 ,2,4-triazole, tetrazole, pyrazine, pyridazine, oxazoline, thiazoline, tetrahydrofuran, tetrahydro- pyran, morpholine, piperidine, piperazine, pyrroline, pyrrolidine, oxazolidine, thiazolidine, oxirane or oxetane.

Preparation of the compounds of formula I can be accomplished according to standard methods of organic chemistry, e.g. by the methods or working examples described in WO 2007/006670, PCT/EP2012/065650 and PCT/EP2012/065651 , without being limited to the routes given there- in.

The preparation of the compounds of formula I above may lead to them being obtained as isomer mixtures. If desired, these can be resolved by the methods customary for this purpose, such as crystallization or chromatography, also on optically active adsorbate, to give the pure isomers.

Agronomically acceptable salts of the compounds I can be formed in a customary manner, e.g. by reaction with an acid of the anion in question.

Preferences

The remarks made below as to preferred embodiments of the variables (substituents) of the compounds of formulae (I) are valid on their own as well as preferably in combination with each other, as well as in combination with the stereoisomers, tautomers, N-oxides or salts thereof, and, where applicable, as well as concerning the uses and methods according to the invention and the compositions according to the invention.

Preferred compounds according to the invention are compounds of formulae (I) or a stereoisomer, N-oxide or salt thereof, wherein the salt is an agriculturally or veterinarily acceptable salt. The compounds I of formula (I) and their examples include their tautomers, racemic mixtures, individual pure enantiomers and diastereomers and their optically active mixtures. Preferred are methods and uses of compounds of formula (I), wherein the compound of formula I is a compound of formula IA:

wherein

R⁴ is halogen, and

wherein the variables R¹, R², R⁷, R⁵, R⁶ and k are as defined herein.

Preferred are methods and uses of compounds of formula (I), in which the compound of formula I is a compound of formula IB:

wherein

R² is selected from the group consisting of bromo, chloro, cyano;

R⁷ is selected from the group consisting of bromo, chloro, trifluoromethyl. OCHF2, and wherein the variables R², R⁷, R⁵, R⁶ and k are as defined herein.

Preferred are methods and uses of compounds of formula (I), in which the compound of formula I is a compound of formula IC:

wherein

R¹ is selected from the group consisting of halogen and halomethyl;

R² is selected from the group consisting of bromo, chloro and cyano, and

wherein the variables R⁵, R⁶ and k are as defined herein. Preferred are methods and uses of compounds of formula (I), in which the compound of formula I is a compound of formula ID:

wherein

R¹ is selected from the group consisting of halogen, methyl and halomethyl;

R² is selected from the group consisting of bromo, chloro and cyano, and

wherein the variables R⁵, R⁶ and k are as defined herein.

Preferred are methods and uses of compounds of formula (I), in which R⁵, R⁶ are selected inde- pendently of one another from the group consisting of hydrogen, Ci-Cio-alkyl, Cs-Cs-cycloalkyl, wherein the aforementioned aliphatic and cycloaliphatic radicals may be substituted with 1 to 10 substituents R^e; or

R⁵ and R⁶ together represent a C2-C7-alkylene chain forming together with the sulfur atom to which they are attached a 3-, 4-, 5-, 6-, 7- or 8- membered saturated, partially unsaturated or fully unsaturated ring, wherein 1 to 4 of the Chb groups in the C2-C7-alkylene chain may be replaced by 1 to 4 groups independently selected from the group consisting of C=0, C=S, O, S, N, NO, SO, SO2 and NH, and wherein the carbon and/or nitrogen atoms in the C2-C7-alkylene chain may be substituted with 1 to 5 substituents independently selected from the group consisting of halogen, cyano, Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy, Ci-C6-haloalkoxy, C1-C6- alkylthio, Ci-C6-haloalkylthio, Cs-Cs-cycloalkyl, Cs-Cs-halocycloalkyl, C2-C6-alkenyl, C2-C6- haloalkenyl, C2-C6-alkynyl and C2-C6-haloalkynyl; said substituents being identical or different from one another if more than one substituent is present.

Preferred are methods and uses of compounds of formula (I), in which R⁵, R⁶ are selected independently of one another from the group consisting of hydrogen, Ci-Cio-alkyl, Cs-Cs-cycloalkyl, wherein the aforementioned aliphatic and cycloaliphatic radicals may be substituted with 1 to 10 substituents R^e.

Preferred are methods and uses of compounds of formula (I), in which R⁷ is selected from the group consisting of bromo, difluoromethyl, trifluoromethyl, cyano, OCHF2, OCH2F and

OCH2CF3, Preferred are methods and uses of compounds of formula (I), in which R⁷ is selected from the group consisting of bromo, difluoromethyl, trifluoromethyl and OCH F2.

Preferred are methods and uses of compounds of formula (I), in which R^e is independently se- lected from the group consisting of halogen, cyano, -OH, -SH , -SCN , Ci-C6-alkyl, C2-C6-alkenyl, C2-C6-alkinyl, Cs-Cs-cycloalkyI, wherein one or more CH2 groups of the aforementioned radicals may be replaced by a C=0 group, and/or the aliphatic and cycloaliphatic moieties of the aforementioned radicals may be unsubstituted, partially or fully halogenated and/or may carry 1 or 2 radicals selected from Ci-C6-alkoxy, Ci-C6-haloalkoxy, Ci-C6-alkylthio, Ci-C6-alkylsulfinyl, Ci- Ce-alkylsulfonyl, Ci-C₆-haloalkylthio, -OR^a, -N R^cR^d, -S(0)_nR^a, -S(0)_nN R^cR^d,

-C(=0)R^a, -C(=0)N R^cR^d, -C(=0)OR^b, -C(=S)R^a, -C(=S)N R^cR^d, -C(=S)OR^b,

-C(=S)SR^b, -C(=N R^c)R^b, -C(=N R^c)N R^cR^d, phenyl, benzyl, pyridyl and phenoxy, wherein the last four radicals may be unsubstituted, partially or fully halogenated and/or carry 1 , 2 or 3 substitu- ents selected from Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy and Ci-C6-haloalkoxy.

Preferred are methods and uses of compounds of formula (I), in which R^e is independently selected from the group consisting of halogen, cyano, -OH, -SH , -SCN , Ci-C6-alkyl, C2-C6-alkenyl, C2-C6-alkinyl, Cs-Cs-cycloalkyI, wherein one or more CH2 groups of the aforementioned radicals may be replaced by a C=0 group, and/or the aliphatic and cycloaliphatic moieties of the afore- mentioned radicals may be unsubstituted, partially or fully halogenated.

Preferred are methods and uses of compounds of formula (I) as described herein, in which in the compound of formula I

R⁵ and R⁶ are selected from methyl, ethyl, isopropyl, n-propyl, n-butyl, isobutyl, tert-butyl, cyclo- propyl, cyclopropylmethyl.

R⁵ and R⁶ are identical.

In a particularly preferred embodiment, the methods and uses according to the invention comprise at least one compound of formula (IA)

wherein

R⁴ is CI,

R¹ is selected from the group consisting of CI, Br, and methyl;

R² is selected from the group consisting of bromo and chloro;

R⁵, R⁶ are selected independently of one another from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl.

R⁷ is selected from the group consisting of difluoromethyl, trifluoromethyl.

Examples of especially preferred anthranilamide compounds I of the present invention are of formula (IA-1 )

wherein R¹, R², R⁷, R⁵, R⁶ are as defined herein.

Examples of preferred compounds of formula I in the methods and uses according to the inven- tion are compiled in tables 1 to 60 below. Moreover, the meanings mentioned below for the individual variables in the tables are per se, independently of the combination in which they are mentioned, a particularly preferred embodiment of the substituents in question.

Table 1 Compounds of the formula (IA-1 ) in which R¹ is F, R² is CI, R⁷ is CF3 and the com- bination of R⁵ and R⁶ for a compound corresponds in each case to one row of Table A;

Table 2 Compounds of the formula (IA-1 ) in which R¹ is Br, R² is CI, R⁷ is CF3 and the combination of R⁵ and R⁶ for a compound corresponds in each case to one row of Table A;

Table 3 Compounds of the formula (IA-1 ) in which R¹ is CI, R² is CI, R⁷ is CF3 and the combination of R⁵ and R⁶ for a compound corresponds in each case to one row of Table A; Table 4 Compounds of the formula (IA-1 ) in which R¹ is methyl, R² is CI, R⁷ is CF3 and the combination of R⁵ and R⁶ for a compound corresponds in each case to one row of Table A;

Table 5 Compounds of the formula (IA-1 ) in which R¹ is F, R² is Br, R⁷ is CF3 and the combination of R⁵ and R⁶ for a compound corresponds in each case to one row of Table A;

Table 6 Compounds of the formula (IA-1 ) in which R¹ is Br, R² is Br, R⁷ is CF3 and the combination of R⁵ and R⁶ for a compound corresponds in each case to one row of Table A; Table 7 Compounds of the formula (IA-1 ) in which R¹ is CI, R² is Br, R⁷ is CF3 and the combination of R⁵ and R⁶ for a compound corresponds in each case to one row of Table A; Table 8 Compounds of the formula (IA-1 ) in which R¹ is methyl, R² is Br, R⁷ is CF3 and the combination of R⁵ and R⁶ for a compound corresponds in each case to one row of Table A;

Table 9 Compounds of the formula (IA-1 ) in which R¹ is F, R² is cyano, R⁷ is CF3 and the combination of R⁵ and R⁶ for a compound corresponds in each case to one row of Table A; Table 10 Compounds of the formula (IA-1 ) in which R¹ is Br, R² is cyano, R⁷ is CF3 and the combination of R⁵ and R⁶ for a compound corresponds in each case to one row of Table A;

Table 1 1 Compounds of the formula (IA-1 ) in which R¹ is CI, R² is cyano, R⁷ is CF3 and the combination of R⁵ and R⁶ for a compound corresponds in each case to one row of Table A;

Table 12 Compounds of the formula (IA-1 ) in which R¹ is methyl, R² is cyano, R⁷ is CF3 and the combination of R⁵ and R⁶ for a compound corresponds in each case to one row of Table A;

Table 13 Compounds of the formula (IA-1 ) in which R¹ is F, R² is CI, R⁷ is CHF₂ and the combination of R⁵ and R⁶ for a compound corresponds in each case to one row of Table A;

Table 14 Compounds of the formula (IA-1 ) in which R¹ is Br, R² is CI, R⁷ is CHF₂ and the combination of R⁵ and R⁶ for a compound corresponds in each case to one row of Table A; Table 15 Compounds of the formula (IA-1 ) in which R¹ is CI, R² is CI, R⁷ is CHF₂ and the combination of R⁵ and R⁶ for a compound corresponds in each case to one row of Table A;

Table 16 Compounds of the formula (IA-1 ) in which R¹ is methyl, R² is CI, R⁷ is CHF2 and the combination of R⁵ and R⁶ for a compound corresponds in each case to one row of Table A;

Table 17 Compounds of the formula (IA-1 ) in which R¹ is F, R² is Br, R⁷ is CHF2 and the combination of R⁵ and R⁶ for a compound corresponds in each case to one row of Table A;

Table 18 Compounds of the formula (IA-1 ) in which R¹ is Br, R² is Br, R⁷ is CHF2 and the combination of R⁵ and R⁶ for a compound corresponds in each case to one row of Table A;

Table 19 Compounds of the formula (IA-1 ) in which R¹ is CI, R² is Br, R⁷ is CHF₂ and the combination of R⁵ and R⁶ for a compound corresponds in each case to one row of Table A; Table 20 Compounds of the formula (IA-1 ) in which R¹ is methyl, R² is Br, R⁷ is CHF₂ and the combination of R⁵ and R⁶ for a compound corresponds in each case to one row of Table A;

Table 21 Compounds of the formula (IA-1 ) in which R¹ is F, R² is cyano, R⁷ is CHF2 and the combination of R⁵ and R⁶ for a compound corresponds in each case to one row of Table A;

Table 22 Compounds of the formula (IA-1 ) in which R¹ is Br, R² is cyano, R⁷ is CHF2 and the combination of R⁵ and R⁶ for a compound corresponds in each case to one row of Table A;

Table 23 Compounds of the formula (IA-1 ) in which R¹ is CI, R² is cyano, R⁷ is CHF2 and the combination of R⁵ and R⁶ for a compound corresponds in each case to one row of Table A;

Table 24 Compounds of the formula (IA-1 ) in which R¹ is methyl, R² is cyano, R⁷ is CHF2 and the combination of R⁵ and R⁶ for a compound corresponds in each case to one row of Table A;

Table 25 Compounds of the formula (IA-1 ) in which R¹ is F, R² is CI, R⁷ is Br and the combination of R⁵ and R⁶ for a compound corresponds in each case to one row of Table A;

Table 26 Compounds of the formula (IA-1 ) in which R¹ is Br, R² is CI, R⁷ is Br and the combination of R⁵ and R⁶ for a compound corresponds in each case to one row of Table A;

Table 27 Compounds of the formula (IA-1 ) in which R¹ is CI, R² is CI, R⁷ is Br and the combination of R⁵ and R⁶ for a compound corresponds in each case to one row of Table A;

Table 28 Compounds of the formula (IA-1 ) in which R¹ is methyl, R² is CI, R⁷ is Br and the combination of R⁵ and R⁶ for a compound corresponds in each case to one row of Table A; Table 29 Compounds of the formula (IA-1 ) in which R¹ is F, R² is Br, R⁷ is Br and the combination of R⁵ and R⁶ for a compound corresponds in each case to one row of Table A;

Table 30 Compounds of the formula (IA-1 ) in which R¹ is Br, R² is Br, R⁷ is Br and the combination of R⁵ and R⁶ for a compound corresponds in each case to one row of Table A;

Table 31 Compounds of the formula (IA-1 ) in which R¹ is CI, R² is Br, R⁷ is Br and the combination of R⁵ and R⁶ for a compound corresponds in each case to one row of Table A;

Table 32 Compounds of the formula (IA-1 ) in which R¹ is methyl, R² is Br, R⁷ is Br and the combination of R⁵ and R⁶ for a compound corresponds in each case to one row of Table A;

Table 33 Compounds of the formula (IA-1 ) in which R¹ is F, R² is cyano, R⁷ is Br and the combination of R⁵ and R⁶ for a compound corresponds in each case to one row of Table A;

Table 34 Compounds of the formula (IA-1 ) in which R¹ is Br, R² is cyano, R⁷ is Br and the combination of R⁵ and R⁶ for a compound corresponds in each case to one row of Table A;

Table 35 Compounds of the formula (IA-1 ) in which R¹ is CI, R² is cyano, R⁷ is Br and the combination of R⁵ and R⁶ for a compound corresponds in each case to one row of Table A; Table 36 Compounds of the formula (IA-1 ) in which R¹ is methyl, R² is cyano, R⁷ is Br and the combination of R⁵ and R⁶ for a compound corresponds in each case to one row of Table A;

Table 37 Compounds of the formula (IA-1 ) in which R¹ is F, R² is CI, R⁷ is CI and the combination of R⁵ and R⁶ for a compound corresponds in each case to one row of Table A;

Table 38 Compounds of the formula (IA-1 ) in which R¹ is Br, R² is CI, R⁷ is CI and the com- bination of R⁵ and R⁶ for a compound corresponds in each case to one row of Table A;

Table 39 Compounds of the formula (IA-1 ) in which R¹ is CI, R² is CI, R⁷ is CI and the combination of R⁵ and R⁶ for a compound corresponds in each case to one row of Table A;

Table 40 Compounds of the formula (IA-1 ) in which R¹ is methyl, R² is CI, R⁷ is CI and the combination of R⁵ and R⁶ for a compound corresponds in each case to one row of Table A; Table 41 Compounds of the formula (IA-1 ) in which R¹ is F, R² is Br, R⁷ is CI and the combination of R⁵ and R⁶ for a compound corresponds in each case to one row of Table A;

Table 42 Compounds of the formula (IA-1 ) in which R¹ is Br, R² is Br, R⁷ is CI and the combination of R⁵ and R⁶ for a compound corresponds in each case to one row of Table A;

Table 43 Compounds of the formula (IA-1 ) in which R¹ is CI, R² is Br, R⁷ is CI and the com- bination of R⁵ and R⁶ for a compound corresponds in each case to one row of Table A;

Table 44 Compounds of the formula (IA-1 ) in which R¹ is methyl, R² is Br, R⁷ is CI and the combination of R⁵ and R⁶ for a compound corresponds in each case to one row of Table A;

Table 45 Compounds of the formula (IA-1 ) in which R¹ is F, R² is cyano, R⁷ is CI and the combination of R⁵ and R⁶ for a compound corresponds in each case to one row of Table A; Table 46 Compounds of the formula (IA-1 ) in which R¹ is Br, R² is cyano, R⁷ is CI and the combination of R⁵ and R⁶ for a compound corresponds in each case to one row of Table A;

Table 47 Compounds of the formula (IA-1 ) in which R¹ is CI, R² is cyano, R⁷ is CI and the combination of R⁵ and R⁶ for a compound corresponds in each case to one row of Table A;

Table 48 Compounds of the formula (IA-1 ) in which R¹ is methyl, R² is cyano, R⁷ is CI and the combination of R⁵ and R⁶ for a compound corresponds in each case to one row of Table A;

Table 49 Compounds of the formula (IA-1 ) in which R¹ is F, R² is CI, R⁷ is OCHF₂ and the combination of R⁵ and R⁶ for a compound corresponds in each case to one row of Table A;

Table 50 Compounds of the formula (IA-1 ) in which R¹ is Br, R² is CI, R⁷ is OCHF₂ and the combination of R⁵ and R⁶ for a compound corresponds in each case to one row of Table A; Table 51 Compounds of the formula (IA-1 ) in which R¹ is CI, R² is CI, R⁷ is OCHF₂ and the combination of R⁵ and R⁶ for a compound corresponds in each case to one row of Table A;

Table 52 Compounds of the formula (IA-1 ) in which R¹ is methyl, R² is CI, R⁷ is OCHF₂ and the combination of R⁵ and R⁶ for a compound corresponds in each case to one row of Table A; Table 53 Compounds of the formula (IA-1 ) in which R¹ is F, R² is Br, R⁷ is OCHF₂ and the combination of R⁵ and R⁶ for a compound corresponds in each case to one row of Table A;

Table 54 Compounds of the formula (IA-1 ) in which R¹ is Br, R² is Br, R⁷ is OCHF₂ and the combination of R⁵ and R⁶ for a compound corresponds in each case to one row of Table A;

Table 55 Compounds of the formula (IA-1 ) in which R¹ is CI, R² is Br, R⁷ is OCHF₂ and the combination of R⁵ and R⁶ for a compound corresponds in each case to one row of Table A;

Table 56 Compounds of the formula (IA-1 ) in which R¹ is methyl, R² is Br, R⁷ is OCHF₂ and the combination of R⁵ and R⁶ for a compound corresponds in each case to one row of Table A;

Table 57 Compounds of the formula (IA-1 ) in which R¹ is F, R² is cyano, R⁷ is OCHF₂ and the combination of R⁵ and R⁶ for a compound corresponds in each case to one row of Table A; Table 58 Compounds of the formula (IA-1 ) in which R¹ is Br, R² is cyano, R⁷ is OCHF₂ and the combination of R⁵ and R⁶ for a compound corresponds in each case to one row of Table A;

Table 59 Compounds of the formula (IA-1 ) in which R¹ is CI, R² is cyano, R⁷ is OCHF₂ and the combination of R⁵ and R⁶ for a compound corresponds in each case to one row of Table A;

Table 60 Compounds of the formula (IA-1 ) in which R¹ is methyl, R² is cyano, R⁷ is OCHF₂ and the combination of R⁵ and R⁶ for a compound corresponds in each case to one row of Table A.

Table A

R⁵ R⁶ R⁵ R⁶

A-1 CHs CH₃ A-20 c-C₆Hi i CH₃

A-2 C₂H5 CH₃ A-21 CH₂-c-C₃H₅ CH₃

A-3 CH=CH₂ CH₃ A-22 CH(CH₃)-c-C₃H₅ CH₃

A-4 CH₂CH₂CH3 CH₃ A-23

CH₃

A-5 CH(CH₃)₂ CH₃ A-24 CH₂-c-CeHi i CH₃

A-6 CH₂CH₂CH₂CH3 CH₃ A-25 C6H5 CH₃

A-7 C(CH₃)₃ CH₃ A-26 CH₃ C₂H5

A-8 CH₂CH(CH₃)₂ CH₃ A-27 C₂H5 C₂H5

A-9 CH(CH₃)CH₂CH₃ CH₃ A-28 CH=CH₂ C₂H5

A-10 CH₂CH=CH₂ CH₃ A-29 CH₂CH₂CH₃ C₂H5

A-1 1 CH₂C≡CH CH₃ A-30 CH(CH₃)₂ C₂H5

A-12 CH(CH₃)CH=CH₂ CH₃ A-31 CH₂CH₂CH₂CH₃ C₂H5

A-13 CH F₂ CH₃ A-32 C(CH₃)₃ C₂H5

A-14 CH₂CI CH₃ A-33 CH₂CH(CH₃)₂ C₂H5

A-15 CH₂CH₂CN CH₃ A-34 CH(CH₃)CH₂CH₃ C₂H5

A-16 CH₂CH₂CI CH₃ A-35 CH₂CH=CH₂ C₂H5

A-17 c-C₃H₅ CH₃ A-36 CH₂C≡CH C₂H5

A-18 C-C4H7 CH₃ A-37 CH(CH₃)CH=CH₂ C₂H5

A-19 C-C5H9 CH₃ A-38 CH F₂ C₂H5 R⁵ R⁶ R⁵ R⁶

A-39 CH2CI C2H5 A-81 CH2CH2CH2CH3 CH2CH2CH₃

A-40 CH2CH2CN C2H5 A-82 C(CH₃)₃ CH2CH2CH₃

A-41 CH2CH2CI C2H5 A-83 CH₂CH(CH₃)₂ CH2CH2CH3

A-42 C-C3H5 C2H5 A-84 CH(CH₃)CH₂CH₃ CH2CH2CH3

A-43 C-C4H7 C2H5 A-85 CH₂CH=CH₂ CH2CH2CH3

A-44 C-C5H9 C2H5 A-86 CH₂C≡CH CH2CH2CH3

A-45 c-C₆Hii C2H5 A-87 CH(CH₃)CH=CH₂ CH2CH2CH3

A-46 CH₂-c-C₃H₅ C2H5 A-88 CHF₂ CH2CH2CH3

A-47 CH(CH₃)-c-C₃H₅ C2H5 A-89 CH2CI CH2CH2CH3

A-48 CH2-C-C5H9 C2H5 A-90 CH2CH2CN CH2CH2CH3

A-49 CH2-C-C6H11 C2H5 A-91 CH2CH2CI CH2CH2CH3

A-50 C6H5 C2H5 A-92 c-CsHs CH2CH2CH3

A-51 CH₃ CH=CH₂ A-93 C-C4H7 CH2CH2CH3

A-52 C2H5 CH=CH₂ A-94 C-C5H9 CH2CH2CH3

A-53 CH=CH₂ CH=CH₂ A-95 c-C₆Hii CH2CH2CH3

A-54 CH2CH2CH₃ CH=CH₂ A-96 CH₂-c-C₃H₅ CH2CH2CH3

A-55 CH(CH₃)₂ CH=CH₂ A-97 CH(CH₃)-c-C₃H₅ CH2CH2CH3

A-56 CH2CH2CH2CH₃ CH=CH₂ A-98 CH2-C-C5H9 CH2CH2CH3

A-57 C(CH₃)₃ CH=CH₂ A-99 CH2-C-C6H11 CH2CH2CH3

A-58 CH₂CH(CH₃)₂ CH=CH₂ A-100 C6H5 CH2CH2CH3

A-59 CH(CH₃)CH₂CH₃ CH=CH₂ A-101 CH₃ CH(CH₃)₂

A-60 CH₂CH=CH₂ CH=CH₂ A-102 C2H5 CH(CH₃)₂

A-61 CH₂C≡CH CH=CH₂ A-103 CH=CH₂ CH(CH₃)₂

A-62 CH(CH₃)CH=CH₂ CH=CH₂ A-104 CH2CH2CH₃ CH(CH₃)₂

A-63 CHF₂ CH=CH₂ A-105 CH(CH₃)₂ CH(CH₃)₂

A-64 CH2CI CH=CH₂ A-106 CH2CH2CH2CH3 CH(CH₃)₂

A-65 CH2CH2CN CH=CH₂ A-107 C(CH₃)₃ CH(CH₃)₂

A-66 CH2CH2CI CH=CH₂ A-108 CH₂CH(CH₃)₂ CH(CH₃)₂

A-67 c-CsHs CH=CH₂ A-109 CH(CH₃)CH₂CH₃ CH(CH₃)₂

A-68 C-C4H7 CH=CH₂ A-1 10 CH₂CH=CH₂ CH(CH₃)₂

A-69 C-C5H9 CH=CH₂ A-1 1 1 CH₂C≡CH CH(CH₃)₂

A-70 c-C₆Hii CH=CH₂ A-1 12 CH(CH₃)CH=CH₂ CH(CH₃)₂

A-71 CH₂-c-C₃H₅ CH=CH₂ A-1 13 CHF₂ CH(CH₃)₂

A-72 CH(CH₃)-c-C₃H₅ CH=CH₂ A-1 14 CH2CI CH(CH₃)₂

A-73 CH2-C-C5H9 CH=CH₂ A-1 15 CH2CH2CN CH(CH₃)₂

A-74 CH2-C-C6H11 CH=CH₂ A-1 16 CH2CH2CI CH(CH₃)₂

A-75 C6H5 CH=CH₂ A-1 17 c-CsHs CH(CH₃)₂

A-76 CH₃ CH2CH2CH₃ A-1 18 C-C4H7 CH(CH₃)₂

A-77 C2H5 CH2CH2CH₃ A-1 19 C-C5H9 CH(CH₃)₂

A-78 CH=CH₂ CH2CH2CH₃ A-120 c-C₆Hii CH(CH₃)₂

A-79 CH2CH2CH₃ CH2CH2CH3 A-121 CH₂-c-C₃H₅ CH(CH₃)₂

A-80 CH(CH₃)₂ CH2CH2CH3 A-122 CH(CH₃)-c-C₃H₅ CH(CH₃)₂ R⁵ R⁶ R⁵ R⁶

A-123 CH2-C-C5H9 CH(CH₃)₂ A-165 CH2CH2CN C(CH₃)₃

A-124 CH2-C-C6H11 CH(CH₃)₂ A-166 CH2CH2CI C(CH₃)₃

A-125 C6H5 CH(CH₃)₂ A-167 c-C₃H₅ C(CH₃)₃

A-126 CHs CH2CH2CH2CH₃ A-168 C-C4H7 C(CH₃)₃

A-127 C2H5 CH2CH2CH2CH₃ A-169 C-C5H9 C(CH₃)₃

A-128 CH=CH₂ CH2CH2CH2CH₃ A-170 c-C₆Hii C(CH₃)₃

A-129 CH2CH2CH3 CH2CH2CH2CH₃ A-171 CH₂-c-C₃H₅ C(CH₃)₃

A-130 CH(CH₃)₂ CH2CH2CH2CH₃ A-172 CH(CH₃)-c-C₃H₅ C(CH₃)₃

A-131 CH2CH2CH2CH3 CH2CH2CH2CH₃ A-173 CH2-C-C5H9 C(CH₃)₃

A-132 C(CH₃)₃ CH2CH2CH2CH₃ A-174 CH2-C-C6H11 C(CH₃)₃

A-133 CH₂CH(CH₃)₂ CH2CH2CH2CH₃ A-175 C6H5 C(CH₃)₃

A-134 CH(CH₃)CH₂CH₃ CH2CH2CH2CH₃ A-176 CH₃ CH₂CH(CH₃)₂

A-135 CH₂CH=CH₂ CH2CH2CH2CH₃ A-177 C2H5 CH₂CH(CH₃)₂

A-136 CH₂C≡CH CH2CH2CH2CH₃ A-178 CH=CH₂ CH₂CH(CH₃)₂

A-137 CH(CH₃)CH=CH₂ CH2CH2CH2CH₃ A-179 CH2CH2CH₃ CH₂CH(CH₃)₂

A-138 CHF₂ CH2CH2CH2CH₃ A-180 CH(CH₃)₂ CH₂CH(CH₃)₂

A-139 CH2CI CH2CH2CH2CH₃ A-181 CH2CH2CH2CH₃ CH₂CH(CH₃)₂

A-140 CH2CH2CN CH2CH2CH2CH₃ A-182 C(CH₃)₃ CH₂CH(CH₃)₂

A-141 CH2CH2CI CH2CH2CH2CH₃ A-183 CH₂CH(CH₃)₂ CH₂CH(CH₃)₂

A-142 c-C₃H₅ CH2CH2CH2CH₃ A-184 CH(CH₃)CH₂CH₃ CH₂CH(CH₃)₂

A-143 C-C4H7 CH2CH2CH2CH₃ A-185 CH₂CH=CH₂ CH₂CH(CH₃)₂

A-144 C-C5H9 CH2CH2CH2CH₃ A-186 CH₂C≡CH CH₂CH(CH₃)₂

A-145 c-C₆Hii CH2CH2CH2CH₃ A-187 CH(CH₃)CH=CH₂ CH₂CH(CH₃)₂

A-146 CH₂-c-C₃H₅ CH2CH2CH2CH₃ A-188 CHF₂ CH₂CH(CH₃)₂

A-147 CH(CH₃)-c-C₃H₅ CH2CH2CH2CH₃ A-189 CH2CI CH₂CH(CH₃)₂

A-148 CH2-C-C5H9 CH2CH2CH2CH₃ A-190 CH2CH2CN CH₂CH(CH₃)₂

A-149 CH2-C-C6H11 CH2CH2CH2CH₃ A-191 CH2CH2CI CH₂CH(CH₃)₂

A-150 C6H5 CH2CH2CH2CH₃ A-192 c-C₃H₅ CH₂CH(CH₃)₂

A-151 CH₃ C(CH₃)₃ A-193 C-C4H7 CH₂CH(CH₃)₂

A-152 C2H5 C(CH₃)₃ A-194 C-C5H9 CH₂CH(CH₃)₂

A-153 CH=CH₂ C(CH₃)₃ A-195 c-C₆Hii CH₂CH(CH₃)₂

A-154 CH2CH2CH₃ C(CH₃)₃ A-196 CH₂-c-C₃H₅ CH₂CH(CH₃)₂

A-155 CH(CH₃)₂ C(CH₃)₃ A-197 CH(CH₃)-c-C₃H₅ CH₂CH(CH₃)₂

A-156 CH2CH2CH2CH₃ C(CH₃)₃ A-198 CH2-C-C5H9 CH₂CH(CH₃)₂

A-157 C(CH₃)₃ C(CH₃)₃ A-199 CH2-C-C6H11 CH₂CH(CH₃)₂

A-158 CH₂CH(CH₃)₂ C(CH₃)₃ A-200 C6H5 CH₂CH(CH₃)₂

A-159 CH(CH₃)CH₂CH₃ C(CH₃)₃ A-201 CH₃ CH(CH₃)CH₂CH₃

A-160 CH₂CH=CH₂ C(CH₃)₃ A-202 C2H5 CH(CH₃)CH₂CH₃

A-161 CH₂C≡CH C(CH₃)₃ A-203 CH=CH₂ CH(CH₃)CH₂CH₃

A-162 CH(CH₃)CH=CH₂ C(CH₃)₃ A-204 CH2CH2CH₃ CH(CH₃)CH₂CH₃

A-163 CHF₂ C(CH₃)₃ A-205 CH(CH₃)₂ CH(CH₃)CH₂CH₃

A-164 CH2CI C(CH₃)₃ A-206 CH2CH2CH2CH₃ CH(CH₃)CH₂CH₃ R⁵ R⁶ R⁵ R⁶

A-207 C(CH₃)₃ CH(CH₃)CH₂CH₃ A-249 CH₂-c-C6Hi i CH₂CH=CH₂

A-208 CH₂CH(CH₃)₂ CH(CH₃)CH₂CH₃ A-250 C6H5 CH₂CH=CH₂

A-209 CH(CH₃)CH₂CH₃ CH(CH₃)CH₂CH₃ A-251 CH₃ CH₂C≡CH

A-210 CH₂CH=CH₂ CH(CH₃)CH₂CH₃ A-252 C₂H5 CH₂C≡CH

A-21 1 CH₂C≡CH CH(CH₃)CH₂CH₃ A-253 CH=CH₂ CH₂C≡CH

A-212 CH(CH₃)CH=CH₂ CH(CH₃)CH₂CH₃ A-254 CH₂CH₂CH₃ CH₂C≡CH

A-213 CHF₂ CH(CH₃)CH₂CH₃ A-255 CH(CH₃)₂ CH₂C≡CH

A-214 CH₂CI CH(CH₃)CH₂CH₃ A-256 CH₂CH₂CH₂CH₃ CH₂C≡CH

A-215 CH₂CH₂CN CH(CH₃)CH₂CH₃ A-257 C(CH₃)₃ CH₂C≡CH

A-216 CH₂CH₂CI CH(CH₃)CH₂CH₃ A-258 CH₂CH(CH₃)₂ CH₂C≡CH

A-217 c-C₃H₅ CH(CH₃)CH₂CH₃ A-259 CH(CH₃)CH₂CH₃ CH₂C≡CH

A-218 C-C4H7 CH(CH₃)CH₂CH₃ A-260 CH₂CH=CH₂ CH₂C≡CH

A-219 C-C5H9 CH(CH₃)CH₂CH₃ A-261 CH2C≡CH CH₂C≡CH

A-220 c-C₆Hii CH(CH₃)CH₂CH₃ A-262 CH(CH₃)CH=CH₂ CH₂C≡CH

A-221 CH₂-c-C₃H₅ CH(CH₃)CH₂CH₃ A-263 CHF₂ CH₂C≡CH

A-222 CH(CH₃)-c-C₃H₅ CH(CH₃)CH₂CH₃ A-264 CH₂CI CH₂C≡CH

A-223 CH2-C-C5H9 CH(CH₃)CH₂CH₃ A-265 CH₂CH₂CN CH₂C≡CH

A-224 CH₂-c-C6Hi i CH(CH₃)CH₂CH₃ A-266 CH₂CH₂CI CH₂C≡CH

A-225 C6H5 CH(CH₃)CH₂CH₃ A-267 c-C₃H₅ CH₂C≡CH

A-226 CH₃ CH₂CH=CH₂ A-268 C-C4H7 CH₂C≡CH

A-227 C₂H5 CH₂CH=CH₂ A-269 C-C5H9 CH₂C≡CH

A-228 CH=CH₂ CH₂CH=CH₂ A-270 c-C₆Hii CH₂C≡CH

A-229 CH₂CH₂CH₃ CH₂CH=CH₂ A-271 CH₂-c-C₃H₅ CH₂C≡CH

A-230 CH(CH₃)₂ CH₂CH=CH₂ A-272 CH(CH₃)-c-C₃H₅ CH₂C≡CH

A-231 CH₂CH₂CH₂CH₃ CH₂CH=CH₂ A-273 Chb-C-CsHg CH₂C≡CH

A-232 C(CH₃)₃ CH₂CH=CH₂ A-274 CH₂-c-C6Hi i CH₂C≡CH

A-233 CH₂CH(CH₃)₂ CH₂CH=CH₂ A-275 C6H5 CH₂C≡CH

A-234 CH(CH₃)CH₂CH₃ CH₂CH=CH₂ A-276 CH₃ CH(CH₃)CH=CH₂

A-235 CH₂CH=CH₂ CH₂CH=CH₂ A-277 C₂H5 CH(CH₃)CH=CH₂

A-236 CH₂C≡CH CH₂CH=CH₂ A-278 CH=CH₂ CH(CH₃)CH=CH₂

A-237 CH(CH₃)CH=CH₂ CH₂CH=CH₂ A-279 CH₂CH₂CH₃ CH(CH₃)CH=CH₂

A-238 CHF₂ CH₂CH=CH₂ A-280 CH(CH₃)₂ CH(CH₃)CH=CH₂

A-239 CH₂CI CH₂CH=CH₂ A-281 CH₂CH₂CH₂CH₃ CH(CH₃)CH=CH₂

A-240 CH₂CH₂CN CH₂CH=CH₂ A-282 C(CH₃)₃ CH(CH₃)CH=CH₂

A-241 CH₂CH₂CI CH₂CH=CH₂ A-283 CH₂CH(CH₃)₂ CH(CH₃)CH=CH₂

A-242 c-C₃H₅ CH₂CH=CH₂ A-284 CH(CH₃)CH₂CH₃ CH(CH₃)CH=CH₂

A-243 C-C4H7 CH₂CH=CH₂ A-285 CH₂CH=CH₂ CH(CH₃)CH=CH₂

A-244 C-C5H9 CH₂CH=CH₂ A-286 CH₂C≡CH CH(CH₃)CH=CH₂

A-245 c-C₆Hii CH₂CH=CH₂ A-287 CH(CH₃)CH=CH₂ CH(CH₃)CH=CH₂

A-246 CH₂-c-C₃H₅ CH₂CH=CH₂ A-288 CHF₂ CH(CH₃)CH=CH₂

A-247 CH(CH₃)-c-C₃H₅ CH₂CH=CH₂ A-289 CH₂CI CH(CH₃)CH=CH₂

A-248 CH2-C-C5H9 CH₂CH=CH₂ A-290 CH₂CH₂CN CH(CH₃)CH=CH₂ R⁵ R⁶ R⁵ R⁶

A-291 CH2CH2CI CH(CH₃)CH=CH₂ A-333 CH₂CH(CH₃)₂ CH2CI

A-292 C-C3H5 CH(CH₃)CH=CH₂ A-334 CH(CH₃)CH₂CH₃ CH2CI

A-293 C-C4H7 CH(CH₃)CH=CH₂ A-335 CH₂CH=CH₂ CH2CI

A-294 C-C5H9 CH(CH₃)CH=CH₂ A-336 CH₂C≡CH CH2CI

A-295 c-C₆Hii CH(CH₃)CH=CH₂ A-337 CH(CH₃)CH=CH₂ CH2CI

A-296 CH₂-c-C₃H₅ CH(CH₃)CH=CH₂ A-338 CHF₂ CH2CI

A-297 CH(CH₃)-c-C₃H₅ CH(CH₃)CH=CH₂ A-339 CH2CI CH2CI

A-298 CH2-C-C5H9 CH(CH₃)CH=CH₂ A-340 CH2CH2CN CH2CI

A-299 CH2-C-C5H9 CH(CH₃)CH=CH₂ A-341 CH2CH2CI CH2CI

A-300 C6H5 CH(CH₃)CH=CH₂ A-342 c-C₃H₅ CH2CI

A-301 CH₃ CHF₂ A-343 C-C4H7 CH2CI

A-302 C2H5 CHF₂ A-344 C-C5H9 CH2CI

A-303 CH=CH₂ CHF₂ A-345 c-C₆Hii CH2CI

A-304 ChbChbCHs CHF₂ A-346 CH₂-c-C₃H₅ CH2CI

A-305 CH(CH₃)₂ CHF₂ A-347 CH(CH₃)-c-C₃H₅ CH2CI

A-306 CH2CH2CH2CH₃ CHF₂ A-348 CH2-C-C5H9 CH2CI

A-307 C(CH₃)₃ CHF₂ A-349 CH2-C-C6H11 CH2CI

A-308 CH₂CH(CH₃)₂ CHF₂ A-350 C6H5 CH2CI

A-309 CH(CH₃)CH₂CH₃ CHF₂ A-351 CH₃ CH2CH2CN

A-310 CH₂CH=CH₂ CHF₂ A-352 C2H5 CH2CH2CN

A-31 1 CH₂C≡CH CHF₂ A-353 CH=CH₂ CH2CH2CN

A-312 CH(CH₃)CH=CH₂ CHF₂ A-354 CH2CH2CH₃ CH2CH2CN

A-313 CHF₂ CHF₂ A-355 CH(CH₃)₂ CH2CH2CN

A-314 CH2CI CHF₂ A-356 CH2CH2CH2CH₃ CH2CH2CN

A-315 CH2CH2CN CHF₂ A-357 C(CH₃)₃ CH2CH2CN

A-316 CH2CH2CI CHF₂ A-358 CH₂CH(CH₃)₂ CH2CH2CN

A-317 c-C₃H₅ CHF₂ A-359 CH(CH₃)CH₂CH₃ CH2CH2CN

A-318 C-C4H7 CHF₂ A-360 CH₂CH=CH₂ CH2CH2CN

A-319 C-C5H9 CHF₂ A-361 CH₂C≡CH CH2CH2CN

A-320 c-C₆Hii CHF₂ A-362 CH(CH₃)CH=CH₂ CH2CH2CN

A-321 CH₂-c-C₃H₅ CHF₂ A-363 CHF₂ CH2CH2CN

A-322 CH(CH₃)-c-C₃H₅ CHF₂ A-364 CH2CI CH2CH2CN

A-323 CH2-C-C5H9 CHF₂ A-365 CH2CH2CN CH2CH2CN

A-324 CH2-C-C6H11 CHF₂ A-366 CH2CH2CI CH2CH2CN

A-325 C6H5 CHF₂ A-367 c-C₃H₅ CH2CH2CN

A-326 CH₃ CH2CI A-368 C-C4H7 CH2CH2CN

A-327 C2H5 CH2CI A-369 C-C5H9 CH2CH2CN

A-328 CH=CH₂ CH2CI A-370 c-C₆Hii CH2CH2CN

A-329 ChbChbCHs CH2CI A-371 CH₂-c-C₃H₅ CH2CH2CN

A-330 CH(CH₃)₂ CH2CI A-372 CH(CH₃)-c-C₃H₅ CH2CH2CN

A-331 CH2CH2CH2CH₃ CH2CI A-373 CH2-C-C5H9 CH2CH2CN

A-332 C(CH₃)₃ CH2CI A-374 CH2-C-C5H9 CH2CH2CN R⁵ R⁶ R⁵ R⁶

A-375 C6H5 CH2CH2CN A-417 c-C₃H₅ c-C₃H₅

A-376 CHs CH2CH2CI A-418 C-C4H7 c-C₃H₅

A-377 C2H5 CH2CH2CI A-419 C-C5H9 c-C₃H₅

A-378 CH=CH₂ CH2CH2CI A-420 c-C₆Hii c-C₃H₅

A-379 CH2CH2CH3 CH2CH2CI A-421 CH₂-c-C₃H₅ c-C₃H₅

A-380 CH(CH₃)₂ CH2CH2CI A-422 CH(CH₃)-c-C₃H₅ c-C₃H₅

A-381 CH2CH2CH2CH3 CH2CH2CI A-423 CH2-C-C5H9 c-C₃H₅

A-382 C(CH₃)₃ CH2CH2CI A-424 CH2-C-C6H11 c-C₃H₅

A-383 CH₂CH(CH₃)₂ CH2CH2CI A-425 C6H5 c-C₃H₅

A-384 CH(CH₃)CH₂CH₃ CH2CH2CI A-426 CH₃ C-C4H7

A-385 CH₂CH=CH₂ CH2CH2CI A-427 C2H5 C-C4H7

A-386 CH₂C≡CH CH2CH2CI A-428 CH=CH₂ C-C4H7

A-387 CH(CH₃)CH=CH₂ CH2CH2CI A-429 CH2CH2CH₃ C-C4H7

A-388 CHF₂ CH2CH2CI A-430 CH(CH₃)₂ C-C4H7

A-389 CH2CI CH2CH2CI A-431 CH2CH2CH2CH₃ C-C4H7

A-390 CH2CH2CN CH2CH2CI A-432 C(CH₃)₃ C-C4H7

A-391 CH2CH2CI CH2CH2CI A-433 CH₂CH(CH₃)₂ C-C4H7

A-392 c-C₃H₅ CH2CH2CI A-434 CH(CH₃)CH₂CH₃ C-C4H7

A-393 C-C4H7 CH2CH2CI A-435 CH₂CH=CH₂ C-C4H7

A-394 C-C5H9 CH2CH2CI A-436 CH₂C≡CH C-C4H7

A-395 c-C₆Hii CH2CH2CI A-437 CH(CH₃)CH=CH₂ C-C4H7

A-396 CH₂-c-C₃H₅ CH2CH2CI A-438 CHF₂ C-C4H7

A-397 CH(CH₃)-c-C₃H₅ CH2CH2CI A-439 CH2CI C-C4H7

A-398 CH2-C-C5H9 CH2CH2CI A-440 CH2CH2CN C-C4H7

A-399 CH2-C-C6H11 CH2CH2CI A-441 CH2CH2CI C-C4H7

A-400 C6H5 CH2CH2CI A-442 c-C₃H₅ C-C4H7

A-401 CH₃ c-C₃H₅ A-443 C-C4H7 C-C4H7

A-402 C2H5 c-C₃H₅ A-444 C-C5H9 C-C4H7

A-403 CH=CH₂ c-C₃H₅ A-445 c-C₆Hii C-C4H7

A-404 CH2CH2CH₃ c-C₃H₅ A-446 CH₂-c-C₃H₅ C-C4H7

A-405 CH(CH₃)₂ c-C₃H₅ A-447 CH(CH₃)-c-C₃H₅ C-C4H7

A-406 CH2CH2CH2CH₃ c-C₃H₅ A-448 CH2-C-C5H9 C-C4H7

A-407 C(CH₃)₃ c-C₃H₅ A-449 CH2-C-C6H11 C-C4H7

A-408 CH₂CH(CH₃)₂ c-C₃H₅ A-450 C6H5 C-C4H7

A-409 CH(CH₃)CH₂CH₃ c-C₃H₅ A-451 CH₃ C-C5H9

A-410 CH₂CH=CH₂ c-C₃H₅ A-452 C2H5 C-C5H9

A-41 1 CH₂C≡CH c-C₃H₅ A-453 CH=CH₂ C-C5H9

A-412 CH(CH₃)CH=CH₂ c-C₃H₅ A-454 CH2CH2CH₃ C-C5H9

A-413 CHF₂ c-C₃H₅ A-455 CH(CH₃)₂ C-C5H9

A-414 CH2CI c-C₃H₅ A-456 CH2CH2CH2CH₃ C-C5H9

A-415 CH2CH2CN c-C₃H₅ A-457 C(CH₃)₃ C-C5H9

A-416 CH2CH2CI c-C₃H₅ A-458 CH₂CH(CH₃)₂ C-C5H9 R⁵ R⁶ R⁵ R⁶

A-459 CH(CH₃)CH₂CH₃ C-C5H9 A-501 CH₃ CH₂-c-C₃H₅

A-460 CH₂CH=CH₂ C-C5H9 A-502 C₂H5 CH₂-c-C₃H₅

A-461 CH₂C≡CH C-C5H9 A-503 CH=CH₂ CH₂-c-C₃H₅

A-462 CH(CH₃)CH=CH₂ C-C5H9 A-504 CH₂CH₂CH₃ CH₂-c-C₃H₅

A-463 CHF₂ C-C5H9 A-505 CH(CH₃)₂ CH₂-c-C₃H₅

A-464 CH₂CI C-C5H9 A-506 CH₂CH₂CH₂CH₃ CH₂-c-C₃H₅

A-465 CH₂CH₂CN C-C5H9 A-507 C(CH₃)₃ CH₂-c-C₃H₅

A-466 CH₂CH₂CI C-C5H9 A-508 CH₂CH(CH₃)₂ CH₂-c-C₃H₅

A-467 C-C3H5 C-C5H9 A-509 CH(CH₃)CH₂CH₃ CH₂-c-C₃H₅

A-468 C-C4H7 C-C5H9 A-510 CH₂CH=CH₂ CH₂-c-C₃H₅

A-469 C-C5H9 C-C5H9 A-51 1 CH₂C≡CH CH₂-c-C₃H₅

A-470 c-C₆Hii C-C5H9 A-512 CH(CH₃)CH=CH₂ CH₂-c-C₃H₅

A-471 CH₂-c-C₃H₅ C-C5H9 A-513 CHF₂ CH₂-c-C₃H₅

A-472 CH(CH₃)-c-C₃H₅ C-C5H9 A-514 CH₂CI CH₂-c-C₃H₅

A-473 Chb-C-CsHg C-C5H9 A-515 CH₂CH₂CN CH₂-c-C₃H₅

A-474 CH₂-c-C6Hi i C-C5H9 A-516 CH₂CH₂CI CH₂-c-C₃H₅

A-475 C6H5 C-C5H9 A-517 c-CsHs CH₂-c-C₃H₅

A-476 CH₃ c-C₆Hii A-518 C-C4H7 CH₂-c-C₃H₅

A-477 C₂H5 c-C₆Hii A-519 C-C5H9 CH₂-c-C₃H₅

A-478 CH=CH₂ c-C₆Hii A-520 c-C₆Hii CH₂-c-C₃H₅

A-479 CH₂CH₂CH₃ c-C₆Hii A-521 CH₂-c-C₃H₅ CH₂-c-C₃H₅

A-480 CH(CH₃)₂ c-C₆Hii A-522 CH(CH₃)-c-C₃H₅ CH₂-c-C₃H₅

A-481 CH₂CH₂CH₂CH₃ c-C₆Hii A-523 CH₂-C-C5Hg CH₂-c-C₃H₅

A-482 C(CH₃)₃ c-C₆Hii A-524 CH₂-c-C6Hi i CH₂-c-C₃H₅

A-483 CH₂CH(CH₃)₂ c-C₆Hii A-525 C6H5 CH₂-c-C₃H₅

A-484 CH(CH₃)CH₂CH₃ c-C₆Hii A-526 CH₃ CH(CH₃)-c-C₃H₅

A-485 CH₂CH=CH₂ c-C₆Hii A-527 C₂H5 CH(CH₃)-c-C₃H₅

A-486 CH₂C≡CH c-C₆Hii A-528 CH=CH₂ CH(CH₃)-c-C₃H₅

A-487 CH(CH₃)CH=CH₂ c-C₆Hii A-529 CH₂CH₂CH₃ CH(CH₃)-c-C₃H₅

A-488 CHF₂ c-C₆Hii A-530 CH(CH₃)₂ CH(CH₃)-c-C₃H₅

A-489 CH₂CI c-C₆Hii A-531 CH₂CH₂CH₂CH₃ CH(CH₃)-c-C₃H₅

A-490 CH₂CH₂CN c-C₆Hii A-532 C(CH₃)₃ CH(CH₃)-c-C₃H₅

A-491 CH₂CH₂CI c-C₆Hii A-533 CH₂CH(CH₃)₂ CH(CH₃)-c-C₃H₅

A-492 c-CsHs c-C₆Hii A-534 CH(CH₃)CH₂CH₃ CH(CH₃)-c-C₃H₅

A-493 C-C4H7 c-C₆Hii A-535 CH₂CH=CH₂ CH(CH₃)-c-C₃H₅

A-494 C-C5H9 c-C₆Hii A-536 CH₂C≡CH CH(CH₃)-c-C₃H₅

A-495 c-C₆Hii c-C₆Hii A-537 CH(CH₃)CH=CH₂ CH(CH₃)-c-C₃H₅

A-496 CH₂-c-C₃H₅ c-C₆Hii A-538 CHF₂ CH(CH₃)-c-C₃H₅

A-497 CH(CH₃)-c-C₃H₅ c-C₆Hii A-539 CH₂CI CH(CH₃)-c-C₃H₅

A-498 Chb-C-CsHg c-C₆Hii A-540 CH₂CH₂CN CH(CH₃)-c-C₃H₅

A-499 CH₂-c-C6Hi i c-C₆Hii A-541 CH₂CH₂CI CH(CH₃)-c-C₃H₅

A-500 C6H5 c-C₆Hii A-542 c-CsHs CH(CH₃)-c-C₃H₅ R⁵ R⁶ R⁵ R⁶

A-543 C-C4H7 CH(CH₃)-c-C₃H₅ A-585 CH₂CH=CH₂ CH₂-c-C₆Hii

A-544 C-C5H9 CH(CH₃)-c-C₃H₅ A-586 CH₂C≡CH CH₂-c-C₆Hii

A-545 c-C₆Hii CH(CH₃)-c-C₃H₅ A-587 CH(CH₃)CH=CH₂ CH₂-c-C₆Hii

A-546 CH₂-c-C₃H₅ CH(CH₃)-c-C₃H₅ A-588 CHF₂ CH₂-c-C₆Hii

A-547 CH(CH₃)-c-C₃H₅ CH(CH₃)-c-C₃H₅ A-589 CH2CI CH₂-c-C₆Hii

A-548 CH2-C-C5H9 CH(CH₃)-c-C₃H₅ A-590 CH2CH2CN CH₂-c-C₆Hii

A-549 CH2-C-C6H11 CH(CH₃)-c-C₃H₅ A-591 CH2CH2CI CH₂-c-C₆Hii

A-550 C6H5 CH(CH₃)-c-C₃H₅ A-592 c-C₃H₅ CH₂-c-C₆Hii

A-551 CH₃ CH2-C-C5H9 A-593 C-C4H7 CH₂-c-C₆Hii

A-552 C2H5 CH2-C-C5H9 A-594 C-C5H9 CH₂-c-C₆Hii

A-553 CH=CH₂ CH2-C-C5H9 A-595 c-C₆Hii CH₂-c-C₆Hii

A-554 CH2CH2CH₃ CH2-C-C5H9 A-596 CH₂-c-C₃H₅ CH₂-c-C₆Hii

A-555 CH(CH₃)₂ CH2-C-C5H9 A-597 CH(CH₃)-c-C₃H₅ CH₂-c-C₆Hii

A-556 ChbChbChbCHs CH2-C-C5H9 A-598 CH2-C-C5H9 CH₂-c-C₆Hii

A-557 C(CH₃)₃ CH2-C-C5H9 A-599 CH2-C-C6H11 CH₂-c-C₆Hii

A-558 CH₂CH(CH₃)₂ CH2-C-C5H9 A-600 C6H5 CH₂-c-C₆Hii

A-559 CH(CH₃)CH₂CH₃ CH2-C-C5H9 A-601 CH₃ C6H5

A-560 CH₂CH=CH₂ CH2-C-C5H9 A-602 C2H5 C6H5

A-561 CH₂C≡CH CH2-C-C5H9 A-603 CH=CH₂ C6H5

A-562 CH(CH₃)CH=CH₂ CH2-C-C5H9 A-604 CH2CH2CH₃ C6H5

A-563 CHF₂ CH2-C-C5H9 A-605 CH(CH₃)₂ C6H5

A-564 CH2CI CH2-C-C5H9 A-606 CH2CH2CH2CH₃ C6H5

A-565 CH2CH2CN CH2-C-C5H9 A-607 C(CH₃)₃ C6H5

A-566 CH2CH2CI CH2-C-C5H9 A-608 CH₂CH(CH₃)₂ C6H5

A-567 c-C₃H₅ CH2-C-C5H9 A-609 CH(CH₃)CH₂CH₃ C6H5

A-568 C-C4H7 CH2-C-C5H9 A-610 CH₂CH=CH₂ C6H5

A-569 C-C5H9 CH2-C-C5H9 A-61 1 CH₂C≡CH C6H5

A-570 c-C₆Hii CH2-C-C5H9 A-612 CH(CH₃)CH=CH₂ C6H5

A-571 CH₂-c-C₃H₅ CH2-C-C5H9 A-613 CHF₂ C6H5

A-572 CH(CH₃)-c-C₃H₅ CH2-C-C5H9 A-614 CH2CI C6H5

A-573 CH2-C-C5H9 CH2-C-C5H9 A-615 CH2CH2CN C6H5

A-574 CH2-C-C6H11 CH2-C-C5H9 A-616 CH2CH2CI C6H5

A-575 C6H5 CH2-C-C5H9 A-617 c-C₃H₅ C6H5

A-576 CH₃ CH₂-c-C₆Hii A-618 C-C4H7 C6H5

A-577 C2H5 CH₂-c-C₆Hii A-619 C-C5H9 C6H5

A-578 CH=CH₂ CH₂-c-C₆Hii A-620 c-C₆Hii C6H5

A-579 CH2CH2CH₃ CH₂-c-C₆Hii A-621 CH₂-c-C₃H₅ C6H5

A-580 CH(CH₃)₂ CH₂-c-C₆Hii A-622 CH(CH₃)-c-C₃H₅ C6H5

A-581 ChbChbChbCHs CH₂-c-C₆Hii A-623 CH2-C-C5H9 C6H5

A-582 C(CH₃)₃ CH₂-c-C₆Hii A-624 CH2-C-C5H9 C6H5

A-583 CH₂CH(CH₃)₂ CH₂-c-C₆Hii A-625 C6H5 C6H5

A-584 CH(CH₃)CH₂CH₃ CH₂-c-C₆Hii A-626 CH₃ CH2-C-C4H7 R⁵ R⁶ R⁵ R⁶

A-627 C2H5 CH2-C-C4H7 A-669 C-C5H9 CH₂CH₂-c-C₃H₅

A-628 CH=CH₂ CH2-C-C4H7 A-670 c-C₆Hii CH₂CH₂-c-C₃H₅

A-629 CH2CH2CH3 CH2-C-C4H7 A-671 CH₂-c-C₃H₅ CH₂CH₂-c-C₃H₅

A-630 CH(CH₃)₂ CH2-C-C4H7 A-672 CH(CH₃)-c-C₃H₅ CH₂CH₂-c-C₃H₅

A-631 CH2CH2CH2CH3 CH2-C-C4H7 A-673 CH2-C-C5H9 CH₂CH₂-c-C₃H₅

A-632 C(CH₃)₃ CH2-C-C4H7 A-674 CH2-C-C6H11 CH₂CH₂-c-C₃H₅

A-633 CH₂CH(CH₃)₂ CH2-C-C4H7 A-675 C6H5 CH₂CH₂-c-C₃H₅

A-634 CH(CH₃)CH₂CH₃ CH2-C-C4H7 A-676 CH₃ CH₂(CH₂)₃CH₃

A-635 CH₂CH=CH₂ CH2-C-C4H7 A-677 C2H5 CH₂(CH₂)₃CH₃

A-636 CH₂C≡CH CH2-C-C4H7 A-678 CH=CH₂ CH₂(CH₂)₃CH₃

A-637 CH(CH₃)CH=CH₂ CH2-C-C4H7 A-679 ChbChbCHs CH₂(CH₂)₃CH₃

A-638 CHF₂ CH2-C-C4H7 A-680 CH(CH₃)₂ CH₂(CH₂)₃CH₃

A-639 CH2CI CH2-C-C4H7 A-681 CH2CH2CH2CH₃ CH₂(CH₂)₃CH₃

A-640 CH2CH2CN CH2-C-C4H7 A-682 C(CH₃)₃ CH₂(CH₂)₃CH₃

A-641 CH2CH2CI CH2-C-C4H7 A-683 CH₂CH(CH₃)₂ CH₂(CH₂)₃CH₃

A-642 c-C₃H₅ CH2-C-C4H7 A-684 CH(CH₃)CH₂CH₃ CH₂(CH₂)₃CH₃

A-643 C-C4H7 CH2-C-C4H7 A-685 CH₂CH=CH₂ CH₂(CH₂)₃CH₃

A-644 C-C5H9 CH2-C-C4H7 A-686 CH₂C≡CH CH₂(CH₂)₃CH₃

A-645 c-C₆Hii CH2-C-C4H7 A-687 CH(CH₃)CH=CH₂ CH₂(CH₂)₃CH₃

A-646 CH₂-c-C₃H₅ CH2-C-C4H7 A-688 CHF₂ CH₂(CH₂)₃CH₃

A-647 CH(CH₃)-c-C₃H₅ CH2-C-C4H7 A-689 CH2CI CH₂(CH₂)₃CH₃

A-648 CH2-C-C5H9 CH2-C-C4H7 A-690 CH2CH2CN CH₂(CH₂)₃CH₃

A-649 CH2-C-C6H11 CH2-C-C4H7 A-691 CH2CH2CI CH₂(CH₂)₃CH₃

A-650 C6H5 CH2-C-C4H7 A-692 c-C₃H₅ CH₂(CH₂)₃CH₃

A-651 CH₃ CH₂CH₂-c-C₃H₅ A-693 C-C4H7 CH₂(CH₂)₃CH₃

A-652 C2H5 CH₂CH₂-c-C₃H₅ A-694 C-C5H9 CH₂(CH₂)₃CH₃

A-653 CH=CH₂ CH₂CH₂-c-C₃H₅ A-695 c-C₆Hii CH₂(CH₂)₃CH₃

A-654 CH2CH2CH₃ CH₂CH₂-c-C₃H₅ A-696 CH₂-c-C₃H₅ CH₂(CH₂)₃CH₃

A-655 CH(CH₃)₂ CH₂CH₂-c-C₃H₅ A-697 CH(CH₃)-c-C₃H₅ CH₂(CH₂)₃CH₃

A-656 CH2CH2CH2CH₃ CH₂CH₂-c-C₃H₅ A-698 CH2-C-C5H9 CH₂(CH₂)₃CH₃

A-657 C(CH₃)₃ CH₂CH₂-c-C₃H₅ A-699 CH2-C-C6H11 CH₂(CH₂)₃CH₃

A-658 CH₂CH(CH₃)₂ CH₂CH₂-c-C₃H₅ A-700 C6H5 CH₂(CH₂)₃CH₃

A-659 CH(CH₃)CH₂CH₃ CH₂CH₂-c-C₃H₅ A-701 CH₃ CH(CH₃)CH(CH₃)₂

A-660 CH₂CH=CH₂ CH₂CH₂-c-C₃H₅ A-702 C2H5 CH(CH₃)CH(CH₃)₂

A-661 CH₂C≡CH CH₂CH₂-c-C₃H₅ A-703 CH=CH₂ CH(CH₃)CH(CH₃)₂

A-662 CH(CH₃)CH=CH₂ CH₂CH₂-c-C₃H₅ A-704 ChbChbCHs CH(CH₃)CH(CH₃)₂

A-663 CHF₂ CH₂CH₂-c-C₃H₅ A-705 CH(CH₃)₂ CH(CH₃)CH(CH₃)₂

A-664 CH2CI CH₂CH₂-c-C₃H₅ A-706 CH2CH2CH2CH₃ CH(CH₃)CH(CH₃)₂

A-665 CH2CH2CN CH₂CH₂-c-C₃H₅ A-707 C(CH₃)₃ CH(CH₃)CH(CH₃)₂

A-666 CH2CH2CI CH₂CH₂-c-C₃H₅ A-708 CH₂CH(CH₃)₂ CH(CH₃)CH(CH₃)₂

A-667 c-C₃H₅ CH₂CH₂-c-C₃H₅ A-709 CH(CH₃)CH₂CH₃ CH(CH₃)CH(CH₃)₂

A-668 C-C4H7 CH₂CH₂-c-C₃H₅ A-710 CH₂CH=CH₂ CH(CH₃)CH(CH₃)₂ R⁵ R⁶ R⁵ R⁶

A-71 1 CH₂C≡CH CH(CH₃)CH(CH₃)₂ A-729 CH₂(CH₂)4CH₃ CH₂(CH₂)4CH₃

A-712 CH(CH₃)CH=CH₂ CH(CH₃)CH(CH₃)₂ A-730 CH₃ 2-EtHex

A-713 CHF₂ CH(CH₃)CH(CH₃)₂ A-731 C2H5 2-EtHex

A-714 CH2CI CH(CH₃)CH(CH₃)₂ A-732 C(CH₃)₃ 2-EtHex

A-715 CH2CH2CN CH(CH₃)CH(CH₃)₂ A-733 2-EtHex 2-EtHex

A-716 CH2CH2CI CH(CH₃)CH(CH₃)₂ A-734 CH₃ CH2CH2OH

A-717 C-C3H5 CH(CH₃)CH(CH₃)₂ A-735 C2H5 CH2CH2OH

A-718 C-C4H7 CH(CH₃)CH(CH₃)₂ A-736 C(CH₃)₃ CH2CH2OH

A-719 C-C5H9 CH(CH₃)CH(CH₃)₂ A-737 CH2CH2CH2CH₃ CH2CH2OH

A-720 c-C₆Hii CH(CH₃)CH(CH₃)₂ A-738 CH₂(CH₂)₃CH₃ CH2CH2OH

A-721 CH₂-c-C₃H₅ CH(CH₃)CH(CH₃)₂ A-739 CH2CH2OH CH2CH2OH

A-722 CH(CH₃)-c-C₃H₅ CH(CH₃)CH(CH₃)₂ A-740 CH2-C-C4H7 CH2-C-C4H7

A-723 CH2-C-C5H9 CH(CH₃)CH(CH₃)₂ A-741 CH₂CH₂-c-C₃H₅ CH₂CH₂-c-C₃H₅

A-724 CH2-C-C6H11 CH(CH₃)CH(CH₃)₂ A-742 CH(CH₃)CH(CH₃)₂ CH(CH₃)CH(CH₃)₂

A-725 C6H5 CH(CH₃)CH(CH₃)₂ A-743 CH₂(CH₂)₃CH₃ CH₂(CH₂)₃CH₃

A-726 CH₃ CH₂(CH₂)4CH₃ A-744 (CH₂)₄

A-727 C2H5 CH₂(CH₂)4CH₃ A-745 CH2CH2SCH2

A-728 C(CH₃)₃ CH₂(CH₂)4CH₃

c-C₃H₅: cyclopropyl; C-C4H7: cyclobutyl; C-C5H9: cyclopentyl; c-CeHu: cyclohexyl;

CH2-c-C₃H₅: cyclopropylmethyl; CH(CH₃)-c-C₃H₅: 1 -cyclopropylethyl;

CH2-C-C5H9: cyclopentylmethyl; CH2-C-C5H9: cyclopentylmethyl; CeH₅: phenyl;

CH₂CH₂-c-C₃H₅: 2-cyclopropylethyl; CH₂-c-C₄H₇: 2-cyclobutylmethyl; 2-EtHex:

A group of especially preferred compounds of formula I are compounds 1-1 to I-40 of formula IA-1 which are listed in the table C in the example section.

In one embodiment, a compound selected from the compounds 1-1 to I-40 as defined in Table C in the Example Section at the end of the description, are preferred in the methods and uses according to the invention.

In one embodiment, a compound selected from compounds 1-1 1 , 1-16, 1-21 , I-26, 1-31 is the compound I in the methods and uses according to the invention, which are defined in accord- ance with Table C of the example section: Table C

In one embodiment, 1-1 1 is the compound I in the methods and uses according to the invention. In one embodiment, 1-16 is the compound I in the methods and uses according to the invention. In one embodiment, 1-21 is the compound I in the methods and uses according to the invention. In one embodiment, I-26 is the compound I in the methods and uses according to the invention. In one embodiment, 1-31 is the compound I in the methods and uses according to the invention. Methods of improving plant health

The compounds of formula (I) as defined herein, or a stereoisomer, salt, tautomer or N-oxide thereof, or the compositions comprising them, are used for improving the health of plants when applied to plants, parts of plants, propagules of the plants or to their actual or intended locus of growth.

Thus, the invention also relates to a method for improving the health of plants, which comprises treating the plant, a part of the plant, the locus where the plant is growing or is expected to grow, and/or the propagules from which the plant grows with the compound or composition used according to the invention.

As a matter of course, the compound of formula (I) is used in an effective and non-phytotoxic amount. This means that they are used in a quantity which allows to obtain the desired effect but which does not give rise to any phytotoxic symptom on the treated plant or on the plant grown from the treated propagule or treated soil. The plants to be treated are generally plants of economic importance and/or men-grown plants. Thus, they are preferably selected from agricultural, silvicultural and ornamental plants.

The term "plant health" (health of a plant) is defined as a condition of the plant and/or its prod- ucts which is determined by several aspects alone or in combination with each other such as yield (for example increased biomass and/or increased content of valuable ingredients), plant vigor (for example improved plant growth and/or greener leaves ("greening effect")), quality (for example improved content or composition of certain ingredients) and tolerance to abiotic and/or biotic stress.

The above identified indicators for the health condition of a plant may be interdependent or they may result from each other. Each listed plant health indicator listed below, and which is selected from the groups consisting of yield, plant vigor, quality and tolerance to abiotic and/or biotic stress, is to be understood as a preferred embodiment of the present invention either each on its own or preferably in combination with each other.

One indicator for the condition of the plant is the crop yield. "Crop yield" is to be understood as any plant product of economic value that is produced by the plant such as grains, fruits in the proper sense, vegetables, nuts, grains, seeds, wood (e.g. in the case of silviculture plants) or even flowers (e.g. in the case of gardening plants, ornamentals). The plant products may in addition be further utilized and/or processed after harvesting.

Thus, the invention relates to a method for increasing the yield of a plant or its product.

According to the present invention, "increased yield" of a plant, in particular of an agricultural, silvicultural and/or ornamental plant means that the yield of a product of the respective plant is increased by a measurable amount over the yield of the same product of the plant produced under the same conditions, but without the application of the compound or composition of the invention. Increased crop yield can be characterized, among others, by following improved properties of the plant:

• increased plant weight,

• increased plant height,

• increased biomass such as higher overall fresh weight

· higher grain yield

• more tillers

• larger leaves

• increased shoot growth

• increased protein content

· increased oil content

• increased starch content

• increased pigment content According to one embodiment of the present invention, the yield is increased by at least 1 %. According to one embodiment of the present invention, the yield is increased by at least 2%. According to one embodiment of the present invention, the yield is increased by at least 4%. According to one embodiment of the present invention, the yield is increased by at least 5 %. According to another embodiment of the present invention, the yield is increased by least 10%. According to another embodiment of the present invention, the yield is increased by least 15%. According to another embodiment of the present invention, the yield is increased by least 30%.

Another indicator for the condition of the plant is the plant vigor. The plant vigor becomes mani- fest in several aspects such as the general visual appearance.

Thus, the invention relates to a method for increasing the vigor of a plant or its product.

Improved plant vigor can be characterized, among others, by following improved properties of the plant:

• improved vitality of the plant,

· improved plant growth,

• improved plant development,

• improved visual appearance,

• improved plant stand (less plant verse/lodging),

• improved emergence,

· enhanced root growth and/or more developed root system,

• enhanced nodulation, in particular rhizobial nodulation,

• bigger leaf blade,

• bigger size,

• increased plant weight,

· increased plant height,

• increased tiller number,

• increased shoot growth,

• increased root growth (extensive root system),

• increased yield when grown on poor soils or unfavorable climate,

· enhanced photosynthetic activity

• enhanced pigment content (e.g. Chlorophyll content)

• earlier flowering,

• earlier fruiting,

• earlier and improved germination,

· earlier grain maturity,

• improved self-defence mechanisms

• improved stress tolerance and resistance of the plants against biotic and abiotic stress factors such as fungi, bacteria, viruses, insects, heat stress, cold stress, drought stress, UV stress and/or salt stress

· less non-productive tillers,

• less dead basal leaves,

• less input needed (such as fertilizers or water)

• greener leaves complete maturation under shortened vegetation periods

less fertilizers needed,

less seeds needed,

easier harvesting

faster and more uniform ripening

longer shelf-life

longer panicles,

delay of senescence,

stronger and/or more productive tillers,

better extractability of ingredients

• improved quality of seeds (for being seeded in the following seasons for seed production)

• reduced production of ethylene and/or the inhibition of its reception by the plant The improvement of the plant vigor according to the present invention particularly means that the improvement of any one or several or all of the above mentioned plant characteristics are improved independently of the pesticidal action of the composition or active ingredients.

Another indicator for the condition of the plant is the "quality" of a plant and/or the products of the respective plant. According to the present invention, enhanced quality means that certain crop characteristics such as the content or composition of certain ingredients are increased or improved by a measurable or noticeable amount over the same factor of the plant produced under the same conditions, but without the application of the composition of the present invention. The quality of a product of the respective plant becomes manifest in several aspects. Thus, the invention relates to a method for increasing the quality of a plant or its product.

Enhanced quality can be characterized, among others, by following improved properties of the plant or its product:

increased nutrient content

increased protein content

increased content of fatty acids

increased metabolite content

increased carotenoid content

increased sugar content

increased amount of essential amino acids

improved nutrient composition

improved protein composition

improved composition of fatty acids

improved metabolite composition

improved carotenoid composition

improved sugar composition

improved amino acids composition

improved or optimal fruit color • improved leaf color

• higher storage capacity

• higher processability of the harvested products Another indicator for the condition of the plant is the plant's tolerance or resistance to biotic and/or abiotic stress factors. Biotic and abiotic stress, especially over longer terms, can have harmful effects on plants.

Thus, the invention relates to a method for increasing the tolerance and/or resistance of a plant or its product against biotic and/or abiotic stress.

Biotic stress is caused by living organisms while abiotic stress is caused for example by environmental extremes. According to the present invention, "enhanced tolerance or resistance to biotic and/or abiotic stress factors" means (1 .) that certain negative factors caused by biotic and/or abiotic stress are diminished in a measurable or noticeable amount as compared to plants exposed to the same conditions, but without being treated with the compound or compo- sition of the invention and (2.) that the negative effects are not diminished by a direct action of the composition on the stress factors, e.g. by its fungicidal or insecticidal action which directly destroys the microorganisms or pests, but rather by a stimulation of the plants' own defensive reactions against said stress factors. Increased tolerance or resistance can be characterized, among others, by following improved properties of the plant or its product: when grown under the impact of biotic and/or abiotic stress factors.

Negative factors caused by biotic stress such as pathogens and pests are widely known and range from dotted leaves to total destruction of the plant. Biotic stress can be caused by living organisms, such as:

• pests (for example insects, arachnides, nematodes),

• competing plants (for example weeds),

• microorganisms such as phythopathogenic fungi bacteria,

· viruses

Negative factors caused by abiotic stress are also well-known and can often be observed as reduced plant vigor (see above), for example dotted leaves, "burned leaves", reduced growth, less flowers, less biomass, less crop yields, reduced nutritional value of the crops, later crop maturity, to give just a few examples. Abiotic stress can be caused for example by:

• extremes in temperature such as heat or cold (heat stress / cold stress),

• strong variations in temperature,

• temperatures unusual for the specific season,

· drought (drought stress),

• extreme wetness,

• high salinity (salt stress),

• radiation (for example by increased UV radiation due to the decreasing ozone layer), • increased ozone levels (ozone stress)

• organic pollution (for example by phythotoxic amounts of pesticides)

• inorganic pollution (for example by heavy metal contaminants). Thus, in one embodiment, the invention relates to a method for increasing the resistance to heat, cold or strong variations in temperature.

As a result of biotic and/or abiotic stress factors, the quantity and the quality of the stressed plants, their crops and fruits decrease. As far as quality is concerned, reproductive development is usually severely affected with consequences on the crops which are important for fruits or seeds. Synthesis, accumulation and storage of proteins are mostly affected by temperature; growth is slowed by almost all types of stress; polysaccharide synthesis, both structural and storage is reduced or modified: these effects bring to a decrease in biomass (yield) and to changes in the nutritional value of the product.

Advantageous properties, obtained especially from treated seeds, are e.g. improved germination and field establishment, better vigor, more homogen field establishment.

The above identified indicators for the health condition of a plant may be interdependent and may result from each other. For example, an increased resistance to biotic and/or abiotic stress may lead to a better plant vigor, e.g. to better and bigger crops, and thus to an increased yield. Inversely, a more developed root system may result in an increased resistance to biotic and/or abiotic stress. However, these interdependencies and interactions are neither all known nor fully understood and therefore the different indicators will be described separately.

In one embodiment, the invention relates to a methods and uses according to the invention wherein the plant is an agricultural, silvicultural and/or ornamental plant.

In one embodiment of the invention, the present invention provides the use of the compound of the invention for increasing the yield of a plant or its product, preferably of an agricultural, silvicultural and/or ornamental plant.

In one embodiment of the invention, the present invention provides the use of the compound of the invention for increasing the vigor of a plant or its product, preferably of an agricultural, silvi- cultural and/or ornamental plant.

In one embodiment of the invention, the present invention provides the use of the compound of the invention for increasing the quality of a plant or its product, preferably of an agricultural, silvicultural and/or ornamental plant.

In one embodiment of the invention, the present invention provides the use of the compound of the invention for increasing the tolerance and/or resistance of a plant or its product against biotic and/or abiotic stress, preferably of an agricultural, silvicultural and/or ornamental plant. In one embodiment of the invention, the present invention provides the use of the compound of the invention for increasing the yield and/or improving the vigor of a plant, e.g. of an agricultural, silvicultural and/or ornamental plant. In one embodiment of the invention, the tolerance of and/or resistance against biotic stress factors is enhanced. Thus, according to a preferred embodiment of the present invention, the inventive compounds or compositions are used for stimulating the natural defensive reactions of a plant against a pathogen and/or a pest. Thereby, the plant can be protected against unwanted microorganisms such as phytopathogenic fungi and/or bacteria or even viruses and/or against pests such as insects, arachnids and nematodes, and it has been found that the inventive compositions result in plant strengthening effects. Therefore, they are useful for mobilizing the plant's defense mechanisms against the attack of unwanted microorganisms and/or pests. Consequently, the plant becomes tolerant or even resistant towards these microorganisms and/or pests.

In one embodiment of the invention, the tolerance of and/or resistance against abiotic stress factors is enhanced. Thus, according to a further embodiment of the present invention, the inventive compounds or compositions are used for stimulating a plant's own defensive reactions against abiotic stress such as extremes in temperature, e.g. heat or cold or strong variations in temperature or temperatures unusual for the specific season, drought, extreme wetness, high salinity, radiation (e.g. increased UV radiation due to the decreasing ozone protective layer), increased ozone levels, organic pollution (e.g. by phythotoxic amounts of pesticides) and/or inorganic pollution (e.g. by heavy metal contaminants). In one embodiment of the invention, the inventive compositions are used for stimulating a plant's own defensive reactions against abiotic stress, where the abiotic stress factors are preferably selected from extremes in temperature, drought, salt and extreme wetness.

Therefore, the invention relates to the use of a compound of formula (I) as defined herein, or a composition comprising said compound, for

• improving the health of a plant, and/or

• for increasing the yield of a plant or its product, , and/or

• for increasing the vigor of a plant or its product., and/or

• for increasing the quality of a plant or its product, and/or

· for increasing the tolerance and/or resistance of a plant or its product against biotic and/or abiotic stress, and/or

• for increasing the resistance to heat, cold or strong variations in temperature.

In one embodiment, the invention relates to a method for improving the health of a plant, which method comprises applying a compound of formula I, which is selected from the compounds 1-1 to I-40 as defined in Table C. More specifically, the compound I is selected from compounds I- 1 1 , 1-16, 1-21 , I-26, 1-31 which are defined in accordance with Table C of the example section, more specifically compound 1-1 1 , more specifically compound 1-16, more specifically compound 1-21 , more specifically compound I-26, more specifically compound 1-31 .

In one embodiment, the invention relates to a method for increasing the yield of a plant or its product, which method comprises applying a compound of formula I, which is selected from the compounds 1-1 to I-40 as defined in Table C. More specifically, the compound I is selected from compounds 1-1 1 , 1-16, 1-21 , I-26, 1-31 which are defined in accordance with Table C of the example section, more specifically compound 1-1 1 , more specifically compound 1-16, more specifically compound 1-21 , more specifically compound I-26, more specifically compound 1-31 .

In one embodiment, the invention relates to a method for increasing the vigor of a plant or its product, which method comprises applying a compound of formula I, which is selected from the compounds 1-1 to I-40 as defined in Table C. More specifically, the compound I is selected from compounds 1-1 1 , 1-16, 1-21 , I-26, 1-31 which are defined in accordance with Table C of the example section, more specifically compound 1-1 1 , more specifically compound 1-16, more specifically compound 1-21 , more specifically compound I-26, more specifically compound 1-31 .

In one embodiment, the invention relates to a method for increasing the quality of a plant or its product, which method comprises applying a compound of formula I, which is selected from the compounds 1-1 to I-40 as defined in Table C. More specifically, the compound I is selected from compounds 1-1 1 , 1-16, 1-21 , I-26, 1-31 which are defined in accordance with Table C of the example section, more specifically compound 1-1 1 , more specifically compound 1-16, more specifi- cally compound 1-21 , more specifically compound I-26, more specifically compound 1-31 .

In one embodiment, the invention relates to a method for increasing the tolerance and/or resistance of a plant or its product against biotic and/or abiotic stress, which method comprises applying a compound of formula I, which is selected from the compounds 1-1 to I-40 as defined in Table C. More specifically, the compound I is selected from compounds 1-1 1 , 1-16, 1-21 , I-26, 1-31 which are defined in accordance with Table C of the example section, more specifically compound 1-1 1 , more specifically compound 1-16, more specifically compound 1-21 , more specifically compound I-26, more specifically compound 1-31 .

In one embodiment, the invention relates to a method for increasing the resistance to heat, cold or strong variations in temperature, which method comprises applying a compound of formula I, which is selected from the compounds 1-1 to I-40 as defined in Table C. More specifically, the compound I is selected from compounds 1-1 1 , 1-16, 1-21 , I-26, 1-31 which are defined in accordance with Table C of the example section, more specifically compound 1-1 1 , more specifically compound 1-16, more specifically compound 1-21 , more specifically compound I-26, more specifically compound 1-31 .

In one embodiment of the invention, the plant of which the health is to be improved by the treatment with the compound or composition of the invention is an agricultural plant. Agricultural plants are plants of which a part or all is harvested or cultivated on a commercial scale or which serve as an important source of feed, food, fibers (e.g. cotton, linen), combustibles (e.g. wood, bioethanol, biodiesel, biomass) or other chemical compounds. Agricultural plants also horticultural plants, i.e. plants grown in gardens (and not on fields), such as certain fruits and vegetables. It has to be emphasized that the above mentioned effects of the compound or composition according to the invention, i.e. enhanced health of the plant, are also present when the plant is not under biotic stress and in particular when the plant is not under fungal- or pest pressure. It is evident that a plant suffering from fungal or insecticidal attack produces a smaller biomass and a smaller crop yield as compared to a plant which has been subjected to curative or preventive treatment against the pathogenic fungus or pest and which can grow without the damage caused by the biotic stress factor. However, the method according to the invention leads to an enhanced plant health even in the absence of any biotic stress and in particular of any phyto- pathogenic fungi or pest. This means that the positive effects of the compound or composition of the invention cannot be explained just by the fungicidal or insecticidal activities of the compounds of components (A) and (B), but are based on further activity profiles. But of course, plants under biotic stress can be treated, too, according to the methods of the present invention.

Method and uses for reducing nitrous oxide emission

As mentioned above, the uses and methods according to the invention also include methods for reducing nitrous oxide emission from soils. These methods may also be considered as methods improving plant health, due to the beneficial effect on the plant itself.

Thus, the present invention relates to a method for reducing nitrous oxide emission from soils comprising treating a plant growing on the respective soil and/or the locus where the plant is growing or is intended to grow and/or the seeds from which the plant grows with at least one compound of formula I according to the invention, more preferably a compound of formula IA, also preferably a compound of formula IB, also preferably a compound of formula IC, also preferably a compound of formula ID; more preferably a compound selected from the compounds I- 1 to I-40 as defined in Table C; more preferably a compound selected from compounds 1-1 1 , I- 16, 1-21 , I-26, 1-31 according to Table C/C.

The present invention relates to a method for reducing nitrous oxide emission from soils comprising treating a plant growing on the respective soil and/or the locus where the plant is growing or is intended to grow and/or the seeds from which the plant grows with

A) at least one compound of formula I according to the invention, more preferably a compound of formula IA, also preferably a compound of formula IB, also preferably a compound of formula IC, also preferably a compound of formula ID; more preferably a compound selected from the compounds 1-1 to I-40 as defined in Table C; more preferably a compound selected from compounds 1-1 1 , 1-16, 1-21 , I-26, 1-31 according to Table C/C,

B) and at least one ammonium- or urea-containing fertilizer (compound B) selected from the group consisting of:

(B1 ) inorganic fertilizer:

NPK fertilizer, ammonium nitrate, calcium ammonium nitrate, ammonium sulfate;

nitrate, ammonium sulfate and ammonium phosphate;

(B2) organic fertilizer:

liquid manure, semi-liquid manure, stable manure and straw manure, worm castings, compost, seaweed and guano; The invention relates to such a method as described above, wherein the application of at least one compound I (A) and at least one compound (B) is carried out with a time lag of at least 1 day.

In addition, the present invention relates to a method for reducing nitrous oxide emission from soils as described above, wherein the ammonium- or urea-containing fertilizer (compound B) is applied together with at least one nitrification inhibitor (compound C) selected from the group consisting of 2-(3,4-dimethyl-pyrazol-1 -yl)-succinic acid, 3,4-dimethylpyrazolephosphate (DMPP), dicyandiamide (DCD), 1 H-1 ,2,4-triazole, 3-methylpyrazole (3-MP), 2-chloro-6- (trichloromethyl)-pyridine, 5-ethoxy-3-trichloromethyl-1 ,2,4-thiadiazol, 2-amino-4-chloro-6- methyl-pyrimidine, 2-mercapto-benzothiazole, 2-sulfanilamidothiazole, thiourea, sodium azide, potassium azide, 1 -hydroxypyrazole, 2-methylpyrazole-1 -carboxamide, 4-amino-1 ,2,4-triazole, 3-mercapto-1 ,2,4-triazole, 2,4-diamino-6-trichloromethyl-5-triazine, carbon bisulfide, ammonium thiosulfate, sodium trithiocarbonate, 2,3-dihydro-2,2-dimethyl-7-benzofuranol methyl carbamate and N-(2,6-dimethylphenyl)-N-(methoxyacetyl)-alanine methyl ester.

Nitrogen is an essential element for plant growth and reproduction. About 25% of the plant- available nitrogen in soils (ammonium and nitrate) originate from decomposition processes (mineralization) of organic nitrogen compounds such as humus, plant and animal residues and organic fertilizers. Approximately 5% derive from rainfall. On a global basis, the biggest part (70%), however, are supplied to the plant by inorganic nitrogen fertilizers. Without the use of nitrogenous fertilizers, the earth would not be able to support its current population.

Soil microorganisms convert organic nitrogen to ammonium (NH₄ ⁺) which is subsequently oxidized to nitrate (NO3^") in a process known as nitrification. Nitrate is very important in agriculture, because it is one form of nitrogen which is preferably taken up by the plants due to its high plant-availability. However, nitrate is also highly mobile in the soil. As a consequence, it may be readily lost from soils leaching to groundwater. In addition, nitrogen is lost by denitrification which is the microbiological conversion of nitrate and nitrite (NO2^") to gaseous forms of nitrogen such as nitrous oxide (N2O) and molecular nitrogen (N2). As a result of the various losses, ap- proximately 50% of the applied nitrogen is lost during the year following fertilizer addition (cf. Nelson and Huber; Nitrification inhibitors for corn production (2001 ). National Corn Handbook, Iowa State University).

Consequently, there is great concern that the intensive use of fertilizer and the application of livestock wastes may lead to increased nitrogen levels in the groundwater and surface waters which in turn could lead to increased eutrophication of lakes and streams.

In addition, nitrogen fertilization and livestock wastes may increase the production of nitrous oxide, significantly contributing to the stratospheric ozone destruction and global warming. Be- sides nitrous oxide, carbon dioxide (CO2) and methane (CH₄) are important gases produced by native and agricultural soils. Depending on various parameters such as weather and soil type, increased fertilization and tillage can additionally increase nitrous oxide emissions. As a consequence, one of the biggest challenge to the world community in the coming years will be the reduction of gases responsible for the greenhouse effect in the atmosphere or at least the stabilization of greenhouse gas concentrations in the atmosphere at a level that would prevent dangerous anthropogenic interference with the climate system. This concern is expressed in the Kyoto Protocol in which the ratifying countries commit to reduce their emissions of greenhouse gases or engage in emissions trading if they maintain or increase emissions of these gases.

One of the best known greenhouse gases is carbon dioxide. However, nitrous oxide is another cause of great concern. Throughout the 20th century and continuing into the 21 st century, nitrous oxide has increased by 50 parts per billion in the atmosphere and is rising further by 0.25% each year. Although nitrous oxide only accounts for around 9% of the total greenhouse gas emissions, one has to keep in mind that it has a 300-fold greater global warming potential than carbon dioxide over the next 100 years and an atmospheric lifetime of approximately 150 years.

The above listed trends may result in increased levels of nitrogen in natural waters, crop residue, and municipal and agricultural wastes, creating national and international concerns about the environment and the public health.

Dharnaraj P.S. in Lai and Lai (Editors) (Effects of pesticides on nitrification and denitrification (1988). Pesticides and Nitrogen Cycle) describes the effect of various pesticides on nitrification and denitrification. The studies described therein show that most fungicides do not have any effect on nitrification and denitrification. In addition, the method steps according to the invention as well as the surprising effect are not disclosed.

Mosier et al. (Nitrous oxide emission from agricultural fields; Assessment, measurement and mitigation (1996). Plant and Soil 131 : 95.108) summarized the effects of nitrification inhibitors on N2O emissions from fertilized soils. A number of studies indicated that nitrification inhibitors did limit N2O emission from soils fertilized with ammonium-based fertilizers.

Furthermore, Kinney et al. (Effects of fungicides on trace gas fluxes (2004). Journal of Geophysical Research 109: 1 - 15) have hypothesized that the variations in gases flux from agricultural soils may also be affected by the quantity and type of agricultural chemicals (pesticides) used. They carried out field experiments and determined the effect to two commonly used multi- site fungicides, mancozeb and chlorothalonil, on trace gas exchange.

Kinney et al. (Laboratory investigations into the effects of the pesticides mancozeb, chlorothalonil , and prosulfuron on nitrous oxide and nitric oxide production in fertilized soil (2005). Soil Biology & Biochemistry 37: 837-850) additionally investigated the effects of mancozeb, chlor- thalonil and the herbicide prosulfuron on N2O production by nitrifying and denitrifying bacteria in fertilized soil.

Somda et al. (1991 ). Influence of biocides on tomato nitrogen uptake and soil nitrification and denitirification. Journal of Plant Nutrition 14 (1 1 ): 1 187-99) investigated the impact of benlate, captan, and lime-sulfur fungicides compared to nitrification inhibitors on nitrification. WO 98/05607 is directed to the use of inorganic or organic polyacids for the treatment of inorganic fertilizers, in particular the use of the polyacids as a mixture with at least one nitrification inhibitor for the treatment of inorganic fertilizers.

WO 08/059053 relates to a method for increasing the carbon dioxide sequestration from the atmosphere by treating a plant, a part of the plant, the locus where the plant is growing or is intended to grow and/or the plant propagules with certain active ingredients. The invention also relates to the use of the compounds for increasing the dry biomass of a plant.

Nitrification and denitrification are the two main processes by which nitrous oxide is produced in soil environments. It is expected that the yearly application of nitrogen fertilizers and pesticides will more than double over the next 50 years. In addition, the agricultural cropland is expected to increase by 5,5 x 10⁸ ha hectares by the year 2050 (cf. Tilman et al. (2001 ): Forecasting agriculturally driven global environmental change. Science. Vol. 292: 281 -284). As a consequence, agricultural soils will likely have an ever-increasing influence on the global atmospheric budgets of carbon dioxide, nitrous oxide and methane. With respect to agricultural production systems, it could be shown that fertilization and tillage more than double N2O emissions from soils.

There is also concern that the intensive use of fertilizer and the application of livestock wastes could lead to increased nitrogen levels in groundwater and surface waters, and that this in turn could lead to increased eutrophication of lakes and streams.

Besides the potential impact on global warming, the production of N2O reduces the amount of nitrogen available to the plants.

It was therefore an object of the present invention to provide a reliable method which solves the problems outlined above, and which should, in particular, reduce nitrous oxide emission from soils. In particular, from soils which are fertilized.

Surprisingly, we have found that this object is achieved when treating a plant and/or the locus such as the soil where the plant is growing or is intended to grow and/or the seeds from which the plant grows with at least one compound of formula I according to the invention (compound A) and at least one ammonium- or urea-containing fertilizer (compound B) wherein the application of compound (A) and compound (B) is carried out with a time lag of at least 1 day.

The object of the present invention can also be achieved when treating a plant and/or the locus such as the soil where the plant is growing or is intended to grow and/or the seeds from which the plant grows with an agrochemical mixture, comprising at least one compound of formula I according to the invention, in combination with at least one compound II as defined herein (compound group A), and at least one ammonium- or urea-containing fertilizer (compound B) wherein the application of the mixture comprising at least two compounds (A) and compound (B) must be carried out with a time lag of at least 1 day.

The time gap between the application of a compound of formula I according to the invention (or a respective mixture thereof) (compound A) from the application of a fertilizer (compound B) is the crucial method step because it could be shown that the joint application may have no impact or even results in an increased N2O emission while only a timely separated application of a fungicide and a fertilizer according to the method of the present invention, results in a strong decrease of N2O emission. Consequently, the time gap between the application of a fungicide (compound A) and a fertilizer (compound B) is a special technical feature which results in a surprising effect being a new and inventive technical teaching to any person skilled in the art.

The application of active ingredients according to the method of the invention provides significant ecological and economical advantages. From an ecological stand point, the cutback of N2O emissions significantly reduces the impact of modern agriculture on the environment and its atmosphere as well as on global warming. In addition, losses of nitrogen to the groundwater, risk of eutrophication of lakes and streams are also minimized due to an optimized use of soil nitrogen. The compounds of formula I may be combined with further pesticides in the methods and uses. In one embodiment of the method according to the invention, the nitrous oxide emission from soils is reduced by applying a compound of formula I together with a compound II selected from the group consisting of azoxystrobin, coumethoxystrobin, coumoxystrobin, dimoxystrobin, ene- stroburin, fenaminstrobin, fenoxystrobin (flufenoxystrobin), fluoxastrobin, kresoxim-methyl, mandestrobin, metominostrobin, orysastrobin, picoxystrobin, pyraclostrobin, pyrametostrobin, pyraoxystrobin, pyribencarb, triclopyricarb (chlorodincarb), trifloxystrobin, 2-[2-(2,5-dimethyl- phenoxymethyl)-phenyl]-3-methoxy-acrylic acid methyl ester and 2-(2-(3-(2,6-di-chlorophenyl)- 1 -methyl-allylidene-aminooxy-methyl)-phenyl)-2-methoxyimino-N-methyl-acetamide.

In a preferred embodiment of the method according to the invention, compound II is a strobilurin selected from the group consisting of azoxystrobin, dimoxystrobin, fluoxastrobin, kresoxim- methyl, metominostrobin, orysastrobin, picoxystrobin, pyraclostrobin and trifloxystrobin.

In a preferred embodiment of the method according to the invention, compound II is a strobilurin selected from the group consisting of pyraclostrobin, orysastrobin, azoxystrobin, dimoxystrobin, enestroburin, fluoxastrobin, kresoxim-methyl, metominostrobin, picoxystrobin, pyribencarb and trifloxystrobin.

In a preferred embodiment of the method according to the invention, compound II is a strobilurin selected from the group consisting of azoxystrobin, pyraclostrobin and trifloxystrobin.

In an especially preferred embodiment of the method according to the invention, compound II is pyraclostrobin.

In one embodiment of the method according to the invention, compound (B) is an ammonium- or urea-containing fertilizer (compound B) selected from the group of inorganic fertilizer (B1 ) consisting of NPK fertilizer, ammonium nitrate, calcium ammonium nitrate, ammonium sulfate nitrate, ammonium sulfate and ammonium phosphate.

In a preferred embodiment of the method according to the invention, compound (B) is selected from the group consisting of ammonium sulfate nitrate and ammonium sulfate.

In another embodiment of the method according to the invention, compound (B) is an ammoni- um- or urea-containing fertilizer (compound B) selected from the group of organic fertilizer (B2) consisting of liquid manure, semi-liquid manure, stable manure and straw manure, worm castings, compost, seaweed and guano.

In a preferred embodiment of the method according to the invention, compound (B) is liquid manure.

In one embodiment of the method according to the invention, the application of at least one compound (A) and at least one compound (B) is carried out with a time lag of at least 1 day. In a preferred embodiment of the method according to the invention, the application of at least one compound (A) and at least one compound (B) is carried out with a time lag of at least 4 days.

In another preferred embodiment of the method according to the invention, the application of at least one compound (A) and at least one compound (B) is carried out with a time lag of at least 8 days.

In another preferred embodiment of the method according to the invention, the application of at least one compound (A) and at least one compound (B) is carried out with a time lag of at least 10 days.

In yet another preferred embodiment of the method according to the invention, the application of at least one compound (A) and at least one compound (B) is carried out with a time lag of at least 16 days.

In one embodiment of the method according to the invention, the nitrous oxide emission from soils is reduced by applying the compound of formula I according to the invention (compound A) and the ammonium- or urea-containing fertilizer (compound B) together with at least one nitrifi- cation inhibitor (compound C) selected from the group consisting of 2-(3,4-dimethyl-pyrazol-1 - yl)-succinic acid, 3,4-dimethylpyrazolephosphate (DMPP), dicyandiamide (DCD), I H-1 ,2,4- triazole, 3-methylpyrazole (3-MP), 2-chloro-6-(trichloromethyl)-pyridine, 5-ethoxy-3- trichloromethyl-1 ,2,4-thiadiazol, 2-amino-4-chloro-6-methyl-pyrimidine, 2-mercapto- benzothiazole, 2-sulfanilamidothiazole, thiourea, sodium azide, potassium azide, 1 - hydroxypyrazole, 2-methylpyrazole-1 -carboxamide, 4-amino-1 ,2,4-triazole, 3-mercapto-1 ,2,4- triazole, 2,4-diamino-6-trichloromethyl-5-triazine, carbon bisulfide, ammonium thiosulfate, sodium trithiocarbonate, 2,3-dihydro-2,2-dimethyl-7-benzofuranol methyl carbamate and N-(2,6- dimethylphenyl)-N-(methoxyacetyl)-alanine methyl ester. In a preferred embodiment of the method according to the invention, the nitrous oxide emission from soils is reduced by applying the compound of formula I according to the invention (compound A) and the ammonium- or urea-containing fertilizer (compound B) together with at least one nitrification inhibitor (compound C) selected from the group consisting of 2-(3,4-dimethyl- pyrazol-1 -yl)-succinic acid, 3,4-dimethylpyrazole-phosphate (DMPP), dicyandiamide (DCD), 1 H- 1 ,2,4-triazole, 3-methylpyrazole (3-MP), 2-chloro-6-(trichloromethyl)-pyridine and 5-ethoxy-3- trichloromethyl-1 ,2,4-thiadiazol. In another embodiment of the method according to the invention, the nitrous oxide emission from soils is reduced by applying an agrochemical mixture comprising at lease one the compound of formula I according to the invention (compound A) and at least one compound (B) and at least one nitrification inhibitor (compound C).

In another embodiment of the method according to the invention, the nitrous oxide emission from soils is reduced by applying an agrochemical mixture comprising one compound of formula I according to the invention (compound A) and one compound (B) and one nitrification inhibitor (compound C).

The secondary mixtures listed in table BC, comprising one compound (B) and one compound (C) are a preferred embodiment of the method of the current invention.

Table BC:

In the terms of the present invention "agrochemical mixture" is not restricted to a physical mixture comprising at least two compounds, but refers to any preparation form of at least one compound I according to the invention and at least one further compound, the use of which is time- and locus-related.

In one embodiment of the invention "agrochemical mixture" refers to a physical mixture comprising compounds A and B.

In one embodiment of the invention "agrochemical mixture" refers to a physical mixture of at lease one compound A and at least one compound (B) and at least one compound (C).

The agrochemical mixtures may be formulated separately but applied in a temporal relationship, i.e. simultaneously or subsequently, the subsequent application having a time interval which allows a combined action of the compounds.

Furthermore, the individual compounds of the agrochemical mixtures according to the invention such as parts of a kit or parts of the binary mixture may be mixed by the user himself in a spray tank and further auxiliaries may be added, if appropriate (tank mix). This applies also in case ternary mixtures are used according to the invention.

In one embodiment of the invention, the method according to the invention comprises the steps a) application of at least one compound (A) as defined in any of the embodiments above; and b) application of at least one compound (B) as defined in any of the embodiments above; to a plant and/or the locus where the plant is growing or is intended to grow and/or the seeds from which the plant grows, wherein the application of at least one compound (A) in step a) and at least one compound (B) in step b) is carried out with a time lag of at least 1 day.

In another embodiment of the invention, the method according to the invention comprises the steps a) application of at least one compound (A) as defined in any of the embodiments above; and b) application of at least one compound (B) as defined in any of the embodiments above together with at least one compound (C) as defined in any of the embodiments above; to a plant and/or the locus where the plant is growing or is intended to grow and/or the seeds from which the plant grows wherein the application of at least one compound (A) in step a) and at least one compound (B) together with at least one compound (C) in step b) is carried out with a time lag of at least 1 day.

In yet another embodiment of the invention, the method according to the invention comprises the steps a) application of at least one compound (B) as defined in any of the embodiments above; and b) application of at least one compound (A) as defined in any of the embodiments above; to a plant and/or the locus where the plant is growing or is intended to grow and/or the seeds from which the plant grows, wherein the application of at least one compound (B) in step a) and at least one compound (a) in step b) is carried out with a time lag of at least 1 day.

In yet another embodiment of the invention, the method according to the invention comprises the steps a) application of at least one compound (B) as defined in any of the embodiments above together with at least one compound (C) as defined in any of the embodiments above; and b) application of at least one compound (A) as defined in any of the embodiments above to a plant and/or the locus where the plant is growing or is intended to grow and/or the seeds from which the plant grows; wherein the application of at least one compound (B) together with at least one compound (C) in step a) and the application of at least one compound (A) in step b) is carried out with a time lag of at least 1 day.

The plants to be treated according to the invention are selected from the group consisting of agricultural, silvicultural, ornamental and horticultural plants, each in its natural or genetically modified form, more preferably from agricultural plants.

More preferred agricultural plants are field crops, such as potatoes, sugar beets, wheat, barley, rye, oat, sorghum, rice, corn, cotton, rape, oilseed rape, canola, soybeans, peas, field beans, sunflowers, sugar cane; cucumbers, tomatoes, onions, leeks, lettuce, squashes; even more preferably the plant is selected from the group consisting of wheat, barley, oat, rye, soybean, corn, oilseed rape, cotton, sugar cane, rice and sorghum.

In an especially preferred embodiment of the current invention, the plants to be treated are selected from the group consisting of wheat, barley, oat, rye, soybean, corn, oilseed rape, canola, sunflower, cotton, sugar cane, sugar beet, rice and sorghum.

In one embodiment, the aforementioned method for reducing nitrous oxide emission from soils comprises treating the plant propagules, preferably the seeds of an agricultural, horticultural, ornamental or silivcultural plant selected from the group consisting of transgenic or non- transgenic plants. The term "plants" is to be understood as plants of economic importance and/or men-grown plants. They are preferably selected from agricultural, silvicultural and horticultural (including ornamental) plants. The term "plant" as used herein includes all parts of a plant such as germinating seeds, emerging seedlings, herbaceous vegetation as well as established woody plants including all belowground portions (such as the roots) and aboveground portions.

The term "nitrification inhibitors" is to be understood as any chemical substance which slows down or stops the nitrification process. Nitrification inhibitors retard the natural transformation of ammonium into nitrate, by inhibiting the activity of bacteria such as Nitrosomonas spp..

The term "nitrification" is to be understood as the biological oxidation of ammonia (NH3) or ammonium (NH₄ ⁺) with oxygen into nitrite (NO2^") followed by the oxidation of these nitrites into nitrates (NO3^") by microorganisms. Besides nitrate (NO3^") nitrous oxide is also produced though nitrification. Nitrification is an important step in the nitrogen cycle in soil.

The term "denitrification" is to be understood as the microbiological conversion of nitrate (NO3^") and nitrite (NO2^") to gaseous forms of nitrogen, generally N2 or N2O. This respiratory process reduces oxidized forms of nitrogen in response to the oxidation of an electron donor such as organic matter. The preferred nitrogen electron acceptors in order of most to least thermody- namically favorable include: nitrate (NO^3-), nitrite (NO^2-), nitric oxide (NO), and nitrous oxide (N2O). Within the general nitrogen cycle, denitrification completes the cycle by returning N2 to the atmosphere. The process is performed primarily by heterotrophic bacteria (such as Para- coccus denitrificans and various pseudomonads), although autotrophic denitrifiers have also been identified (e.g. Thiobacillus denitrificans). Denitrifiers are represented in all main phyloge- netic groups. When faced with a shortage of oxygen many bacterial species, are able switch from using oxygen to using nitrates to support respiration in a process known as denitrification, during which the water-soluble nitrates are converted to gaseous products, including nitrous oxide, that are emitted into the atmosphere. "Nitrous oxide", commonly known as happy gas or laughing gas, is a chemical compound with the chemical formula N2O. At room temperature, it is a colorless non-flammable gas. Nitrous oxide is produced naturally in soils through the microbial processes of nitrification and denitrification. These natural emissions of nitrous oxide can be increased by a variety of agricultural practices and activities including for example a) direct addition of nitrogen to soils by using min- eral and organic fertilizers b) growing of nitrogen-fixing crops c) cultivation of high organic content soils d) application of livestock manure to croplands and pasture.

The term "fertilizers" is to be understood as chemical compounds applied to promote plant and fruit growth. Fertilizers are typically applied either through the soil (for uptake by plant roots) or by foliar feeding (for uptake through leaves). The term "fertilizers" can be subdivided into two major categories: a) organic fertilizers (composed of decayed plant/animal matter) and b) inorganic fertilizers (composed of chemicals and minerals). Organic fertilizers include manure, slurry, worm castings, peat, seaweed, sewage, and guano. Green manure crops are also regularly grown to add nutrients (especially nitrogen) to the soil. Manufactured organic fertilizers include compost, blood meal, bone meal and seaweed extracts. Further examples are enzyme digested proteins, fish meal, and feather meal. The decomposing crop residue from prior years is another source of fertility. In addition, naturally occurring minerals such as mine rock phosphate, sulfate of potash and limestone are also considered inorganic fertilizers. Inorganic fertilizers are usually manufactured through chemical processes (such as the Haber process), also using naturally occurring deposits, while chemically altering them (e.g. concentrated triple superphosphate). Naturally occurring inorganic fertilizers include Chilean sodium nitrate, mine rock phosphate, and limestone.

"NPK fertilizer" are inorganic fertilizers formulated in appropriate concentrations and combinations comprising the three main nutrients nitrogen (N), phosphorus (P) and potassium (K).

In one embodiment, the plant to be treated according to the method of the invention is an agri- cultural plant. "Agricultural plants" are plants of which a part (e.g. seeds) or all is harvested or cultivated on a commercial scale or which serve as an important source of feed, food, fibres (e.g. cotton, linen), combustibles (e.g. wood, bioethanol, biodiesel, biomass) or other chemical compounds. Preferred agricultural plants are for example cereals, e.g. wheat, rye, barley, tritica- le, oats, sorghum or rice, beet, e.g. sugar beet or fodder beet; fruits, such as pomes, stone fruits or soft fruits, e.g. apples, pears, plums, peaches, almonds, cherries, strawberries, raspberries, blackberries or gooseberries; leguminous plants, such as lentils, peas, alfalfa or soybeans; oil plants, such as rape, oil-seed rape, canola, linseed, mustard, olives, sunflowers, coconut, cocoa beans, castor oil plants, oil palms, ground nuts or soybeans; cucurbits, such as squashes, cucumber or melons; fiber plants, such as cotton, flax, hemp or jute; citrus fruit, such as oranges, lemons, grapefruits or mandarins; vegetables, such as spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes, cucurbits or paprika; lauraceous plants, such as avocados, cinnamon or camphor; energy and raw material plants, such as corn, soybean, rape, canola, sugar cane or oil palm; tobacco; nuts; coffee; tea; bananas; vines (table grapes and grape juice grape vines); hop; turf; natural rubber plants.

In one embodiment, the plant to be treated according to the method of the invention is a horticultural plant. The term "horticultural plants" are to be understood as plants which are commonly used in horticulture - e.g. the cultivation of ornamentals, vegetables and/or fruits. Examples for ornamentals are turf, geranium, pelargonia, petunia, begonia and fuchsia. Examples for vegeta- bles are potatoes, tomatoes, peppers, cucurbits, cucumbers, melons, watermelons, garlic, onions, carrots, cabbage, beans, peas and lettuce and more preferably from tomatoes, onions, peas and lettuce. Examples for fruits are apples, pears, cherries, strawberry, citrus, peaches, apricots and blueberries. In one embodiment, the plant to be treated according to the method of the invention is an ornamental plants. "Ornamental plants" are plants which are commonly used in gardening, e.g. in parks, gardens and on balconies. Examples are turf, geranium, pelargonia, petunia, begonia and fuchsia. In one embodiment, the plant to be treated according to the method of the invention is a silvicul- tural plants. The term "silvicultural plant" is to be understood as trees, more specifically trees used in reforestation or industrial plantations. Industrial plantations generally serve for the commercial production of forest products, such as wood, pulp, paper, rubber tree, Christmas trees, or young trees for gardening purposes. Examples for silvicultural plants are conifers, like pines, in particular Pinus spec, fir and spruce, eucalyptus, tropical trees like teak, rubber tree, oil palm, willow (Salix), in particular Salix spec, poplar (cottonwood), in particular Populus spec, beech, in particular Fagus spec, birch, oil palm, and oak.

The term "locus" is to be understood as any type of environment, soil, area or material where the plant is growing or intended to grow. Especially preferred according to the invention is soil.

The term "at least one" is to be understood as 1 , 2, 3 or more of the respective compound se- lected from the group consisting of compound of formula I (compound A), fertilizer (compound B) and nitrification inhibitors (compound C).

The reduction of nitrous oxide emission is independent of the presence of pests. Accordingly, in a preferred embodiment of the method, the application of the active ingredients (compound A) and/or mixtures comprising at least one compound (A) is carried out in the absence of pest pressure.

The term "BBCH principal growth stage" refers to the extended BBCH-scale which is a system for a uniform coding of phenologically similar growth stages of all mono- and dicotyledonous plant species in which the entire developmental cycle of the plants is subdivided into clearly recognizable and distinguishable longer-lasting developmental phases. The BBCH-scale uses a decimal code system, which is divided into principal and secondary growth stages. The abbreviation BBCH derives from the Federal Biological Research Centre for Agriculture and Forestry (Germany), the Bundessortenamt (Germany) and the chemical industry.

In one embodiment of the invention, at least one compound (A) is applied at a growth stage (GS) between GS 00 and GS 65 BBCH of the plant.

In preferred embodiment of the invention, at least one compound (A) is applied at a growth stage between GS 14 and GS 55 BBCH of the plant.

In a more preferred embodiment of the invention, at least one compound (A) is applied at the growth stage between GS 14 and GS 47 BBCH of the plant.

In one embodiment of the invention, at least one fertilizer (compound B) is applied before and at sowing, before emergence, and until harvest (GS 00 to GS 89 BBCH).

In another embodiment of the invention, at least one fertilizer (compound B) is applied together with at least one nitrification inhibitor (compound C) before and at sowing, before emergence, and until harvest (GS 00 to GS 89 BBCH).

In another embodiment of the invention, at least one compound (A) is applied during leaf development to flowering (GS 14 to GS 65 BBCH) of the treated plant, provided that the application of at least one compound (A) and at least one compound (B) is carried out with a time lag of at least 1 day.

In a preferred embodiment of the invention, an agrochemical mixture comprising an ammonium- or urea-containing fertilizer (compound B) and at least one nitrification inhibitor (compound C) is applied at least once during the growth stages GS 00 to GS 89 BBCH (before sowing until harvest) while at least one compound (A) is applied at least once during the growth stages GS 14 to GS 65 BBCH (leaf development to flowering) of the treated plant, provided that the application of at least one compound (A) and at least one compound (B) is carried out with a time lag of at least 1 day.

In another embodiment of the invention, the agrochemical mixture comprising an ammonium- or urea-containing fertilizer (compound B) and at least one nitrification inhibitor (compound C) is applied before and at sowing, before emergence, and until shooting/shoot development (GS 00 to GS 33 BBCH) of the plant while at least one compound (A) is applied during leaf develop- ment to inflorescence emergence (GS 14 to GS 55 BBCH) provided that the application of at least one compound (A) and at least one compound (B) is carried out with a time lag of at least 1 day.

If an agricultural mixture comprising at least two compounds (A) according to the present inven- tion(compound of formula I and a compound II) is used in this inventive method, the plant prop- agules are preferably treated simultaneously (together or separately) or subsequently.

The subsequent application is carried out with a time interval which allows a combined action of the applied compounds. Preferably, the time interval for a subsequent application of a first compound (A) and a second compound (A) ranges from a few seconds up to 3 months, preferably, from a few seconds up to 1 month, more preferably from a few seconds up to 2 weeks, even more preferably from a few seconds up to 3 days and in particular from 1 second up to 24 hours.

In a preferred embodiment of the invention, the application according to the method of the current invention is repeatedly carried out. In one embodiment, the application is repeated two to ten times, preferably, two to five times; most preferably two times.

In one embodiment, the application of at least one compound (A) is repeatedly carried out. In another embodiment, the application of at least one compound (B) is repeatedly carried out. In yet another embodiment, the application of one compound (B) together with one compound (C) is repeatedly applied. In each case, there must be a time lag of at least 1 day between the last application of at least one compound (A) and the last application of at least one compound (B) (optionally together with at least one compound C).

As a matter of course, compounds (A), (B) and (C) and in case mixtures are employed, compounds selected from the group consisting of compounds (A), (B) and (C) are used in an effec- tive and non-phytotoxic amount. This means that they are used in a quantity which allows to obtain the desired effect but which does not give rise to any phytotoxic symptoms on the treated plant or on the plant raised from the treated propagule or treated soil. Application rates for compounds of formula I, also in seed treatment, are as defined in this application.

For the use according to the invention, the application rates of compounds (B) are between 10 kg and 300 kg of N per hectare, preferably between 50 kg and 250 kg of N per hectare.

In all embodiments, the agrochemical mixtures are applied in nitrous oxide emission from soils reducing amounts. In one embodiment, the agrochemical mixtures are applied in synergistically the nitrous oxide emission from soils reducing amounts.

In an especially preferred embodiment of the method for reducing nitrous oxide emission, com- pound (A) is applied as seed treatment.

In another especially preferred embodiment of the method for reducing nitrous oxide emission, compound (A) is applied as foliar and/or in-furrow application.

Formulations

In the methods and uses according to the invention, the compounds of formula (I) are used in the form of agrochemical compositions comprising an auxiliary and at least one compound of formula (I) according to the invention, or a stereoisomer, salt, tautomer or N-oxide thereof.

An agrochemical composition comprises a pesticidally effective amount of a compound of for- mula (I). The term "effective amount" denotes an amount of the composition or of the compounds I, which is sufficient for controlling invertebrate pests on cultivated plants or in the protection of materials and which does not result in a substantial damage to the treated plants or material. Such an amount can vary in a broad range and is dependent on various factors, such as the invertebrate (e.g. insect) species to be controlled, the treated cultivated plant or material, the climatic conditions and the specific compound I used.

The compounds I, and their stereoisomers, salts, tautomers and N-oxides, can be converted into customary types of agrochemical compositions, e. g. solutions, emulsions, suspensions, dusts, powders, pastes, granules, pressings, capsules, and mixtures thereof. Examples for composition types are suspensions (e.g. SC, OD, FS), emulsifiable concentrates (e.g. EC), emulsions (e.g. EW, EO, ES, ME), capsules (e.g. CS, ZC), pastes, pastilles, wettable powders or dusts (e.g. WP, SP, WS, DP, DS), pressings (e.g. BR, TB, DT), granules (e.g. WG, SG, GR, FG, GG, MG), insecticidal articles (e.g. LN), as well as gel formulations for the treatment of plant propagation materials such as seeds (e.g. GF). These and further compositions types are defined in the "Catalogue of pesticide formulation types and international coding system", Tech- nical Monograph No. 2, 6^th Ed. May 2008, CropLife International.

The compositions are prepared in a known manner, such as described by Mollet and Grube- mann, Formulation technology, Wiley VCH, Weinheim, 2001 ; or Knowles, New developments in crop protection product formulation, Agrow Reports DS243, T&F Informa, London, 2005.

Examples for suitable auxiliaries are solvents, liquid carriers, solid carriers or fillers, surfactants, dispersants, emulsifiers, wetters, adjuvants, solubilizers, penetration enhancers, protective colloids, adhesion agents, thickeners, humectants, repellents, attractants, feeding stimulants, compatibilizers, bactericides, anti-freezing agents, anti-foaming agents, colorants, tackifiers and binders. Suitable solvents and liquid carriers are water and organic solvents, such as mineral oil fractions of medium to high boiling point, e.g. kerosene, diesel oil; oils of vegetable or animal origin; aliphatic, cyclic and aromatic hydrocarbons, e. g. toluene, paraffin, tetrahydronaphthalene, alkylated naphthalenes; alcohols, e.g. ethanol, propanol, butanol, benzylalcohol, cyclohexanol; glycols; DMSO; ketones, e.g. cyclohexanone; esters, e.g. lactates, carbonates, fatty acid esters, gamma-butyrolactone; fatty acids; phosphonates; amines; amides, e.g. N-methylpyrrolidone, fatty acid dimethylamides; and mixtures thereof.

Suitable solid carriers or fillers are mineral earths, e.g. silicates, silica gels, talc, kaolins, limestone, lime, chalk, clays, dolomite, diatomaceous earth, bentonite, calcium sulfate, magnesium sulfate, magnesium oxide; polysaccharide powders, e.g. cellulose, starch; fertilizers, e.g. ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas; products of vegetable origin, e.g. cereal meal, tree bark meal, wood meal, nutshell meal, and mixtures thereof.

Suitable surfactants are surface-active compounds, such as anionic, cationic, nonionic and amphoteric surfactants, block polymers, polyelectrolytes, and mixtures thereof. Such surfactants can be used as emusifier, dispersant, solubilizer, wetter, penetration enhancer, protective colloid, or adjuvant. Examples of surfactants are listed in McCutcheon's, Vol.1 : Emulsifiers & Detergents, McCutcheon's Directories, Glen Rock, USA, 2008 (International Ed. or North American Ed.).

Suitable anionic surfactants are alkali, alkaline earth or ammonium salts of sulfonates, sulfates, phosphates, carboxylates, and mixtures thereof. Examples of sulfonates are alkylarylsulfonates, diphenylsulfonates, alpha-olefin sulfonates, lignine sulfonates, sulfonates of fatty acids and oils, sulfonates of ethoxylated alkylphenols, sulfonates of alkoxylated arylphenols, sulfonates of condensed naphthalenes, sulfonates of dodecyl- and tridecylbenzenes, sulfonates of naphthalenes and alkylnaphthalenes, sulfosuccinates or sulfosuccinamates. Examples of sulfates are sulfates of fatty acids and oils, of ethoxylated alkylphenols, of alcohols, of ethoxylated alcohols, or of fatty acid esters. Examples of phosphates are phosphate esters. Examples of carboxylates are alkyl carboxylates, and carboxylated alcohol or alkylphenol ethoxylates.

Suitable nonionic surfactants are alkoxylates, N-subsituted fatty acid amides, amine oxides, esters, sugar-based surfactants, polymeric surfactants, and mixtures thereof. Examples of alkoxylates are compounds such as alcohols, alkylphenols, amines, amides, arylphenols, fatty acids or fatty acid esters which have been alkoxylated with 1 to 50 equivalents. Ethylene oxide and/or propylene oxide may be employed for the alkoxylation, preferably ethylene oxide. Examples of N-subsititued fatty acid amides are fatty acid glucamides or fatty acid alkanolamides. Examples of esters are fatty acid esters, glycerol esters or monoglycerides. Examples of sugar- based surfactants are sorbitans, ethoxylated sorbitans, sucrose and glucose esters or al- kylpolyglucosides. Examples of polymeric surfactants are home- or copolymers of vinylpyrroli- done, vinylalcohols, or vinylacetate.

Suitable cationic surfactants are quaternary surfactants, for example quaternary ammonium compounds with one or two hydrophobic groups, or salts of long-chain primary amines. Suitable amphoteric surfactants are alkylbetains and imidazolines. Suitable block polymers are block polymers of the A-B or A-B-A type comprising blocks of polyethylene oxide and polypropylene oxide, or of the A-B-C type comprising alkanol, polyethylene oxide and polypropylene oxide. Suitable polyelectrolytes are polyacids or polybases. Examples of polyacids are alkali salts of polyacrylic acid or polyacid comb polymers. Examples of polybases are polyvinylamines or pol- yethyleneamines.

Suitable adjuvants are compounds, which have a neglectable or even no pesticidal activity themselves, and which improve the biological performance of the compound I on the target. Examples are surfactants, mineral or vegetable oils, and other auxilaries. Further examples are listed by Knowles, Adjuvants and additives, Agrow Reports DS256, T&F Informa UK, 2006, chapter 5.

Suitable thickeners are polysaccharides (e.g. xanthan gum, carboxymethylcellulose), anorganic clays (organically modified or unmodified), polycarboxylates, and silicates.

Suitable bactericides are bronopol and isothiazolinone derivatives such as alkylisothiazolinones and benzisothiazolinones.

Suitable anti-freezing agents are ethylene glycol, propylene glycol, urea and glycerin.

Suitable anti-foaming agents are silicones, long chain alcohols, and salts of fatty acids.

Suitable colorants (e.g. in red, blue, or green) are pigments of low water solubility and water- soluble dyes. Examples are inorganic colorants (e.g. iron oxide, titan oxide, iron hexacyanofer- rate) and organic colorants (e.g. alizarin-, azo- and phthalocyanine colorants).

Suitable tackifiers or binders are polyvinylpyrrolidone, polyvinylacetates, polyvinyl alcohols, pol- yacrylates, biological or synthetic waxes, and cellulose ethers. Examples for composition types and their preparation are:

i) Water-soluble concentrates (SL, LS)

10-60 wt% of a compound I according to the invention and 5-15 wt% wetting agent (e.g. alcohol alkoxylates) are dissolved in water and/or in a water-soluble solvent (e.g. alcohols) up to 100 wt%. The active substance dissolves upon dilution with water.

ii) Dispersible concentrates (DC)

5-25 wt% of a compound I according to the invention and 1 -10 wt% dispersant (e. g. polyvinylpyrrolidone) are dissolved in up to 100 wt% organic solvent (e.g. cyclohexanone). Dilution with water gives a dispersion.

iii) Emulsifiable concentrates (EC)

15-70 wt% of a compound I according to the invention and 5-10 wt% emulsifiers (e.g. calcium dodecylbenzenesulfonate and castor oil ethoxylate) are dissolved in up to 100 wt% water- insoluble organic solvent (e.g. aromatic hydrocarbon). Dilution with water gives an emulsion. iv) Emulsions (EW, EO, ES)

5-40 wt% of a compound I according to the invention and 1 -10 wt% emulsifiers (e.g. calcium dodecylbenzenesulfonate and castor oil ethoxylate) are dissolved in 20-40 wt% water-insoluble organic solvent (e.g. aromatic hydrocarbon). This mixture is introduced into up to 100 wt% water by means of an emulsifying machine and made into a homogeneous emulsion. Dilution with water gives an emulsion.

v) Suspensions (SC, OD, FS)

In an agitated ball mill, 20-60 wt% of a compound I according to the invention are comminuted with addition of 2-10 wt% dispersants and wetting agents (e.g. sodium lignosulfonate and alcohol ethoxylate), 0,1 -2 wt% thickener (e.g. xanthan gum) and up to 100 wt% water to give a fine active substance suspension. Dilution with water gives a stable suspension of the active sub- stance. For FS type composition up to 40 wt% binder (e.g. polyvinylalcohol) is added.

vi) Water-dispersible granules and water-soluble granules (WG, SG)

50-80 wt% of a compound I according to the invention are ground finely with addition of up to 100 wt% dispersants and wetting agents (e.g. sodium lignosulfonate and alcohol ethoxylate) and prepared as water-dispersible or water-soluble granules by means of technical appliances (e. g. extrusion, spray tower, fluidized bed). Dilution with water gives a stable dispersion or solution of the active substance.

vii) Water-dispersible powders and water-soluble powders (WP, SP, WS)

50-80 wt% of a compound I according to the invention are ground in a rotor-stator mill with addi- tion of 1 -5 wt% dispersants (e.g. sodium lignosulfonate), 1 -3 wt% wetting agents (e.g. alcohol ethoxylate) and up to 100 wt% solid carrier, e.g. silica gel. Dilution with water gives a stable dispersion or solution of the active substance.

viii) Gel (GW, GF)

In an agitated ball mill, 5-25 wt% of a compound I according to the invention are comminuted with addition of 3-10 wt% dispersants (e.g. sodium lignosulfonate), 1 -5 wt% thickener (e.g. car- boxymethylcellulose) and up to 100 wt% water to give a fine suspension of the active substance. Dilution with water gives a stable suspension of the active substance.

ix) Microemulsion (ME)

5-20 wt% of a compound I according to the invention are added to 5-30 wt% organic solvent blend (e.g. fatty acid dimethylamide and cyclohexanone), 10-25 wt% surfactant blend (e.g. alkohol ethoxylate and arylphenol ethoxylate), and water up to 100 %. This mixture is stirred for 1 h to produce spontaneously a thermodynamically stable microemulsion.

x) Microcapsules (CS)

An oil phase comprising 5-50 wt% of a compound I according to the invention, 0-40 wt% water insoluble organic solvent (e.g. aromatic hydrocarbon), 2-15 wt% acrylic monomers (e.g.

methylmethacrylate, methacrylic acid and a di- or triacrylate) are dispersed into an aqueous solution of a protective colloid (e.g. polyvinyl alcohol). Radical polymerization initiated by a radical initiator results in the formation of poly(meth)acrylate microcapsules. Alternatively, an oil phase comprising 5-50 wt% of a compound I according to the invention, 0-40 wt% water insolu- ble organic solvent (e.g. aromatic hydrocarbon), and an isocyanate monomer (e.g. diphenylme- thene-4,4'-diisocyanatae) are dispersed into an aqueous solution of a protective colloid (e.g. polyvinyl alcohol). The addition of a polyamine (e.g. hexamethylenediamine) results in the formation of a polyurea microcapsules. The monomers amount to 1 -10 wt%. The wt% relate to the total CS composition.

xi) Dustable powders (DP, DS)

1 -10 wt% of a compound I according to the invention are ground finely and mixed intimately with up to 100 wt% solid carrier, e.g. finely divided kaolin.

xii) Granules (GR, FG)

0.5-30 wt% of a compound I according to the invention is ground finely and associated with up to 100 wt% solid carrier (e.g. silicate). Granulation is achieved by extrusion, spray-drying or the fluidized bed.

xiii) Ultra-low volume liquids (UL)

1 -50 wt% of a compound I according to the invention are dissolved in up to 100 wt% organic solvent, e.g. aromatic hydrocarbon.

The compositions types i) to xiii) may optionally comprise further auxiliaries, such as 0,1 -1 wt% bactericides, 5-15 wt% anti-freezing agents, 0,1 -1 wt% anti-foaming agents, and 0,1 -1 wt% col- orants.

The agrochemical compositions generally comprise between 0.01 and 95%, preferably between 0.1 and 90%, and most preferably between 0.5 and 75%, by weight of active substance. The active substances are employed in a purity of from 90% to 100%, preferably from 95% to 100% (according to NMR spectrum).

In one embodiment, a suspoconcentration (SC) is preferred for the application in crop protection. In one sub-embodiment thereof, the SC agrochemical composition comprises between 50 to 500 g/L (grams per Litre), or between 100 and 250 g/L, or 100 g/L or 150g/L or 200g/L or 250 g/L.

In a further embodiment, the granules according to formulation type xii are especially preferred for the application in rice.

Water-soluble concentrates (LS), Suspoemulsions (SE), flowable concentrates (FS), powders for dry treatment (DS), water-dispersible powders for slurry treatment (WS), water-soluble powders (SS), emulsions (ES), emulsifiable concentrates (EC) and gels (GF) are usually employed for the purposes of treatment of plant propagation materials, particularly seeds. The compositions in question give, after two-to-tenfold dilution, active substance concentrations of from 0.01 to 60% by weight, preferably from 0.1 to 40% by weight, in the ready-to-use preparations. Appli- cation can be carried out before or during sowing. Methods for applying or treating compound I and compositions thereof, respectively, on to plant propagation material, especially seeds include dressing, coating, pelleting, dusting, soaking and in-furrow application methods of the propagation material. Preferably, compound I or the compositions thereof, respectively, are applied on to the plant propagation material by a method such that germination is not induced, e. g. by seed dressing, pelleting, coating and dusting.

When employed in plant protection, the amounts of active substances applied are, depending on the kind of effect desired, from 0.001 to 2 kg per ha, preferably from 0.001 to 1 kg per ha, more preferably from 0.005 to 0.9 kg per ha, in particular from 0.005 to 0.5 kg per ha.

In treatment of plant propagation materials such as seeds, e. g. by dusting, coating or drenching seed, amounts of active substance of from 0.1 to 1000 g, preferably from 0.1 to 300 g, more preferably from 0.1 to 100 g and most preferably from 0.25 to 100 g, per 100 kilogram of plant propagation material (preferably seed) are generally required.

When used in the protection of materials or stored products, the amount of active substance applied depends on the kind of application area and on the desired effect. Amounts customarily applied in the protection of materials are 0.001 g to 2 kg, preferably 0.005 g to 1 kg, of active substance per cubic meter of treated material. Various types of oils, wetters, adjuvants, fertilizer, or micronutrients, and other pesticides (e.g. herbicides, insecticides, fungicides, growth regulators, safeners) may be added to the active substances or the compositions comprising them as premix or, if appropriate not until immediately prior to use (tank mix). These agents can be admixed with the compositions according to the invention in a weight ratio of 1 : 100 to 100: 1 , preferably 1 : 10 to 10: 1.

The user applies the composition according to the invention usually from a predosage device, a knapsack sprayer, a spray tank, a spray plane, or an irrigation system. Usually, the agrochemical composition is made up with water, buffer, and/or further auxiliaries to the desired applica- tion concentration and the ready-to-use spray liquor or the agrochemical composition according to the invention is thus obtained. Usually, 20 to 2000 liters, preferably 50 to 400 liters, of the ready-to-use spray liquor are applied per hectare of agricultural useful area.

According to one embodiment, individual components of the composition according to the invention such as parts of a kit or parts of a binary or ternary mixture may be mixed by the user himself in a spray tank and further auxiliaries may be added, if appropriate.

In a further embodiment, either individual components of the composition according to the invention or partially premixed components, e. g. components comprising compounds I and/or active substances , e.g. from the groups M or F, may be mixed by the user in a spray tank and further auxiliaries and additives may be added, if appropriate.

In a further embodiment, either individual components of the composition according to the invention or partially premixed components, e. g. components comprising compounds I and/or active substances from the group M or F, can be applied jointly (e.g. after tank mix) or consecutively.

Mixtures

In the methods and uses according to the invention, the compounds of the present invention, including their stereoisomers, salts, tautomers and N-oxides, may be applied with other active ingredients, for example with other pesticides, insecticides, herbicides, fertilizers such as ammonium nitrate, urea, potash, and superphosphate, phytotoxicants and plant growth regulators, safeners and nematicides. These additional ingredients may be used sequentially or in combination with the above-described compositions, if appropriate also added only immediately prior to use (tank mix). For example, the plant(s) may be sprayed with a

composition of this invention either before or after being treated with other active ingredients. In a particular embodiment of the invention, in the methods and uses according to the invention, the compound of formula I is combined with one or more other pesticidally active compound(s) II selected from insecticides or fungicides.

Therefore, the present invention also relates to methods and uses, wherein a mixture or composition comprising at least one compound of formula (I), or a stereoisomer, tautomer , N-oxide or agriculturally or veterinarily acceptable salt thereof, and at least one further pesticide.

The compounds of formula (I), and their stereoisomers, salts, tautomers and N-oxides, may be applied with other insecticides as compound II, which are listed in the following categorized list M of pesticides, which are, whenever possible, classified according to the Insecticide Resistance Action Committee (IRAC).

M.1 Acetylcholine esterase (AChE) inhibitors from the class of

M.1 A carbamates, for example aldicarb, alanycarb, bendiocarb, benfuracarb, butocarboxim, butoxycarboxim, carbaryl, carbofuran, carbosulfan, ethiofencarb, fenobucarb, formetanate, furathiocarb, isoprocarb, methiocarb, methomyl, metolcarb, oxamyl, pirimicarb, propoxur, thiodi- carb, thiofanox, trimethacarb, XMC, xylylcarb and triazamate; or from the class of

M.1 B organophosphates, for example acephate, azamethiphos, azinphos-ethyl, azinphosme- thyl, cadusafos, chlorethoxyfos, chlorfenvinphos, chlormephos, chlorpyrifos, chlorpyrifos-methyl, coumaphos, cyanophos, demeton-S-methyl, diazinon, dichlorvos/ DDVP, dicrotophos, dimetho- ate, dimethylvinphos, disulfoton, EPN, ethion, ethoprophos, famphur, fenamiphos, fenitrothion, fenthion, fosthiazate, heptenophos, imicyafos, isofenphos, isopropyl O- (methoxyaminothio- phosphoryl) salicylate, isoxathion, malathion, mecarbam, methamidophos, methidathion, mevinphos, monocrotophos, naled, omethoate, oxydemeton-methyl, parathion, parathion- methyl, phenthoate, phorate, phosalone, phosmet, phosphamidon, phoxim, pirimiphos- methyl, profenofos, propetamphos, prothiofos, pyraclofos, pyridaphenthion, quinalphos, sulfotep, tebupi- rimfos, temephos, terbufos, tetrachlorvinphos, thiometon, triazophos, trichlorfon and vamidothi- on;

M.2. GABA-gated chloride channel antagonists such as:

M.2A cyclodiene organochlorine compounds, as for example endosulfan or chlordane; or M.2B fiproles (phenylpyrazoles), as for example ethiprole, fipronil, flufiprole, pyrafluprole and pyriprole;

M.3 Sodium channel modulators from the class of

M.3A pyrethroids, for example acrinathrin, allethrin, d-cis-trans allethrin, d-trans allethrin, bifen- thrin, bioallethrin, bioallethrin S-cylclopentenyl, bioresmethrin, cycloprothrin, cyfluthrin, beta- cyfluthrin, cyhalothrin, lambda-cyhalothrin, gamma-cyhalothrin, cypermethrin, alpha- cypermethrin, beta-cypermethrin, theta-cypermethrin, zeta-cypermethrin, cyphenothrin, del- tamethrin, empenthrin, esfenvalerate, etofenprox, fenpropathrin, fenvalerate, flucythrinate, flumethrin, tau-fluvalinate, halfenprox, imiprothrin, meperfluthrin,metofluthrin, momfluorothrin, permethrin, phenothrin, prallethrin, profluthrin, pyrethrin (pyrethrum), resmethrin, silafluofen, tefluthrin, tetramethylfluthrin, tetramethrin, tralomethrin and transfluthrin; or

M.3B sodium channel modulators such as DDT or methoxychlor;

M.4 Nicotinic acetylcholine receptor agonists (nAChR) from the class of

M.4A neonicotinoids, for example acteamiprid, chlothianidin, dinotefuran, imidacloprid, niten- pyram, thiacloprid and thiamethoxam; or the compounds

M.4A.1 : 1 -[(6-chloro-3-pyridinyl)methyl]-2,3,5,6,7,8-hexahydro-9-nitro-(5S,8R)-5,8-epoxy-1 H- imidazo[1 ,2-a]azepine; or

M.4A.2: 1 -[(6-chloro-3-pyridyl)methyl]-2-nitro-1 -[(E)-pentylideneamino]guanidine; or M.4A.3: 1 -[(6-chloro-3-pyndyl)methyl]-7-methyl-8-nitro-5-propoxy-3,5,67-tetrahydro-2H- imidazo[1 ,2-a]pyridine; or

M.4B nicotine. M.5 Nicotinic acetylcholine receptor allosteric activators from the class of spinosyns, for example spinosad or spinetoram;

M.6 Chloride channel activators from the class of avermectins and milbemycins, for example abamectin, emamectin benzoate, ivermectin, lepimectin or milbemectin;

M.7 Juvenile hormone mimics, such as

M.7A juvenile hormone analogues as hydroprene, kinoprene and methoprene; or others as

M.7B fenoxycarb, or

M.7C pyriproxyfen;

M.8 miscellaneous non-specific (multi-site) inhibitors, for example

M.8A alkyl halides as methyl bromide and other alkyl halides, or

M.8B chloropicrin, or

M.8C sulfuryl fluoride, or

M.8D borax, or

M.8E tartar emetic;

M.9 Selective homopteran feeding blockers, for example

M.9B pymetrozine, or

M.9C flonicamid;

M.10 Mite growth inhibitors, for example

M.10A clofentezine, hexythiazox and diflovidazin, or

M.10B etoxazole; M.1 1 Microbial disruptors of insect midgut membranes, for example bacillus thuringiensis or bacillus sphaericus and the insecticdal proteins they produce such as bacillus thuringiensis subsp. israelensis, bacillus sphaericus, bacillus thuringiensis subsp. aizawai, bacillus thuringiensis subsp. kurstaki and bacillus thuringiensis subsp. tenebrionis, or the Bt crop proteins: CrylAb, CrylAc, Cryl Fa, Cry2Ab, mCry3A, Cry3Ab, Cry3Bb and Cry34/35Ab1 ;

M.12 Inhibitors of mitochondrial ATP synthase, for example

M.12A diafenthiuron, or

M.12B organotin miticides such as azocyclotin, cyhexatin or fenbutatin oxide, or M.12C pro- pargite, or

M.12D tetradifon;

M.13 Uncouplers of oxidative phosphorylation via disruption of the proton gradient, for example chlorfenapyr, DNOC or sulfluramid; M.14 Nicotinic acetylcholine receptor (nAChR) channel blockers, for example nereistoxin analogues as bensultap, cartap hydrochloride, thiocyclam or thiosultap sodium;

M.15 Inhibitors of the chitin biosynthesis type 0, such as benzoylureas as for example bistriflu- ron, chlorfluazuron, diflubenzuron, flucycloxuron, flufenoxuron, hexaflumuron, lufenuron, novalu- ron, noviflumuron, teflubenzuron or triflumuron;

M.16 Inhibitors of the chitin biosynthesis type 1 , as for example buprofezin; M.17 Moulting disruptors, Dipteran, as for example cyromazine;

M.18 Ecdyson receptor agonists such as diacylhydrazines, for example methoxyfenozide, tebufenozide, halofenozide, fufenozide or chromafenozide;

M.19 Octopamin receptor agonists, as for example amitraz;

M.20 Mitochondrial complex III electron transport inhibitors, for example

M.20A hydramethylnon, or

M.20B acequinocyl, or

M.20C fluacrypyrim;

M.21 Mitochondrial complex I electron transport inhibitors, for example

M.21 A METI acaricides and insecticides such as fenazaquin, fenpyroximate, pyrimidifen, pyridaben, tebufenpyrad or tolfenpyrad, or

M.21 B rotenone;

M.22 Voltage-dependent sodium channel blockers, for example

M.22A indoxacarb, or

M.22B metaflumizone; or

M.22C 1 -[(E)-[2-(4-cyanophenyl)-1 -[3-(trifluoromethyl)phenyl]ethylidene]amino]-3-[4- (difluoromethoxy)phenyl]urea;

M.23 Inhibitors of the of acetyl CoA carboxylase, such as Tetronic and Tetramic acid derivatives, for example spirodiclofen, spiromesifen or spirotetramat; M.24 Mitochondrial complex IV electron transport inhibitors, for example

M.24A phosphine such as aluminium phosphide, calcium phosphide, phosphine or

zinc phosphide, or

M.24B cyanide. M.25 Mitochondrial complex II electron transport inhibitors, such as beta-ketonitrile derivatives, for example cyenopyrafen or cyflumetofen;

M.26 Ryanodine receptor-modulators from the class of diamides, as for example flubendiamide, chlorantraniliprole (rynaxypyr®), cyantraniliprole (cyazypyr®), or the phthalamide compounds

M.26.1 : (R)-3-Chlor-N 1 -{2-methyl-4-[1 ,2,2,2 -tetrafluor-1 -(trifluormethyl)ethyl]phenyl}-N2-(1 - methyl-2-methylsulfonylethyl)phthalamid and

M.26.2: (S)-3-Chlor-N1 -{2-methyl-4-[1 ,2,2,2 -tetrafluor-1 -(trifluormethyl)ethyl]phenyl}-N2-(1 - methyl-2-methylsulfonylethyl)phthalamid, or the compound

M.26.3: 3-bromo-N-{2-bromo-4-chloro-6-[(1 -cyclopropylethyl)carbamoyl]phenyl}-1 -(3- chlorpyridin-2-yl)-1 H-pyrazole-5-carboxamide (proposed ISO name: cyclaniliprole), or the compound

M.26.4: methyl-2-[3,5-dibromo-2-({[3-bromo-1 -(3-chlorpyridin-2-yl)-1 H-pyrazol-5- yl]carbonyl}amino)benzoyl]-1 ,2-dimethylhydrazinecarboxylate; or a compound selected from M.26.5a) to M.26.5d):

M.26.5a: N-[2-(5-amino-1 ,3,4-thiadiazol-2-yl)-4-chloro-6-methyl-phenyl]-5-bromo-2-(3-chloro- 2-pyridyl)pyrazole-3-carboxamide;

M.26.5b: 5-chloro-2-(3-chloro-2-pyridyl)-N-[2,4-dichloro-6-[(1 -cyano-1 -methyl- ethyl)carbamoyl]phenyl]pyrazole-3-carboxamide;

M.26.5c: 5-bromo-N-[2,4-dichloro-6-(methylcarbamoyl)phenyl]-2-(3,5-dichloro-2- pyridyl)pyrazole-3-carboxamide;

M.26.5d: N-[2-(tert-butylcarbamoyl)-4-chloro-6-methyl-phenyl]-2-(3-chloro-2-pyridyl)-5- (fluoromethoxy)pyrazole-3-carboxamide; or

M.26.6: N2-(1 -cyano-1 -methyl-ethyl)-N1 -(2,4-dimethylphenyl)-3-iodo-phthalamide; or M.26.7: 3-chloro-N2-(1 -cyano-1 -methyl-ethyl)-N1 -(2,4-dimethylphenyl)phthalamide;

M.X insecticidal active compounds of unknown or uncertain mode of action, as for example afidopyropen, azadirachtin, amidoflumet, benzoximate, bifenazate, bromopropylate, chinome- thionat, cryolite, dicofol, flufenerim, flometoquin, fluensulfone, flupyradifurone, piperonyl butox- ide, pyridalyl, pyrifluquinazon, sulfoxaflor, pyflubumide, or the compounds

M.X.1 : 4-[5-(3,5-Dichloro-phenyl)-5-trifluoromethyl-4,5-dihydro-isoxazol-3-yl]-2-methyl-N-[(2,2,2- trifluoro-ethylcarbamoyl)-methyl]-benzamide, or the compound

M.X.2: cyclopropaneacetic acid, 1 ,1 '-[(3S,4R,4aR,6S,6aS,12R,12aS,12bS)-4-[[(2- cyclopropylacetyl)oxy]methyl]-1 ,3,4,4a,5,6,6a,12,12a,12b-decahydro-12-hydroxy-4,6a,12b- trimethyl-1 1 -oxo-9-(3-pyridinyl)-2H,1 1 H-naphtho[2,1 -b]pyrano[3,4-e]pyran-3,6-diyl] ester, or the compound

M.X.3: 1 1 -(4-chloro-2,6-dimethylphenyl)-12-hydroxy-1 ,4-dioxa-9-azadispiro[4.2.4.2]-tetradec-1 1 - en-10-one, or the compound

M.X.4: 3-(4'-fluoro-2,4-dimethylbiphenyl-3-yl)-4-hydroxy-8-oxa-1 -azaspiro[4.5]dec-3-en-2-one, or the compound

M.X.5: 1 -[2-fluoro-4-methyl-5-[(2,2,2-trifluoroethyl)sulfinyl]phenyl]-3-(trifluoromethyl)-1 H-1 ,2,4- triazole-5-amine, or actives on basis of bacillus firmus (Votivo, 1-1582), or

M.X.6: a compound selected from the group of

M.X.6a: (E/Z)-N-[1 -[(6-chloro-3-pyridyl)methyl]-2-pyridylidene]-2,2,2-trifluoro-acetamide;

M.X.6b: (E/Z)-N-[1 -[(6-chloro-5-fluoro-3-pyridyl)methyl]-2-pyridylidene]-2,2,2-trifluoro-acetamide; M.X.6c: (E/Z)-2,2,2-trifluoro-N-[1 -[(6-fluoro-3-pyridyl)methyl]-2-pyridylidene]acetamide; M.X.6d: (E/Z)-N-[1 -[(6-bromo-3-pyridyl)methyl]-2-pyridylidene]-2,2,2-trifluoro-acetamide;

M.X.6e: (E/Z)-N-[1 -[1 -(6-chloro-3-pyridyl)ethyl]-2-pyridylidene]-2,2,2-trifluoro-acetamide;

M.X.6f: (E/Z)-N-[1 -[(6-chloro-3-pyndyl)methyl]-2-pyridylidene]-2,2-difluoro-acetamide;

M.X.6g: (E/Z)-2-chloro-N-[1 -[(6-chloro-3-pyridyl)methyl]-2-pyridylidene]-2,2-difluoro-acetamide; M.X.6h: (E/Z)-N-[1 -[(2-chloropyrimidin-5-yl)methyl]-2-pyridylidene]-2,2,2-trifluoro-acetamide and Μ.Χ.6Ϊ: (E/Z)-N-[1 -[(6-chloro-3-pyridyl)methyl]-2-pyridylidene]-2,2,3,3,3-pentafluoro- propanamide); or

M.X.7: triflumezopyrim; or

M.X.8: 4-[5-[3-chloro-5-(trifluoromethyl)phenyl]-5-(trifluoromethyl)-4H-isoxazol-3-yl]-N-[2- oxo-2-(2,2,2-trifluoroethylamino)ethyl]naphthalene-1 -carboxamide, or

M.X.9: 3-[3-chloro-5-(trifluoromethyl)phenyl]-4-oxo-1 -(pyrimidin-5-ylmethyl)pyrido[1 ,2- a]pyrimidin-1 -ium-2-olate; or

M.X.10: 8-chloro-N-[2-chloro-5-methoxyphenyl)sulfonyl]-6-trifluoromethyl)-imidazo[1 ,2- a]pyridine-2-carboxamide; or

M.X.1 1 : 4-[5-(3,5-dichlorophenyl)-5-(trifluoromethyl)-4H-isoxazol-3-yl]-2-methyl-N-(1 - oxothietan-3-yl)benzamide; or

M.X.12: 5-[3-[2,6-dichloro-4-(3,3-dichloroallyloxy)phenoxy]propoxy]-1 H-pyrazole; or M.Y Biopesticides, e.g.

M.Y-1 : Microbial pesticides with insecticidal, acaricidal, molluscidal and/or nematicidal activity: Bacillus firmus, B. thuringiensis ssp. israelensis, B. t. ssp. galleriae, B. t. ssp. kurstaki, Beauveria bassiana, Burkholderia sp., Chromobacterium sub-tsugae, Cydia pomonella granulosis virus, Isaria fumosorosea, Lecanicillium longisporum, L. muscarium (formerly Verticillium lecanii), Metarhizium an-isopliae, M. anisopliae var. acridum, Paecilomyces fumosoroseus, P. lilacinus, Paenibacillus poppiliae, Pasteuria spp., P. nishizawae, P. reneformis, P. us-agae, Pseudomonas fluorescens, Steinernema feltiae, Streptomces galbus;

M.Y-2) Biochemical pesticides with insecticidal, acaricidal, molluscidal, pheromone and/or nematicidal activity: L-carvone, citral, (E,Z)-7,9-dodecadien-1 -yl ace-tate, ethyl formate, (E,Z)- 2,4-ethyl decadienoate (pear ester), (Z,Z,E)-7,1 1 ,13-hexadecatrienal, heptyl butyrate, isopropyl myristate, lavanulyl senecioate, 2-methyl 1 -butanol, methyl eugenol, methyl jasmonate, (E,Z)- 2,13-octadecadien-1 -ol, (E,Z)-2,13-octadecadien-1 -ol acetate, (E,Z)-3,13-octadecadien-1 -ol, R- 1 -octen-3-ol, pentatermanone, potassium silicate, sorbitol actanoate, (E,Z,Z)-3,8,1 1 - tetradecatrienyl acetate, (Z,E)-9,12-tetradecadien-1 -yl acetate, Z-7-tetradecen-2-one, Z-9- tetradecen-1 -yl acetate, Z-1 1 -tetradecenal, Z-1 1 -tetradecen-1 -ol, Acacia negra extract, extract of grapefruit seeds and pulp, extract of Chenopodium ambrosiodae, Catnip oil, Neem oil, Quillay extract, Ta-getes oil.

The commercially available compounds of the group M listed above may be found in The Pesticide Manual, 15th Edition, C. D. S. Tomlin, British Crop Protection Council (201 1 ) among other publications.

The quinoline derivative flometoquin is shown in WO2006/013896. The aminofuranone compounds flupyradifurone is known from WO 2007/1 15644. The sulfoximine compound sulfoxaflor is known from WO2007/149134. The pyrethroid momfluorothrin is known from US6908945. The pyrazole acaricide pyflubumide is known from WO2007/020986. The isoxazoline compound M.X.1 has been described in WO2005/085216, M.X.8 in WO2009/002809 and in

WO201 1/149749 and the isoxazoline M.X.1 1 in WO2013/050317. The pyripyropene derivative M.X.2 has been described in WO 2006/129714. The spiroketal-substituted cyclic ketoenol de- rivative M.X.3 is known from WO2006/089633 and the biphenyl-substituted spirocyclic ke-toenol derivative M.X.4 from WO2008/06791 1. Triazoylphenylsulfide like M.X.5 have been described in WO2006/043635 and biological control agents on basis of bacillus firmus in WO2009/124707. The neonicotionids M4A.1 is known from WO20120/069266 and WO201 1/06946, the M.4A.2 from WO2013/003977, the M4A.3.from WO2010/069266. The metaflumizone analogue M.22C is described in CN 10171577.

Cyantraniliprole (Cyazypyr) is known from e.g. WO 2004/067528. The phthalamides M.26.1 and M.26.2 are both known from WO 2007/101540. The anthranilamide M.26.3 has been described in WO 2005/077934. The hydrazide compound M.26.4 has been described in WO

2007/043677. The anthranilamide M.26.5a) is described in WO201 1/085575, the M.26.5b) in WO2008/134969, the M.26.5c) in US201 1/046186 and the M.26.5d in WO2012/034403. The diamide compounds M.26.6 and M.26.7 can be found in CN102613183.

The compounds M.X.6a) to Μ.Χ.6Ϊ) listed in M.X.6 have been described in WO2012/029672. The mesoionic antagonist compound M.X.9 was described in WO2012/0921 15, the nemati-cide M.X.10 in WO2013/055584 and the Pyridalyl-type analogue M.X.12 in WO2010/060379.

Biopesticides

The biopesticides from group M.Y, and from group F.XIII) as described below, their preparation and their biological activity e.g. against harmful fungi, pests is known (e-Pesticide Manual V 5.2 (ISBN 978 1 901396 85 0) (2008-201 1 ); http://www.epa.gov/opp00001/biopesticides/, see product lists therein; http://www.omri.org/omri-lists, see lists therein; Bio-Pesticides Database BPDB http://sitem.herts.ac.uk/aeru/bpdb/, see A to Z link therein). Many of these biopesticides are registered and/or are commercially available: aluminium silicate (SCREEN™ DUO from Certis LLC, USA), Ampelomyces quisqualis M-10 (e.g. AQ 10® from Intrachem Bio GmbH & Co. KG, Germany), Ascophyllum nodosum (Norwegian kelp, Brown kelp) extract (e.g. ORKA GOLD from Becker Underwood, South Africa), Aspergillus flavus NRRL 21882 (e.g. AFLA-GUARD® from Syngenta, CH), Aureobasidium pullulans (e.g. BOTECTOR® from bio-ferm GmbH, Germany), Azospirillum brasilense XOH (e.g. AZOS from Xtreme Gardening, USA USA or RTI Reforestation Technologies International; USA), Bacillus amyloliquefaciens IT-45 (CNCM I 3800, NCBI 1091041 ) (e.g. RHIZOCELL C from ITHEC, France), B. amyloliquefaciens subsp. plantarum MBI600 (NRRL B-50595, deposited at United States Department of Agriculture) (e.g. INTE- GRAL®, CLARITY, SUBTILEX NG from Becker Underwood, USA), B. pumilus QST 2808 (NRRL Accession No. B 30087) (e.g. SONATA® and BALLAD® Plus from AgraQuest Inc., USA), B. subtilis GB03 (e.g. KODIAK from Gustafson, Inc., USA), B. subtilis GB07 (EPIC from Gustafson, Inc., USA), B. subtilis QST-713 (NRRL-Nr. B 21661 in RHAPSODY®, SERENADE® MAX and SERENADE® ASO from Agra-Quest Inc., USA), B. subtilis var. amylolique-'faciens FZB24 (e.g. TAEGRO® from Novozyme Biologicals, Inc., USA), B. subtilis var. amyloliquefaciens D747 (e.g. Double Nickel 55 from Certis LLC, USA), Bacillus thuringiensis ssp. kurstaki SB4 (e.g. BETA PRO® from Becker Underwood, South Africa), Beauveria bassiana GHA (BOTANIGARD® 22WGP from Laverlam Int. Corp., USA), B. bassiana 12256 (e.g. BIOEX- PERT® SC from Live Sytems Technology S.A., Colombia), B. bassiana PRPI 5339 (ARSEF number 5339 in the USDA ARS collection of entomopathogenic fungal cultures) (e.g.

BROADBAND® from Becker Underwood, South Africa), Bradyrhizobium sp. (e.g. VAULT® from Becker Underwood, USA), B. japonicum (e.g. VAULT® from Becker Underwood, USA), Candida oleophila 1-82 (e.g. ASPIRE® from Ecogen Inc., USA), Candida saitoana (e.g. BIO- CURE® (in mixture with lysozyme) and BIOCOAT® from Micro Flo Company, USA (BASF SE) and Arysta), Chitosan (e.g. ARMOUR-ZEN from BotriZen Ltd., NZ), Clonostachys rosea f. ca- tenulata, also named Gliocladium catenulatum (e.g. isolate J1446: PRESTOP® from Verdera, Finland), Coniothyrium minitans CON/M/91 -08 (e.g. Contans® WG from Prophyta, Germany), Cryphonectria parasitica (e.g. Endothia parasitica from CNICM, France), Cryptococcus albidus (e.g. YIELD PLUS® from Anchor Bio-Technologies, South Africa), Ecklonia maxima (kelp) extract (e.g. KELPAK SL from Kelp Products Ltd, South Africa), Fusarium oxysporum (e.g. BIO- FOX® from S.I.A.P.A., Italy, FUSACLEAN® from Natural Plant Protection, France), Glomus intraradices (e.g. MYC 4000 from ITHEC, France), Glomus intraradices RTI-801 (e.g. MYKOS from Xtreme Gardening, USA or RTI Reforestation Technologies International; USA), grapefruit seeds and pulp extract (e.g. BC-1000 from Chemie S.A., Chile), Isaria fumosorosea Apopka-97 (ATCC 20874) (PFR-97™ from Certis LLC, USA), Lecanicillium muscarium (formerly Verticillium lecanii) (e.g. MYCOTAL from Koppert BV, Netherlands), Lecanicillium longisporum KV42 and KV71 (e.g. VERTALEC® from Koppert BV, Netherlands), Metarhizium anisopliae var. acridum IMI 330189 (deposited in European Culture Collections CABI) (e.g. GREEN MUSCLE® from Becker Underwood, South Africa), M. anisopliae FI-1045 (e.g. BIOCANE® from Becker Underwood Pty Ltd, Australia), M. anisopliae var. acridum FI-985 (e.g. GREEN GUARD® SC from Becker Underwood Pty Ltd, Australia), M. anisopliae F52 (e.g. MET52® Novozymes Biologicals BioAg Group, Canada), M. anisopliae ICIPE 69 (e.g. METATHRhPOL from ICIPE, Kenya), Metschnikowia fructicola (e.g. SHEMER® from Agrogreen, Israel), Microdochium dimerum (e.g. ANTIBOT® from Agrauxine, France), Neem oil (e.g. TRILOGY®, TRIACT® 70 EC from Certis LLC, USA), Paecilomyces fumosoroseus strain FE 9901 (e.g. NO FLY™ from Natural Industries, Inc., USA), P. lilacinus DSM 15169 (e.g. NEMATA® SC from Live Systems Technology S.A., Colombia), P. lilacinus BCP2 (e.g. PL GOLD from Becker Underwood BioAg SA Ltd, South Africa), mixture of Paenibacillus alvei NAS6G6 and Bacillus pumilis (e.g. BAC-UP from Becker Underwood South Africa), Penicillium bilaiae (e.g. JUMP START® from Novozymes Biologicals BioAg Group, Canada), Phlebiopsis gigantea (e.g. ROTSTOP® from Verdera, Finland), potassium silicate (e.g. Sil-MATRIX™ from Certis LLC, USA), Pseudozyma flocculosa (e.g. SPORODEX® from Plant Products Co. Ltd., Canada), Pythium oligandrum DV74 (e.g. POLYVERSUM® from Remeslo SSRO, Biopreparaty, Czech Rep.), Reynoutria sachlinensis extract (e.g. REGALIA® from Marrone Biolnnovations, USA), Rhizobium leguminosarum bv. phaseolii (e.g. RHIZO-STICK from Becker Underwood, USA), R. I. trifolii (e.g. DORMAL from Becker Underwood, USA), R. I. bv. viciae (e.g. NODULATOR from Becker Underwood, USA), Sinorhizobium meliloti (e.g. DORMAL ALFALFA from Becker Underwood, USA; NITRAGIN® Gold from Novozymes Biologicals BioAg Group, Canada), Steinernema feltiae (NE-

MA->SHIELD® from BioWorks, Inc., USA), Streptomyces lydicus WYEC 108 (e.g. Actinovate® from Natural Industries, Inc., USA, US 5,403,584), S. violaceusniger YCED-9 (e.g. DT-9® from Natural Industries, Inc., USA, US 5,968,503), Talaromyces flavus V1 17b (e.g. PROTUS® from Prophyta, Germany), Trichoderma asperellum SKT-1 (e.g. ECO-HOPE® from Kumiai Chemical Industry Co., Ltd., Japan), T. atroviride LC52 (e.g. SENTINEL® from Agrimm Technologies Ltd, NZ), T. fertile JM41 R (e.g. RICHPLUS™ from Becker Underwood Bio Ag SA Ltd, South Africa), T. harzianum T-22 (e.g. PLANTSHIELD® der Firma BioWorks Inc., USA), T. harzianum TH 35 (e.g. ROOT PRO® from Mycontrol Ltd., Israel), T. harzianum T-39 (e.g. TRICHODEX® and TRICHODERMA 2000® from Mycontrol Ltd., Israel and Makhteshim Ltd., Israel), T. harzianum and T. viride (e.g. TRICHOPEL from Agrimm Technologies Ltd, NZ), T. harzianum ICC012 and T. viride ICC080 (e.g. REMEDIER® WP from Isagro Ricerca, Italy), T. polysporum and T. harzianum (e.g. BINAB® from BINAB Bio-Innovation AB, Sweden), T. stromaticum (e.g. TRICO- VAB® from C.E.P.L.A.C., Brazil), T. virens GL-21 (also named Gliocladium virens) (e.g. SOIL- GARD® from Certis LLC, USA), T. viride (e.g. TRIECO® from Ecosense Labs. (India) Pvt. Ltd., Indien, BIO-CURE® F from T. Stanes & Co. Ltd., Indien), T. viride TV1 (e.g. T. viride TV1 from Agribiotec srl, Italy), Ulocladium oudemansii HRU3 (e.g. BOTRY-ZEN® from Botry-Zen Ltd, NZ), Bacillus amyloliquefaciens AP-136 (NRRL B-50614), B. amyloliquefaciens AP-188 (NRRL B-50615), B. amyloliquefaciens AP-218 (NRRL B-50618), B. amyloliquefaciens AP-219 (NRRL B-50619), B. amyloliquefaciens AP-295 (NRRL B-50620), B. mojavensis AP-209 (No. NRRL B- 50616), B. solisalsi AP-217 (NRRL B-50617), B. pumilus strain INR-7 (otherwise referred to as BU-F22 (NRRL B-50153) and BU-F33 (NRRL B-50185)), B. simplex ABU 288 (NRRL B-50340) and B. amyloliquefaciens subsp. plantarum MBI600 (NRRL B-50595) have been mentioned i.a. in US patent appl. 20120149571 , WO 2012/079073. Beauveria bassiana DSM 12256 is known from US200020031495. Bradyrhizobium japonicum USDA is known from US patent 7,262,151. Sphaerodes mycoparasitica IDAC 301008-01 (IDAC = International Depositary Authority of Canada Collection) is known from WO 201 1/022809.

Bacillus amyloliquefaciens subsp. plantarum MBI600 having the accession number NRRL B- 50595 is deposited with the United States Department of Agriculture on Nov. 10, 201 1 under the strain designation Bacillus subtilis 1430. It has also been deposited at The National Collections of Industrial and Marine Bacteria Ltd. (NCIB), Torry Research Station, P.O. Box 31 , 135 Abbey Road, Aberdeen, AB9 8DG, Scotland. under accession number 1237 on December 22, 1986. Bacillus amyloliquefaciens MBI600 is known as plant growth-promoting rice seed treatment from Int. J. Microbiol. Res. ISSN 0975-5276, 3(2) (201 1 ), 120-130 and further described e.g. in US 2012/0149571 A1 . This strain MBI600 is commercially available as liquid formulation product Integral® (Becker-Underwood Inc., USA). Recently, the strain MBI 600 has been reclassified as Bacillus amyloliquefaciens subsp. plantarum based on polyphasic testing which combines classical microbiological methods relying on a mixture of traditional tools (such as culture-based methods) and molecular tools (such as genotyping and fatty acids analysis).

Thus, Bacillus subtilis MBI600 (or MBI 600 or MBI-600) is identical to Bacillus amyloliquefaciens subsp. plantarum MBI600, formerly Bacillus subtilis MBI600.

Metarhizium anisopliae IMI33 is commercially available from Becker Underwood as product Green Guard. M. anisopliae var acridium strain IMI 330189 (NRRL-50758) is commercially available from Becker Underwood as product Green Muscle.

Bacillus subtilis strain FB17 was originally isolated from red beet roots in North America (System Appl. Microbiol 27 (2004) 372-379). This Bacillus subtilis strain promotes plant health (US 2010/0260735 A1 ; WO 201 1/109395 A2). B. subtilis FB17 has also been deposited at American Type Culture Collection (ATCC), Manassas, VA, USA, under accession number PTA-1 1857 on April 26, 201 1. Bacillus subtilis strain FB17 may also be referred to as UD1022 or UD10-22.

According to one embodiment of the inventive mixtures, the at least one biopesticide II is se- lected from the groups M.Y-1 to M.Y-2:

M.Y-1 : Microbial pesticides with insecticidal, acaricidal, molluscidal and/or nematicidal activity:

Bacillus firmus St 1582, B. thuringiensis ssp. israelensis SUM-6218, B. t. ssp. galleriae SDS-502, B. t. ssp. kurstaki, Beauveria bassiana GHA, B. bassiana H123, B. bassiana DSM 12256, B. bassiana PRPI 5339, Burkholderia sp. A396, Chromobacterium sub- tsugae PRAA4-1 T, Cydia pomonella granulosis virus isolate V22, Isaria fumosorosea

Apopka-97, Lecanicillium longisporum KV42, L. longisporum KV71 , L. muscarium (formerly Verticillium lecanii), Metarhizium anisopliae FI-985, M. anisopliae FI-1045, M. an- isopliae F52, M. anisopliae ICIPE 69, M. anisopliae var. acridum IMI 330189, Paeci- lomyces fumosoroseus FE 9901 , P. lilacinus DSM 15169, P. lilacinus BCP2, Paeni- bacillus poppiliae Dutky-1940 (NRRL B-2309 = ATCC 14706), P. poppiliae KLN 3, P. poppiliae Dutky 1 , Pasteuria spp. Ph3, P. nishizawae PN-1 , P. reneformis Pr-3, P. us- agae, Pseudomonas fluorescens CL 145A, Steinernema feltiae, Streptomces galbus; M.Y-2: Biochemical pesticides with insecticidal, acaricidal, molluscidal, pheromone and/or nematicidal activity: L-carvone, citral, (E,Z)-7,9-dodecadien-1 -yl acetate, ethyl formate, (E,Z)-2,4-ethyl decadienoate (pear ester), (Z,Z,E)-7,1 1 ,13-hexadecatrienal, heptyl bu- tyrate, isopropyl myristate, lavanulyl senecioate, 2-methyl 1 -butanol, methyl eugenol, methyl jasmonate, (E,Z)-2,13-octadecadien-1 -ol, (E,Z)-2,13-octadecadien-1 -ol acetate, (E,Z)-3,13-octadecadien-1 -ol, R-1 -octen-3-ol, pentatermanone, potassium silicate, sorbitol actanoate, (E,Z,Z)-3,8,1 1 -tetradecatrienyl acetate, (Z,E)-9,12-tetradecadien-1 -yl acetate, Z-7-tetradecen-2-one, Z-9-tetradecen-1 -yl acetate, Z-1 1 -tetradecenal, Z-1 1 - tetradecen-1 -ol, Acacia negra extract, extract of grapefruit seeds and pulp, extract of Chenopodium ambrosiodae, Catnip oil, Neem oil, Quillay extract, Tagetes oil;

According to one embodiment of the inventive mixtures, the at least one biopesticide II is se- lected from group M.Y-1.

According to one embodiment of the inventive mixtures, the at least one biopesticide II is selected from M.Y-2.

According to one embodiment of the inventive mixtures, the at least one biopesticide II is Bacil- lus amyloliquefaciens subsp. plantarum MBI600. These mixtures are particularly suitable in soybean.

According to another embodiment of the inventive mixtures, the at least one biopesticide II is B. pumilus strain INR-7 (otherwise referred to as BU-F22 (NRRL B-50153) and BU-F33 (NRRL B- 50185; see WO 2012/079073). These mixtures are particularly suitable in soybean and corn. According to another embodiment of the inventive mixtures, the at least one biopesticide II is Bacillus pumilus, preferably B. pumilis strain INR-7 (otherwise referred to as BU-F22 (NRRL B- 50153) and BU-F33 (NRRL B-50185). These mixtures are particularly suitable in soybean and corn. According to another embodiment of the inventive mixtures, the at least one biopesticide II is Bacillus simplex, preferably B. simplex strain ABU 288 (NRRL B-50340). These mixtures are particularly suitable in soybean and corn.

According to another embodiment of the inventive mixtures, the at least one biopesticide II is selected from Trichoderma asperellum, T. atroviride, T. fertile, T. gamsii, T. harmatum; mixture of T. harzia-'num and T. viride; mixture of T. polysporum and T. harzianum; T. stromaticum, T. virens (also named Gliocladium virens) and T. viride; preferably Trichoderma fertile, in particular T. fertile strain JM41 R. These mixtures are particularly suitable in soybean and corn.

According to another embodiment of the inventive mixtures, the at least one biopesticide II is Sphaerodes mycoparasitica, preferably Sphaerodes mycoparasitica strain IDAC 301008-01 (also referred to as strain SMCD2220-01 ). These mixtures are particularly suitable in soybean and corn.

According to another embodiment of the inventive mixtures, the at least one biopesticide II is Beauveria bassiana, preferably Beauveria bassiana strain PPRI5339. These mixtures are par- ticularly suitable in soybean and corn.

According to another embodiment of the inventive mixtures, the at least one biopesticide II is Metarhizium anisopliae or M. anisopliae var. acridium, preferably selectged from M anisolpiae strain IMI33 and M. anisopliae var. acridium strain IMI 330189. These mixtures are particularly suitable in soybean and corn.

According to another embodiment of the inventive mixtures, Bradyrhizobium sp. (meaning any Bradyrhizobium species and/or strain) as biopesticide II is Bradyrhizobium japonicum (B. japonicum). These mixtures are particularly suitable in soybean. Preferably B. japonicum is not one of the strains TA-1 1 or 532c. B. japonicum strains were cultivated using media and fermentation techniques known in the art, e.g. in yeast extract-mannitol broth (YEM) at 27°C for about 5 days.

References for various B. japonicum strains are given e.g. in US 7,262,151 (B. japonicum strains USDA 1 10 (= IITA 2121 , SEMIA 5032, RCR 3427, ARS 1-1 10, Nitragin 61A89; isolated from Glycine max in Florida in 1959, Serogroup 1 10; Appl Environ Microbiol 60, 940-94, 1994), USDA 31 (= Nitragin 61A164; isolated from Glycine max in Wisoconsin in 1941 , USA,

Serogroup 31 ), USDA 76 (plant passage of strain USDA 74 which has been isolated from Glycine max in California, USA, in 1956, Serogroup 76), USDA 121 (isolated from Glycine max in Ohio, USA, in 1965), USDA 3 (isolated from Glycine max in Virginia, USA, in 1914, Serogroup 6) and USDA 136 (= CB 1809, SEMIA 586, Nitragin 61A136, RCR 3407; isolated from Glycine max in Beltsville, Maryland in 1961 ; Appl Environ Microbiol 60, 940-94, 1994). USDA refers to United States Department of Agriculture Culture Collection, Beltsville, Md., USA (see e.g. Beltsville Rhizobium Culture Collection Catalog March 1987 ARS-30). Further suitable B. japonicum strain G49 (INRA, Angers, France) is described in Fernandez-Flouret, D. & Cleyet-Marel, J. C. (1987) C R Acad Agric Fr 73, 163-171 ), especially for soybean grown in Europe, in particular in France. Further suitable B. japonicum strain TA-1 1 (TA1 1 NOD+) (NRRL B-18466) is i.a. de- scribed in US 5,021 ,076; Appl Environ Microbiol (1990) 56, 2399-2403 and commercially available as liquid inoculant for soybean (VAULT® NP, Becker Underwood, USA). Further B. japonicum strains as example for biopesticide II are described in US2012/0252672A. Further suitable and especially in Canada commercially available strain 532c (The Nitragin Company, Milwau- kee, Wisconsin, USA, field isolate from Wisconsin; Nitragin strain collection No. 61A152; Can J Plant Sci 70 (1990), 661 -666).

Other suitable and commercially available B. japonicum strains (see e.g. AppI Environ Microbiol 2007, 73(8), 2635) are SEMIA 566 (isolated from North American inoculant in 1966 and used in Brazilian commercial inoculants from 1966 to 1978), SEMIA 586 (= CB 1809; originally isolated in Maryland, USA but received from Austrailia in 1966 and used in Brazilian inoculants in 1977), CPAC 15 (= SEMIA 5079; a natural varaiant of SEMIA 566 used in commercial inoculants since 1992) and CPAC 7 (= SEMIA 5080; a natural variant of SEMIA 586 used in commercial inoculants since 1992). These strains are especially suitable for soybean grown in Australia or South America, in particular in Brazil. Some of the abovementioned strains have been re-classified as a novel species Bradyrhizobium elkanii, e.g. strain USDA 76 (Can. J. Microbiol., 1992, 38, 501 - 505).

Another suitable and commercially available B. japonicum strain is E-109 (variant of strain USDA 138, see e.g. Eur. J. Soil Biol. 45 (2009) 28-35; Biol Fertil Soils (201 1 ) 47:81-89, depos- ited at Agriculture Collection Laboratory of the Instituto de Microbiologia y Zoologia Agncola (IMYZA), Instituto Nacional de Tecnologi^'a Agropecuaria (INTA), Castelar, Argentina). This strain is especially suitable for soybean grown in South America, in particular in Argentina. The present invention also relates to mixtures, wherein the at least one biopesticide II is selected from Bradyrhizobium elkanii and Bradyrhizobium liaoningense (B. elkanii and B. liaoningen- se), more preferably from B. elkanii. These mixtures are particularly suitable in soybean. B. elkanii and liaoningense were cultivated using media and fermentation techniques known in the art, e.g. in yeast extract-mannitol broth (YEM) at 27°C for about 5 days.

Suitable and commercially available B. elkanii strains are SEMIA 587 and SEMIA 5019 (=29W) (see e.g. AppI Environ Microbiol 2007, 73(8), 2635) and USDA 3254 and USDA 76 and USDA 94. Further commercially available B. elkanii strains are U-1301 and U-1302 (e.g. product Ni- troagin® Optimize from Novozymes Bio As S.A., Brazil or NITRASEC for soybean from LAGE y Cia, Brazil). These strains are especially suitable for soybean grown in Australia or South America, in particular in Brazil.

The present invention also relates to mixtures, wherein the at least one biopesticide II is select- ed from Bradyrhizobium japonicum (B. japonicum) and further comprisies a compound III, wherein compound III is selected from jasmonic acid or salts or derivatives thereof including cis- jasmone, preferably methyl-jasmonate or cis-jasmone.

The present invention also relates to mixtures, wherein biopesticide II is selected from Bradyrhizobium sp. (Arachis) (B. sp. Arachis) which shall describe the cowpea miscellany cross- inoculation group which includes inter alia indigenous cowpea bradyrhizobia on cowpea (Vigna unguiculata), siratro (Macroptilium atropurpureum), lima bean (Phaseolus lunatus), and peanut (Arachis hypogaea). This mixture comprising as biopesticide II B. sp. Arachis is especially suitable for use in peanut, Cowpea, Mung bean, Moth bean, Dune bean, Rice bean, Snake bean and Creeping vigna, in particular peanut.

Suitable and commercially available B. sp. (Arachis) strain is CB1015 (= IITA 1006, USDA 3446 presumably originally collected in India; from Australian Inoculants Research Group; see e.g. http://www.qaseeds.com.au/inoculant_applic.php; Beltsville Rhizobium Culture Collection Catalog March 1987 USDA-ARS ARS-30). These strains are especially suitable for peanut grown in Australia, North America or South America, in particular in Brazil. Further suitable strain is brad- yrhizobium sp. PNL01 (Becker Underwood; ISO Rep Marita McCreary, QC Manager Padma Somasageran; IDENTIFICATION OF RHIZOBIA SPECIES THAT CAN ESTABLISH NITROGEN-FIXING NODULES IN CROTALARIA LONGIROSTRATA. April 29, 2010, University of Massachusetts Amherst: http://www.wpi.edu/Pubs/E-project/Available/E-project-042810-

163614/unrestricted/Bisson.Mason._ldentification_of_Rhizobia_Species_That_can_Establish_Nit rogen-Fixing_Nodules_in_Crotalia_Longirostrata.pdf).

Suitable and commercially available Bradyrhizobium sp. (Arachis) strains especially for cowpea and peanut but also for soybean are Bradyrhizobium SEMIA 6144, SEMIA 6462 (= BR 3267) and SEMIA 6464 (= BR 3262) (deposited at FEPAGRO-MIRCEN, R. Gongalves Dias, 570 Porto

Alegre - RS, 90130-060, Brazil; see e.g. FEMS Microbiology Letters (2010) 303(2), 123-131 ;

Revista Brasileira de Ciencia do Solo (201 1 ) 35(3);739-742, ISSN 0100-0683).

The present invention also relates to mixtures wherein the at least one biopesticide II is selected from Bradyrhizobium sp. (Arachis) and further comprises a compound III, wherein compound III is selected from jasmonic acid or salts or derivatives thereof including cis-jasmone, preferably methyl-jasmonate or cis-jasmone.

The present invention also relates to mixtures, wherein the at least one biopesticide II is selected from Bradyrhizobium sp. (Lupine) (also called B. lupini, B. lupines or Rhizobium lupini). This mixture is especially suitable for use in dry beans and lupins.

Suitable and commercially available B. lupini strain is LL13 (isolated from Lupinus iuteus nodules from French soils; deposited at INRA, Dijon and Angers, France;

http://agriculture.gouv.fr/IMG/pdf/ch20060216.pdf). This strain is especially suitable for lupins grown in Australia, North America or Europe, in particular in Europe.

Further suitable and commercially available B. lupini strains WU425 (isolated in Esperance, Western Australia from a non-Australian legume Ornthopus compressus), WSM4024 (isolated from lupins in Australia by CRS during a 2005 survey) and WSM471 (isolated from Ornithopus pinnatus in Oyster Harbour, Western Australia) are described e.g. in Palta J.A. and Berger J.B. (eds), 2008, Proceedings 12th International Lupin Conference, 14-18 Sept. 2008, Fremantle, Western Australia. International Lupin Association, Canterbury, New Zealand, 47-50, ISBN 0- 86476-153-8:

http://www.lupins.org/pdf/conference/2008/Agronomy%20and%20Production/John%20Howieso n%20and%20G%20OHara.pdf; Appl Environ Microbiol (2005) 71 , 7041 -7052 and Australian J. Exp. Agricult. (1996) 36(1 ), 63-70.

The present invention also relates to mixtures wherein the at least one biopesticide II is selected from Bradyrhizobium sp. (Lupine) (B. lupini) and further comprises a compound III, wherein compound III is selected from jasmonic acid or salts or derivatives thereof including cis- jasmone, preferably methyl-jasmonate or cis-jasmone.

The present invention also relates to mixtures, wherein the at least one biopesticide II is selected from Mesorhizobium sp. (meaning any Mesorhizobium species and/or strain), more prefera- bly Mesorhizobium ciceri. These mixtures are particularly suitable in cowpea.

Suitable and commercially available M. sp. strains are e.g. M. ciceri CC1 192 (=UPM 848, CECT 5549; from Horticultural Research Station, Gosford, Australia; collected in Israel from Cicer ari- etinum nodules; Can J Microbial (2002) 48, 279-284) and Mesorhizobium sp. strains WSM1271 (collected in Sardinia, Italy, from plant host Biserrula pelecinus), WSM 1497 (collected in Myko- nos, Greece, from plant host Biserrula pelecinus), M. loti strains CC829 (commerical inoculant for Lotus pedunculatus and L. ulginosus in Australia, isolated from L. ulginosus nodules in USA) and SU343 (commercial inoculant for Lotus corniculatus in Australia; isolated from host nodules in USA) all of which are deposited at Western Australian Soil Microbiology (WSM) culture collection, Australia and/or CSIRO collection (CC), Canberra, Australian Capirtal Territory (see e.g. Soil Biol Biochem (2004) 36(8), 1309-1317; Plant and Soil (201 1 ) 348(1 -2), 231 -243).

Suitable and commercially available M. loti strains are e.g. M. loti CC829 for Lotus pedunculatus.

The present invention also relates to mixtures wherein the at least one biopesticide II is selected from Mesorhizobium huakuii, also referred to as Rhizobium huakuii (see e.g. Appl. Environ. Microbiol. 201 1 , 77(15), 5513-5516). These mixtures are particularly suitable in Astralagus, e.g. Astalagus sinicus (Chinese milkwetch), Thermopsis, e.g. Thermopsis luinoides (Goldenbanner) and alike.

Suitable and commercially available M. huakuii strain is HN3015 which was isolated from Astra- lagus sinicus in a rice-growing field of Southern China (see e.g. World J. Microbiol. Biotechn. (2007) 23(6), 845-851 , ISSN 0959-3993).

The present invention also relates to mixtures wherein the at least one biopesticide II is selected from Mesorhizobium huakuii and further comprises a compound III, wherein compound III is selected from jasmonic acid or salts or derivatives thereof including cis-jasmone, preferably me- thyl-jasmonate or cis-jasmone.

The present invention also relates to mixtures, wherein the at least one biopesticide II is selected from Azospirillum amazonense, A. brasilense, A. lipoferum, A. irakense, A. halopraeferens, more preferably from A. brasilense, in particular selected from A. brasilense strains BR 1 1005 (SP 245) and AZ39 which are both commercially used in Brazil and are obtainable from EM- BRAPA, Brazil. These mixtures are particularly suitable in soybean.

Humates are humic and fulvic acids extracted from a form of lignite coal and clay, known as leonardite. Humic acids are organic acids that occur in humus and other organically derived materials such as peat and certain soft coal. They have been shown to increase fertilizer efficiency in phosphate and micro-nutrient uptake by plants as well as aiding in the development of plant root systems.

Salts of jasmonic acid (jasmonate) or derivatives include without limitation the jasmonate salts potassium jasmonate, sodium jasmonate, lithium jasmonate, ammonium jasmonate, dime- thylammonium jasmonate, isopropylammonium jasmonate, diolammonium jasmonate, diethtri- ethanolammonium jasmonate, jasmonic acid methyl ester, jasmonic acid amide, jasmonic acid methylamide, jasmonic acid-L-amino acid (amide-linked) conjugates (e.g., conjugates with L- isoleucine, L- valine, L-leucine, or L-phenylalanine), 12-oxo-phytodienoic acid, coronatine, coro- nafacoyl- L-serine, coronafacoyl-L-threonine, methyl esters of 1 - oxo-indanoyl-isoleucine, methyl esters of 1 -oxo-indanoyl-leucine, coronalon (2- [ (6- ethyl-l-oxo-indane-4-carbonyl) -amino] - 3- methyl -pentanoic acid methyl ester), linoleic acid or derivatives thereof and cis-jasmone, or combinations of any of the above.

According to one embodiment, the microbial pesticides embrace not only the isolated, pure cultures of the respective micro-organism as defined herein, but also its cell-free extract, its sus- pensions in a whole broth culture or as a metabolite-containing supernatant or a purified metabolite obtained from a whole broth culture of the microorganism or microorganism strain.

According to a further embodiment, the microbial pesticides embrace not only the isolated, pure cultures of the respective micro-organism as defined herein, but also a cell-free extract thereof or at least one metabolite thereof, and/or a mutant of the respective micro-organism having all the identifying characteristics thereof and also a cell-free extract or at least one metabolite of the mutant.

"Whole broth culture" refers to a liquid culture containing both cells and media.

"Supernatant" refers to the liquid broth remaining when cells grown in broth are removed by centrifugation, filtration, sedimentation, or other means well known in the art.

The term "metabolite" refers to any compound, substance or byproduct produced by a microorganism (such as fungi and bacteria) that has improves plant growth, water use efficiency of the plant, plant health, plant appearance, or the population of beneficial microorganisms in the soil around the plant activity.

The term "mutant" refers a microorganism obtained by direct mutant selection but also includes microorganisms that have been further mutagenized or otherwise manipulated (e.g., via the introduction of a plasmid). Accordingly, embodiments include mutants, variants, and or derivatives of the respective microorganism, both naturally occurring and artificially induced mutants. For example, mutants may be induced by subjecting the microorganism to known mutagens, such as N-methyl-nitrosoguanidine, using conventional methods.

According to the invention, the solid material (dry matter) of the biopesticides (with the exception of oils such as Neem oil, Tagetes oil, etc.) are considered as active components (e.g. to be obtained after drying or evaporation of the extraction medium or the suspension medium in case of liquid formulations of the microbial pesticides).

In accordance with the present invention, the weight ratios and percentages used herein for biological extract such as Quillay extract are based on the total weight of the dry content (solid material) of the respective extract(s).

For microbial pesticides, weight ratios and/or percentages refer to the total weight of a preparation of the respective biopesticide with at least 1 x 106 CFU/g ("colony forming units per gram total weight"), preferably with at least 1 x 108 CFU/g, even more preferably from 1 x 108 to 1 x 1012 CFU/g dry matter. Colony forming unit is measure of viable microbial cells, in particular fungal and bacterial cells. In addition, here CFU may also be understood as number of (juvenile) individual nematodes in case of (entomo-'pathogenic) nematode biopesticides, such as Stei- nernema feltiae.

Herein, microbial pesticides may be supplied in any physiological state such as active or dormant. Such dormant active component may be supplied for example frozen, dried, or lyophi- lized or partly desiccated (procedures to produce these partly desiccated organisms are given in WO2008/002371 ) or in form of spores. Microbial pesticides used as organism in an active state can be delivered in a growth medium without any additional additives or materials or in combination with suitable nutrient mixtures. According to a further embodiment, microbial pesticides are delivered and formulated in a dormant stage, more preferably in form of spores.

The total weight ratios of compositions, which comprise a microbial pesticide as component 2, can be determined based on the total weight of the solid material (dry matter) of component 1 ) and using the amount of CFU of component 2) to calclulate the total weight of component 2) with the following equation that 1 x 10⁹ CFU equals one gram of total weight of component 2). According to one embodiment, the compositions, which comprise a microbial pesticide, com- prise between 0.01 and 90% (w/w) of dry matter (solid material) of component 1 ) and from 1 x

10⁵ CFU to 1 x 10¹² CFU of component 2) per gram total weight of the composition.

According to another embodiment, the compositions, which comprise a microbial pesticide, comprise between 5 and 70% (w/w) of dry matter (solid material) of component 1 ) and from 1 x

10⁶ CFU to 1 x 10¹⁰ CFU of component 2) per gram total weight of the composition.

According to another embodiment, the compositions, wherein one component is a microbial pesticide, comprise between 25 and 70% (w/w) of dry matter (solid material) of component 1 ) and from 1 x 10⁷ CFU to 1 x 10⁹ CFU of component 2) per gram total weight of the composition. In the case of mixtures comprising a microbial pesticide, the application rates preferably range from about 1 x 10⁶ to 5 x 10¹⁵ (or more) CFU/ha. Preferably, the spore concentration is about 1 x 107 to about 1 x 101 1 CFU/ha. In the case of (entomopathogenic) nematodes as microbial pesticides (e.g. Steinernema feltiae), the application rates preferably range inform about 1 x 10⁵ to 1 x 10¹² (or more), more preferably from 1 x 10⁸ to 1 x 10¹¹, even more preferably from 5 x 10⁸ to 1 x 10¹⁰ individuals (e.g. in the form of eggs, juvenile or any other live stages, preferably in an infetive juvenile stage) per ha.

In the case of mixtures comprising microbial pesticides, the application rates with respect to plant propagation material preferably range from about 1 x 10⁶ to 1 x 10¹² (or more) CFU/seed. Preferably, the concentration is about 1 x 10⁶ to about 1 x 10¹¹ CFU/seed. In the case of microbial pesticides, the application rates with respect to plant propagation material also preferably range from about 1 x 10⁷ to 1 x 10¹⁴ (or more) CFU per 100 kg of seed, preferably from 1 x 10⁹ to about 1 x 10¹¹ CFU per 100 kg of seed.

The combined use of the compounds of formula (I) with other pesticides may result in potential synergistic effects. The examples of insecticidal mixing partners are provided with the intention to illustrate the possible combinations, but not to impose any limitation to the obtainable mixtures.

In another embodiment of the invention, the compounds of formula (I), or their stereoisomers, salts, tautomers and N-oxides, may also be applied with fungicides as compound II.

The following list F of active substances, in conjunction with which the compounds according to the invention can be used, is intended to illustrate the possible combinations but does not limit them:

F.I) Respiration Inhibitors

F.1-1 ) Inhibitors of complex III at Qo site: strobilurins: azoxystrobin, coumethoxystrobin, coumoxystrobin, dimoxystrobin, enestroburin, fluoxastrobin, kresoxim-methyl, mandestrobin, metominostrobin, orysastrobin, picoxystrobin, pyraclostrobin, pyrametostrobin, pyraoxystrobin, pyribencarb, triclopyricarb/chlorodincarb, tri- floxystrobin, 2-[2-(2,5-dimethyl-phenoxymethyl)-phenyl]-3-methoxy-acrylic acid methyl ester and 2 (2-(3-(2,6-dichlorophenyl)-1 -methyl-allylideneaminooxymethyl)-phenyl)-2-methoxyimino-N methyl-acetamide;

oxazolidinediones and imidazolinones: famoxadone, fenamidone;

F.I-2) Inhibitors of complex II (e.g. carboxamides):

carboxanilides: benodanil, benzovindiflupyr ,bixafen, boscalid, carboxin, fenfuram, fenhexamid, fluopyram, flutolanil, furametpyr, isofetamid, isopyrazam, isotianil, mepronil, oxycarboxin, pen- flufen, penthiopyrad, sedaxane, tecloftalam, thifluzamide, tiadinil, 2-amino-4 methyl-thiazole-5- carboxanilide, N-(3',4',5' trifluorobiphenyl-2 yl)-3-difluoromethyl-1 -methyl-1 H-pyrazole-4 carbox- amide (fluxapyroxad), N-(4'-trifluoromethylthiobiphenyl-2-yl)-3 difluoromethyl-1 -methyl-1 H pyra- zole-4-carboxamide, N-(2-(1 ,3,3-trimethyl-butyl)-phenyl)-1 ,3-dimethyl-5 fluoro-1 H-pyrazole-4 carboxamide, 3-(difluoromethyl)-1 -methyl-N-(1 ,1 ,3-trimethylindan-4-yl)pyrazole-4-carboxamide, 3-(trifluoromethyl)-1 -methyl-N-(1 ,1 ,3-trimethylindan-4-yl)pyrazole-4-carboxamide, 1 ,3-dimethyl- N-(1 ,1 ,3-trimethylindan-4-yl)pyrazole-4-carboxamide, 3-(trifluoromethyl)-1 ,5-dimethyl-N-(1 ,1 ,3- trimethylindan-4-yl)pyrazole-4-carboxamide, 3-(difluoromethyl)-1 ,5-dimethyl-N-(1 ,1 ,3- trimethylindan-4-yl)pyrazole-4-carboxamide, 1 ,3,5-trimethyl-N-(1 ,1 ,3-trimethylindan-4- yl)pyrazole-4-carboxamide, 3-(difluoromethyl)-1 -methyl-N-(1 ,1 ,3-trimethylindan-4-yl)pyrazole-4- carboxamide, 3-(trifluoromethyl)-1 -methyl-N-(1 , 1 ,3-trimethylindan-4-yl)pyrazole-4-carboxamide, 1 ,3-dimethyl-N-(1 ,1 ,3-trimethylindan-4-yl)pyrazole-4-carboxamide, 3-(trifluoromethyl)-1 ,5- dimethyl-N-(1 ,1 ,3-trimethylindan-4-yl)pyrazole-4-carboxamide, 3-(difluoromethyl)-1 ,5-dimethyl- N-(1 ,1 ,3-trimethylindan-4-yl)pyrazole-4-carboxamide, 3-(trifluorometrHyl)-1 ,5-dimethyl-N-(1 ,1 ,3- trimethylindan^-yl^pyrazole^-carboxamide, 1 ,3,5-trimethyl-N-(1 ,1 ,3-trimethylindan-4- yl)pyrazole-4-carboxamide, N-(7-fluoro-1 ,1 ,3-trimethyl-indan-4-yl)-1 ,3-dimethyl-pyrazole-4- carbox-'amide, N-[2-(2,4-dichlorophenyl)-2-methoxy-1 -methyl-ethyl]-3-(difluoromethyl)-1 -methyl- pyrazole-4-carboxamide;

F.I-3) Inhibitors of complex III at Qi site: cyazofamid, amisulbrom, [(3S,6S,7R,8R)-8-benzyl-3- [(3-acetoxy-4-methoxy-pyridine-2-carbonyl)amino]-6-methyl-4,9-dioxo-1 ,5-dioxonan-7-yl] 2-methylpropanoate, [(3S,6S,7R,8R)-8-benzyl-3-[[3-(acetoxymethoxy)-4-methoxy-pyridine- 2-carbonyl]amino]-6-methyl-4,9-dioxo-1 ,5-dioxonan-7-yl] 2-methylpropanoate, [(3S,6S,7R,8R)- 8-benzyl-3-[(3-isobutoxycarbonyloxy-4-methoxy-pyridine-2-carbonyl)amino]-6-methyl-4,9-dioxo- 1 ,5-dioxonan-7-yl] 2-methylpropanoate, [(3S,6S,7R,8R)-8-benzyl-3-[[3-(1 ,3-benzodioxol-5- ylmethoxy)-4-methoxy-pyridine-2-carbonyl]amino]-6-methyl-4,9-dioxo-1 ,5-dioxonan-7-yl] 2- methylpropanoate, 3S,6S,7R,8R)-3-[[(3-hydroxy-4-methoxy-2-pyridinyl)carbonyl]amino]- 6-methyl-4,9-dioxo-8-(phenylmethyl)-1 ,5-dioxonan-7-yl 2-methylpropanoate;

F.I-4) Other respiration inhibitors (complex I, uncouplers) diflumetorim; (5,8-difluoroquinazolin-4- yl)-{2-[2-fluoro-4-(4-trifluoromethylpyridin-2-yloxy)-phenyl]-ethyl}-amine; tecnazen;ametoctradin; silthiofam; nitrophenyl derivates: binapacryl, dinobuton, dinocap, fluazinam, ferimzone, nitrthal- isopropyl,

and including organometal compounds: fentin salts, such as fentin-acetate, fentin chloride or fentin hydroxide; F.ll) Sterol biosynthesis inhibitors (SBI fungicides)

F.II-1 ) C14 demethylase inhibitors (DMI fungicides, e.g. triazoles, imidazoles)

triazoles: azaconazole, bitertanol, bromuconazole, cyproconazole, difenoconazole, dinicona- zole, diniconazole-M, epoxiconazole, fenbuconazole, fluquinconazole, flusilazole, flutriafol, hex- aconazole, imibenconazole, ipconazole, metconazole, myclobutanil, paclobutrazole, pen- conazole, propiconazole, prothioconazole, simeconazole, tebuconazole, tetraconazole, triad- imefon, triadimenol, triticonazole, uniconazole, 1 -[re/-(2S;3R)-3-(2-chlorophenyl)-2-(2,4- difluorophenyl)-oxiranylmethyl]-5-thiocyanato-1 H-[1 ,2,4]triazole, 2-[re/-(2S;3R)-3-(2- chlorophenyl)-2-(2,4-difluorophenyl)-oxiranylmethyl]-2H-[1 ,2,4]triazole-3-thiol, 2-[2-chloro-4-(4- chlorophenoxy)phenyl]-1 -(1 ,2,4-triazol-1 -yl)pentan-2-ol, 1 -[4-(4-chlorophenoxy)-2-

(trifluoromethyl)phenyl]-1 -cyclopropyl-2-(1 ,2,4-triazol-1 -yl)ethanol, 2-[4-(4-chlorophenoxy)-2- (trifluoromethyl)phenyl]-1 -(1 ,2,4-triazol-1 -yl)butan-2-ol, 2-[2-chloro-4-(4-chlorophenoxy)phenyl]-

1 - (1 ,2,4-triazol-1 -yl)butan-2-ol, 2-[4-(4-chlorophenoxy)-2-(trifluoromethyl)phenyl]-3-methyl-1 - (1 ,2,4-triazol-1 -yl)butan-2-ol, 2-[4-(4-chlorophenoxy)-2-(trifluoromethyl)phenyl]-1 -(1 ,2,4-triazol-1 - yl)propan-2-ol, 2-[2-chloro-4-(4-chlorophenoxy)phenyl]-3-methyl-1 -(1 ,2,4-triazol-1 -yl)butan-2-ol,

2- [4-(4-chlorophenoxy)-2-(trifluoromethyl)phenyl]-1 -(1 ,2,4-triazol-1 -yl)pentan-2-ol, 2-[4-(4- fluorophenoxy)-2-(trifluoromethyl)phenyl]-1 -(1 ,2,4-triazol-1 -yl)propan-2-ol;

imidazoles: imazalil, pefurazoate, oxpoconazole, prochloraz, triflumizole;

pyrimidines, pyridines and piperazines: fenarimol, nuarimol, pyrifenox, triforine,[3-(4-chloro-2- fluoro-phenyl)-5-(2,4-difluorophenyl)isoxazol-4-yl]-(3-pyridyl)methanol;

F.II-2) Delta14-reductase inhitors (Amines, e.g. morpholines, piperidines)

morpholines: aldimorph, dodemorph, dodemorph-acetate, fenpropimorph, tridemorph;

piperidines: fenpropidin, piperalin; spiroketalamines: spiroxamine;

F.II-3) Inhibitors of 3-keto reductase: hydroxyanilides: fenhexamid;

F.lll) Nucleic acid synthesis inhibitors

F.III-1 ) RNA, DNA synthesis

phenylamides or acyl amino acid fungicides: benalaxyl, benalaxyl-M, kiralaxyl, metalaxyl, met- alaxyl-M (mefenoxam), ofurace, oxadixyl;

isoxazoles and iosothiazolones: hymexazole, octhilinone;

F.III-2) DNA topisomerase inhibitors: oxolinic acid;

F.III-3) Nucleotide metabolism (e.g. adenosin-deaminase), hydroxy (2-amino)-pyrimidines: bupi- rimate;

F.IV) Inhibitors of cell division and or cytoskeleton

F.IV-1 ) Tubulin inhibitors: benzimidazoles and thiophanates: benomyl, carbendazim, fuber- idazole, thiabendazole, thiophanate-methyl;

triazolopyrimidines: 5-chloro-7 (4-methylpiperidin-1 -yl)-6-(2,4,6-trifluorophenyl)- [1 ,2,4]triazolo[1 ,5 a]pyrimidine;

F.IV-2) Other cell division inhibitors

benzamides and phenyl acetamides: diethofencarb, ethaboxam, pencycuron, fluopicolide, zox- amide;

F.IV-3) Actin inhibitors: benzophenones: metrafenone; pyriofenone;

F.V) Inhibitors of amino acid and protein synthesis

F.V-1 ) Methionine synthesis inhibitors (anilino-pyrimidines) anilino-pyrimidines: cyprodinil, mepanipyrim, nitrapyrin, pyrimethanil;

F.V-2) Protein synthesis inhibitors (anilino-pyrimidines)

antibiotics: blasticidin-S, kasugamycin, kasugamycin hydrochloride-hydrate, mildiomycin, streptomycin, oxytetracyclin, polyoxine, validamycin A;

F.VI) Signal transduction inhibitors

F.VI-1 ) MAP / Histidine kinase inhibitors (e.g. anilino-pyrimidines)

dicarboximides: fluoroimid, iprodione, procymidone, vinclozolin;

phenylpyrroles: fenpiclonil, fludioxonil;

F.VI-2) G protein inhibitors: quinolines: quinoxyfen;

F.VI I) Lipid and membrane synthesis inhibitors

F.VI 1-1 ) Phospholipid biosynthesis inhibitors

organophosphorus compounds: edifenphos, iprobenfos, pyrazophos;

dithiolanes: isoprothiolane;

F.VII-2) Lipid peroxidation: aromatic hydrocarbons: dicloran, quintozene, tecnazene, tolclofos- methyl, biphenyl, chloroneb, etridiazole;

F.VII-3) Carboxyl acid amides (CAA fungicides)

cinnamic or mandelic acid amides: dimethomorph, flumorph, mandiproamid, pyrimorph;

valinamide carbamates: benthiavalicarb, iprovalicarb, pyribencarb, valifenalate and N-(1 -(1 -(4- cyano-phenyl)ethanesulfonyl)-but-2-yl) carbamic acid-(4-fluorophenyl) ester;

F.VII-4) Compounds affecting cell membrane permeability and fatty acids:

1 -[4-[4-[5-(2,6-difluorophenyl)-4,5-dihydro-3-isoxazolyl]-2-thiazolyl]-1 -piperidinyl]-2-[5-methyl-3- (trifluoromethyl)-l H-pyrazol-1 -yl]ethanone, carbamates: propamocarb, propamocarb- hydrochlorid,

F.VII-5) fatty acid amide hydrolase inhibitors: 1 -[4-[4-[5-(2,6-difluorophenyl)-4,5-dihydro- 3-isoxazolyl]-2-thiazolyl]-1 -piperidinyl]-2-[5-methyl-3-(trifluoromethyl)-1 H-pyrazol-1 -yl]ethanone;

F.VI II) Inhibitors with Multi Site Action

F.VI 11-1 ) Inorganic active substances: Bordeaux mixture, copper acetate, copper hydroxide, copper oxychloride, basic copper sulfate, sulfur;

F.VIII-2) Thio- and dithiocarbamates: ferbam, mancozeb, maneb, metam, methasulphocarb, metiram, propineb, thiram, zineb, ziram;

F.VIII-3) Organochlorine compounds (e.g. phthalimides, sulfamides, chloronitriles):

anilazine, chlorothalonil, captafol, captan, folpet, dichlofluanid, dichlorophen, flusulfamide, hex- achlorobenzene, pentachlorphenole and its salts, phthalide, tolylfluanid, N-(4-chloro-2-nitro- phenyl)-N-ethyl-4-methyl-benzenesulfonamide;

F.VIII-4) Guanidines and other: guanidine, dodine, dodine free base, guazatine, guazatine- acetate, iminoctadine, iminoctadine-triacetate, iminoctadine-tris(albesilate), dithianon, 2,6- dimethyl-1 H,5H-[1 ,4]dithiino[2,3-c:5,6-c']dipyrrole-1 ,3,5,7(2H,6H)-tetraone;

F.VIII-5) Ahtraquinones: dithianon;

F.IX) Cell wall synthesis inhibitors

F.IX-1 ) Inhibitors of glucan synthesis: validamycin, polyoxin B;

F.IX-2) Melanin synthesis inhibitors: pyroquilon, tricyclazole, carpropamide, dicyclomet, fenoxanil; F.X) Plant defence inducers

F.X-1 ) Salicylic acid pathway: acibenzolar-S-methyl;

F.X-2) Others: probenazole, isotianil, tiadinil, prohexadione-calcium;

phosphonates: fosetyl, fosetyl-aluminum, phosphorous acid and its salts;

F.XI) Unknown mode of action:bronopol, chinomethionat, cyflufenamid, cymoxanil, dazomet, debacarb, diclomezine, difenzoquat, difenzoquat-methylsulfate, diphenylamin, fenpyrazamine, flumetover, flusulfamide, flutianil, methasulfocarb, nitrapyrin, nitrothal-isopropyl, oxathiapiprolin, oxin-copper, proquinazid, tebufloquin, tecloftalam, triazoxide, 2-butoxy-6-iodo-3-propylchromen- 4-one, N-(cyclopropylmethoxyimino-(6-difluoro-methoxy-2,3-difluoro-phenyl)-methyl)-2-phenyl acetamide, N'-(4-(4-chloro-3-trifluoromethyl-phenoxy)-2,5-dimethyl-phenyl)-N-ethyl-N methyl formamidine, N' (4-(4-fluoro-3-trifluoromethyl-phenoxy)-2,5-dimethyl-phenyl)-N-ethyl-N-methyl formamidine, N'-(2-methyl-5-trifluoromethyl-4-(3-trimethylsilanyl-propoxy)-phenyl)-N-ethyl-N- methyl formamidine, N'-(5-difluoromethyl-2 methyl-4-(3-trimethylsilanyl-propoxy)-phenyl)-N- ethyl-N-methyl formamidine, 2-{1 -[2-(5-methyl-3-trifluoromethyl-pyrazole-1 -yl)-acetyl]-piperidin- 4-yl}-thiazole-4-carboxylic acid methyl-(1 ,2,3,4-tetrahydro-naphthalen-1 -yl)-amide, 2-{1 -[2-(5- methyl-3-trifluoromethyl-pyrazole-1 -yl)-acetyl]-piperidin-4-yl}-thiazole-4-carboxylic acid methyl- (R)-1 ,2,3,4-tetrahydro-naphthalen-1 -yl-amide, methoxy-acetic acid 6-tert-butyl-8-fluoro-2,3- dimethyl-quinolin-4-yl ester and N-Methyl-2-{1 -[(5-methyl-3-trifluoromethyl-1 H-pyrazol-1 -yl)- acetyl]-piperidin-4-yl}-N-[(1 ,2,3,4-tetrahydronaphthalen-1 -yl]-4-thiazolecarboxamide, 3-[5-(4- chloro-phenyl)-2,3-dimethyl-isoxazolidin-3 yl]-pyridine, pyrisoxazole, 5-amino-2-isopropyl-3-oxo- 4-ortho-tolyl-2,3-dihydro-pyrazole-1 carbothioic acid S-allyl ester, N-(6-methoxy-pyridin-3-yl) cyclopropanecarboxylic acid amide, 5-chloro-1 (4,6-dimethoxy-pyrimidin-2-yl)-2-methyl-1 H- benzoimidazole, 2-(4-chloro-phenyl)-N-[4-(3,4-dimethoxy-phenyl)-isoxazol-5-yl]-2-prop-2- ynyloxy-acetamide, ethyl (Z) 3 amino-2-cyano-3-phenyl-prop-2-enoate , tert-butyl N-[6-[[(Z)-[(1 - methyltetrazol-5-yl)-phenyl-methylene]amino]oxymethyl]-2-pyridyl]carbamate , pentyl N-[6-[[(Z)- [(1 -methyltetrazol-5-yl)-phenyl-methylene]amino]oxymethyl]-2-pyridyl]carbamate , 2-[2-[(7,8- difluoro-2-methyl-3-quinolyl)oxy]-6-fluoro-phenyl]propan-2-ol, 2-[2-fluoro-6-[(8-fluoro-2-methyl-3- quinolyl)oxy]phenyl]propan-2-ol , 3-(5-fluoro-3,3,4,4-tetramethyl-3,4-dihydroiso^quinolin-1 - yl)quinoline, 3-(4,4-difluoro-3,3-dimethyl-3,4-dihydroisoquinolin-1 -yl)-"quinoline, 3-(4,4,5- trifluoro-3,3-dimethyl-3,4-dihydroisoquinolin-1 -yl)quinoline;

F.XI I) Growth regulators: abscisic acid, amidochlor, ancymidol, 6-benzylaminopurine, brassino- lide, butralin, chlormequat (chlormequat chloride), choline chloride, cyclanilide, daminozide, dikegulac, dimethipin, 2,6-dimethylpuridine, ethephon, flumetralin, flurprimidol, fluthiacet, forchlorfenuron, gibberellic acid, inabenfide, indole-3-acetic acid, maleic hydrazide, mefluidide, mepiquat (mepiquat chloride), naphthaleneacetic acid, N 6-benzyladenine, paclobutrazol, pro- hexadione (prohexadione-calcium), prohydrojasmon, thidiazuron, triapenthenol, tributyl phos- phorotrithioate, 2,3,5 tri iodobenzoic acid, trinexapac-ethyl and uniconazole;

F.XI II) Biopesticides

F.XI 11-1 ) Microbial pesticides with fungicidal, bactericidal, viricidal and/or plant defense acti- vator activity: Ampelomyces quisqualis, Aspergillus flavus, Aureobasidium pullulans, Bacillus amyloliquefaciens, B. mojavensis, B. pumilus, B. simplex, B. solisalsi, B. subtilis, B. subtilis var. amyloliquefaciens, Candida oleophila, C. saitoana, Clavibacter michiganensis (bacteriophages), Coniothyrium minitans, Cryphonectria parasitica, Cryptococcus albidus, Fusarium oxysporum, Clonostachys rosea f. catenulate (also named Gliocladium catenulatum), Glio-cladium roseum, Met-"schnikowia fructicola, Microdochium dimerum, Paeni-bacillus polymyxa, Pantoea agglom- erans, Phlebiopsis gigantea, Pseudozyma flocculosa, Pythium oligandrum, Sphaerodes myco- parasitica, Streptomyces lydicus, S. violaceusniger, Talaromyces flavus, Trichoderma asperel- lum, T. atroviride, T. fertile, T. gamsii, T. harmatum; mixture of T. harzia^num and T. viride; mixture of T. polysporum and T. harzianum; T. stromaticum, T. virens (also named Gliocladium virens), T. viride, Typhula phacorrhiza, Ulocladium oudema, U. oudemansii, Verticillium dahlia, zucchini yellow mosaic virus (avir-ulent strain);

F.XIII-2) Biochemical pesticides with fungicidal, bactericidal, viricidal and/or plant de-fense activator activity: chitosan (hydrolysate), jasmonic acid or salts or de-rivatives thereof, laminarin, Menhaden fish oil, natamycin, Plum pox virus coat protein, Reynoutria sachlinensis extract, salicylic acid, tea tree oil;

F.XIII-3) Microbial pesticides with plant stress reducing, plant growth regulator, plant growth promoting and/or yield enhancing activity: Azospirillum amazonense A. brasilense, A. lipoferum, A. irakense, A. halopraeferens, Bradyrhizobium sp., B. japonicum, Glomus intraradices, Meso- rhizobium sp., Paenibacillus alvei, Penicillium bilaiae, Rhizobium leguminosarum bv. phaseolii, R. I. trifolii, R. I. bv. viciae, Sinorhizobium meliloti;

F.XIII-4) Biochemical pesticides with plant stress reducing, plant growth regulator and/or plant yield enhancing activity: abscisic acid, aluminium silicate (kaolin), 3-decen-2-one, homo- brassinlide, humates, lysophosphatidyl ethanolamine, polymeric polyhydroxy acid, Ascophyllum nodosum (Norwegian kelp, Brown kelp) extract and Ecklonia maxima (kelp) extract.

The commercially available compounds II of the group F listed above may be found in The Pesticide Manual, 15th Edition, C. D. S. Tomlin, British Crop Protection Council (201 1 ) among other publications. Their preparation and their activity against harmful fungi is known (cf.:

http://www.alanwood.net/pesticides/); these substances are commercially available. The compounds described by lUPAC nomenclature, their preparation and their fungicidal activity are also known (cf. Can. J. Plant Sci. 48(6), 587-94, 1968; EP A 141 317; EP-A 152 031 ; EP-A 226 917; EP A 243 970; EP A 256 503; EP-A 428 941 ; EP-A 532 022; EP-A 1 028 125; EP-A 1 035 122; EP A 1 201 648; EP A 1 122 244, JP 2002316902; DE 19650197; DE 10021412; DE 102005009458; US 3,296,272; US 3,325,503; WO 98/46608; WO 99/14187; WO 99/24413; WO 99/27783; WO 00/29404; WO 00/46148; WO 00/65913; WO 01/54501 ; WO 01/56358; WO 02/22583; WO 02/40431 ; WO 03/10149; WO 03/1 1853; WO 03/14103; WO 03/16286; WO 03/53145; WO 03/61388; WO 03/66609; WO 03/74491 ; WO 04/49804; WO 04/83193; WO 05/120234; WO 05/123689; WO 05/123690; WO 05/63721 ; WO 05/87772; WO 05/87773; WO 06/15866; WO 06/87325; WO 06/87343; WO 07/82098; WO 07/90624, WO 1 1/028657).

The biopesticides of group F.XIII are disclosed above in the paragraphs about biopesticides from group ll-M.Y. The compounds I and the one or more compound(s) II are usually applied in a weight ratio of from 5000:1 to 1 :5000, preferably from 1000:1 to 1 :1000, preferably from 625:1 to 1 :625, preferably 500:1 to 1 :100, preferably from 100:1 to 1 :100 preferably from 20:1 to 1 :50, preferably from 20:1 to 1 :20, preferably from 10:1 to 1 :10, in particular from 5:1 to 1 :20, in particular from 5:1 to 1 :10, in particular from 5:1 to 1 :5.

Depending on the desired effect, the application rates of the mixtures according to the invention are from 5 g/ha to 2000 g/ha, preferably from 0.5 g/ha to 1000 g/ha, preferably from 1 to 750 g/ha, in particular from 5 to 500 g/ha.

The mixtures, as described above for the methods and uses of the invention, may optionally comprise more than one compound II as combination partner. The mixture may comprise, apart from the compound of formula (I), one active compound II (binary mixture), two active com- pounds II (ternary mixture), three active compounds II (4-way mixture), four active compounds II (5-way mixture).

All explanations and preferences as described for the methods and uses for the compound of formula (I) or a stereoisomer, salt, tautomer or N-oxide thereof, also apply for the methods and uses wherein a mixture is used, e.g. the explanations and preferences regarding pests to be controlled, insecticides to which the target organism is resistant, formulations, applications, and also the compounds of formula (I) itself.

Applications

In the methods and uses according to the invention, the application of the the compounds of the present invention, including their stereoisomers, salts, tautomers and N-oxides, is preferably as explained in the following.

The animal pest (also referred to as "invertebrate pest"), i.e. the insects, arachnids and nema- todes, the plant, soil or water in which the plant is growing can be contacted with the present compounds of formula I or composition(s) comprising them by any application method known in the art. As such, "contacting" includes both direct contact (applying the compounds/compositions directly on the animal pest or plant - typically to the foliage, stem or roots of the plant) and indirect contact (applying the compounds/compositions to the locus of the ani- mal pest or plant).

The compounds of formula I or the pesticidal compositions comprising them may be used to protect growing plants and crops from attack or infestation by animal pests, especially insects, acaridae or arachnids by contacting the plant/crop with a pesticidally effective amount of compounds of formula I. The term "crop" refers both to growing and harvested crops.

The compounds of the present invention and the compositions comprising them are particularly important in the control of a multitude of insects on various cultivated plants, such as cereal, root crops, oil crops, vegetables, spices, ornamentals, for example seed of durum and other wheat, barley, oats, rye, maize (fodder maize and sugar maize / sweet and field corn), soybeans, oil crops, crucifers, cotton, sunflowers, bananas, rice, oilseed rape, turnip rape, sugar- beet, fodder beet, eggplants, potatoes, grass, lawn, turf, fodder grass, tomatoes, leeks, pumpkin/squash, cabbage, iceberg lettuce, pepper, cucumbers, melons, Brassica species, melons, beans, peas, garlic, onions, carrots, tuberous plants such as potatoes, sugar cane, tobacco, grapes, petunias, geranium/pelargoniums, pansies and impatiens. The compounds of the present invention are employed as such or in form of compositions by treating the insects or the plants, plant propagation materials, such as seeds, soil, surfaces, materials or rooms to be protected from insecticidal attack with an insecticidally effective amount of the active compounds. The application can be carried out both before and after the infection of the plants, plant propagation materials, such as seeds, soil, surfaces, materials or rooms by the insects.

The present invention also includes a method of combating animal pests which comprises contacting the animal pests, their habitat, breeding ground, food supply, cultivated plants, seed, soil, area, material or environment in which the animal pests are growing or may grow, or the materials, plants, seeds, soils, surfaces or spaces to be protected from animal attack or infestation with a pesticidally effective amount of a mixture of at least one active compound I.

Moreover, animal pests may be controlled by contacting the target pest, its food supply, habitat, breeding ground or its locus with a pesticidally effective amount of compounds of formula I. As such, the application may be carried out before or after the infection of the locus, growing crops, or harvested crops by the pest.

The compounds of the invention can also be applied preventively to places at which occurrence of the pests is expected.

The compounds of formula I may be also used to protect growing plants from attack or infestation by pests by contacting the plant with a pesticidally effective amount of compounds of formu- la I. As such, "contacting" includes both direct contact (applying the compounds/compositions directly on the pest and/or plant - typically to the foliage, stem or roots of the plant) and indirect contact (applying the compounds/compositions to the locus of the pest and/or plant).

"Locus" means a habitat, breeding ground, plant, seed, soil, area, material or environment in which a pest or parasite is growing or may grow.

The term "plant propagation material" is to be understood to denote all the generative parts of the plant such as seeds and vegetative plant material such as cuttings and tubers (e. g. potatoes), which can be used for the multiplication of the plant. This includes seeds, roots, fruits, tubers, bulbs, rhizomes, shoots, sprouts and other parts of plants. Seedlings and young plants, which are to be transplanted after germination or after emergence from soil, may also be in- eluded. These plant propagation materials may be treated prophylactically with a plant protection compound either at or before planting or transplanting.

The term "cultivated plants" is to be understood as including plants which have been modified by breeding, mutagenesis or genetic engineering. Genetically modified plants are plants, the genetic material of which has been so modified by the use of recombinant DNA techniques that under natural circumstances cannot readily be obtained by cross breeding, mutations or natural recombination. Typically, one or more genes have been integrated into the genetic material of a genetically modified plant in order to improve certain properties of the plant. Such genetic modifications also include but are not limited to targeted post-transtional modification of protein(s) (oligo- or polypeptides) for example by glycosylation or polymer additions such as prenylated, acetylated or farnesylated moieties or PEG moieties(e.g. as disclosed in Biotechnol Prog. 2001 Jul-Aug;17(4):720-8., Protein Eng Des Sel. 2004 Jan;17(1 ):57-66, Nat Protoc. 2007;2(5): 1225- 35., Curr Opin Chem Biol. 2006 Oct;10(5):487-91. Epub 2006 Aug 28., Biomaterials. 2001 Mar;22(5):405-17, Bioconjug Chem. 2005 Jan-Feb;16(1 ):1 13-21 ). The term "cultivated plants" is to be understood also including plants that have been rendered tolerant to applications of specific classes of herbicides, such as hydroxy- phenyl pyruvate diox- ygenase (HPPD) inhibitors; acetolactate synthase (ALS) inhibitors, such as sulfonyl ureas (see e. g. US 6,222,100, WO 01/82685, WO 00/26390, WO 97/ 41218, WO 98/02526, WO

98/02527, WO 04/106529, WO 05/20673, WO 03/14357, WO 03/13225, WO 03/14356, WO 04/16073) or imidazolinones (see e. g. US 6222100, WO 01/82685, WO 00/26390, WO

97/41218, WO 98/02526, WO 98/02527, WO 04/ 106529, WO 05/20673, WO 03/14357, WO 03/13225, WO 03/14356, WO 04/16073); enolpyruvylshikimate-3-phosphate synthase (EPSPS) inhibitors, such as glyphosate (see e. g. WO 92/00377); glutamine synthetase (GS) inhibitors, such as glufosinate (see e. g. EP-A-0242236, EP-A-242246) or oxynil herbicides (see e. g. US 5,559,024) as a result of conventional methods of breeding or genetic engineering. Several cultivated plants have been rendered tolerant to herbicides by conventional methods of breeding (mutagenesis), for example Clearfield® summer rape (Canola) being tolerant to imidazolinones, e. g. imazamox. Genetic engineering methods have been used to render cultivated plants, such as soybean, cotton, corn, beets and rape, tolerant to herbicides, such as glyphosate and glufosinate, some of which are commercially available under the trade names RoundupReady® (glyphosate) and LibertyLink® (glufosinate).

The term "cultivated plants" is to be understood also including plants that are by the use of recombinant DNA techniques capable to synthesize one or more insecticidal proteins, especially those known from the bacterial genus Bacillus, particularly from Bacillus thuringiensis, such as a-endotoxins, e. g. CrylA(b), CrylA(c), CrylF, CrylF(a2), CryllA(b), CrylllA, CrylllB(bl ) or Cry9c; vegetative insecticidal proteins (VIP), e. g. VIP1 , VIP2, VIP3 or VIP3A; insecticidal proteins of bacteria colonizing nematodes, for example Photorhabdus spp. or Xenorhabdus spp.; toxins produced by animals, such as scorpion toxins, arachnid toxins, wasp toxins, or other insect- specific neurotoxins; toxins produced by fungi, such Streptomycetes toxins, plant lectins, such as pea or barley lectins; agglutinins; proteinase inhibitors, such as trypsin inhibitors, serine protease inhibitors, patatin, cystatin or papain inhibitors; ribosome-inactivating proteins (RIP), such as ricin, maize-RIP, abrin, luffin, saporin or bryodin; steroid metabolism enzymes, such as 3- hydroxysteroid oxidase, ecdysteroid-IDP-glycosyl-transferase, cholesterol oxidases, ecdysone inhibitors or HMG-CoA-reductase; ion channel blockers, such as blockers of sodium or calcium channels; juvenile hormone esterase; diuretic hormone receptors (helicokinin receptors); stilben synthase, bibenzyl synthase, chitinases or glucanases. In the context of the present invention these insecticidal proteins or toxins are to be understood expressly also as pre-toxins, hybrid proteins, truncated or otherwise modified proteins. Hybrid proteins are characterized by a new combination of protein domains, (see, for example WO 02/015701 ). Further examples of such toxins or genetically-modified plants capable of synthesizing such toxins are dis-closed, for example, in EP-A 374 753, WO 93/007278, WO 95/34656, EP-A 427 529, EP-A 451 878, WO 03/018810 und WO 03/052073. The methods for producing such genetically modified plants are generally known to the person skilled in the art and are described, for example, in the publica- tions mentioned above. These insecticidal proteins contained in the genetically modified plants impart to the plants producing these proteins protection from harmful pests from certain taxo- nomic groups of arthropods, particularly to beetles (Coleoptera), flies (Diptera), and butterflies and moths (Lepidoptera) and to plant parasitic nematodes (Nematoda). The term "cultivated plants" is to be understood also including plants that are by the use of recombinant DNA techniques capable to synthesize one or more proteins to increase the resistance or tolerance of those plants to bacterial, viral or fungal pathogens. Examples of such proteins are the so-called "pathogenesis-related proteins" (PR proteins, see, for example EP-A 0 392 225), plant disease resistance genes (for example potato cultivars, which express resistance genes acting against Phytophthora infestans derived from the mexican wild potato So- lanum bulbocastanum) or T4-lyso-zym (e. g. potato cultivars capable of synthesizing these proteins with increased resistance against bacteria such as Erwinia amylvora). The methods for producing such genetically modified plants are generally known to the person skilled in the art and are described, for example, in the publications mentioned above.

The term "cultivated plants" is to be understood also including plants that are by the use of recombinant DNA techniques capable to synthesize one or more proteins to increase the productivity (e. g. bio mass production, grain yield, starch content, oil content or protein content), tolerance to drought, salinity or other growth-limiting environ-mental factors or tolerance to pests and fungal, bacterial or viral pathogens of those plants.

The term "cultivated plants" is to be understood also including plants that contain by the use of recombinant DNA techniques a modified amount of substances of content or new substances of content, specifically to improve human or animal nutrition, for ex-ample oil crops that produce health-promoting long-chain omega-3 fatty acids or unsaturated omega-9 fatty acids (e. g. Nex- era® rape).

The term "cultivated plants" is to be understood also including plants that contain by the use of recombinant DNA techniques a modified amount of substances of content or new substances of content, specifically to improve raw material production, for example potatoes that produce increased amounts of amylopectin (e. g. Amflora® potato).

In general, "pesticidally effective amount" means the amount of active ingredient needed to achieve an observable effect on growth, including the effects of necrosis, death, retardation, prevention, and removal, destruction, or otherwise diminishing the occurrence and activity of the target organism. The pesticidally effective amount can vary for the various com- pounds/compositions used in the invention. A pesticidally effective amount of the compositions will also vary according to the prevailing conditions such as desired pesticidal effect and duration, weather, target species, locus, mode of application, and the like.

In the case of foliar treatment ,the quantity of active ingredient ranges from 0.0001 to 500 g per 100 m², preferably from 0.001 to 20 g per 100 m², or from 1 to 100 g per hectare, preferably from 10 to 50 g per hectare, or from 12 to 50 g per hectare, or from 10 to 30 g per hectare, or from 20 to 40 g per hectare, or from 10 to 20 g per hectare, or from 20 to 30 g per hectare, or from 30 to 40 g per hectare, or from 40 to 50 g per hectare.

In the case of soil treatment or of application to the pests dwelling place or nest, the quantity of active ingredient ranges from 0.0001 to 500 g per 100 m², preferably from 0.001 to 20 g per 100 m².

Customary application rates in the protection of materials are, for example, from 0.01 g to 1000 g of active compound per m² treated material, desirably from 0.1 g to 50 g per m². Insecticidal compositions for use in the impregnation of materials typically contain from 0.001 to 95 weight %, preferably from 0.1 to 45 weight %, and more preferably from 1 to 25 weight % of at least one repellent and/or insecticide.

For use in treating crop plants, the rate of application of the active ingredients of this invention may be in the range of 0.1 g to 4000 g per hectare, desirably from 25 g to 600 g per hectare, more desirably from 50 g to 500 g per hectare.

The compounds of formula I are effective through both contact (via soil, glass, wall, bed net, carpet, plant parts or animal parts), and ingestion (bait, or plant part).

The compounds of the invention may also be applied against non-crop insect pests, such as ants, termites, wasps, flies, mosquitos, crickets, or cockroaches. For use against said non-crop pests, compounds of formula I are preferably used in a bait composition.

The bait can be a liquid, a solid or a semisolid preparation (e.g. a gel). Solid baits can be formed into various shapes and forms suitable to the respective application e.g. granules, blocks, sticks, disks. Liquid baits can be filled into various devices to ensure proper application, e.g. open containers, spray devices, droplet sources, or evaporation sources. Gels can be based on aqueous or oily matrices and can be formulated to particular necessities in terms of stickyness, moisture retention or aging characteristics.

The bait employed in the composition is a product, which is sufficiently attractive to incite insects such as ants, termites, wasps, flies, mosquitos, crickets etc. or cockroaches to eat it. The attractiveness can be manipulated by using feeding stimulants or sex pheromones. Food stimulants are chosen, for example, but not exclusively, from animal and/or plant proteins (meat-, fish- or blood meal, insect parts, egg yolk), from fats and oils of animal and/or plant origin, or mono-, oligo- or polyorganosaccharides, especially from sucrose, lactose, fructose, dextrose, glucose, starch, pectin or even molasses or honey. Fresh or decaying parts of fruits, crops, plants, animals, insects or specific parts thereof can also serve as a feeding stimulant. Sex pheromones are known to be more insect specific. Specific pheromones are described in the literature and are known to those skilled in the art.

For use in bait compositions, the typical content of active ingredient is from 0.001 weight % to 15 weight %, desirably from 0.001 weight % to 5% weight % of active compound.

Formulations of compounds of formula I as aerosols (e.g in spray cans), oil sprays or pump sprays are highly suitable for the non-professional user for controlling pests such as flies, fleas, ticks, mosquitos or cockroaches. Aerosol recipes are preferably composed of the active compound, solvents such as lower alcohols (e.g. methanol, ethanol, propanol, butanol), ketones (e.g. acetone, methyl ethyl ketone), paraffin hydrocarbons (e.g. kerosenes) having boiling rang- es of approximately 50 to 250 °C, dimethylformamide, N-methylpyrrolidone, dimethyl sulfoxide, aromatic hydrocarbons such as toluene, xylene, water, furthermore auxiliaries such as emulsifi- ers such as sorbitol monooleate, oleyl ethoxylate having 3-7 mol of ethylene oxide, fatty alcohol ethoxylate, perfume oils such as ethereal oils, esters of medium fatty acids with lower alcohols, aromatic carbonyl compounds, if appropriate stabilizers such as sodium benzoate, amphoteric surfactants, lower epoxides, triethyl orthoformate and, if required, propellants such as propane, butane, nitrogen, compressed air, dimethyl ether, carbon dioxide, nitrous oxide, or mixtures of these gases.

The oil spray formulations differ from the aerosol recipes in that no propellants are used. For use in spray compositions, the content of active ingredient is from 0.001 to 80 weights %, preferably from 0.01 to 50 weight % and most preferably from 0.01 to 15 weight %.

The compounds of formula I and its respective compositions can also be used in mosquito and fumigating coils, smoke cartridges, vaporizer plates or long-term vaporizers and also in moth papers, moth pads or other heat-independent vaporizer systems.

Methods to control infectious diseases transmitted by insects (e.g. malaria, dengue and yellow fever, lymphatic filariasis, and leishmaniasis) with compounds of formula I and its respective compositions also comprise treating surfaces of huts and houses, air spraying and impregnation of curtains, tents, clothing items, bed nets, tsetse-fly trap or the like. Insecticidal compositions for application to fibers, fabric, knitgoods, nonwovens, netting material or foils and tarpaulins preferably comprise a mixture including the insecticide, optionally a repellent and at least one binder. Suitable repellents for example are Ν,Ν-Diethyl-meta-toluamide (DEET), N,N- diethylphenylacetamide (DEPA), 1 -(3-cyclohexan-1 -yl-carbonyl)-2-methylpiperine, (2- hydroxymethylcyclohexyl) acetic acid lactone, 2-ethyl-1 ,3-hexandiol, indalone, Methyl- neodecanamide (MNDA), a pyrethroid not used for insect control such as {(+/-)-3-allyl-2-methyl- 4-oxocyclopent-2-(+)-enyl-(+)-trans-chrysantemate (Esbiothrin), a repellent derived from or identical with plant extracts like limonene, eugenol, (+)-Eucamalol (1 ), (-)-l -epi-eucamalol or crude plant extracts from plants like Eucalyptus maculata, Vitex rotundifolia, Cymbopogan martinii, Cymbopogan citratus (lemon grass), Cymopogan nartdus (citronella). Suitable binders are se- lected for example from polymers and copolymers of vinyl esters of aliphatic acids (such as such as vinyl acetate and vinyl versatate), acrylic and methacrylic esters of alcohols, such as butyl acrylate, 2-ethylhexylacrylate, and methyl acrylate, mono- and di-ethylenically unsaturated hydrocarbons, such as styrene, and aliphatic diens, such as butadiene.

The impregnation of curtains and bednets is done in general by dipping the textile material into emulsions or dispersions of the insecticide or spraying them onto the nets.

The compounds of formula I and its compositions can be used for protecting wooden materials such as trees, board fences, sleepers, etc. and buildings such as houses, outhouses, factories, but also construction materials, furniture, leathers, fibers, vinyl articles, electric wires and cables etc. from ants and/or termites, and for controlling ants and termites from doing harm to crops or human being (e.g. when the pests invade into houses and public facilities). The compounds of formula I are applied not only to the surrounding soil surface or into the under-floor soil in order to protect wooden materials but it can also be applied to lumbered articles such as surfaces of the under-floor concrete, alcove posts, beams, plywoods, furniture, etc., wooden articles such as particle boards, half boards, etc. and vinyl articles such as coated electric wires, vinyl sheets, heat insulating material such as styrene foams, etc. In case of application against ants doing harm to crops or human beings, the ant controller of the present invention is applied to the crops or the surrounding soil, or is directly applied to the nest of ants or the like.

Seed treatment

In the methods and uses according to the invention, the compounds of formula I are also suitable for improving plant health, by the application of the compounds according to the invention to plant propagagation material, especially seeds, and/or soil. In the methods and uses according to the invention, the compounds of formula I are also suitable for the treatment of soil. Soil application techniques and soil application methods according to the present invention, are methods wherein the active compound(s) are applied by drenching the soil, applied by drip irrigation, applied by soil injection. Another soil application technique in the sense of the present invention is a method, wherein the active compound(s) are applied by dipping roots, tubers or bulbs.

An alternative method of soil application technique is that the active compound(s) are applied with drip application systems. In the case of soil treatment or of application to the pests dwelling place or nest, the quantity of active ingredient ranges from 0.0001 to 500 g per 100 m², prefera- bly from 0.001 to 20 g per 100 m².

The compounds of formula I are particularly useful for improving plant health of seed by application of the compounds according to the invention in the soil. The improvement of plant health of the resulting plant's roots and shoots is preferred.

The present invention therefore comprises a method for the improvement of plant health of seeds, said method comprising contacting the seeds before sowing and/or after pregermination with a compound of the general formula I or a salt thereof. Particularly preferred is a method, wherein the plant health of the plant's roots and shoots is improved.

The term seed embraces seeds and plant propagules of all kinds including but not limited to true seeds, seed pieces, suckers, corms, bulbs, fruit, tubers, grains, cuttings, cut shoots and the like and means in a preferred embodiment true seeds.

The term seed treatment comprises all suitable seed treatment techniques known in the art, such as seed dressing, seed coating, seed dusting, seed soaking and seed pelleting.

The present invention also comprises seeds coated with or containing the active compound. The term "coated with and/or containing" generally signifies that the active ingredient is for the most part on the surface of the propagation product at the time of application, although a greater or lesser part of the ingredient may penetrate into the propagation product, depending on the method of application. When the said propagation product is (re)planted, it may absorb the active ingredient.

Suitable seed is seed of cereals, root crops, oil crops, vegetables, spices, ornamentals, for example seed of durum and other wheat, barley, oats, rye, maize (fodder maize and sugar maize / sweet and field corn), soybeans, oil crops, crucifers, cotton, sunflowers, bananas, rice, oilseed rape, turnip rape, sugarbeet, fodder beet, eggplants, potatoes, grass, lawn, turf, fodder grass, tomatoes, leeks, pumpkin/squash, cabbage, iceberg lettuce, pepper, cucumbers, melons, Bras- sica species, melons, beans, peas, garlic, onions, carrots, tuberous plants such as potatoes, sugar cane, tobacco, grapes, petunias, geranium/pelargoniums, pansies and impatiens.

In addition, the active compound may also be used for the treatment of seeds from plants, which tolerate the action of herbicides or fungicides or insecticides owing to breeding, including genetic engineering methods.

For example, the active compound can be employed in treatment of seeds from plants, which are resistant to herbicides from the group consisting of the sulfonylureas, imidazolinones, glufosinate-ammonium or glyphosate-isopropylammonium and analogous active substances (see for example, EP-A 242 236, EP-A 242 246) (WO 92/00377) (EP-A 257 993, U.S. 5,013,659) or in transgenic crop plants, for example cotton, with the capability of producing Bacillus thuringiensis toxins (Bt toxins) which make the plants resistant to certain pests (EP-A 142 924, EP-A 193 259),

Furthermore, the active compound can be used also for the treatment of seeds from plants, which have modified characteristics in comparison with existing plants consist, which can be generated for example by traditional breeding methods and/or the generation of mutants, or by recombinant procedures). For example, a number of cases have been described of recombinant modifications of crop plants for the purpose of modifying the starch synthesized in the plants (e.g. WO 92/1 1376, WO 92/14827, WO 91/19806) or of transgenic crop plants having a modi- fied fatty acid composition (WO 91/13972).

The seed treatment application of the active compound is carried out by spraying or by dusting the seeds before sowing of the plants and before emergence of the plants.

Compositions which are especially useful for seed treatment are e.g.:

A Soluble concentrates (SL, LS)

D Emulsions (EW, EO, ES)

E Suspensions (SC, OD, FS)

F Water-dispersible granules and water-soluble granules (WG, SG)

G Water-dispersible powders and water-soluble powders (WP, SP, WS)

H Gel-Formulations (GF)

I Dustable powders (DP, DS)

Conventional seed treatment formulations include for example flowable concentrates FS, solutions LS, powders for dry treatment DS, water dispersible powders for slurry treatment WS, wa- ter-soluble powders SS and emulsion ES and EC and gel formulation GF. These formulations can be applied to the seed diluted or undiluted. Application to the seeds is carried out before sowing, either directly on the seeds or after having pregerminated the latter

In a preferred embodiment a FS formulation is used for seed treatment. Typcially, a FS formulation may comprise 1 -800 g/l of active ingredient, 1-200 g/l Surfactant, 0 to 200 g/l antifreezing agent, 0 to 400 g/l of binder, 0 to 200 g/l of a pigment and up to 1 liter of a solvent, preferably water.

Especially preferred FS formulations of compounds of formula I for seed treatment usually comprise from 0.1 to 80% by weight (1 to 800 g/l) of the active ingredient, from 0.1 to 20 % by weight (1 to 200 g/l) of at least one surfactant, e.g. 0.05 to 5 % by weight of a wetter and from 0.5 to 15 % by weight of a dispersing agent, up to 20 % by weight, e.g. from 5 to 20 % of an anti-freeze agent, from 0 to 15 % by weight, e.g. 1 to 15 % by weight of a pigment and/or a dye, from 0 to 40 % by weight, e.g. 1 to 40 % by weight of a binder (sticker /adhesion agent), optionally up to 5 % by weight, e.g. from 0.1 to 5 % by weight of a thickener, optionally from 0.1 to 2 % of an anti-foam agent, and optionally a preservative such as a biocide, antioxidant or the like, e.g. in an amount from 0.01 to 1 % by weight and a filler/vehicle up to 100 % by weight.

Seed Treatment formulations may additionally also comprise binders and optionally colorants. Binders can be added to improve the adhesion of the active materials on the seeds after treatment. Suitable binders are homo- and copolymers from alkylene oxides like ethylene oxide or propylene oxide, polyvinylacetate, polyvinylalcohols, polyvinylpyrrolidones, and copolymers thereof, ethylene-vinyl acetate copolymers, acrylic homo- and copolymers, polyethyleneamines, polyethyleneamides and polyethyleneimines, polysaccharides like celluloses, tylose and starch, polyolefin homo- and copolymers like olefin/maleic anhydride copolymers, polyurethanes, poly- esters, polystyrene homo and copolymers

Optionally, also colorants can be included in the formulation. Suitable colorants or dyes for seed treatment formulations are Rhodamin B, C.I. Pigment Red 1 12, C.I. Solvent Red 1 , pigment blue 15:4, pigment blue 15:3, pigment blue 15:2, pigment blue 15:1 , pigment blue 80, pigment yellow 1 , pigment yellow 13, pigment red 1 12, pigment red 48:2, pigment red 48:1 , pigment red 57: 1 , pigment red 53: 1 , pigment orange 43, pigment orange 34, pigment orange 5, pigment green 36, pigment green 7, pigment white 6, pigment brown 25, basic violet 10, basic violet 49, acid red 51 , acid red 52, acid red 14, acid blue 9, acid yellow 23, basic red 10, basic red 108. Examples of a gelling agent is carrageen (Satiagel^®)

In the treatment of seed, the application rates of the compounds I are generally from 0.1 g to 10 kg per 100 kg of seed, preferably from 1 g to 5 kg per 100 kg of seed, more preferably from 1 g to 1000 g per 100 kg of seed and in particular from 1 g to 200 g per 100 kg of seed.

Examples

The present invention is now illustrated in further detail by the following examples.

A. Chemistry

The compounds I of formula I can be accomplished according to standard methods of organic chemistry, e.g. by the methods or working examples described in WO 2007/006670,

PCT/EP2012/065650, PCT/E P2012/065651.

The characterization can be done by coupled High Performance Liquid Chromatography / mass spectrometry (HPLC/MS), by NMR or by their melting points.

Method A: Analytical HPLC column: RP-18 column Chromolith Speed ROD from Merck KgaA (Germany). Elution: acetonitrile + 0.1 % trifluoroacetic acid (TFA) / water + 0.1 % trifluoroacetic acid (TFA) in a ratio of from 5:95 to 95:5 in 5 minutes at 40 °C.

Method B: Analytical UPLC column: Phenomenex Kinetex 1 ,7 μηι XB-C18 100A; 50 x 2.1 mm; mobile phase: A: water + 0.1 % trifluoroacetic acid (TFA); B: acetonitrile + 0.1 % TFA; gradient: 5-100% B in 1.50 minutes; 100% B 0.20 min; flow: 0,8-1 ,0mL/min in 1 ,50 minutes at 60°C. MS-method: ESI positive.

¹H-NMR. The signals are characterized by chemical shift (ppm) vs. tetramethylsilane, by their multiplicity and by their integral (relative number of hydrogen atoms given). The following abbreviations are used to characterize the multiplicity of the signals: m = multiplett, q = quartett, t = triplett, d = doublet and s = singulett.

Preparation Examples:

logP determinations were performed via capillary electrophorese on a cePro9600™ from CombiSep.

Starting materials 6,8-dichloro-1 H-benzo[d][1 ,3]oxazine-2,4-dione and 6-chloro-8-methyl-1 H-3,1 - benzoxazine-2,4-dione were prepared according to WO 2007/43677.

S,S-Diisopropyl-S-aminosulfonium 2,4,6-trimethylphenylsulfonat was prepared according to Y. Tamura et al, Tetrahedron 1975, 31 , 3035-3040.

2-(3-Chloropyridin-2-yl)-5-bromo-2H-pyrazole-3-carbonyl chloride was prepared according to WO 2007/24833.

Preparation Examples P.1 to P.4 Example P.1 : S,S-Dimethyl sulfinium sulfate

To a solution of sodium methylate (15.76 g of a 30% solution in methanol, 87.54 mmol, 1 .100 equiv.) in methanol (60 mL) was added dimethyl sulphide (5.44 g, 6.40 mL, 87.6 mmol, 1 .10 equiv.) at -5-0°C. To this mixture was added a pre-cooled solution (-20°C) of hydroxyla- mine-O-sulfonic acid (9.00 g, 79.6 mmol) in methanol (60 mL) and the internal temperature was maintained at -5-0°C. After stirring at room temperature overnight, all solids were removed by filtration. The filtrate was concentrated in vacuo and the residue was triturated with acetonitrile (50 mL) to yield the title compound (7.88 g, 39%).

The following compounds were prepared by analogy to example P.1 :

S,S-diethyl sulfinium sulfate

S-ethyl-S-isopropyl sulfinium sulfate

S,S-diisopropyl sulfinium sulfate

S,S-bis(2-cyclopropylmethyl) sulfinium sulfate

S,S-bis(2-cyclopropylethyl) sulfinium sulfate

S,S-bis(cyclobutylmethyl) sulfinium sulfate

S,S-bis(cyclopentylmethyl) sulfinium sulfate

S-cyclopropylmethyl-S-ethyl sulfinium sulfate

S-(2-cyclopropylethyl)-S-ethyl sulfinium sulfate

S-(2-cyclopropylethyl)-S-isopropyl sulfinium sulfate

S-(1 -cyclopropylethyl)-S-isopropyl sulfinium sulfate

S-cyclobutylmethyl-S-ethyl sulfinium sulfate

S-cyclopentylmethyl-S-ethyl sulfinium sulfate

S-cyclopropylmethyl-S-isopropyl sulfinium sulfate

S-cyclobutylmethyl-S-isopropyl sulfinium sulfate

S-cyclopentylmethyl-S-isopropyl sulfinium sulfate

S,S-di-n-propyl sulfinium sulfate

S-vinyl-S-ethyl sulfinium sulfate

Example P.2: 8-Bromo-6-chloro-1 H-benzo[d][1 ,3]oxazine-2,4-dione

To a solution of 2-amino-3-bromo-5-chlorobenzoic acid (10.0 g, 39.9 mmol) in dioxane (170 mL) was added phosgene (20% in toluene, 42.0 mL, 79.9 mmol) over a period of 15 mins. The reaction was stirred at ambient temperature for 48 h and then concentrated in vacuo. The resulting solid was crushed and further dried in vacuo to yield the desired product (12.6 g, 1 14%) which was used in the subsequent step without further purification.

The following compounds were prepared by analogy to example P.2:

6,8-dichloro-1 H-benzo[d][1 ,3]oxazine-2,4-dione,

6,8-dibromo-1 H-benzo[d][1 ,3]oxazine-2,4-dione,

6-Bromo-8-chloro-1 H-benzo[d][1 ,3]oxazine-2,4-dione,

8-Bromo-6-chloro-1 H-benzo[d][1 ,3]oxazine-2,4-dione,

6-chloro-8-methyl-1 H-benzo[d][1 ,3]oxazine-2,4-dione,

6-bromo-8-methyl-1 H-benzo[d][1 ,3]oxazine-2,4-dione,

6-cyano-8-methyl-1 H-benzo[d][1 ,3]oxazine-2,4-dione,

6-chloro-8-trifluoromethyl-1 H-benzo[d][1 ,3]oxazine-2,4-dione,

8-chloro-6-trifluoromethyl-1 H-benzo[d][1 ,3]oxazine-2,4-dione,

6-bromo-8-trifluoromethyl-1 H-benzo[d][1 ,3]oxazine-2,4-dione,

8-bromo-6-trifluoromethyl-1 H-benzo[d][1 ,3]oxazine-2,4-dione,

8-chloro-6-cyano-1 H-benzo[d][1 ,3]oxazine-2,4-dione,

6-chloro-8-methoxy-1 H-benzo[d][1 ,3]oxazine-2,4-dione,

6-chloro-8-cyclopropyl-1 H-benzo[d][1 ,3]oxazine-2,4-dione,

6-chloro-8-ethyl-1 H-benzo[d][1 ,3]oxazine-2,4-dione,

6-difluoromethoxy-8-methyl-1 H-benzo[d][1 ,3]oxazine-2,4-dione,

6-cyano-8-methoxy-1 H-benzo[d][1 ,3]oxazine-2,4-dione,

6-fluoro-8-methyl-1 H-benzo[d][1 ,3]oxazine-2,4-dione,

6-iodo-8-methyl-1 H-benzo[d][1 ,3]oxazine-2,4-dione,

6-nitro-8-methyl-1 H-benzo[d][1 ,3]oxazine-2,4-dione,

6-(5-chloro-2-thienyl)-8-methyl-1 H-benzo[d][1 ,3]oxazine-2,4-dione,

6-(3-pyrazol-1 H-yl)-8-methyl-1 H-benzo[d][1 ,3]oxazine-2,4-dione,

6-(3-isoxazolyl)-8-methyl-1 H-benzo[d][1 ,3]oxazine-2,4-dione,

6-(hydroxyiminomethyl)-8-methyl-1 H-benzo[d][1 ,3]oxazine-2,4-dione,

6-(methoxyiminomethyl)-8-methyl-1 H-benzo[d][1 ,3]oxazine-2,4-dione,

6-(dimethylhydrazonomethyl)-8-methyl-1 H-benzo[d][1 ,3]oxazine-2,4-dione and

6-(2,2,2-trifluoroethylhydrazonomethyl)-8-methyl-1 H-benzo[d][1 ,3]oxazine-2,4-dione.

Example P.3: 1 -(3-chloro-2-pyridyl)-3-trifluoromethyl-1 H-pyrazol

a) 2.71 kg of 1 ,1 ,1 -trifluoro-4-methoxy-but-3-en-2-one, 2,44 kg of ethanol and 3.10 kg of water were charged into a reaction vessel. 20 ml of concentrated hydrochloric acid and 0,80 kg of hydrazine hydrate were successively added and the mixture was heated to reflux for 4 h. The mixtures was allowed to cool and neutralized by addition of 10 % aqueous NaOH to about pH 4-5. Then the mixture was evaporated. Toluene was added and the mixture was again evaporated to yield 2 kg of raw 3-trifluoromethylpyrazole with a purity of > 85 %.

b) 1 .72 kg (10.75 mol) of the raw 3-trifluoromethylpyrazole obtained in step a), 1.75 kg (1 1.83 mol) of 2,3-dichloropyridine and 4.73 kg of dimethyl formamide were charged to a reaction vessel. 2.97 kg (21 .50 mol) of potassium carbonate were added, the mixture was heated to 120°C with stirring and kept at 120-125°C for further 3 h. The reaction mixtures was cooled to 25°C and poured into 20 I of water. The thus obtained mixture was extracted twice with 5 L of tert- butylmethyl ether. The combined organic phases were washed with 4 I of water and then evaporated to dryness. Toluene was added and the mixture was again evaporated to dryness. Thereby, the 2.7 kg of the title compound was obtained (purity > 75% as determined by GC; yield 81.5%). The product can be purified by distillation.

H-NMR (400 MHz, CDCI₃): δ [delta] = 6.73 (d, 1 H), 7.38 (d, 1 H), 7.95 (m, 1 H), 8.14 (m, 1 H), 8.46 (m, 1 H).

Example P.4: 2-(3-Chloropyridin-2-yl)-5-trifluoromethyl-2H-pyrazole-3-carbonyl chloride

In a reaction vessel equipped with a thermometer, septum, nitrogen inlet and stirring bar, 10.0 g (40.4 mmol) of 1 -(3-chloro-2-pyridyl)-3-trifloromethyl-1 H-pyrazole were dissolved in 50 ml of dry dimethoxyethane. By means of a syringe, 40.4 ml of a 2 M solution (80.8 mmol, 2.0 equiv.) of isopropyl magnesium chloride in tetrahydrofuran were added dropwise with stirring, while cooling the vessel with an ice bath and keeping the internal temperature at about 5°C. The mixture was stirred for further 2 hours at 5°C. Then the ice-bath was removed and carbon dioxide was bubbled through mixture causing an increase of the temperature up to 28°C. After 10 minutes, the exothermic reaction has ceased, and, the mixture was cooled and all volatiles were removed by evaporation. The residue containing the carboxylate compound l-A was taken up in 50 mL of dichloromethane and one drop of dry DMF was added. To this mixture, 14.41 g (121 .2 mmol, 3.0 equiv.) of thionyl chloride were added and heated to reflux for 3 hours. After cooling, the resulting precipitate was removed by filtration and the mother liquid was concentrated in vacuum to obtain 13.0 g of the title compound (purity >85%, yield 100%) which was used in the next step without further purification.

H-NMR (400 MHz, CDC ): 5[delta] = 7.43-7.54 (m, 2H), 7.93 (d, 1 H), 8.52 (m, 1 H).

Example P.5: 2-amino-5-chloro-N-(dimethyl- ⁴-sulfanylidene)-3-methyl-benzamide

To a solution of 6-chloro-8-methyl-1 H-3,1 -benzoxazine-2,4-dione (3.00 g, 12.8 mmol) in dichloromethane (40 mL) was added dimethyl sulfinium sulfate (2.25 g, 8.93 mmol, 0.70 equiv.) and potassium tert-butylate (1 .58 g, 14.0 mmol, 1 .10 equiv.) at room temperature. The mixture was stirred for 1.5 h, upon which water was added and the layers were separated. The aqueous layer was extracted with dichloromethane, combined organic layers were dried over sodium sulphate and concentrated in vacuo. The residue was purified by flash-chromatography on silica gel to yield the title compound (2.63 g, 84%).

Characterization by HPLC-MS: 1 .855 min, M = 245.00.

Example P.6: 2-amino-5-chloro-N-(bis-2-methylpropyl- ⁴-sulfanylidene)-3-methyl-benzamide To a solution of 6-chloro-8-methyl-1 H-3,1 -benzoxazine-2,4-dione (3.00 g, 12.8 mmol) in dichloromethane (40 mL) was added bis-2-methylpropyl sulfinium sulfate (3.76 g, 8.93 mmol, 0.70 equiv.) and potassium tert-butylate (1.58 g, 14.0 mmol, 1 .10 equiv.) at room temperature. The mixture was stirred for 1 .5 h, upon which water was added and the layers were separated. The aqueous layer was extracted with dichloromethane, combined organic layers were dried over sodium sulphate and concentrated in vacuo. The residue was purified by flash-chromatography on silica gel to yield the title compound (2.89 g, 69%). Characterization by H-NMR (400 MHz, DMSO-de): 5[delta] = 1.04 (m, 12 H), 2.06 (s, 3H), 2.96 (m, 2H), 3.01 (m, 2H), 6.62 (br. s, 2H), 7.03 (s, 1 H), 7.72 (s, 1 H).

Example P.7: 2-amino-5-chloro-N-(diethyl- ⁴-sulfanylidene)-3-methyl-benzamide

To a solution of 6-chloro-8-methyl-1 H-3,1 -benzoxazine-2,4-dione (2 g, 0.01 mol) in anhydrous propylene carbonate (30 mL) was added bis-2-ethyl sulfinium sulfate (2.04 g, 0.01 mol, 0.70 equiv.) and triethyl amine (1 .38 mL, 1.0 g g, 0.01 mol, 1.05 equiv.) at room temperature. The mixture was stirred for 4.5 h, and then added dropwise to ice-water. The mixture was extracted with dichloromethane and the combined organic layers were dried over sodium sulphate and concentrated in vacuo. The residue was triturated with ether to yield the title compound (1.43 g, 55%).

Characterization by H-NMR (400 MHz, CDCI₃): 5[delta] = 1.39 (t, 6 H), 2.13 (s, 3H), 3.02 (q, 4H), 5.95 (br. S, 2H), 7.01 (s, 1 H), 7.98 (s, 1 H).

Example P.8: 2-amino-3,5-dichloro-N-(bis-2-methylpropyl- ⁴-sulfanylidene)-benzamide

The title compound was prepared by analogy to the method of example P.6

Yield: 60%

Characterization by H-NMR (400 MHz, DMSO-d₆): 5[delta] = 1.23 (d, 6H), 1 .38 (d, 6H), 3.42 (m, 2H), 7.02 (br. s, 2H), 7.41 (s, 1 H), 7.95 (s, 1 H). Example P.9: 2-amino-3,5-dibromo-N-(bis-2-methylpropyl- ⁴-sulfanylidene)-benzamide

The title compound was prepared by analogy to the method of example P.6

Yield: 66%

Characterization by HPLC-MS: 3.409 min, m/z = 410.90 (Method A) Preparation of the compounds of formula IA-1 (Examples 1 to 4) Example 1 : 2-(3-chloro-2-pyridyl)-N-[2,4-dichloro-6-[(diethyl- ⁴- sulfanylidene)carbamoyl]phenyl]-5-(trifluoromethyl)pyrazole-3-carboxamide (Compound 1-16) To a suspension of potassium carbonate (8.08 g, 58.5 mmol, 1 .50 equiv) and 2-amino-3,5- dichloro-N-(diethyl- ⁴-sulfanylidene)benzamide (1 1.43 g, 38.98 mmol) in acetonitrile (100 mL) was added a solution of 2-(3-chloro-2-pyridyl)-5-(trifluoromethyl)pyrazole-3-carbonyl chloride (15.8 g, 43.31 mmol, 1 .10 equiv.) in acetonitrile (50 mL) at room temperature. After 6 h at this temperature, the solids were filtered off. The resulting filtrate was washed with water and dried over Na2S0₄. After filtration, the filtrate was concentrated in vacuum and the resulting solids were crystallized from diisopropyl ether to yield the title compound (19.53 g, 88%).

Characterization by ¹H-NMR (400 MHz, DMSO-afe):

5[delta] = 1.13 (t, 6H), 2.91 (m, 2H), 3.08 (m, 2H), 7.67 (dd, 1 H), 7.77 (s, 2H), 7.89 (s, 1 H), 8.22 (d, 1 H), 8.51 (d, 1 H), 10.73 (s, 1 H). Example 2: Synthesis of 2-(3-chloro-2-pyridyl)-N-[2,4-dichloro-6-[(bis-2-propyl- ⁴- sulfanylidene)carbamoyl]phenyl]-5-(trifluoromethyl)pyrazole-3-carboxamide (Compound (I-26) To a suspension of potassium carbonate (0.892 g, 6.46 mmol, 1 .10 equiv) and 2-amino-3,5- dichloro-N-(bis-2-propyl- ⁴-sulfanylidene)benzamide (2.05 g, 5.87 mmol) in toluene (30 mL) was added a solution of 2-(3-chloro-2-pyridyl)-5-(trifluoromethyl)pyrazole-3-carbonyl chloride (2.02 g, 5.87 mmol, 1.00 equiv.) in toluene (20 mL) at 60°C. After 45 min at this temperature, the mixture was cooled and water was added. The resulting precipitate was collected by filtration, washed with water and toluene and dried to obtain the title compound (3.07 g, 84%).

Characterization by HPLC-MS: 1 .395 min, M = 602.1 (Method B)

Characterization by ¹H-NMR (400 MHz, DMSO-afe):

5[delta] = 1 .18 (d, 6H), 1.22 (d, 6H), 3.30 (m, 2H), 7.68 (dd, 1 H), 7.75 (m, 2H), 7.81 (s, 1 H), 8.21 (d, 1 H), 8.54 (d, 1 H), 10.76 (s, 1 H). Example 3: Synthesis of 2-(3-chloro-2-pyridyl)-N-[2-methyl-4-chloro-6-[(bis-2-propyl- ⁴- sulfanylidene)carbamoyl]phenyl]-5-(trifluoromethyl)pyrazole-3-carboxamide (Compound 1-21 ) To a suspension of potassium carbonate (126.01 g, 91 1 .76 mmol, 1.30 equiv) and 2-amino-3- methyl-5-chloro-N-(bis-2-propyl- ⁴-sulfanylidene)benzamide (21 1 g, 701 mmol) in

dichloromethane (300 mL) was added a solution of 2-(3-chloro-2-pyridyl)-5- (trifluoromethyl)pyrazole-3-carbonyl chloride (256.78 g, 771 .49 mmol, 1.10 equiv.) in

dichloromethane (200 mL) at room temperature. After 2 h at this temperature, the solids were filtered off. The resulting filtrate was washed with water and dried over Na2S0₄. After filtration, the filtrate was concentrated in vacuum and the resulting solids were crystallized from diisopro- pyl ether to yield the title compound (344.2 g, 85%).

Characterization by HPLC-MS: 1.303 min, M= 574.3 (Method B)

Characterization by H-NMR (400 MHz, DMSO-d₆): 5[delta] = 1.20 (d, 6H), 1.30 (d, 6H), 2.15 (s, 3H), 3.30 (m, 2H), 7.41 (s, 1 H), 7.62 (m, 2H), 7.80 (s, 1 H), 8.22 (d, 1 H), 8.52(d, 1 H), 10.88 (s, 1 H). Example 4a: 2-(3-chloro-2-pyridyl)-N-[2-methyl-4-chloro-6-[(diethyl- ⁴- sulfanylidene)carbamoyl]phenyl]-5-(trifluoromethyl)pyrazole-3-carboxamide (Compound 1-1 1 ) To a suspension of potassium carbonate (0.71 g, 10 mmol, 1.3 equiv) and 2-amino-3-methyl-5- chloro-N-(diethyl- ⁴-sulfanylidene)benzamide (1.42 g, 3.96 mmol) in propylene carbonate (20 mL) was added a solution of 2-(3-chloro-2-pyridyl)-5-(trifluoromethyl)pyrazole-3-carbonyl chloride (1 .35 g, 4.35 mmol, 1.10 equiv.) in propylene carbonate (10 mL) at room temperature. After 24 h at this temperature, the mixture was poured onto water and spiked with ethanol under vigorous stirring. The resulting solids were collected by filtration and contained pure title compound (1.57 g, 73%).

Characterization by HPLC-MS: 1 .19 min, m/z 546.1 (M+H)⁺; (Method B)

Characterization by H-NMR (500 MHz, DMSO) [delta]: 10.87 (s, 1 H), 8.53 (d, 1 H), 8.22 (d, 1 H), 7.75 (s, 1 H), 7.65 (m, 2H), 7.40 (s, 1 H), 3.09 (m, 2H), 2.92 (m, 2H) 1 .15 (m, 6H).

Example 4b: 2-(3-chloro-2-pyridyl)-N-[2-methyl-4-chloro-6-[(diethyl- ⁴- sulfanylidene)carbamoyl]phenyl]-5-(trifluoromethyl)pyrazole-3-carboxamide (Compound 1-1 1 ) To a solution of 2-(3-chloro-2-pyridyl)-5-(trifluoromethyl)pyrazole-3-carbonyl chloride

(150 g, 435 mmol) in acetonitrile (900 mL) at room temperature was added potassium carbonate (59 g, 427 mmol). A solution of 2-amino-5-chloro-N-(diethyl-sulfanylidene)-3-methyl- benzamide (1 17 g, 427 mmol) in acetonitrile (100 mL) was added dropwise within 1 hour while maintaining a reaction temperature of 25-28°C with occasional cooling (slightly exothermic reaction). The mixture was stirred for 16 hours at room temperature. The reaction mixture was then poured on ice-water mixture (5

L) and the pH was adjusted to 7-8 with concentrated HCI. The mixture stirred for an additional 2 hours. The light brown solid was filtered, washed with water and dried under air to give the crude product (229 g).

3 combined batches of crude product (789 g) were suspended in acetonitrile (2.6 L) and dissolved upon heating at 60°C. After 1 hour of stirring at 60°C the solution was cooled by means of an ice-bath and the thereby formed solid was filtered off. The mother-liquor was concentrated to 300 mL and cooled with ice-bath. Thereby additional solid formed was filtered. The combined solids were washed with cold acetonitrile and dried at 50°C in a vacuum-oven over night to give the title product (703 g, 89%) as a crystalline white solid.

By the methods described in examples 1 to 4 or analogy therof, the compounds of formula (IA- 1 ) summarized in table C were prepared:

Table C

R R2 R⁷ R⁵ R⁶ MS RT[min] m/z

1-1 Me CI CF₃ CHs CHs logP: 2.9 [pH=10.0] ; m.p:

182°C

I-2 Me CI CHF₂ CHs CHs B 1 .06 500.2

I-3 Me CI Br CHs CHs A 3.067 529.95

I-4 Me CI CI CHs CHs

I-5 Me CI CN CHs CHs

I-6 CI CI CF₃ CHs CHs A 3.372 539.95

I -7 CI CI CHF₂ CHs CHs B 1 .062 520.2

I-8 CI CI Br CHs CHs A 3.015 549.80

I-9 CI CI CI CHs CHs

1-10 CI CI CN CHs CHs

1-1 1 Me CI CF₃ C2H5 C2H5 B 1 .207 546.1

B. Biology B.1 Root length in cucumber seed treatment.

The compounds according to the invention and other diamide compounds (cyantraniliprole and chlorantraniliprole) were tested for increase of root length in cucumbers. The compound was dissolved in acetone, and then water was added to achieve a final concentration of 0.5% acetone. Rates were 1 and 10 ppm. Four cucumber seeds (Cucumis sativus 'National Pickling') were placed in a germination pouch and 18 ml of solution was added. Pouches were held upright in an incubator (22 °C, 14 hours light: 10 hours dark). Root length of each cucumber plant was measured 9 days after treatment (DAT). Five replicates (pouches) were prepared for each treatment. Analysis of variance was conducted, and mean separation was performed using Stu- dent-Newman-Keul's HSD (a = 0.05). The mean root length relative to that of the infested and uninfested solvent blank treatments was calculated.

Table Exp-B.1 . Root length of cucumbers after treatment with compounds

The compound 1-16 according to the present invention showed an increased root length.

B.2 Plant emergence, shoot height and root mass in corn seed treatment The compounds according to the invention, in formulated form, were tested for plant health effect upon corn seed treatment. Pots were filled with soil mixture (1 :1 loamy sand:sand) and watered prior to treatment and planting. Formulations were diluted in distilled water and then applied to 20 g corn seed in a volume of 188 μΙ in a Hege 1 1 liquid seed treater and spun for 30 s. One seed was planted per pot 1-3 days after treatment. Five replicates (pots) were prepared for each treatment. Pots were arranged in a randomized complete block design in the greenhouse and top watered daily. Pots were maintained in a growth chamber (26 °C, 10 hours light: 14 hours dark) and bottom-watered as needed. Plant emergence and shoot phytotoxicity were evaluated 5 days after planting. Shoot height and fresh root mass were evaluated 12-13 days after planting. Analysis of variance was conducted, and mean separation was performed using Student-Newman-Keul's HSD (a = 0.05). % increase % increase

Mean Mean

Table Exp-B.2.1 : Plant emerPlant of shoot of root

Shoot Root

gence, shoot height and root Emergence height relamass relaHeight Mass

mass of corn as corn seed (%) tive to soltive to sol(cm) (9)

treatment vent blank vent blank

Rate

5 days after

Treatment (g ai/kg 13 days after planting

planting

seed)

0.5 100 26.7 83% 0.680 103%

1-1 1

1 .0 100 33.8 105% 0.678 103%

0.5 100 27.8 86% 0.688 104%

1-21

1 .0 100 29.6 92% 0.701 106%

Solvent Blank 90 32.3 100% 0.661 100%

The compounds tested showed improved plant height and root mass relative to the solvent blank.

B.3 Effect on the reduction of N2O emission in corn seed treatment

Corn seeds (Zea mays, cultivar "Shorty") were treated with a formulation containing the compounds of the invention (see table Exp-B-3 below) at a rate of 5 g / 100 kg seeds. Seeds were

10 planted 1 seed / pot in standard greenhause soil (mixture of peat, loam and sand) and grown in a climate chamber at 20°C and 60% humidity. Plants were grown for ten days in a completely randomized set-up. On day 6, plants were watered to full water holding capacity but not fertilized. Afterwards, they were left to dry out. On day 10 (10 days after the seeds had been treated with the compounds), the plants were separated out and each pot was set onto a plant saucer

15 designed with an inner compartment for the pot and an outer ring that is filled with water. At time 0, water with or without various concentrations of NPK fertilizer (compound B) was applied to the plant such that the water holding capacity of the soil exceeded 90%. Then a gas sampling chamber was placed over the plant saucer such that the rim fit into the ring filled with water to create a gas-tight chamber. Subsequently, 20 cubic centimeter (cc) air from the chamber were

20 drawn into a syringe and immediately emptied into a Vacutainer (Labco, 12 ml. volume). This equals the time 0 measurement for each pot. The same procedure was performed with all pots in the experiment. After one hour incubation time, again 20 cc air samples were taken from the gas chambers and emptied into Vacutainers as described above. Plants were then returned to their positions in the climate chamber. The measurements were repeated at precisely the sa-

25 metime of the day for the next two days. Sampies were analyzed in a Shimadzu 2014 GC

equipped with an ECD system. Table Exp-B-3: Determination of the N2O increase over ambient. Results shown are peak values on day 2 of the three day measurement after treatment of controls and seed treated plants with 0.3% of the commercially available NPK fertilizer HaKaPhos® Blue (Compo). N= 18.

As can be seen from table Exp-B-3, the compounds according to the present invention applied as seed treatment are able to significantly reduce the N2O emission from soils when the respective fertilizer (compound B) is applied 10 days after the application.

Claims

1 . A method of improving plant health, which method comprises applying at least one pesti- cidally active anthranilamide compound of formula (I):

wherein

R¹ is selected from the group consisting of halogen, methyl and halomethyl;

R² is selected from the group consisting of hydrogen, halogen, halomethyl and cyano;

R³ is selected from hydrogen, C1-C6 alkyl, C1-C6 haloalkyl, C2-C6-alkenyl, C2-C6- haloalkenyl, C2-C6-alkinyl, C2-C6-haloalkinyl, Cs-Cs-cycloalkyl, Cs-Cs-halocycloalkyl, Ci-C4-alkoxy-Ci-C4-alkyl, Ci-C4-haloalkoxy-Ci-C4-alkyl,

C(=0)R^a, C(=0)OR^b and C(=0)NR^cR^d;

R⁴ is hydrogen or halogen;

R⁵, R⁶ are selected independently of one another from the group consisting of hydrogen, Ci-Cio-alkyl, Cs-Cs-cycloalkyl, C2-Cio-alkenyl, C2-Cio-alkynyl, wherein the aforementioned aliphatic and cycloaliphatic radicals may be substituted with 1 to 10 substitu- ents R^e, and phenyl, which is unsubstituted or carries 1 to 5 substituents R^f; or

R⁵ and R⁶ together represent a C2-C7-alkylene, C2-C7-alkenylene or

C6-Cg-alkynylene chain forming together with the sulfur atom to which they are attached a 3-, 4-, 5-, 6-, 7-, 8-, 9- or 10-membered saturated, partially unsaturated or fully unsaturated ring, wherein 1 to 4 of the CH2 groups in the C2-C7-alkylene chain or 1 to 4 of any of the CH2 or CH groups in the C2-C7-alkenylene chain or 1 to 4 of any of the CH2 groups in the C6-Cg-alkynylene chain may be replaced by 1 to 4 groups independently selected from the group consisting of C=0, C=S, O, S, N, NO, SO, SO2 and NH , and wherein the carbon and/or nitrogen atoms in the C2- C7-alkylene, C2-C7-alkenylene or Ce-Cg-alkynylene chain may be substituted with 1 to 5 substituents independently selected from the group consisting of halogen, cy- ano, Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy, Ci-C6-haloalkoxy, Ci-C6-alkylthio, Ci-C6-haloalkylthio, Cs-Cs-cycloalkyl, C3-Cs-halocycloalkyl, C2-C6-alkenyl, C2-C6- haloalkenyl, C2-C6-alkynyl and C2-C6-haloalkynyl; said substituents being identical or different from one another if more than one substituent is present;

R⁷ is selected from the group consisting of bromo, chloro, difluoromethyl, trifluorome- thyl, nitro, cyano, OCH₃, OCHF₂, OCH₂F, OCH2CF3, S(=0)_nCH₃, and S(=0)_nCF₃;

R^a is selected from the group consisting of Ci-C6-alkyl, C2-C6-alkenyl, C2-C6-alkinyl, Cs- Cs-cycloalkyl, Ci-C6-alkoxy, Ci-C6-alkylthio, Ci-C6-alkylsulfinyl, Ci-C6-alkylsulfonyl, wherein one or more CH2 groups of the aforementioned radicals may be replaced by a C=0 group, and/or the aliphatic and cycloaliphatic moieties of the aforementioned radicals may be unsubstituted, partially or fully halogenated and/or may carry 1 or 2 substituents selected from C1-C4 alkoxy;

phenyl, benzyl, pyridyl and phenoxy, wherein the last four radicals may be unsubstituted, partially or fully halogenated and/or carry 1 , 2 or 3 substituents selected from Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy, Ci-C6-haloalkoxy, (Ci-C6-alkoxy)carbonyl, Ci-C6-alkylamino and di-(Ci-C6-alkyl)amino,

R^b is selected from the group consisting of Ci-C6-alkyl, C2-C6-alkenyl, C2-C6-alkinyl, Cs- Cs-cycloalkyl, Ci-C6-alkoxy, Ci-C6-alkylthio, Ci-C6-alkylsulfinyl, Ci-C6-alkylsulfonyl, wherein one or more CH2 groups of the aforementioned radicals may be replaced by a C=0 group, and/or the aliphatic and cycloaliphatic moieties of the aforementioned radicals may be unsubstituted, partially or fully halogenated and/or may carry 1 or 2 substituents selected from Ci-C4-alkoxy;

Ci-C6-alkoxy, Ci-C6-haloalkoxy, Ci-C6-alkylthio, Ci-C6-alkylsulfinyl, C1-C6- alkylsulfonyl, Ci-C6-haloalkylthio, phenyl, benzyl, pyridyl and phenoxy, wherein the four last mentioned radicals may be unsubstituted, partially or fully halogenated and/or carry 1 , 2 or 3 substituents selected from Ci-C6-alkyl, Ci-C6-haloalkyl, C1-C6- alkoxy, C1-C6 haloalkoxy and (Ci-C6-alkoxy)carbonyl; or R^c and R^d, together with the nitrogen atom to which they are bound, may form a 3-, 4-, 5-, 6- or 7-membered saturated, partially unsaturated or fully unsaturated heterocyclic ring which may additionally contain 1 or 2 further heteroatoms or heteroatom groups selected from N , O, S, NO, SO and SO2, as ring members, where the heterocyclic ring may optionally be substituted with halogen, Ci-C4-haloalkyl, C1-C4- alkoxy or Ci-C4-haloalkoxy;

R^e is independently selected from the group consisting of halogen, cyano, nitro, -OH , - SH , -SCN , Ci-C6-alkyl, C2-C6-alkenyl, C2-C6-alkinyl, Cs-Cs-cycloalkyl, wherein one or more CH2 groups of the aforementioned radicals may be replaced by a C=0 group, and/or the aliphatic and cycloaliphatic moieties of the aforementioned radicals may be unsubstituted, partially or fully halogenated and/or may carry 1 or 2 radicals selected from C1-C4 alkoxy;

Ci-C6-alkoxy, Ci-C6-haloalkoxy, Ci-C6-alkylthio, Ci-C6-alkylsulfinyl, C1-C6- alkylsulfonyl, Ci-C₆-haloalkylthio, -OR^a, -N R^cR^d, -S(0)_nR^a, -S(0)_nN R^cR^d,

-C(=0)R^a, -C(=0)N R^cR^d, -C(=0)OR^b, -C(=S)R^a, -C(=S)N R^cR^d, -C(=S)OR^b,

-C(=S)SR^b, -C(=N R^c)R^b, -C(=N R^c)N R^cR^d, phenyl, benzyl, pyridyl and phenoxy, wherein the last four radicals may be unsubstituted, partially or fully halogenated and/or carry 1 , 2 or 3 substituents selected from Ci-C6-alkyl, Ci-C6-haloalkyl, C1-C6- alkoxy and Ci-C6-haloalkoxy; or

two vicinal radicals R^e together form a group =0, =CH(Ci-C4-alkyl), =C(Ci-C₄- alkyl)Ci-C₄-alkyl, =N (Ci-C₆-alkyl) or =NO(Ci-C₆-alkyl);

R^f is independently selected from the group consisting of halogen, cyano, nitro, -OH , - SH , -SCN , Ci-C6-alkyl, C2-C6-alkenyl, C2-C6-alkinyl, Cs-Cs-cycloalkyl, wherein one or more CH2 groups of the aforementioned radicals may be replaced by a C=0 group, and/or the aliphatic and cycloaliphatic moieties of the aforementioned radicals may be unsubstituted, partially or fully halogenated and/or may carry 1 or 2 radicals selected from C1-C4 alkoxy;

-C(=0)R^a, -C(=0)N R^cR^d, -C(=0)OR , -C(=S)R^a, -C(=S)N R^cR^d, -C(=S)OR ,

-C(=S)SR , -C(=N R^c)R , and -C(=N R^c)N R^cR^d; k is O or l ; n is 0, 1 or 2; or a stereoisomer, salt, tautomer or N-oxide thereof.

Method according to claim 1 , in which the compound of formula I is a compound of formula IA:

Method according to claim 1 or 2, in which the compound of formula I is a compound of formula IB:

R² is selected from the group consisting of bromo, chloro, cyano;

R⁷ is selected from the group consisting of bromo, chloro, trifluoromethyl. OCHF2.

Method according to claim 1 or 2, in which the compound of formula I is a compound of formula IC:

wherein

R¹ is selected from the group consisting of halogen and halomethyl;

R² is selected from the group consisting of bromo, chloro and cyano.

Method according to claim 1 or 2, in which the compound of formula I is a compound of formula ID:

wherein

R¹ is selected from the group consisting of halogen, methyl and halomethyl;

R² is selected from the group consisting of bromo, chloro and cyano.

Method according to any of claims 1 to 5, in which in the compound of formula I

R⁵ and R⁶ are selected from methyl, ethyl, isopropyl, n-propyl, n-butyl, isobutyl, tert-butyl, cyclopropyl, cyclopropylmethyl.

Method according to any of claims 1 to 6, in which in the compound of formula I

R⁵ and R⁶ are identical.

Method according to any of claims 1 to 7, wherein the method for improving plant health comprises treating the plant, a part of the plant, the locus where the plant is growing or is expected to grow, and/or the propagules from which the plant grows with the compound as defined in any of claims 1 to 7, or a composition comprising said compound.

9. Method according to any of claims 1 to 8, wherein the method for improving plant health is a method for increasing the yield of a plant or its product.

10. Method according to any of claims 1 to 8, wherein the method for improving plant health is a method for increasing the vigor of a plant or its product. 1 1 . Method according to any of claims 1 to 8, wherein the method for improving plant health is a method for increasing the quality of a plant or its product.

12. Method according to any of claims 1 to 8, wherein the method for improving plant health is a method for increasing the tolerance and/or resistance of a plant or its product against biotic and/or abiotic stress.

13. Method according to claim 12, wherein the method is a method for increasing the resistance to heat, cold or strong variations in temperature. 14. Method according to any of claims 1 to 13, wherein the plant is an agricultural, silvicultural and/or ornamental plant.

15. Use of a compound of formula (I) as defined in any of claims 1 to 7, or a composition

comprising said compound, for

· improving the health of a plant, and/or

• for increasing the yield of a plant or its product, and/or

• for increasing the vigor of a plant or its product, and/or

• for increasing the quality of a plant or its product, and/or

• for increasing the tolerance and/or resistance of a plant or its product against biotic and/or abiotic stress, and/or

6. A method for reducing nitrous oxide emission from soils comprising treating a plant growing on the respective soil and/or the locus where the plant is growing or is intended to grow and/or the seeds from which the plant grows with at least one fungicide (compound A) selected from the group consisting of:

A) at least one compound of formula I as defined in any of claims 1 to 7,

and at least one ammonium- or urea-containing fertilizer (compound B) selected from the group consisting of:

(B1 ) inorganic fertilizer:

NPK fertilizer, ammonium nitrate, calcium ammonium nitrate, ammonium sulfate nitrate, ammonium sulfate and ammonium phosphate;

(B2) organic fertilizer:

liquid manure, semi-liquid manure, stable manure and straw manure, worm castings, compost, seaweed and guano; wherein the application of at least one compound (A) and at least one compound (B) is carried out with a time lag of at least 1 day.

17. The method according to claim 16, wherein the time lag between the application of compound (A) and compound (B) is at least 8 days.

18. The method according to any one of claims 16 or 17, wherein the ammonium- or urea- containing fertilizer (compound B) is applied together with at least one nitrification inhibitor

(compound C) selected from the group consisting of 2-(3,4-dimethyl-pyrazol-1 -yl)-succinic acid, 3,4-dimethylpyrazolephosphate (DMPP), dicyandiamide (DCD), 1 H-1 ,2,4-triazole, 3- methylpyrazole (3-MP), 2-chloro-6-(trichloromethyl)-pyridine, 5-ethoxy-3-trichloromethyl- 1 ,2,4-thiadiazol, 2-amino-4-chloro-6-methyl-pyrimidine, 2-mercapto-benzothiazole, 2- sulfanilamidothiazole, thiourea, sodium azide, potassium azide, 1 -hydroxypyrazole, 2- methylpyrazole-1 -carboxamide, 4-amino-1 ,2,4-triazole, 3-mercapto-1 ,2,4-triazole, 2,4- diamino-6-trichloromethyl-5-triazine, carbon bisulfide, ammonium thiosulfate, sodium tri- thiocarbonate, 2,3-dihydro-2,2-dimethyl-7-benzofuranol methyl carbamate and N-(2,6- dimethylphenyl)-N-(methoxyacetyl)-alanine methyl ester.

19. The method according to any one of claims 16 to 18, wherein compound (A) is applied as seed treatment.

20. The method according to any one of claims 16 to 18, wherein compound (A) is applied as foliar and/or in-furrow application.

21 . The method according to any one of claims 16 to 21 , wherein the application of at least one compound (A) is repeatedly carried out. 22. The method according to any one of claims 16 to 21 , wherein the treated plant is selected from the group consisting of agricultural, silvicultural, ornamental and horticultural plants, each in its natural or genetically modified form.

23. The method according to claim 22, wherein the plant is selected from the group consisting of wheat, barley, oat, rye, soybean, corn, oilseed rape, canola, sunflower, cotton, sugar cane, sugar beet, rice and sorghum.