WO2019042932A1

WO2019042932A1 - Method of controlling rice pests in rice

Info

Publication number: WO2019042932A1
Application number: PCT/EP2018/073014
Authority: WO
Inventors: Joachim Dickhaut; Huazhang Huang; Anil Menon
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 2017-08-31
Filing date: 2018-08-27
Publication date: 2019-03-07
Anticipated expiration: 2020-02-29
Also published as: JP7233415B2; PH12020500312A1; JP2020531551A; KR102659381B1; KR20200041892A; WO2019043183A1; CN111031798A

Abstract

Method for controlling rice pest invertebrates The present invention relates to methods for controlling rice pest invertebrates, which methods comprise applying pyrimidinium compounds of formula (I), the stereoisomers, salts, tautomers and N-oxides thereof, their mixtures and compositions comprising such compounds or mixtures: (I) wherein R1 and R2 are defined as in the description.

Description

Method of controlling rice pests in rice

Rice (Oryza species, especially Oryza sativa) is an important basic food in the world. It is a staple food in Asia and is an important part of many cultures. Rice is therefore an important crop and is cultivated in large areas, especially in Asia.

Invertebrate pests and, in particular, insects, arthropods and nematodes cause significant damage to growing and harvested rice crop, thereby causing large economic loss to the food supply and to property. While a large number of pesticidal agents are known, due to the ability of target pests to develop resistance to said agents, there is an ongoing need for new agents for combating invertebrate pests such as insects, arachnids and nematodes. Further, rice cultivation requires special pesticides suitable for the farming methods used in rice, e.g. use of nursery boxes, paddy fields, aquatic environment and so on. Pesticides suitable for the use in rice must also be tolerated well by the rice plants. They must also be tolerated well by the environment of the rice plants, e.g. from an ecotoxicological point of view, i.e. they must not harm beneficial or- ganisms. Further, they must survive the conditions in which they are applied, to ensure efficacy. This is especially a challenge in the aquatic environment and the high temperature climate conditions, in which rice is usually grown. On the other hand, they must degrade within a reasonable period of time so that they do not have any negative impact on the environment. They must not impact the health of the farmer and the consumer. They should not be present in the rice product later on (low or no residues), to ensure safety of the human beings consuming the rice. Furthermore, many pests have developed resistance against pesticides commonly used in rice. Therefore, pesticides suitable for the use in rice should be effective against those pests have developed resistance to other pesticides. Not all pesticides are able fulfil the requirements to be used in these conditions.

It is therefore an object of the present invention to provide compounds having a good pesticidal activity and showing a good activity spectrum against a large number of different invertebrate pests occurring in rice, especially against insects, arachnids and nematodes that are difficult to control, while still showing a good regulatory profile.

It has been found that these objectives can be achieved by S-containing pyrimidinium com- pounds of the general formula (I), as defined below, including their stereoisomers, their salts, in particular their agriculturally or veterinary acceptable salts, their tautomers and their N-oxides.

In a first aspect, the invention relates to a method of controlling rice pest invertebrates in rice, which method comprises applying to said rice pest invertebrates at least one pesticidally active pyrimidinium compound of formula (I)

wherein R¹ is Ci-C4-alkyl, C3-C6-cycloalkyl, C2-C4-alkenyl or benzyl, which groups may be partially or fully substituted with halogen, Ci-C4-alkyl or Het;

R² is a five-or six membered carbo- or heterocyclic ring, which ring may be unsubsti- tuted, partially, or fully substituted with R^2a;

Het is selected from D-1 , D-2 and D-3:

wherein

R^a is halogen, Ci-C4-haloalkyl, CiC4-alkoxy or Ci-C4-alkylthio or phenyl, n is 0, 1 or 2, and

# denotes the bond in formula (I);

R^2a is halogen, Ci-C₆-haloalkyl, Ci-C₆-haloalkoxy, OR^c, C(=0)OR^c, C(=0)NR^bR^c, phenyl, or pyridyl, which may be substituted with halogen, Ci-C6-haloalkyl or Ci-C6-haloal- koxy;

R^b is each independently hydrogen, Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy, C1-C6- haloalkoxy;

R^c is each independently hydrogen, Ci-C4-alkyl, Ci-C4-haloalkyl, C1-C6 cycloalkyl;

wherein two geminally bound groups R^bR^b, R^cR^b or R^CR^C together with the atom to which they are bound, may form a 3-, 4-, 5-, 6- or 7- membered saturated, partially unsatu- rated or aromatic carbo- or heterocyclic ring;

or a stereoisomer, tautomer, salt, or N-oxide thereof;

WO2014/167084 and EP17164175.6 describe certain substituted pyrimidinium compounds with heterocyclic substituents for combating invertebrate pests.

In one aspect, the invention relates to a method of controlling rice pest invertebrates in rice as described herein, wherein the compound of formula (I) is dicloromezotiaz (DMT), which is a compound of formula (IB), in which

R¹ is methyl substituted with 2-chloro-1 ,3-thiazol-5-yl)methyl; and

R² is 3,5-dichlorophenyl:

Moreover, the present invention relates to and includes the following embodiments:

- a compound of formula (I) for use in controlling rice pests, especially rice pest invertebrates, in rice

- compositions comprising at least one compound of formula (I), for use in controlling rice pests, especially rice pest invertebrates, in rice;

- agricultural compositions comprising an amount of at least one compound of formula (I) or an enantiomer, diasteromer or salt thereof as defined above, for use in controlling rice pests, especially rice pest invertebrates, in rice;

- a method for combating rice pest invertebrates, infestation, or infection by rice pest invertebrates, which method comprises contacting said pest or its food supply, habitat or breeding grounds with a pesticidally effective amount of at least one compound of formula (I) as defined above or a composition thereof;

- a method for controlling rice pest invertebrates, infestation, or infection by invertebrate pests, which method comprises contacting said pest or its food supply, habitat or breeding grounds with a pesticidally effective amount of at least one compound of formula (I) as defined above or a composition comprising at least one compound of formula (I);

- a method for preventing or protecting against rice pest invertebrates comprising contacting the rice pest invertebrates, or their food supply, habitat or breeding grounds with a substituted pyrimidinium compounds of the general formula (I) as defined above or a composition comprising at least one compound of formula (I) as defined above or a composition comprising at least one compound of formula (I);

- a method for protecting rice, rice plants, rice plant propagation material and/or growing rice plants from attack or infestation by rice pest invertebrates comprising contacting or treating the rice, rice plants, rice plant propagation material and growing rice plants, or soil, material, surface, space, area or water in which the rice, rice plants, rice plant propagation material is stored or the rice plant is growing, with a pesticidally effective amount of at least one compound of formula (I) as defined above or a composition comprising at least one compound of formula (I);

- a method for increasing the health of rice plants, especially in paddy rice fields, comprising the treatment with at least one compound of formula (I);

- a method for increasing the yield of rice plants, comprising the treatment with at least one compound of formula (I);

- rice seed comprising a compound of formula (I) as defined above, in an amount of from 0.1 g to 10 kg per 100 kg of seed;

- the use of the compounds of formula (I) as defined above for protecting growing rice plants or rice plant propagation material from attack or infestation by rice pest invertebrates;

All the compounds of the present invention including if applicable their stereoisomers, their tautomers, their salts or their N-oxides as well as compositions thereof are particularly useful for controlling invertebrate pests, in particular for controlling arthropods and nematodes and especially insects. Therefore, the invention relates to the use of a compound as disclosed in the present invention, for combating or controlling invertebrate pests, in particular invertebrate pests of the group of insects, arachnids or nematodes. The term "compound(s) according to the invention" or "compound(s) of formula (I)" as used in the present invention refers to and comprises the compound(s) as defined herein and/or stereoisomers), salt(s), tautomer(s) or N-oxide(s) thereof. The term "compound(s) of the present invention" is to be understood as equivalent to the term "compound(s) according to the invention", therefore also comprising stereoisomer(s), salt(s), tautomer(s) or N-oxide(s) of compounds of formula (I).

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) according to the invention as defined above, therefore also including a stereoisomer, an agriculturally or vet- erinary acceptable salt, tautomer or an N-oxide of the compounds of formula (I).

Compounds of formula (I)

The compounds of the formula (I) are present in mesomeric forms. These forms may be expressed in different isoelectronic formulae, each having the formal positive and negative charges on different atoms. The present invention extends to all representative isoelectronic structures of compounds of formula I.

The compounds of the formula (I) have one or, depending on the substitution pattern, more centers of chirality, in which case they are present as mixtures of enantiomers or diastereomers. The invention provides both the single pure enantiomers or pure diastereomers of the com- pounds 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 or amide group. The term "stereoisomer(s)" encompasses both optical iso- mers, 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). The present invention relates to every possible stereoisomer of the compounds of formula (I), i.e. to single enantiomers or diastereomers, as well as to mixtures thereof.

Depending on the substitution pattern, the compounds of the formula (I) may be present in the form of their tautomers. Hence the invention also relates to the tautomers of the formula (I) and the stereoisomers, salts, tautomers and N-oxides of said tautomers.

Salts of the compounds of the formula (I) are preferably agriculturally and/or veterinary acceptable salts. They can be formed in a customary method, e.g. by reacting the compound with an acid of the anion in question if the compound of formula (I) has a basic functionality or by re- acting an acidic compound of formula (I) with a suitable base.

Suitable agriculturally or veterinary useful 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-hydroxy- alkyl, 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 methylammonium, isopropylammonium, dimethylammonium, diisopropylammonium, trimethylammonium, tetramethylammonium, tetrae- thylammonium, tetrabutylammonium, 2-hydroxyethylammonium, 2-(2-hydroxyethoxy)ethyl-am- monium, bis(2-hydroxyethyl)ammonium, benzyltrimethylammonium and benzyltriethylammo- nium, furthermore phosphonium ions, sulfonium 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 term "N-oxide" includes any compound of the present invention which has at least one ter- tiary nitrogen atom that is oxidized to an N-oxide moiety.

The organic moieties groups 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 Cn-Cm indicates in each case the possible number of carbon atoms in the group.

"Halogen" denotes in each case fluorine, bromine, chlorine or iodine, in particular fluorine, 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.

The term "C_n-C_m-alkyl" as used herein refers to a branched or unbranched saturated hydrocarbon group having n to m, e.g. 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, for example methyl, ethyl, propyl, 1 -methylethyl, butyl, 1 -methylpropyl, 2-methylpropyl, 1 ,1 -dimethylethyl, pentyl, 1 -methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1 -ethylpropyl, 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-di- methylbutyl, 3,3-dimethylbutyl, 1 -ethylbutyl, 2-ethylbutyl, 1 ,1 ,2-trimethylpropyl, 1 ,2,2-trime- thylpropyl, 1 -ethyl-1 -methylpropyl, 1 -ethyl-2-methylpropyl, heptyl, octyl, 2-ethylhexyl, nonyl and decyl and their isomers. Ci-C4-alkyl means for example methyl, ethyl, propyl, 1 -methylethyl, butyl, 1 -methylpropyl, 2-methylpropyl or 1 ,1 -dimethylethyl.

The term "C_n-C_m-haloalkyl" as used herein refers to a straight-chain or branched alkyl group having n to m carbon atoms, e.g. 1 to 10 in particular 1 to 6 carbon atoms (as mentioned above), where some or all of the hydrogen atoms in these groups may be replaced by halogen atoms as mentioned above, for example Ci-C4-haloalkyl, such as chloromethyl, bromomethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 1 -chloroethyl, 1 -bromoethyl, 1 -fluoroethyl, 2-fluoro- ethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2-chloro-2-fluoroethyl, 2-chloro-2,2-difluoroethyl, 2,2- dichloro-2-fluoroethyl, 2,2,2-trichloroethyl, pentafluoroethyl and the like. The term Ci-Cio-haloal- kyl in particular comprises Ci-C2-fluoroalkyl, which is synonym with methyl or ethyl, wherein 1 , 2, 3, 4 or 5 hydrogen atoms are substituted by fluorine atoms, such as fluoromethyl, difluorome- thyl, trifluoromethyl, 1 -fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl and pen- tafluoromethyl.

Similarly, "C_n-C_m-alkoxy" and "C_n-C_m-alkylthio" (or C_n-C_m-alkylsulfenyl, respectively) refer to straight-chain or branched alkyl groups having n to m carbon atoms, e.g. 1 to 10, in particular 1 to 6 or 1 to 4 carbon atoms (as mentioned above) bonded through oxygen (or sulfur linkages, respectively) at any bond in the alkyl group. Examples include Ci-C4-alkoxy such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, sec-butoxy, isobutoxy and tert-butoxy, further Ci-C₄-al- kylthio such as methylthio, ethylthio, propylthio, isopropylthio, and n-butylthio.

Accordingly, the term "C_n-C_m-haloalkoxy" refers to straight-chain or branched alkyl groups having n to m carbon atoms, e.g. 1 to 10, in particular 1 to 6 or 1 to 4 carbon atoms (as mentioned above) bonded through oxygen linkags, respectively, at any bond in the alkyl group, where some or all of the hydrogen atoms in these groups may be replaced by halogen atoms as mentioned above, for example Ci-C2-haloalkoxy, such as chloromethoxy, bromomethoxy, dichloro- methoxy, trichloromethoxy, fluoromethoxy, difluoromethoxy, trifluoromethoxy, chlorofluorometh- oxy, dichlorofluoromethoxy, chlorodifluoromethoxy, 1 -chloroethoxy, 1 -bromoethoxy, 1 -fluoroeth- oxy, 2-fluoroethoxy, 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 and pentafluoroethoxy. Similarly the terms Ci-C2-fluoroalkoxy refer to Ci-C2-fluoroalkyl which is bound to the remainder of the molecule via an oxygen atom .

The term "C2-C_m-alkenyl" as used herein intends a branched or unbranched unsaturated hydrocarbon group having 2 to m, e.g. 2 to 10 or 2 to 6 carbon atoms and a double bond in any position, such as ethenyl, 1 -propenyl, 2-propenyl, 1 -methyl-ethenyl, 1 -butenyl, 2-butenyl, 3-bu- tenyl, 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-di- methyl-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-bu- tenyl, 1 ,1 -dimethyl-3-butenyl, 1 ,2-dimethyl-1 -butenyl, 1 ,2-dimethyl-2-butenyl, 1 ,2-dimethyl-3-bu- tenyl, 1 ,3-dimethyl-1 -butenyl, 1 ,3-dimethyl-2-butenyl, 1 ,3-dimethyl-3-butenyl, 2,2-dimethyl-3-bu- tenyl, 2,3-dimethyl-1 -butenyl, 2,3-dimethyl-2-butenyl, 2,3-dimethyl-3-butenyl, 3,3-dimethyl-1 -bu- tenyl, 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-pro- penyl, 1 -ethyl-2-methyl-1 -propenyl and 1 -ethyl-2-methyl-2-propenyl.

The term "aryl" as used herein refers to a mono-, bi- or tricyclic aromatic hydrocarbon radical such as phenyl or naphthyl, in particular phenyl (also referred as to C6H₅ as subsitituent).

The term "ring system" denotes two or more directly connected rings. The term "C3-C_m-cycloalkyl" as used herein refers to a monocyclic ring of 3- to m-membered saturated cycloaliphatic radicals, e.g. cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclohep- tyl, cyclooctyl and cyclodecyl.

The term "five- or six-membered carbo- or heterocyclic ring" as used herein refers to satu- rated, partially unsaturated or aromatic rings which may contain 1 , 2, 3 or 4 heteroatoms or het- eroatom groups, wherein those heteroatom(s) (group(s)) are selected from N (N-substituted groups), O and S (S-substituted groups) as used herein refers to monocyclic radicals, the monocyclic radicals being saturated, partially unsaturated or aromatic (completely unsaturated). The heterocyclic radical may be attached to the remainder of the molecule via a carbon ring member or via a nitrogen ring member.

Examples of five- or six-membered carbo- or heterocyclic rings include cyclopentane and cyclo- hexane, cyclohexen, phenyl, pyridinyl, 2-tetrahydrofuranyl, 3-tetrahydrofuranyl, 2-tetrahy- drothienyl, 3-tetrahydrothienyl, 2-pyrrolidinyl, 3-pyrrolidinyl, 3-pyrazolidinyl, 4-pyrazolidinyl, 5-py- razolidinyl, 2-imidazolidinyl, 4-imidazolidinyl, 2-oxazolidinyl, 4-oxazolidinyl, 5-oxazolidinyl, 3-isox- azolidinyl, 4-isoxazolidinyl, 5-isoxazolidinyl, 2-thiazolidinyl, 4-thiazolidinyl, 5-thiazolidinyl, 3-isothi- azolidinyl, 4-isothiazolidinyl, 5-isothiazolidinyl, 1 ,2,4-oxadiazolidin-3-yl, 1 ,2,4-oxadiazolidin 5 yl, 1 ,2,4-thiadiazolidin-3-yl, 1 ,2,4-thiadiazolidin-5-yl, 1 ,2,4-triazolidin-3-yl,-1 ,3,4-oxadiazolidin-2-yl, 1 ,3,4-thiadiazolidin-2-yl, 1 ,3,4-triazolidin-2-yl, 2-tetrahydropyranyl, 4-tetrahydropyranyl, 1 ,3-di- oxan-5-yl, 1 ,4-dioxan-2-yl, 2-piperidinyl, 3-piperidinyl, 4-piperidinyl, 3-hexahydropyridazinyl, 4- hexahydropyridazinyl, 2-hexahydropyrimidinyl, 4-hexahydropyrimidinyl, 5-hexahydropyrimidinyl, 2-piperazinyl, 1 ,3,5-hexahydrotriazin-2-yl and 1 ,2,4-hexahydrotriazin-3-yl, 2-morpholinyl, 3-mor- pholinyl, 2-thiomorpholinyl, 3-thiomorpholinyl, 1 -oxothiomorpholin-2-yl, 1 -oxothiomorpholin-3-yl, 1 ,1 -dioxothiomorpholin-2-yl, 1 ,1 -dioxothiomorpholin-3-yl, and the like.

Examples of 5- or 6-membered partially unsaturated heterocyclyl or heterocyclic rings include: 2,3-dihydrofur-2-yl, 2,3-dihydrofur-3-yl, 2,4-dihydrofur-2-yl, 2,4-dihydrofur-3-yl, 2,3-dihydrothien-

2- yl, 2,3-dihydrothien-3-yl, 2,4-dihydrothien-2-yl, 2,4-dihydrothien-3-yl, 2-pyrrolin-2-yl, 2-pyrrolin-

3- yl, 3-pyrrolin-2-yl, 3-pyrrolin-3-yl, 2-isoxazolin-3-yl, 3-isoxazolin-3-yl, 4-isoxazolin 3 yl, 2-isoxa- zolin-4-yl, 3-isoxazolin-4-yl, 4-isoxazolin-4-yl, 2-isoxazolin-5-yl, 3-isoxazolin-5-yl, 4-isoxazolin-5- yl, 2-isothiazolin-3-yl, 3-isothiazolin-3-yl, 4-isothiazolin-3-yl, 2-isothiazolin-4-yl, 3-isothiazolin-4- yl, 4-isothiazolin-4-yl, 2-isothiazolin-5-yl, 3-isothiazolin-5-yl, 4-isothiazolin-5-yl, 2,3 dihydropyra- zol-1 -yl, 2,3-dihydropyrazol-2-yl, 2,3-dihydropyrazol-3-yl, 2,3-dihydropyrazol-4-yl, 2,3-dihydropy- razol-5-yl, 3,4-dihydropyrazol-1 -yl, 3,4-dihydropyrazol-3-yl, 3,4-dihydropyrazol-4-yl, 3,4-dihydro- pyrazol-5-yl, 4,5-dihydropyrazol-1 -yl, 4,5-dihydropyrazol-3-yl, 4,5-dihydropyrazol-4-yl, 4,5-dihy- dropyrazol-5-yl, 2,3-dihydrooxazol-2-yl, 2,3-dihydrooxazol-3-yl, 2,3-dihydrooxazol-4-yl, 2,3-dihy- drooxazol-5-yl, 3,4-dihydrooxazol-2-yl, 3,4-dihydrooxazol-3-yl, 3,4-dihydrooxazol-4-yl, 3,4-dihy- drooxazol-5-yl, 3,4-dihydrooxazol-2-yl, 3,4-dihydrooxazol-3-yl, 3,4-dihydrooxazol-4-yl, 2-, 3-, 4-, 5- or 6-di- or tetrahydropyridinyl, 3-di- or tetrahydropyridazinyl, 4-di- or tetrahydropyridazinyl, 2- di- or tetrahydropyrimidinyl, 4-di- or tetrahydropyrimidinyl, 5-di- or tetrahydropyrimidinyl, di- or tetrahydropyrazinyl, 1 ,3, 5-di- or tetrahydrotriazin-2-yl, 1 ,2, 4-di- or tetrahydrotriazin-3-yl.

Examples of 5- or 6-membered aromatic heterocyclic (hetaryl) or heteroaromatic rings are: 2- furyl, 3-furyl, 2-thienyl, 3-thienyl, 2-pyrrolyl, 3-pyrrolyl, 3-pyrazolyl, 4-pyrazolyl, 5-pyrazolyl, 2-ox- azolyl, 4-oxazolyl, 5-oxazolyl, 2-thiazolyl, 4-thiazolyl, 5-thiazolyl, 2-imidazolyl, 4-imidazolyl, 1 ,3,4-triazol-2-yl, 2-pyridinyl, 3-pyridinyl, 4-pyridinyl, 3-pyridazinyl, 4-pyridazinyl, 2-pyrimidinyl, 4- pyrimidinyl, 5-pyrimidinyl and 2-pyrazinyl.

Dicloromezotiaz is known and is commercially available.

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

In one embodiment of the invention, R¹ is Ci-C4-alkyl, C3-C6-cycloalkyl, C2-C4-alkenyl.

In a further embodiment, R¹ is Ci-C4-alkyl. In a further embodiment, R¹ is methyl or ethyl.

In a further embodiment, R¹ is Ci-C4-alkyl substituted with Het.

In a further embodiment, R¹ is methyl or ethyl, substituted with Het.

In one embodiment of the invention, R² is phenyl, pyridinyl or thiophene, which may be unsub- stituted, partially, or fully substituted with R^2a.

In a further embodiment, R² is phenyl, which may be unsubstituted, partially, or fully substi- tuted with R^2a, wherein R^2a is halogen, d-Ce-haloalkyl, Ci-C₆-haloalkoxy, OR^c, C(=0)OR^c,

C(=0)NR^bR^c, phenyl, or pyridyl, which may be substituted with halogen, Ci-C6-haloalkyl or Ci- C6-haloalkoxy.

In a further embodiment, R² is phenyl, which may be unsubstituted, partially, or fully substituted with halogen, Ci-C4-alkyl or Ci-C3-haloalkyl.

In a further embodiment, R² is phenyl, which may be unsubstituted, partially, or fully substituted with trifluoromethyl or halogen, preferably chloro;

In a further embodiment, R² is phenyl, 3,5-dichlorophenyl, 3-trifluoromethylphenyl.

In a further embodiment, R² is phenyl.

In a further embodiment, R² is 3,5-dichlorophenyl.

In a further embodiment, R² is 3-trifluoromethylphenyl.

In one embodiment of the invention, Het is a five- or six-membered carbo- or heterocyclic aromatic ring.

In one embodiment of the invention, Het is selected from D-1 , D-2 and D-3, wherein

R^a is chloro,

n is 1 .

In a further embodiment, Het is D-1 a, D-2a and D-3a:

In a further embodiment, Het is D-1 a.

In a further embodiment, Het is D-2a.

In a further embodiment, Het is D-3a. In one embodiment of the invention, the compound of formula (I) is one of the following pounds 1-1 to I-7:

In one embodiment of the invention, the compound of formula is the compound -1 .

In one embodiment of the invention, the compound of formula is the compound -2.

In one embodiment of the invention, the compound of formula is the compound -3.

In one embodiment of the invention, the compound of formula is the compound -4.

In one embodiment of the invention, the compound of formula is the compound -5.

In one embodiment of the invention, the compound of formula is the compound -6.

In one embodiment of the invention, the compound of formula is the compound -7.

Rice pests

In the context of this invention, rice pest invertebrates are animal pests, which occur in rice. The rice pest invertebrates include insects, acarids and nematodes, preferably insects. Rice pest invertebrates, which are well-known in rice, include but are not limited to the following spe- cies:

Hemiptera:

brown planthopper - Nilaparvata lugens

small brown planthopper - Laodelphax striatellus

white-backed planthopper - Sogatella furcifera

white leafhopper - Cofana spectra

green leafhopper - Nephotettix virescens, N. nigriceps, N. cincticeps, N. malayanus zig zag leafhopper - Recilia dorsalis

maize orange leafhopper - Cicadulina bipunctata

aster leafhopper - Macrosteles fascifrons

rice earhead bug, Leptocorisa orator/us, L. acuta rice stink bugs - Nezara viridula, Pygomenida varipennis, Eysarcoris, Tibraca Iimbatriventris, Eysarcoris ventralis

small stink bug - Oebalus poecilus, O. pugnax

coreid bug - Eysarcoris sp

chinch bug - Blissus leucopterus leucopterus

rice mealybug, Brevennia rehi, Pseudococcus saccharicola

rice aphids, Rhopaiosiphum rufiabdominalis, Macrosiphum a venae, Hysteroneura setariae, Tetraneuro nigriabdominalis

bean root aphid - Smynthurodes betae

Lepidoptera:

rice skipper - Parnara guttata, Melanitis leda ismene

rice stem borer / striped stem borer - Chilo suppressalis, Chilo polychrusus, Chilo partellus, Chilo plejadellus

rice stalk borer - Chilotraea polychrysa

pink rice borer - Sesamia inferens

yellow rice borer - Tryporyza (=Scirpophaga) incertulas

white rice borer - Tryporyza innotata

rice leafroller / leaf folder - Cnaphalocrocis medinalis, Marasmia patnalis, M. exigua rice ear-cutting caterpillar / armyworm- Pseudaletia separata

green caterpillar - Xanthodes transversa

green rice caterpillar - Narnaga aenescens

green horned caterpillars - Melanitis leda ismene, Mycalesis sp

fall army worm - Spodoptera frugiperda

cutworm - Mythimna separata

rice case worm - Nymphula depunctalis

black hairy caterpillar, Amata sp.

hairy caterpillar- Mods frugalis

yellow caterpillar, Psalis pennatula

rice semi-brown looper, Mods frugalis

rice semi-looper, Chrysodeixis chalcites

grass webworm - Herpetogramma licarsisalis

sugarcane borer - Diatraea saccharalis

corn stalk borer - Elasmopalpus lignosellus

striped grass looper - Mods latipes

european corn borer - Ostrinia nubilalis

Mexican rice borer - Eoreuma loftini

Coleoptera:

water weevil - Lissorhopterus oryzophilus

rice plant weevil - Echinocnemus squamous

rice weevil - Oryzophagus oryzae

rice hispa - Diclodispa armigera

rice leaf beetle - Oulema oryzae

rice blackbug - Scotinophora vermiduiate, S. vermiduiate, S. lurida, S. latiuscuia rice flea beetle - Chaetocnima basalis

grubs - Leucopholis irrorata, Leucopholis irrorata, Phyllophaga sp, Heteronychus sp scarab beetle (bicho torito) - DHoboderus abderus

billbugs - Sphenophorus spp

grape colaspis - Colaspis brunnea, C. louisianae

rice pollen beetle, Chilolaba acuta

Diptera:

stem maggot - Chlorops oryzae

leafminer - Agromyza oryzae

rice whorl maggot / rice stem maggot - Hydrellia sasakii

rice whorl maggot / small rice leafminer - Hydrellia griseola

rice gall midge - Orseolia (=Pachydip/osisJ oryzae

rice shoot fly- Atherigona oryzae

rice seed midge - Chironomus cavazzai, Chironomus spp, Cricotopus spp

Thysanoptera:

rice thrips- Chioethrips oryzae, Stenochaetothrips biformis, Perrisothrips sp., Hopiothrips sp., Orthoptera:

rice grasshoppers, H/erog/yphus ban/an, H/erog/yphus n/grorep/etus, Catantops pinguis, At- tractomorpha burri, A. crenulate, A. psittacina psittacina, A. Bedeli, Oxya adenttata, Oxya eb- neri, Oxya hyla intricata, Acrida turricata

locusts - Locusta migratoria manilensis

mole cricket, Grylotalpa africana

field cricket: Gryllus bimaculatus, Teleogryllus occipitalis, Euscyrtus concinus

katydid - Conocephalus longipennis

Isoptera:

termites - Macrotermes gilvus, Syntermes molestans

Hymenoptera:

ants - Solenopsis geminata

rice white tip nematode - Aphelenchoides besseyi

Acari:

rice panicle mite - Steotarsonemus pinki

Crustacea:

tadpole shrimp - Triops longicaudatus. T. cancriformis

rice crayfish - Procambarus clarkii, Orconectes virilis.

In addition, rice is affected by a range of bugs including Leptocorisa chinensis, Lagynotomus elongates, Nerzara viridula, Eysacoris parvus, Leptocorisa oratorius, Oebaius pugnax, Cietus trigonus, as well as a variety of mites, caterpillars, beetles, rootworms and maggots.

In one embodiment, the rice pest invertebrate is a biting/chewing insect.

In one embodiment, the rice pest invertebrate is a piercing/sucking insect.

In one embodiment, the rice pest invertebrate is a rasping insect.

In one embodiment, the rice pest invertebrate is a siphoning insect.

In one embodiment, the rice pest invertebrate is a sponging insect. In one embodiment, the rice pest invertebrate is selected from brown planthopper {Nilaparvata lugens), small brown planthopper {Laodelphax striatellus), white-backed planthopper {Sogateiia furcifera), rice stem borer / striped stem borer {Chilo suppressalis), yellow rice borer ( Tryporyza (=Scirpophaga) incertulas), rice leafroller / leaf folder {Cnaphalocrocis medinalis), water weevil {Lissorhopterus oryzophilus).

In one embodiment, the rice pest invertebreate is from the order Hemiptera or Lepidoptera.

In one embodiment, the rice pest invertebrate is from the order Hemiptera. In a further embodiment, the rice pest invertebrate is a hopper, preferably selected from brown planthopper {Nilaparvata lugens), small brown planthopper {Laodelphax striatellus), white-backed planthop- per {Sogateiia furcifera), green leafhopper {Nephotettix virescens). In a further embodiment, the rice pest invertebrate is selected from brown planthopper {Nilaparvata lugens) and green leafhopper {Nephotettix virescens), preferably brown planthopper {Nilaparvata lugens).

In one embodiment, the rice pest invertebrate is the brown planthopper {Nilaparvata lugens).

In one embodiment, the rice pest invertebrate is the green leafhopper {Nephotettix virescens). In a further embodiment, the rice pest invertebrate is a stink bug, preferably selected from rice stink bugs {Nezara viridula, Pygomenida varipennis, Eysarcoris, Tibraca limbatriventris, Eysar- coris ventralis) or small stink bug {Oebalus poecilus, O. pugnax).

In one embodiment, the rice pest invertebrate is from the order Lepidoptera. In a further embodiment, the rice pest invertebrate is a borer, preferably stem borer, preferably rice stem borer {Chilo suppressalis) or yellow rice borer ( Tryporyza (=Scirpophaga) incertulas).

In a further embodiment, the rice pest invertebrate is the rice leafroller / leaf folder {Cnaphalocrocis medinalis, Marasmia patnalis, M. exigua).

In one embodiment, the rice pest invertebrate is from the order Coleoptera. In a further embodiment, the rice pest invertebrate is water weevil {Lissorhopterus oryzophilus). In a further embodiment, the rice pest invertebrate is rice weevil {Oryzophagus oryzae).

In one embodiment, the rice pest invertebrate is from the family of termites (order Isoptera).

Mixtures

The present invention also relates to methods according to the invention, applying a mixture of at least one compound of the present invention with at least one mixing partner as defined herein after. Preferred are binary mixtures of one compound of the present invention as component I with one mixing partner as defined herein after as component II. Preferred weight ratios for such binary mixtures are from 5000:1 to 1 :5000, preferably from 1000:1 to 1 :1000, more preferably from 100:1 to 1 :100, particularly preferably from 10:1 to 1 :10. In such binary mixtures, components I and II may be used in equal amounts, or an excess of component I, or an excess of component II may be used.

Mixing partners can be selected from pesticides, in particular insecticides, nematicides, and acaricides, fungicides, herbicides, plant growth regulators, fertilizers, and the like. Preferred mixing partners are insecticides, nematicides and fungicides.

The following list M of pesticides, grouped and numbered according the Mode of Action Classi- fication of the Insecticide Resistance Action Committee (IRAC), together with which the compounds of the present invention can be used and with which potential synergistic effects might be produced, is intended to illustrate the possible combinations, but not to impose any limitation: M.1 Acetylcholine esterase (AChE) inhibitors: M.1 A carbamates, e.g. aldicarb, alanycarb, ben- diocarb, benfuracarb, butocarboxim, butoxycarboxim, carbaryl, carbofuran, carbosulfan, ethio- fencarb, fenobucarb, formetanate, furathiocarb, isoprocarb, methiocarb, methomyl, metolcarb, oxamyl, pirimicarb, propoxur, thiodicarb, thiofanox, trimethacarb, XMC, xylylcarb and

triazamate; or M.1 B organophosphates, e.g. acephate, azamethiphos, azinphos-ethyl, az- inphosmethyl, cadusafos, chlorethoxyfos, chlorfenvinphos, chlormephos, chlorpyrifos, chlorpyri- fos-methyl, coumaphos, cyanophos, demeton-S-methyl, diazinon, dichlorvos/ DDVP, dicroto- phos, dimethoate, dimethylvinphos, disulfoton, EPN, ethion, ethoprophos, famphur, fenamiphos, fenitrothion, fenthion, fosthiazate, heptenophos, imicyafos, isofenphos, isopropyl 0-(methoxy- aminothio-phosphoryl) salicylate, isoxathion, malathion, mecarbam, methamidophos, methida- thion, 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 vami- dothion;

M.2. GABA-gated chloride channel antagonists: M.2A cyclodiene organochlorine compounds, e.g. endosulfan or chlordane; or M.2B fiproles (phenylpyrazoles), e.g. ethiprole, fipronil, flufiprole, pyrafluprole, and pyriprole;

M.3 Sodium channel modulators from the class of M.3A pyrethroids, e.g. acrinathrin, allethrin, d-cis-trans allethrin, d-trans allethrin, bifenthrin (in particular kappa-bifenthrin), bioallethrin, bio- allethrin S-cylclopentenyl, bioresmethrin, cycloprothrin, cyfluthrin, beta-cyfluthrin, cyhalothrin, lambda-cyhalothrin, gamma-cyhalothrin, cypermethrin, alpha-cypermethrin, beta-cypermethrin, theta-cypermethrin, zeta-cypermethrin, cyphenothrin, deltamethrin, empenthrin, esfenvalerate, etofenprox, fenpropathrin, fenvalerate, flucythrinate, flumethrin, tau-fluvalinate, halfenprox, hep- tafluthrin, imiprothrin, meperfluthrin,metofluthrin, momfluorothrin (in particular epsilon-mom- fluorothrin), permethrin, phenothrin, prallethrin, profluthrin, pyrethrin (pyrethrum), resmethrin, silafluofen, tefluthrin (in particular kappa-tefluthrin), tetramethylfluthrin, tetramethrin, tralome- thrin, and transfluthrin; or M.3B sodium channel modulators such as DDT or methoxychlor; M.4 Nicotinic acetylcholine receptor agonists (nAChR): M.4A neonicotinoids, e.g. acetamiprid, clothianidin, cycloxaprid, dinotefuran, imidacloprid, nitenpyram, thiacloprid and thiamethoxam; or the compounds M.4A.1 4,5-Dihydro-N-nitro-1 -(2-oxiranylmethyl)-1 H-imidazol-2-amine, M.4A.2: (2E-)-1 -[(6-Chloropyridin-3-yl)methyl]-N'-nitro-2-pentylidenehydrazinecarboximidamide; or M4.A.3: 1 -[(6-Chloropyridin-3-yl)methyl]-7-methyl-8-nitro-5-propoxy-1 ,2,3,5,6,7-hexahydroim- idazo[1 ,2-a]pyridine; or M.4B nicotine; M.4C sulfoxaflor; M.4D flupyradifurone; M.4E triflume- zopyrim;

M.5 Nicotinic acetylcholine receptor allosteric activators:spinosyns, e.g. spinosad or spineto- ram;

M.6 Chloride channel activators from the class of avermectins and milbemycins, e.g.

abamectin, emamectin benzoate, ivermectin, lepimectin, or milbemectin;

M.7 Juvenile hormone mimics, such as M.7A juvenile hormone analogues hydroprene, kino- prene, and methoprene; or M.7B fenoxycarb, or M.7C pyriproxyfen; M.8 miscellaneous non-specific (multi-site) inhibitors, e.g. M.8A alkyl halides as methyl bromide and other alkyl halides, M.8B chloropicrin, M.8C sulfuryl fluoride, M.8D borax, or M.8E tartar emetic;

M.9 Chordotonal organ TRPV channel modulators, e.g. M.9B pymetrozine; pyrifluquinazon; M.10 Mite growth inhibitors, e.g. M.10A clofentezine, hexythiazox, and diflovidazin, or M.10B etoxazole;

M.12 Inhibitors of mitochondrial ATP synthase, e.g. M.12A diafenthiuron, or M.12B organotin miticides such as azocyclotin, cyhexatin, or fenbutatin oxide, M.12C propargite, or M.12D tetra- difon;

M.13 Uncouplers of oxidative phosphorylation via disruption of the proton gradient, e.g.

chlorfenapyr, DNOC, or sulfluramid;

M.14 Nicotinic acetylcholine receptor (nAChR) channel blockers, e.g. nereistoxin analogues bensultap, cartap hydrochloride, thiocyclam, or thiosultap sodium;

M.15 Inhibitors of the chitin biosynthesis type 0, such as benzoylureas e.g. bistrifluron, chlorfluazuron, diflubenzuron, flucycloxuron, flufenoxuron, hexaflumuron, lufenuron, novaluron, noviflumuron, teflubenzuron, or triflumuron;

M.16 Inhibitors of the chitin biosynthesis type 1 , e.g. buprofezin;

M.17 Moulting disruptors, Dipteran, e.g. cyromazine;

M.18 Ecdyson receptor agonists such as diacylhydrazines, e.g. methoxyfenozide, tebufeno- zide, halofenozide, fufenozide, or chromafenozide;

M.19 Octopamin receptor agonists, e.g. amitraz;

M.20 Mitochondrial complex III electron transport inhibitors, e.g. M.20A hydramethylnon, M.20B acequinocyl, M.20C fluacrypyrim; or M.20D bifenazate;

M.21 Mitochondrial complex I electron transport inhibitors, e.g. M.21A METI acaricides and in- secticides such as fenazaquin, fenpyroximate, pyrimidifen, pyridaben, tebufenpyrad or tolfen- pyrad, or M.21 B rotenone;

M.22 Voltage-dependent sodium channel blockers, e.g. M.22A indoxacarb, M.22B metaflumi- zone, or M.22B.1 : 2-[2-(4-Cyanophenyl)-1 -[3-(trifluoromethyl)phenyl]ethylidene]-N-[4-(difluoro- methoxy)phenyl]-hydrazinecarboxamide or M.22B.2: N-(3-Chloro-2-methylphenyl)-2-[(4-chloro- phenyl)[4-[methyl(methylsulfonyl)amino]phenyl]methylene]-hydrazinecarboxamide;

M.23 Inhibitors of the of acetyl CoA carboxylase, such as Tetronic and Tetramic acid derivatives, e.g. spirodiclofen, spiromesifen, or spirotetramat; M.23.1 spiropidion

M.24 Mitochondrial complex IV electron transport inhibitors, e.g. 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, e.g. cyenopyrafen or cyflumetofen;

M.28 Ryanodine receptor-modulators from the class of diamides, e.g. flubendiamide, chlor- antraniliprole, cyantraniliprole, tetraniliprole, M.28.1 : (R)-3-Chlor-N 1 -{2-methyl-4-[1 ,2,2,2 -tetra- fluoro-1 -(trifluoromethyl)ethyl]phenyl}-N2-(1 -methyl-2-methylsulfonylethyl)phthalamid, M.28.2: (S)-3-Chloro-N 1 -{2-methyl-4-[1 ,2,2,2-tetrafluoro-1 -(trifluoromethyl)ethyl]phenyl}-N2-(1 -methyl-2- methylsulfonylethyl)phthalamid, M.28.3: cyclaniliprole, or M.28.4: methyl-2-[3,5-dibromo-2-({[3- bromo-1 -(3-chlorpyridin-2-yl)-1 H-pyrazol-5-yl]carbonyl}amino)benzoyl]-1 ,2-dimethylhydrazine- carboxylate; or M.28.5a) N-[4,6-dichloro-2-[(diethyl-lambda-4-sulfanylidene)carbamoyl]-phenyl]- 2-(3-chloro-2-pyridyl)-5-(trifluoromethyl)pyrazole-3-carboxamide; M.28.5b) N-[4-chloro-2-[(di- ethyl-lambda-4-sulfanylidene)carbamoyl]-6-methyl-phenyl]-2-(3-chloro-2-pyridyl)-5-(trifluorom thyl)pyrazole-3-carboxamide; M.28.5c) N-[4-chloro-2-[(di-2-propyl-lambda-4-sulfanylidene)car- bamoyl]-6-methyl-phenyl]-2-(3-chloro-2-pyridyl)-5-(trifluoromethyl)pyrazole-3-carboxamide; M.28.5d) N-[4,6-dichloro-2-[(di-2-propyl-lambda-4-sulfanylidene)carbamoyl]-phenyl]-2-(3-chloro-

2- pyridyl)-5-(trifluoromethyl)pyrazole-3-carboxamide; M.28.5h) N-[4,6-dibromo-2-[(diethyl- lambda-4-sulfanylidene)carbamoyl]-phenyl]-2-(3-chloro-2-pyridyl)-5-(trifluoromethyl)pyrazole-3- carboxamide; M.28.5i) N-[2-(5-Amino-1 ,3,4-thiadiazol-2-yl)-4-chloro-6-methylphenyl]-3-bromo-1 - (3-chloro-2-pyridinyl)-1 H-pyrazole-5-carboxamide; M.28.5j) 3-Chloro-1 -(3-chloro-2-pyridinyl)-N- [2,4-dichloro-6-[[(1 -cyano-1 -methylethyl)amino]carbonyl]phenyl]-1 H-pyrazole-5-carboxamide; M.28.5k) 3-Bromo-N-[2,4-dichloro-6-(methylcarbamoyl)phenyl]-1 -(3,5-dichloro-2-pyridyl)-1 H-py- razole-5-carboxamide; M.28.5I) N-[4-Chloro-2-[[(1 ,1 -dimethylethyl)amino]carbonyl]-6-methyl- phenyl]-1 -(3-chloro-2-pyridinyl)-3-(fluoromethoxy)-1 H-pyrazole-5-carboxamide; or

M.28.6: cyhalodiamide; or

M.29: Chordotonal organ Modulators - undefined target site, e.g. flonicamid;

M.UN. insecticidal active compounds of unknown or uncertain mode of action, e.g. afidopyro- pen, afoxolaner, azadirachtin, amidoflumet, benzoximate, broflanilide, bromopropylate, chino- methionat, cryolite, dicloromezotiaz, dicofol, flufenerim, flometoquin, fluensulfone, fluhexafon, fluopyram, fluralaner, metoxadiazone, piperonyl butoxide, pyflubumide, pyridalyl, tioxazafen, M.UN.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,

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

M.UN.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);

M.UN.6: flupyrimin;

M.UN.8: fluazaindolizine; M.UN.9. a): 4-[5-(3,5-dichlorophenyl)-5-(trifluoromethyl)-4H-isoxazol-

3- yl]-2-methyl-N-(1 -oxothietan-3-yl)benzamide; M.UN.9.b): fluxametamide; M.UN.10: 5-[3-[2,6- dichloro-4-(3,3-dichloroallyloxy)phenoxy]propoxy]-1 H-pyrazole;

M.UN.1 1.b) 3-(benzoylmethylamino)-N-[2-bromo-4-[1 ,2,2,3,3,3-hexafluoro-1 -(trifluorome- thyl)propyl]-6-(trifluoromethyl)phenyl]-2-fluoro-benzamide; M.UN.1 1.c) 3-(benzoylmethylamino)- 2-fluoro-N-[2-iodo-4-[1 ,2,2,2-tetrafluoro-1 -(trifluoromethyl)ethyl]-6-(trifluoromethyl)phenyl]-ben- zamide; M.UN.H .d) N-[3-[[[2-iodo-4-[1 ,2,2,2-tetrafluoro-1 -(trifluoromethyl)ethyl]-6-(trifluorome- thyl)phenyl]amino]carbonyl]phenyl]-N-methyl-benzamide; M.UN.1 1 .e) N-[3-[[[2-bromo-4- [1 ,2,2,2-tetrafluoro-1 -(trifluoromethyl)ethyl]-6-(trifluoromethyl)phenyl]amino]carbonyl]-2-fluor^^ phenyl]-4-fluoro-N-methyl-benzamide; M.UN.1 1 .f) 4-fluoro-N-[2-fluoro-3-[[[2-iodo-4-[1 ,2,2,2-tet- rafluoro-1 -(trifluoromethyl)ethyl]-6-(trifluoromethyl)phenyl]amino]carbonyl]phenyl]-N-methyl-ben zamide; M.UN.H .g) 3-fluoro-N-[2-fluoro-3-[[[2-iodo-4-[1 ,2,2,2-tetrafluoro-1 -(trifluoromethyl)- ethyl]-6-(trifluoromethyl)phenyl]amino]carbonyl]phenyl]-N-methyl-benzamide; M.UN.1 1 .h) 2- chloro-N-[3-[[[2-iodo-4-[1 ,2,2,2-tetrafluoro-1 -(trifluoromethyl)ethyl]-6-(trifluoromethyl)phe- nyl]amino]carbonyl]phenyl]- 3-pyridinecarboxamide; M.UN.1 1.i) 4-cyano-N-[2-cyano-5-[[2,6-di- bromo-4-[1 ,2,2,3,3,3-hexafluoro-1 -(trifluoromethyl)propyl]phenyl]carbamoyl]phenyl]-2-methyl- benzamide; M.UN.1 1.j) 4-cyano-3-[(4-cyano-2-methyl-benzoyl)amino]-N-[2,6-dichloro-4- [1 ,2,2,3,3,3-hexafluoro-1 -(trifluoromethyl)propyl]phenyl]-2-fluoro-benzamide; M.UN.1 1.k) N-[5- [[2-chloro-6-cyano-4-[1 ,2,2,3,3,3-hexafluoro-1 -(trifluoromethyl)propyl]phenyl]carbamoyl]-2-cy- ano-phenyl]-4-cyano-2-methyl-benzamide; M.UN.1 1.1) N-[5-[[2-bromo-6-chloro-4-[2,2,2-trifluoro- 1 -hydroxy-1 -(trifluoromethyl)ethyl]phenyl]carbamoyl]-2-cyano-phenyl]-4-cyano-2-methyl-ben- zamide; M.UN.1 1 .m) N-[5-[[2-bromo-6-chloro-4-[1 ,2,2,3,3,3-hexafluoro-1 -(trifluoromethyl)pro- pyl]phenyl]carbamoyl]-2-cyano-phenyl]-4-cyano-2-methyl-benzamide; M.UN.1 1.n) 4-cyano-N-[2- cyano-5-[[2,6-dichloro-4-[1 ,2,2,3,3,3-hexafluoro-1 -(trifluoromethyl)propyl]phenyl]carbamoyl]phe- nyl]-2-methyl-benzamide; M.UN.1 1 .o) 4-cyano-N-[2-cyano-5-[[2,6-dichloro-4-[1 ,2,2,2-tetrafluoro- 1 -(trifluoromethyl)ethyl]phenyl]carbamoyl]phenyl]-2-methyl-benzamide; M.UN.1 1 .p) N-[5-[[2- bromo-6-chloro-4-[1 ,2,2,2-tetrafluoro-1 -(trifluoromethyl)ethyl]phenyl]carbamoyl]-2-cyano-phe- nyl]-4-cyano-2-methyl-benzamide; or

M.UN.12.a) 2-(1 ,3-Dioxan-2-yl)-6-[2-(3-pyridinyl)-5-thiazolyl]-pyridine; M.UN.12.b) 2-[6-[2-(5- Fluoro-3-pyridinyl)-5-thiazolyl]-2-pyridinyl]-pynmidine; M.UN.12. c) 2-[6-[2-(3-Pyridinyl)-5-thia- zolyl]-2-pyridinyl]-pyrimidine; M.UN.12.d) N-Methylsulfonyl-6-[2-(3-pyridyl)thiazol-5-yl]pyridine-2- carboxamide; M.UN.12.e) N-Methylsulfonyl-6-[2-(3-pyridyl)thiazol-5-yl]pyridine-2-carboxamide; M. U N .12.f) N-Ethyl-N-[4-methyl-2-(3-pyndyl)thiazol-5-yl]-3-methylthio-propanamide; M. U N .12.g) N-Methyl-N-[4-methyl-2-(3-pyndyl)thiazol-5-yl]-3-methylthio-propanamide; M.UN.12.h) N,2-Di- methyl-N-[4-methyl-2-(3-pyndyl)thiazol-5-yl]-3-methylthio-propanamide; M.UN.12.i) N-Ethyl-2- methyl-N-[4-methyl-2-(3-pyndyl)thiazol-5-yl]-3-methylthio-propanamide; M.UN.12.j) N-[4-Chloro- 2-(3-pyridyl)thiazol-5-yl]-N-ethyl-2-methyl-3-methylthio-propanamide; M.UN.12.k) N-[4-Chloro-2- (3-pyridyl)thiazol-5-yl]-N,2-dimethyl-3-methylthio-propanamide; M. UN.12.1) N-[4-Chloro-2-(3- pyridyl)thiazol-5-yl]-N-methyl-3-methylthio-propanamide; M.UN.12.m) N-[4-Chloro-2-(3-pyri- dyl)thiazol-5-yl]-N-ethyl-3-methylthio-propanamide;

M.UN.14a) 1 -[(6-Chloro-3-pyridinyl)methyl]-1 ,2,3,5,67-hexahydro-5-methoxy-7-methyl-8-ni imidazo[1 ,2-a]pyridine; or M. UN.14b) 1 -[(6-Chloropyridin-3-yl)methyl]-7-methyl-8-nitro- 1 ,2,3,5,6,7-hexahydroimidazo[1 ,2-a]pyridin-5-ol;

M. UN.16a) 1 -isopropyl-N,5-dimethyl-N-pyridazin-4-yl-pyrazole-4-carboxamide; or M. UN.16b) 1 -(1 ,2-dimethylpropyl)-N-ethyl-5-methyl-N-pyridazin-4-yl-pyrazole-4-carboxamide; M.UN.16c) N,5-dimethyl-N-pyridazin-4-yl-1 -(2,2,2-trifluoro-1 -methyl-ethyl)pyrazole-4-carboxamide;

M.UN.16d) 1 -[1 -(1 -cyanocyclopropyl)ethyl]-N-ethyl-5-methyl-N-pyridazin-4-yl-pyrazole-4-carbox- amide; M.UN.16e) N-ethyl-1 -(2-fluoro-1 -methyl-propyl)-5-methyl-N-pyridazin-4-yl-pyrazole-4- carboxamide; M.UN.16f) 1 -(1 ,2-dimethylpropyl)-N,5-dimethyl-N-pyridazin-4-yl-pyrazole-4-car- boxamide; M.UN.16g) 1 -[1 -(1 -cyanocyclopropyl)ethyl]-N,5-dimethyl-N-pyridazin-4-yl-pyrazole-4- carboxamide; M.UN.16h) N-methyl-1 -(2-fluoro-1 -methyl-propyl]-5-methyl-N-pyridazin-4-yl-pyra- zole-4-carboxamide; M.UN.16i) 1 -(4,4-difluorocyclohexyl)-N-ethyl-5-methyl-N-pyridazin-4-yl-py- razole-4-carboxamide; or M.UN.16j) 1 -(4,4-difluorocyclohexyl)-N,5-dimethyl-N-pyridazin-4-yl- pyrazole-4-carboxamide,

M. UN.17a) N-(1 -methylethyl)-2-(3-pyridinyl)-2H-indazole-4-carboxamide; M. UN.17b) N-cyclo- propyl-2-(3-pyridinyl)-2H-indazole-4-carboxamide; M.UN.17c) N-cyclohexyl-2-(3-pyridinyl)-2H- indazole-4-carboxamide; M.UN.17d) 2-(3-pyridinyl)-N-(2,2,2-trifluoroethyl)-2H-indazole-4-car- boxamide; M.UN.17e) 2-(3-pyridinyl)-N-[(tetrahydro-2-furanyl)methyl]-2H-indazole-5-carbox- amide; M.UN.17f) methyl 2-[[2-(3-pyridinyl)-2H-indazol-5-yl]carbonyl]hydrazinecarboxylate; M.UN.17g) N-[(2,2-difluorocyclopropyl)methyl]-2-(3-pyridinyl)-2H-indazole-5-carboxamide; M.UN.17h) N-(2,2-difluoropropyl)-2-(3-pyridinyl)-2H-indazole-5-carboxamide; M.UN.17i) 2-(3- pyridinyl )-N-(2-pyrimidinylmethyl )-2H-indazole-5-carboxamide; M.UN.17j) N-[(5-methyl-2-pyra- zinyl)methyl]-2-(3-pyridinyl)-2H-indazole-5-carboxamide,

M. UN.18a) N-[3-chloro-1 -(3-pyridyl)pyrazol-4-yl]-N-ethyl-3-(3,3,3-trifluoropropylsulfanyl)pro- panamide; M. UN.18b) N-[3-chloro-1 -(3-pyridyl)pyrazol-4-yl]-N-ethyl-3-(3,3,3-trifluoropropylsulfi- nyl)propanamide; M. UN.18c) N-[3-chloro-1 -(3-pyridyl)pyrazol-4-yl]-3-[(2,2-difluorocyclopro- pyl)methylsulfanyl]-N-ethyl-propanamide; M.UN.18d) N-[3-chloro-1 -(3-pyridyl)pyrazol-4-yl]-3- [(2,2-difluorocyclopropyl)methylsulfinyl]-N-ethyl-propanamide;

M.UN.19 sarolaner, M.UN.20 lotilaner;

M.UN.21 N-[4-Chloro-3-[[(phenylmethyl)amino]carbonyl]phenyl]-1 -methyl-3-^

oroethyl)-4-(trifluoromethyl)-1 H-pyrazole-5-carboxamide; M. UN.22a 2-(3-ethylsulfonyl-2-pyridyl)- 3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridine, or M. UN.22b 2-[3-ethylsulfonyl-5-(trifluorome- thyl)-2-pyridyl]-3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridine;

M.UN.23a 4-[5-(3,5-dichlorophenyl)-5-(trifluoromethyl)-4H-isoxazol-3-yl]-N-[(4R)-2-ethyl-3-oxo- isoxazolidin-4-yl]-2-methyl-benzamide, or M. UN.23b 4-[5-(3,5-dichloro-4-fluoro-phenyl)-5-(tri- fluoromethyl)-4H-isoxazol-3-yl]-N-[(4R)-2-ethyl-3-oxo-isoxazolidin-4-yl]-2-methyl-benzami

M.UN.24a) N-[4-chloro-3-(cyclopropylcarbamoyl)phenyl]-2-methyl-5-(1 ,1 ,2,2,2-pentafluoro- ethyl)-4-(trifluoromethyl)pyrazole-3-carboxamide or M.UN.24b) N-[4-chloro-3-[(1 -cyanocyclopro- pyl)carbamoyl]phenyl]-2-methyl-5-(1 ,1 ,2,2,2-pentafluoroethyl)-4-(trifluoromethyl)pyrazole-3-car- boxamide; M.UN.25 acynonapyr; M.UN.26 benzpyrimoxan; M.UN.27 2-chloro-N-(1 -cyanocyclo- propyl)-5-[1 -[2-methyl-5-(1 ,1 ,2,2,2-pentafluoroethyl)-4-(trifluoromethyl)pyrazol-3-yl]pyrazol-4- yl]benzamide.

The commercially available compounds of the group M listed above may be found in The Pesticide Manual, 17th Edition, C. MacBean, British Crop Protection Council (2015) among other publications. The online Pesticide Manual is updated regularly and is accessible through http://bcpcdata.com/pesticide-manual.html.

Another online data base for pesticides providing the ISO common names is http://www.alan- wood.net/pesticides.

The M.4 cycloxaprid is known from WO2010/069266 and WO201 1/069456. M.4A.1 is known from CN 103814937; CN 105367557, CN 105481839. M.4A.2, guadipyr, is known from WO 2013/003977, and M.4A.3 (approved as paichongding in China) is known from WO

2007/101369. M.22B.1 is described in CN10171577 and M.22B.2 in CN102126994. Spiropidion M.23.1 is known from WO 2014/191271 . M.28.1 and M.28.2 are known from WO2007/101540. M.28.3 is described in WO2005/077934. M.28.4 is described in WO2007/043677. M.28.5a) to M.28.5d) and M.28.5h) are described in WO 2007/006670, WO2013/024009 and WO

2013/024010, M.28.5i) is described in WO201 1/085575, M.28.5j) in WO2008/134969, M.28.5k) in US201 1/046186 and M.28.5I) in WO2012/034403. M.28.6 can be found in WO2012/034472. M.UN.3 is known from WO2006/089633 and M.UN.4 from WO2008/06791 1 . M.UN.5 is described in WO2006/043635, and biological control agents on the basis of bacillus firmus are de- scribed in WO2009/124707. Flupyrimin is described in WO2012/029672. M.UN.8 is known from WO2013/055584. M.UN.9.a) is described in WO2013/050317. M.UN.9.b) is described in WO2014/126208. M. UN.10 is known from WO2010/060379. Broflanilide and M.UN.H .b) to M.UN.H .h) are described in WO2010/018714, and M.UN.1 1 i) to M.UN.H .p) in WO 2010/127926. M.UN.12.a) to M.UN.12.C) are known from WO2010/006713, M.UN.12.d) and M.UN.12.e) are known from WO2012/000896, and M.UN.12.†) to M.UN.12.m) from WO

2010/129497. M. UN.14a) and M. UN.14b) are known from WO2007/101369. M.UN.16.a) to M.UN.16h) are described in WO2010/034737, WO2012/084670, and WO2012/143317, resp., and M.UN.16i) and M.UN.16j) are described in WO2015/055497. M. UN.17a) to M.UN.17J) are described in WO2015/038503. M. UN.18a) to M.UN.18d) are described in US2014/0213448. M.UN.19 is described in WO2014/036056. M.UN.20 is known from WO2014/090918. M.UN.21 is known from EP2910126. M.UN.22a and M.UN.22b are known from WO2015/059039 and WO2015/190316. M.UN.23a and M.UN.23b are known from WO2013/050302. M.UN.24a and M.UN.24b are known from WO2012/126766. Acynonapyr M.UN.25 is known from WO

201 1/105506. Benzpyrimoxan M.UN.26 is known from WO2016/104516. M.UN.27 is known from WO2016174049.

The following list of fungicides, in conjunction with which the compounds of the present invention can be used, is intended to illustrate the possible combinations in the methods according to the invention but does not limit them:

A) Respiration inhibitors

Inhibitors of complex III at Qo site: azoxystrobin (A.1.1 ), coumethoxystrobin (A.1 .2), coumoxystrobin (A.1.3), dimoxystrobin (A.1 .4), enestroburin (A.1 .5), fenaminstrobin (A.1.6), fenoxystrobin/flufenoxystrobin (A.1.7), fluoxastrobin (A.1 .8), kresoxim-methyl (A.1.9), mande- strobin (A.1 .10), metominostrobin (A.1.1 1 ), orysastrobin (A.1.12), picoxystrobin (A.1 .13), pyra- clostrobin (A.1 .14), pyrametostrobin (A.1 .15), pyraoxystrobin (A.1.16), trifloxystrobin (A.1.17), 2 (2-(3-(2,6-dichlorophenyl)-1 -methyl-allylideneaminooxymethyl)-phenyl)-2 methoxyimino-N me- thyl-acetamide (A.1.18), pyribencarb (A.1 .19), triclopyricarb/chlorodincarb (A.1.20), famoxadone (A.1.21 ), fenamidone (A.1.21 ), methyl-N-[2-[(1 ,4-dimethyl-5 phenyl-pyrazol-3-yl)oxylmethyl]phe- nyl]-N-methoxy-carbamate (A.1.22), 1 -[3-chloro-2 [[1 (4-chlorophenyl)-1 H-pyrazol-3-yl]oxyme- thyl]phenyl]-4-methyl-tetrazol-5-one (A.1 .23), 1 -[3-bromo-2-[[1 -(4-chlorophenyl)pyrazol-3-yl]ox- ymethyl]phenyl]-4-methyl-tetrazol-5-one (A.1.24), 1 -[2-[[1 -(4-chlorophenyl)pyrazol-3-yl]oxyme- thyl]-3-methyl-phenyl]-4-methyl-tetrazol-5-one (A.1 .25), 1 -[2-[[1 -(4-chlorophenyl)pyrazol-3-yl]ox- ymethyl]-3-fluoro-phenyl]-4-methyl-tetrazol-5-one (A.1.26), 1 -[2-[[1 -(2,4-dichlorophenyl)pyrazol- 3-yl]oxymethyl]-3-fluoro-phenyl]-4-methyl-tetrazol-5-one (A.1.27), 1 -[3-cyclopropyl-2-[[2-methyl- 4 (1 methylpyrazol-3-yl)phenoxy]methyl]phenyl]-4 methyl-tetrazol-5-one (A.1.30), 1 [3 (difluoro- methoxy)-2-[[2-methyl-4-(1 methylpyrazol-3 yl)phenoxy]methyl]phenyl]-4 methyl-tetrazol-5-one (A.1.31 ), 1 -methyl-4-[3-methyl-2 [[2 methyl-4-(1 -methylpyrazol-3 yl)phenoxy]methyl]phenyl]te- trazol-5-one (A.1.32), (Z,2E)-5-[1 -(2,4-dichlorophenyl)pyrazol-3-yl]-oxy-2-methoxyimino-N,3-di- methyl-pent-3-enamide (A.1 .34), (Z,2E) 5 [1 (4-chlorophenyl)pyrazol-3-yl]oxy-2-methoxyimino- N,3-dimethyl-pent-3-enamide (A.1 .35), pyriminostrobin (A.1 .36), bifujunzhi (A.1.37), 2-(ortho- ((2,5-dimethylphenyl-oxy-methylen)phenyl)-3-methoxy-acrylic acid methylester (A.1.38);

inhibitors of complex III at Qi site: cyazofamid (A.2.1 ), amisulbrom (A.2.2), [(6S,7R,8R) 8 benzyl-3-[(3-hydroxy-4-methoxy-pyridine-2-carbonyl)amino]-6-methyl-4,9-dioxo-1 ,5-dioxonan-7- yl] 2-methylpropanoate (A.2.3), fenpicoxamid (A.2.4);

inhibitors of complex II: benodanil (A.3.1 ), benzovindiflupyr (A.3.2), bixafen (A.3.3), bos- calid (A.3.4), carboxin (A.3.5), fenfuram (A.3.6), fluopyram (A.3.7), flutolanil (A.3.8), fluxapy- roxad (A.3.9), furametpyr (A.3.10), isofetamid (A.3.1 1 ), isopyrazam (A.3.12), mepronil (A.3.13), oxycarboxin (A.3.14), penflufen (A.3.15), penthiopyrad (A.3.16), pydiflumetofen (A.3.17), pyrazi- flumid (A.3.18), sedaxane (A.3.19), tecloftalam (A.3.20), thifluzamide (A.3.21 ), 3 (difluorome- thyl)-1 -methyl-N-(1 ,1 ,3-trimethylindan-4-yl)pyrazole-4 carboxamide (A.3.22), 3 (trifluoromethyl)- 1 -methyl-N-(1 ,1 ,3-trimethylindan-4-yl)pyrazole-4 carboxamide (A.3.23), 1 ,3-dimethyl-N-(1 ,1 ,3- trimethylindan-4-yl)pyrazole-4-carboxamide (A.3.24), 3-(trifluoromethyl)-1 ,5 dimethyl-N-(1 ,1 ,3- trimethylindan-4-yl)pyrazole-4-carboxamide (A.3.25), 1 ,3,5-trimethyl-N-(1 ,1 ,3-trimethylindan-4- yl)pyrazole-4-carboxamide (A.3.26), 3-(difluoromethyl)-1 ,5 dimethyl-N-(1 ,1 ,3-trimethylindan-4- yl)pyrazole-4-carboxamide (A.3.27), 3-(difluoromethyl)-N (7 fluoro-1 ,1 ,3-trimethyl-indan-4-yl)-1 - methyl-pyrazole-4-carboxamide (A.3.28), N-[(5-chloro-2-isopropyl-phenyl)methyl]-N-cyclopropyl- 5-fluoro-1 ,3-dimethyl-pyrazole-4-carboxamide (A.3.29), methyl (E)-2-[2-[(5-cyano-2-methyl-phe- noxy)methyl]phenyl]-3-methoxy-prop-2 enoate (A.3.30), N-[(5-chloro-2-isopropyl-phenyl)methyl]- N-cyclopropyl-3-(difluoromethyl)-5 fluoro-1 -methyl-pyrazole-4-carboxamide (A.3.31 ), 2-(difluoro- methyl)-N-(1 ,1 ,3-trimethyl-indan-4-yl)pyridine-3-carboxamide (A.3.32), 2-(difluoromethyl)-N- [(3R)-1 ,1 ,3-trimethylindan-4-yl]pyridine-3-carboxamide (A.3.33), 2-(difluoromethyl)-N-(3-ethyl- 1 ,1 -dimethyl-indan-4-yl)pyridine-3-carboxamide (A.3.34), 2-(difluoromethyl)-N-[(3R)-3-ethyl-1 ,1 - dimethyl-indan-4-yl]pyridine-3-carboxamide (A.3.35), 2-(difluoromethyl)-N-(1 ,1 -dimethyl-3-pro- pyl-indan-4-yl)pyridine-3-carboxamide (A.3.36), 2-(difluoromethyl)-N-[(3R)-1 ,1 -dimethyl-3-pro- pyl-indan-4-yl]pyridine-3-carboxamide (A.3.37), 2-(difluoromethyl)-N-(3-isobutyl-1 ,1 -dimethyl- indan-4-yl)pyridine-3-carboxamide (A.3.38), 2-(difluoromethyl)-N-[(3R)-3-isobutyl-1 ,1 -dimethyl- indan-4 yl]pyridine-3-carboxamide (A.3.39);

other respiration inhibitors: diflumetorim (A.4.1 ); nitrophenyl derivates: binapacryl (A.4.2), dinobuton (A.4.3), dinocap (A.4.4), fluazinam (A.4.5), meptyldinocap (A.4.6), ferimzone (A.4.7); organometal compounds: fentin salts, e. g. fentin-acetate (A.4.8), fentin chloride (A.4.9) or fentin hydroxide (A.4.10); ametoctradin (A.4.1 1 ); silthiofam (A.4.12);

B) Sterol biosynthesis inhibitors (SBI fungicides)

C14 demethylase inhibitors: triazoles: azaconazole (B.1.1 ), bitertanol (B.1.2), bromu-con- azole (B.1 .3), cyproconazole (B.1.4), difenoconazole (B.1 .5), diniconazole (B.1 .6), diniconazole- M (B.1.7), epoxiconazole (B.1 .8), fenbuconazole (B.1 .9), fluquinconazole (B.1.10), flusilazole (B.1.1 1 ), flutriafol (B.1 .12), hexaconazole (B.1 .13), imibenconazole (B.1.14), ipconazole

(B.1.15), metconazole (B.1 .17), myclobutanil (B.1 .18), oxpoconazole (B.1.19), paclobutrazole (B.1.20), penconazole (B.1.21 ), propiconazole (B.1.22), prothioconazole (B.1 .23), simeconazole (B.1.24), tebuconazole (B.1.25), tetraconazole (B.1.26), triadimefon (B.1.27), triadimenol (B.1.28), triticonazole (B.1.29), uniconazole (B.1.30), ipfentrifluconazole, (B.1 .37), mefentriflu- conazole (B.1 .38), 2-(chloromethyl)-2-methyl-5-(p-tolylmethyl)-1 (1 ,2,4-triazol-1 -ylmethyl)cyclo- pentanol (B.1 .43); imidazoles: imazalil (B.1.44), pefurazoate (B.1.45), prochloraz (B.1.46), tri- flumizol (B.1.47); pyrimidines, pyridines and piperazines: fenarimol (B.1.49), pyrifenox (B.1.50), triforine (B.1 .51 ), [3-(4-chloro-2-fluoro-phenyl)-5-(2,4-difluorophenyl)isoxazol-4-yl]-(3-pyri- dyl)methanol (B.1 .52);

Delta14-reductase inhibitors: aldimorph (B.2.1 ), dodemorph (B.2.2), dodemorph-acetate (B.2.3), fenpropimorph (B.2.4), tridemorph (B.2.5), fenpropidin (B.2.6), piperalin (B.2.7), spirox- amine (B.2.8);

Inhibitors of 3-keto reductase: fenhexamid (B.3.1 );

Other Sterol biosynthesis inhibitors: chlorphenomizole (B.4.1 ); C) Nucleic acid synthesis inhibitors

phenylamides or acyl amino acid fungicides: benalaxyl (C.1.1 ), benalaxyl-M (C.1 .2), kiral- axyl (C.1.3), metalaxyl (C.1.4), metalaxyl-M (C.1.5), ofurace (C.1 .6), oxadixyl (C.1 .7);

other nucleic acid synthesis inhibitors: hymexazole (C.2.1 ), octhilinone (C.2.2), oxolinic acid (C.2.3), bupirimate (C.2.4), 5-fluorocytosine (C.2.5), 5-fluoro-2-(p-tolylmethoxy)pyrimidin-4 amine (C.2.6), 5-fluoro-2-(4-fluorophenylmethoxy)pyrimidin-4 amine (C.2.7), 5-fluoro-2 (4 chlo- rophenylmethoxy)pyrimidin-4 amine (C.2.8);

D) Inhibitors of cell division and cytoskeleton

tubulin inhibitors: benomyl (D.1.1 ), carbendazim (D.1 .2), fuberidazole (D1.3), thia- bendazole (D.1 .4), thiophanate-methyl (D.1.5), 3-chloro-4-(2,6-difluorophenyl)-6-methyl-5-phe- nyl-pyridazine (D.1.6), 3-chloro-6-methyl-5-phenyl-4-(2,4,6-trifluorophenyl)pyridazine (D.1 .7), N ethyl-2-[(3-ethynyl-8-methyl-6-quinolyl)oxy]butanamide (D.1 .8), N-ethyl-2-[(3-ethynyl-8 methyl-6 quinolyl)oxy]-2-methylsulfanyl-acetamide (D.1.9), 2-[(3-ethynyl-8-methyl-6-quinol-yl)oxy]-N (2- fluoroethyl)butanamide (D.1 .10), 2-[(3-ethynyl-8-methyl-6-quinolyl)oxy]-N-(2-flu-oroethyl)-2- methoxy-acetamide (D.1 .1 1 ), 2-[(3-ethynyl-8-methyl-6-quinolyl)oxy]-N-propyl-butanamide

(D.1 .12), 2-[(3-ethynyl-8-methyl-6-quinolyl)oxy]-2-methoxy-N-propyl-acetamide (D.1.13), 2-[(3- ethynyl-8-methyl-6-quinolyl)oxy]-2-methylsulfanyl-N-propyl-acetamide (D.1.14), 2 [(3 ethynyl-8- methyl-6-quinolyl)oxy]-N-(2-fluoroethyl)-2-methylsulfanyl-acetamide (D.1 .15), 4-(2-bromo-4- fluoro-phenyl)-N-(2-chloro-6-fluoro-phenyl)-2,5-dimethyl-pyrazol-3 amine (D.1.16);

- other cell division inhibitors: diethofencarb (D.2.1 ), ethaboxam (D.2.2), pencycuron (D.2.3), fluopicolide (D.2.4), zoxamide (D.2.5), metrafenone (D.2.6), pyriofenone (D.2.7);

E) Inhibitors of amino acid and protein synthesis

methionine synthesis inhibitors: cyprodinil (E.1.1 ), mepanipyrim (E.1 .2), pyrimethanil (E.1.3);

- protein synthesis inhibitors: blasticidin-S (E.2.1 ), kasugamycin (E.2.2), kasugamycin hy- drochloride-hydrate (E.2.3), mildiomycin (E.2.4), streptomycin (E.2.5), oxytetracyclin (E.2.6);

F) Signal transduction inhibitors

MAP / histidine kinase inhibitors: fluoroimid (F.1 .1 ), iprodione (F.1 .2), procymidone (F.1 .3), vinclozolin (F.1.4), fludioxonil (F.1 .5);

- G protein inhibitors: quinoxyfen (F.2.1 );

G) Lipid and membrane synthesis inhibitors

Phospholipid biosynthesis inhibitors: edifenphos (G.1.1 ), iprobenfos (G.1 .2), pyrazophos (G.1.3), isoprothiolane (G.1 .4);

lipid peroxidation: dicloran (G.2.1 ), quintozene (G.2.2), tecnazene (G.2.3), tolclofos-methyl (G.2.4), biphenyl (G.2.5), chloroneb (G.2.6), etridiazole (G.2.7);

phospholipid biosynthesis and cell wall deposition: dimethomorph (G.3.1 ), flumorph (G.3.2), mandipropamid (G.3.3), pyrimorph (G.3.4), benthiavalicarb (G.3.5), iprovalicarb (G.3.6), valifenalate (G.3.7);

compounds affecting cell membrane permeability and fatty acides: propamocarb (G.4.1 ); - inhibitors of oxysterol binding protein: oxathiapiprolin (G.5.1 ), 2-{3-[2-(1 -{[3,5-bis(difluoro- methyl-1 H-pyrazol-1 -yl]acetyl}piperidin-4-yl)-1 ,3-thiazol-4-yl]-4,5-dihydro-1 ,2 oxazol-5-yl}phenyl methanesulfonate (G.5.2), 2-{3-[2-(1 -{[3,5-bis(difluoromethyl)-1 H-pyrazol-1 -yl]acetyl}piperidin-4- yl) 1 ,3-thiazol-4-yl]-4,5-dihydro-1 ,2-oxazol-5 yl}-3-chlorophenyl methanesulfonate (G.5.3), 4-[1 - [2-[3-(difluoromethyl)-5-methyl-pyrazol-1 -yl]acetyl]-4-piperidyl]-N-tetralin-1 -yl-pyri amide (G.5.4), 4-[1 -[2-[3,5-bis(difluoromethyl)pyrazol-1 -yl]acetyl]-4-piperidyl]-N-tetralin-1 -yl-pyri- dine-2-carboxamide (G.5.5), 4-[1 -[2-[3-(difluoromethyl)-5-(trifluoromethyl)pyrazol-1 -yl]acetyl]-4- piperidyl]-N-tetralin-1 -yl-pyridine-2-carboxamide (G.5.6), 4-[1 -[2-[5-cyclopropyl-3-(difluorome- thyl)pyrazol-1 -yl]acetyl]-4-piperidyl]-N-tetralin-1 -yl-pyridine-2-carboxamide (G.5.7), 4-[1 -[2-[5- methyl-3-(trifluoromethyl)pyrazol-1 -yl]acetyl]-4-piperidyl]-N-tetralin-1 -yl-pyndine-2-carb^

(G.5.8), 4-[1 -[2-[5-(difluoromethyl)-3-(trifluoromethyl)pyrazol-1 -yl]acetyl]-4-piperidyl]-N-tetralin-1 - yl-pyridine-2-carboxamide (G.5.9), 4 [1 [2-[3,5-bis(trifluoromethyl)pyrazol-1 -yl]acetyl]-4-piperi- dyl]-N-tetralin-1 -yl-pyridine-2-carboxamide (G.5.10), (4-[1 -[2-[5-cyclopropyl-3-(trifluoromethyl)py- razol-1 -yl]acetyl]-4-piperidyl]-N-tetralin-1 -yl-pyridine-2-carboxamide (G.5.1 1 );

H) Inhibitors with Multi Site Action

inorganic active substances: Bordeaux mixture (H.1.1 ), copper (H.1 .2), copper acetate (H.1 .3), copper hydroxide (H.1 .4), copper oxychloride (H.1.5), basic copper sulfate (H.1.6), sulfur (H.1.7);

- thio- and dithiocarbamates: ferbam (H.2.1 ), mancozeb (H.2.2), maneb (H.2.3), metam (H.2.4), metiram (H.2.5), propineb (H.2.6), thiram (H.2.7), zineb (H.2.8), ziram (H.2.9);

organochlorine compounds: anilazine (H.3.1 ), chlorothalonil (H.3.2), captafol (H.3.3), cap- tan (H.3.4), folpet (H.3.5), dichlofluanid (H.3.6), dichlorophen (H.3.7), hexachlorobenzene (H.3.8), pentachlorphenole (H.3.9) and its salts, phthalide (H.3.10), tolylfluanid (H.3.1 1 );

- guanidines and others: guanidine (H.4.1 ), dodine (H.4.2), dodine free base (H.4.3), guaza- tine (H.4.4), guazatine-acetate (H.4.5), iminoctadine (H.4.6), iminoctadine-triacetate (H.4.7), iminoctadine-tris(albesilate) (H.4.8), dithianon (H.4.9), 2,6-dimethyl-1 H,5H-[1 ,4]dithiino[2,3- c:5,6-c']dipyrrole-1 ,3,5,7(2H,6H)-tetraone (H.4.10);

I) Cell wall synthesis inhibitors

- inhibitors of glucan synthesis: validamycin (1.1.1 ), polyoxin B (1.1 .2);

melanin synthesis inhibitors: pyroquilon (1.2.1 ), tricyclazole (1.2.2), carpropamid (1.2.3), di- cyclomet (I.2.4), fenoxanil (I.2.5);

J) Plant defence inducers

acibenzolar-S-methyl (J.1.1 ), probenazole (J.1 .2), isotianil (J.1.3), tiadinil (J.1.4), prohexa- dione-calcium (J.1.5); phosphonates: fosetyl (J.1 .6), fosetyl-aluminum (J.1.7), phosphorous acid and its salts (J.1.8), calcium phosphonate (J.1.1 1 ), potassium phosphonate (J.1 .12), potassium or sodium bicarbonate (J.1.9), 4 cyclopropyl-N-(2,4-dimethoxyphenyl)thiadiazole-5-carboxamide (J.1 .10);

K) Unknown mode of action

- bronopol (K.1 .1 ), chinomethionat (K.1 .2), cyflufenamid (K.1 .3), cymoxanil (K.1.4), dazomet (K.1.5), debacarb (K.1 .6), diclocymet (K.1.7), diclomezine (K.1 .8), difenzoquat (K.1 .9), difenzo- quat-methylsulfate (K.1 .10), diphenylamin (K.1 .1 1 ), fenitropan (K.1 .12), fenpyrazamine (K.1.13), flumetover (K.1.14), flusulfamide (K.1 .15), flutianil (K.1.16), harpin (K.1 .17), metha-sulfocarb (K.1.18), nitrapyrin (K.1.19), nitrothal-isopropyl (K.1.20), tolprocarb (K.1.21 ), oxin-copper (K.1.22), proquinazid (K.1.23), tebufloquin (K.1 .24), tecloftalam (K.1 .25), triazoxide (K.1.26), N'- (4-(4-chloro-3-trifluoromethyl-phenoxy)-2,5-dimethyl-phenyl)-N-ethyl-N methyl formamidine (K.1.27), N' (4-(4-fluoro-3-trifluoromethyl-phenoxy)-2,5-dimethyl-phenyl)-N-ethyl-N-methyl formamidine (K.1.28), N'-[4-[[3-[(4-chlorophenyl)methyl]-1 ,2,4-thiadiazol-5-yl]oxy]-2,5-dimethyl- phenyl]-N-ethyl-N-methyl-formamidine (K.1 .29), N'-(5-bromo-6-indan-2-yloxy-2-methyl-3-pyri- dyl)-N-ethyl-N-methyl-formamidine (K.1 .30), N'-[5-bromo-6-[1 -(3,5-difluorophenyl)ethoxy]-2-me- thyl-3-pyridyl]-N-ethyl-N-methyl-formamidine (K.1.31 ), N'-[5-bromo-6-(4-isopropylcyclohexoxy)- 2-methyl-3-pyridyl]-N-ethyl-N-methyl-formamidine (K.1 .32), N' [5 bromo-2-methyl-6-(1 -phenyl- ethoxy)-3-pyndyl]-N-ethyl-N-methyl-formamidine (K.1.33), N'-(2-methyl-5-trifluoromethyl-4-(3- trimethylsilanyl-propoxy)-phenyl)-N-ethyl-N-methyl formamidine (K.1.34), N'-(5-difluoromethyl-2 methyl-4-(3-trimethylsilanyl-propoxy)-phenyl)-N-ethyl-N-methyl formamidine (K.1.35), 2-(4-chlo- ro-phenyl)-N-[4-(3,4-dimethoxy-phenyl)-isoxazol-5 yl]-2-prop-2-ynyloxy-acetamide (K.1 .36), 3 [5- (4-chloro-phenyl)-2,3-dimethyl-isoxazolidin-3-yl]-pyridine (pyrisoxazole) (K.1 .37), 3-[5-(4-methyl- phenyl)-2,3-dimethyl-isoxazolidin-3 yl]-pyridine (K.1 .38), 5-chloro-1 (4,6-dimethoxy-pyrimidin-2- yl)-2-methyl-1 H-benzoimidazole (K.1.39), ethyl (Z) 3 amino-2-cyano-3-phenyl-prop-2-enoate (K.1.40), picarbutrazox (K.1.41 ), pentyl N-[6-[[(Z)-[(1 -methyltetrazol-5-yl)-phenyl-methyle- ne]amino]oxymethyl]-2-pyridyl]carbamate (K.1 .42), but-3-ynyl N-[6-[[(Z)-[(1 -methyltetrazol-5-yl)- phenyl-methylene]amino]oxymethyl]-2-pyridyl]carbamate (K.1 .43), 2-[2-[(7,8-difluoro-2-methyl-3- quinolyl)oxy]-6-fluoro-phenyl]propan-2-ol (K.1.44), 2-[2-fluoro-6-[(8-fluoro-2-methyl-3-quino- lyl)oxy]phen-yl]propan-2-ol (K.1.45), quinofumelin (K.1 .47), 9-fluoro-2,2-dimethyl-5-(3-quinolyl)- 3H 1 ,4 benzoxazepine (K.1 .49), 2-(6-benzyl-2-pyridyl)quinazoline (K.1 .50), 2-[6-(3-fluoro-4 methoxy-phenyl)-5-methyl-2-pyridyl]quinazoline (K.1.51 ), dichlobentiazox (K.1.52), N'-(2,5-dime- thyl-4-phenoxy-phenyl)-N-ethyl-N-methyl-formamidine (K.1.53);

dipymetitrone, isoflucypram; fluindapyr, inpyrfluxam, pyrifenamine.

The fungicides described by lUPAC nomenclature, their preparation and their pesticidal activity is 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 10/139271 , WO 1 1/028657, WO2012/168188, WO 2007/006670, WO 201 1/77514; W013/047749, WO 10/069882, WO 13/047441 , WO 03/16303, WO 09/90181 , WO 13/007767, WO 13/010862, WO 13/127704, WO 13/024009, WO 13/024010 and WO 13/047441 , WO 13/162072,

WO 13/092224, WO 1 1/135833), CN 1907024, CN 1456054, CN 103387541 , CN 1309897, WO 12/84812, CN 1907024, WO 09094442, WO 14/60177, WO 13/1 16251 , WO 08/013622, WO 15/65922, WO 94/01546, EP 2865265, WO 07/129454, WO 12/16551 1 , WO 1 1/081 174, WO 13/47441 ).

If the compounds of the present invention are mixed with one or more fungicides, the mixtures are also suitable for combating or controlling plant diseases, as caused by phytophathogenic fungi. Examples of phytophathogenic fungi in rice are

Alternaria species on rice, Bipolaris (e.g. Bipolaris oryzae), and Drechslera species on rice, Cercospora oryzae, Cochliobolus miyabeanus, Curvularia lunata, Sarocladium oryzae, S atten- uatum, Entyloma oryzae, Fusar/um spp such as Fusarium semitectum (and/or moniliforme Gibberella fujikuroi (bakanae), Grainstaining complex (various pathogens), and/or Pythium ssp.

Helminthosporium. spp, for example Helminthosporium oryzae, Microdochium oryzae, Pyricu- laria grisea (syn. Pyricularia oryzae), Rhizoctonia species, for example Rhizoctonia so/anl (syn in rice Pellicula ria sasakil), Cortlclum sasakll and Ustilaginoidea virens.

In a further embodiment, the invention relates to methods according to the invention, applying mixtures comprising a compound of formula (I) as described above, in particular dicloromezo- tiaz, and at least one compound II which is metaaldehyde, in particular granular metaaldehyde.

In a further embodiment, the invention relates to methods according to the invention, applying mixtures comprising a compound of formula (I) as described above and at least one compound II selected from the group of methiadinil, anthraquinones, beta-aminobutyric acid, laminarin, chi- tosan, thiamine and riboflavin.

In a further embodiment, the invention relates to methods according to the invention, applying mixtures comprising a compound of formula (I) as described above and at least one compound II selected from the group of oxyenadenine (also called zeatin), kinetin (oxy)enadenine, brassinolides, insecticidal extracts of Celastrus angulatus, matrine, cnidiadin, tetramycin.

In one embodiment, the methods of the present invention comprise applying a mixture of at least one compound I of the present invention with at least one mixing partner II as defined above. In one embodiment, the invention relates to methods applying binary mixtures of one compound I with one mixing partner II as defined above as component II.

Preferred weight ratios for such binary mixtures are from 5000:1 to 1 :5000, preferably from 1000:1 to 1 :1000, more preferably from 100:1 to 1 :100, particularly preferably from 10:1 to 1 :10. In such binary mixtures, components I and II may be used in equal amounts, or an excess of component I, or an excess of component II may be used.

In the mixtures of the present invention, the ingredients may be used sequentially or in combination with each other, if appropriate also added only immediately prior to use (tank mix). For example, the plant(s) may be sprayed with compound II either before or after being treated with compound I.

In another embodiment, the invention relates to methods applying mixtures of one compound I with one mixing partner II, and optionally further pesticides.

In one embodiment of the invention, the mixtures of the present invention are mixtures of a compound of formula (I), with a compound selected from the group of benomyl, carbendazim, epoxiconazole, fluquinconazole, flutriafol, flusilazole, metconazole, prochloraz, prothioconazole, tebuconazole, triticonazole, pyraclostrobin, trifloxystrobin, boscalid, dimethomorph, penthiopy- rad, dodemorph, famoxadone, fenpropimorph, proquinazid, pyrimethanil, tridemorph, maneb, mancozeb, metiram, thiram, chlorothalonil, dithianon, flusulfamide,metrafenone, fluxapyroxad, bixafen, penflufen, sedaxane, isopyrazam. Especially preferred is pyraclostrobin and fluxapyroxad.

In one embodiment of the invention, the mixtures of the present invention are mixtures of a compound of formula (I), with a compound selected from the group of imidacloprid, clothianidin, dinotefuran, chlorantraniliprole, cyantraniliprole, spinetoram, spinosad, ethiprole, fipronil, tri- flumezopyrim, flonicamid and tetraniliprole. In one embodiment of the invention, the mixtures of the present invention are mixtures of a compound of formula (I), with a compound selected from the group of probenazole, isotianil, tri- cyclazole, pyroquilon, isoprothiolane, tolprocarb, carpropamid, diclocymet, azoxystrobin, orysas- trobin.

In one embodiment of the invention, the mixtures of the present invention are mixtures of a compound of formula (I), with a compound selected from the group of furametpyr, thifluzamide, simeconazole, penflufen, azoxystrobin, orysastrobin,

Especially preferred mixtures in the methods according to the invention are listed in the following table M, wherein the compounds DMT (dicloromezotiaz) are as defined in the description: Table M:

Mixture Comp. I Compound II Mixture Comp. I Compound II

M-1 DMT fipronil M-32 DMT dichlorvos

M-2 DMT alpha-cypermethrin M-33 DMT triazophos

M-3 DMT chlorfenapyr M-34 DMT carta p

M-4 DMT metaflumizone M-35 DMT acephate

M-5 DMT abamectin M-36 DMT carbofuran

M-6 DMT pymetrozine M-37 DMT carbosulfan

M-7 DMT thiamethoxam M-38 DMT emamectin

M-8 DMT imidacloprid M-39 DMT ethiprole

M-9 DMT dinotefuran M-40 DMT etofenprox

M-10 DMT clothianidin M-41 DMT spinetoram

M-1 1 DMT bifenthrin M-42 DMT spinosad

M-12 DMT acetamiprid M-43 DMT fluhexafon

M-13 DMT nitenpyram M-44 DMT tefluthrin

M-14 DMT cypermethrin M-45 DMT momfluorothrin

M-15 DMT cyhalothrin M-46 DMT benzpyrimoxan

M-16 DMT lambda-cyhalothrin M-47 DMT cyhalodiamide

M-17 DMT flonicamid M-48 DMT spiropidion

M-18 DMT spirotetramat M-49 DMT flupyrimin

M-19 DMT buprofezine M-50 DMT cyclaniliprole

M-20 DMT chlorantraniliprole M-51 DMT fluxametamide

M-21 DMT cyantraniliprole M-52 DMT tioxazafen

M-22 DMT tetraniliprole M-53 DMT fluazaindolizine

M-23 DMT sulfoxaflor M-54 DMT pyrifluquinazone

M-24 DMT indoxacarb M-55 DMT metaaldehyde (in

M-25 DMT afidopyropen particular granular)

M-26 DMT broflanilide M-56 DMT benomyl

M-27 DMT pyri prole M-57 DMT epoxiconazole

M-28 DMT triflumezopyrim M-58 DMT fluquinconazole

M-29 DMT flupyradifurone M-59 DMT flutriafol

M-30 DMT dicloromezotiaz M-60 DMT flusilazole

M-31 DMT chlorpyrifos M-61 DMT metconazole Mixture Comp. I Compound II Mixture Comp. I Compound II

M-62 DMT prochloraz M-97 DMT furametpyr

M-63 DMT prothioconazole M-98 DMT simeconazole

M-64 DMT tebuconazole M-99 DMT probenazole

M-65 DMT triticonazole M-100 DMT mancozeb

M-66 DMT pyraclostrobin M-101 DMT propiconazole

M-67 DMT trifloxystrobin M-102 DMT hexaconazole

M-68 DMT boscalid M-103 DMT tebuconazole

M-69 DMT dimethomorph M-104 DMT carbendazim

M-70 DMT penthiopyrad M-105 DMT flutolanil

M-71 DMT dodemorph M-106 DMT hymexazol

M-72 DMT famoxadone M-107 DMT isotianil

M-73 DMT fenpropimorph M-108 DMT orysastrobin

M-74 DMT proquinazid M-109 DMT pencycuron

M-75 DMT pyrimethanil M-1 10 DMT phthalide

M-76 DMT tridemorph M-1 1 1 DMT pyroquilon

M-77 DMT maneb M-1 12 DMT thifluzamide

M-78 DMT metiram M-1 13 DMT thiophanate

M-79 DMT thiram M-1 14 DMT thiophanate-methyl

M-80 DMT chlorothalonil M-1 15 DMT tiadinil

M-81 DMT dithianon M-1 16 DMT validamycin

M-82 DMT flusulfamide M-1 17 DMT tebufloquin

M-83 DMT metrafenone M-1 18 DMT benzovindiflupyr

M-84 DMT fluxapyroxad M-1 19 DMT picarbutrazox

M-85 DMT bixafen M-120 DMT pyraziflumid

M-86 DMT penflufen M-121 DMT dipymetitrone

M-87 DMT sedaxane M-122 DMT pydiflumetofen

M-88 DMT isopyrazam M-123 DMT quinofumelin

M-89 DMT tricyclazole M-124 DMT ipfentrifluconazole

M-90 DMT azoxystrobin M-125 DMT dichlobentiazox

M-91 DMT difenoconazole M-126 DMT fenpicoxamid

M-92 DMT kasugamycin M-127 DMT isoflucypram

M-93 DMT isoprothiolane M-128 DMT fluindapyr

M-94 DMT tolprocarb M-129 DMT inpyrfluxam

M-95 DMT carpropamid M-130 DMT pyrifenamine

M-96 DMT diclocymet M-131 DMT mefentrifluconazole

Additional mixing partners

The mixtures of the present invention may be combined and applied in agriculture in mixture with further active ingredients, for example with other pesticides, insecticides, nematicides, fungicides, herbicides, safeners, fertilizers such as ammonium nitrate, urea, potash, and superphosphate, phytotoxicants and plant growth regulators. These mixtures are also embraced by the term "mixture(s) of the present invention" or "mixture^) according to the invention".

These additional ingredients may be used sequentially or in combination with the mixtures of the invention, if appropriate also added only immediately prior to use (tank mix). For example, the plant(s) may be sprayed with a mixture of this invention either before or after being treated with other active ingredients.

In one embodiment, the invention relates to ternary mixtures, comprising a compound I, a compound II and one further compound III, which is not identical to the compound I or II already present in the mixture.

In a sub-embodiment, the invention relates to a mixture of

(1 ) a compound of formula (I), and

(2) a compound selected from the group of imidacloprid, clothianidin, dinotefuran, chlorantraniliprole, cyantraniliprole, spinetoram, spinosad, ethiprole, fipronil, triflumezopy- rim, flonicamid and tetraniliprole, and

(3) a compound selected from the group of probenazole, isotianil, tricyclazole, pyroqui- lon, isoprothiolane, tolprocarb, carpropamid, diclocymet, azoxystrobin, orysastrobin.

In one embodiment, the invention relates to 4-way mixtures, comprising a compound I, a compound II and two further compounds III, which are not identical to the compound I or II already present in the mixture.

In a sub-embodiment, the invention relates to a mixture of

(1 ) a compound of formula (I), and

(3) a compound selected from the group of probenazole, isotianil, tricyclazole, pyroqui- lon, isoprothiolane, tolprocarb, carpropamid, diclocymet, azoxystrobin, orysastrobin, and (4) a compound selected from the group of furametpyr, thifluzamide, simeconazole, penflufen, azoxystrobin, orysastrobin, provided it is different from the compound under (3). In one embodiment, the invention relates to 5-way mixtures, comprising a compound I, a compound II and three further compounds III, which are not identical to the compound I or II already present in the mixture.

Formulations

The invention also relates to methods, wherein the compounds of formula (I) are provided or applied in agrochemical compositions comprising an auxiliary and at least one compound of formula (I) or a mixture thereof.

An agrochemical composition comprises a pesticidally effective amount of a compound of the present invention or a mixture thereof. The term "pesticidally effective amount" is defined below.

The compounds of the present invention or the mixtures thereof can be converted into customary types of agro-chemical 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", Technical Monograph No. 2, 6th 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, tackifi- ers 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, cyclo^hexanol; 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, sul- fates, phosphates, carboxylates, and mixtures thereof. Examples of sulfonates are alkylaryl-sul- fonates, 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 alkyhnaphthalenes, sulfosuccinates or sulfosuccinamates. Examples of sul- fates are sulfates of fatty acids and oils, of ethoxylated alkylphenols, of alcohols, of ethox-ylated alcohols, or of fatty acid esters. Examples of phosphates are phosphate esters. Exam-pies of carboxylates are alkyl carboxylates, and carboxylated alcohol or alkylphenol eth-oxylates. 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 alkylpoly- glucosides. Examples of polymeric surfactants are homo- or copolymers of vinylpyrrolidone, vi- nylalcohols, 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 ox- ide, 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 poly- acrylic acid or polyacid comb polymers. Examples of polybases are polyvinylamines or polyeth- yleneamines.

Suitable adjuvants are compounds, which have a neglectable or even no pesticidal activity themselves, and which improve the biological performance of the compounds of the present invention 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), anor- ganic clays (organically modified or unmodified), polycarboxylates, and silicates.

Suitable bactericides are bronopol and isothiazolinone derivatives such as alkylisothiazoli- nones 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, polyacrylates, 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 wa- ter 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 substance. 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 ad- dition 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) or nano-emulsion

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. alko- hol 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. methyl- methacrylate, 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 radi-cal 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 alco- hoi). The addition of a polyamine (e.g. hexamethylenediamine) results in the for-mation of a pol- yurea microcapsule. 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 sub-stance. The active substances are employed in a purity of from 90% to 100%, preferably from 95% to 100% (according to NMR spectrum).

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 cormprising 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.

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 used for the appli- cation in rice according to the present invention.

In a further embodiment, the dispersible concentrates DC according to formulation type ii are used for the application in rice according to the present invention.

In a further embodiment, the emulsifiable concentrates EC according to formulation type iii are used for the application in rice according to the present invention, ix. ME).

In a further embodiment, the microemulsions ME according to formulation type ix are used for the application in rice according to the present invention.

In a further embodiment, nano-emulsions are used for the application in rice according to the present invention. The user applies the composition according to the invention usually from a predosage de-vice, 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 application 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 of the present invention and/or mixing partners as defined above, 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 in- vention or partially premixed components, e. g. components comprising compounds of the present invention and/or mixing partners as defined above, can be applied jointly (e.g. after tank mix) or consecutively.

Application methods

The invention also relates to methods, wherein the compounds of formula (I) are suitable for use in protecting rice, rice plants, rice plant propagation materials, such as seeds, or soil or water, in which the rice plants are growing, from attack or infestation by rice pests, especially rice pest invertebrates. Therefore, the present invention also relates to a plant protection methods, which comprises contacting rice, rice plants, rice plant propagation materials, such as seeds, or soil or water, in which the plants are growing, to be protected from attack or infestation by rice pests, especially rice pest invertebrates, with a pesticidally effective amount of a compound of the present invention.

The present invention also relates to a method of combating or controlling rice pests, especially rice pest invertebrates, which comprises contacting the rice pests, especially rice pest invertebrates, their habitat, breeding ground, or food supply, or the rice, rice plants, rice plant propagation materials, such as seeds, or soil or water, or the area, material or environment in which the rice pests, especially rice pest invertebrates, are growing or may grow, with a pesticidally effective amount of a compound of the present invention.

The compounds of the present invention are effective through both contact and ingestion. Furthermore, the compounds of the present invention can be applied to any and all developmental stages, such as egg, larva, pupa, and adult.

The compounds of the present invention can be applied as such or in form of compositions comprising them as defined above. Furthermore, the compounds of the present invention can be applied together with a mixing partner as defined above or in form of compositions comprising said mixtures as defined above. The components of said mixture can be applied simultane- ously, jointly or separately, or in succession, that is immediately one after another and thereby creating the mixture "in situ" on the desired location, e.g. the plant, the sequence, in the case of separate application, generally not having any effect on the result of the control measures. The application can be carried out both before and after the infestation of the rice, rice plants, rice plant propagation materials, such as seeds, soil, or the area, material or environment by the pests.

Suitable application methods include inter alia soil treatment, seed treatment, in furrow appli- cation, water inlet application and foliar application. Soil treatment methods include drenching the soil, dipping roots, or soil injection. Seed treatment techniques include seed dressing, seed coating, seed dusting, seed soaking, and seed pelleting. In furrow applications typically include the steps of making a furrow in cultivated land, seeding the furrow with seeds, applying the pes- ticidally active compound to the furrow, and closing the furrow. Foliar application refers to the application of the pesticidally active compound to plant foliage, e.g. through spray equipment. For foliar applications, it can be advantageous to modify the behavior of the pests by use of pheromones in combination with the compounds of the present invention. Suitable pheromones for specific crops and pests are known to a skilled person and publicly available from databases of pheromones and semiochemicals, such as http://www.pherobase.com.

In the context of rice cultivation and rice crops, the following application types are of special relevance:

— "Granular application" involves manual or mechanical scattering or throwing of insecticide granules or mixtures of insecticides/fungicides and nematicides, directly into a field or nursery box, either on the surface of the soil or on standing water. The granular for- mulation may be mixed with a filler, carrier or fertilizer to allow for uniform distribution in the field.

— "Floating packet application" refers to the application of an insecticide or mixtures of insecticides/fungicides and nematicides in a water soluble sachet/packet by throwing into the paddy field in standing water.

— "Seedling box applications" refers to manual or mechanical incorporation of insecticide formulations (for eg. Granules, liquid) in nursery boxes or seedling boxes containing rice seedlings before being transplanted into the main field.

— "Seed treatment" involves the soaking/mixing of rice seeds in a solution of an insecticide or insecticide/nematicide/fungicide mixture. This application is carried out before sowing, either before or after seed germination.

— "Foliar application" refers to application of an insecticide or an insecticide/fungi- cide/nematicide/selective herbicides in water or oil as a spray application using various application equipment (eg. knapsack, power sprayer, boom sprayer, etc).

— "Soil application" refers to the application of an insecticide or a mixture of an in- secticide/fungicide/nematicide/selective herbicide into the soil either as drench application, water inlet application or as a granular application.

— "Aerial application" refers to the application of a granular or liquid application of an insecticide or a mixture of an insecticide/fungicide/nematicide/selective herbicide to the field using aeroplanes, helicopters or drones.

— "Dust application" involves the directed application of an insecticide or a mixture of an insecticide/fungicide/nematicide/selective herbicide as a dust formulation using specialized applicators (eg. Power dusters) directly into the field. — "Water inlet application" is the application of a liquid formulation of an insecticide or or a mixture of an insecticide/fungicide/nematicide/selective herbicide at the point where irrigation water is released into the paddy field.

— "Encircling application" is a type of application where a liquid or granular formula- tion of an insecticide or a mixture of an insecticide/fungicide/nematicide/selective herbicide is applied to standing water, in a clockwork or anti clockwork direction, to the inside borders of a paddy field.

Preferred applications are granular application, seedling box application and foliar application. In one embodiment, the invention relates to methods, in which the pesticide is applied by gran- ular application.

In one embodiment, the invention relates to methods, in which the pesticide is applied by seedling box application.

In one embodiment, the invention relates to methods, in which the pesticide is applied by foliar application.

As used herein, the term "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, i.e. habitat, breeding ground, plant, seed, soil, area, material or environment in which a pest is growing or may grow, of the animal pest or plant).

In the context of the present invention, the term "animal pest" includes arthropods, gastropods, and nematodes, which are rice pests, especially rice pest invertebrates, especially rice pest insects as described above. Arthropods are preferably insects and arachnids, in particular insects. Insects, which are of particular relevance, are typically referred to as crop insect pests or rice pest insects.

The term "crop" refers to both, growing and harvested rice.

In the context of the present invention, the term "plant" means preferably rice plant (Oryza species, preferably Oryza sativa). Two species of rice are most frequently cultivated, Oryza sativa and Oryza glaberrima. Numerous subspecies of Oryza sativa are commercially important including Oryza sativa subsp. indica, Oryza sativa subsp. japonica, Oryza sativa subsp. javanica, Oryza sativa subsp. glutinosa (glutinous rice), Oryza sativa Aromatica group (e.g., basmati), and Oryza sativa (Floating rice group). The term "plant" is to be understood as including wild type plants and plants, which have been modified by either conventional breeding, or mutagenesis or genetic engineering, or by a combination thereof.

Plants, which have been modified by mutagenesis or genetic engineering, and are of particular commercial importance, include rice. In plants, which have been modified by mutagenesis or genetic engineering, one or more genes have been mutagenized or integrated into the genetic material of the plant. The one or more mutagenized or integrated genes are preferably selected from pat, epsps, crylAb, bar, cry1 Fa2, crylAc, cry34Ab1 , cry35AB1 , cry3A, cryF, cryl F, mcry3a, cry2Ab2, cry3Bb1 , cry1A.105, dfr, barnase, vip3Aa20, barstar, als, bxn, bp40, asnl , and ppo5. The mutagenesis or integration of the one or more genes is performed in order to improve certain properties of the plant. Such properties, also known as traits, include abiotic stress tolerance, altered growth/yield, disease resistance, herbicide tolerance, insect resistance, modified product quality, and pollination control. Of these properties, herbicide tolerance, e.g. imidaz- olinone tolerance, glyphosate tolerance, or glufosinate tolerance, is of particular importance. It has surprisingly been found that the pesticidal activity of the compounds of the present in- vention may be enhanced by the insecticidal trait of a modified plant. Furthermore, it has been found that the compounds of the present invention are suitable for preventing insects to become resistant to the insecticidal trait or for combating pests, which already have become resistant to the insecticidal trait of a modified plant. Moreover, the compounds of the present invention are suitable for combating pests, against which the insecticidal trait is not effective, so that a com- plementary insecticidal activity can advantageously be used.

The term "plant propagation material" refers to all the generative parts of the plant such as seeds, sprouted seeds, seedlings and ratooning. Seedlings and young plants, which are to be transplanted after germination or after emergence from soil, may also be included. These plant propagation materials may be treated prophylactically with a plant protection compound either at or before planting or transplanting.

The term "seed" embraces seeds and plant propagules of all kinds including but not limited to true seeds, seed pieces, suckers, corms, fruit, grains, cuttings, cut shoots and the like, and means in a preferred embodiment true seeds.

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 compounds/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, tar- get species, locus, mode of application, and the like.

In the case of soil treatment, in furrow application 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.

For use in treating rice plants, e.g. by foliar application, the rate of application of the active in- gredients of this invention may be in the range of 0.0001 g to 4000 g per hectare, e.g. from 1 g to 2 kg per hectare or from 1 g to 750 g per hectare, desirably from 1 g to 100 g per hectare, more desirably from 10 g to 50 g per hectare, e.g., 10 to 20 g per hectare, 20 to 30 g per hectare, 30 to 40 g per hectare, or 40 to 50 g per hectare.

The compounds of the present invention are particularly suitable for use in the treatment of seeds in order to protect the seeds from insect pests, in particular from soil-living insect pests, and the resulting seedling's roots and shoots against soil pests and foliar insects. The present invention therefore also relates to a method for the protection of seeds from insects, in particular from soil insects, and of the seedling's roots and shoots from insects, in particular from soil and foliar insects, said method comprising treating the seeds before sowing and/or after pregermina- tion with a compound of the present invention. The protection of the seedling's roots and shoots is preferred. More preferred is the protection of seedling's shoots from piercing and sucking insects, chewing insects and nematodes. The term "seed treatment" comprises all suitable seed treatment techniques known in the art, such as seed dressing, seed coating, seed dusting, seed soaking, seed pelleting, and in-furrow application methods. Preferably, 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.

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.

In the context of the present invention, the seed is seed of rice. The active compounds of the invention may also be used for the treatment of seeds from plants, which have been modified by mutagenisis or genetic engineering, and which e.g. tolerate the action of herbicides or fungi- cides or insecticides. Such modified plants have been described in detail above.

Conventional seed treatment formulations include for example flowable concentrates FS, solutions LS, suspoemulsions (SE), powders for dry treatment DS, water dispersible powders for slurry treatment WS, water-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. Preferably, the formulations are applied such that germination is not included.

The active substance concentrations in ready-to-use formulations, which may be obtained after two-to-tenfold dilution, are preferably from 0.01 to 60% by weight, more preferably from 0.1 to 40 % by weight.

In a preferred embodiment a FS formulation is used for seed treatment. Typically, 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 the compounds of the present invention for seed treat- ment 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.

In the treatment of seed, the application rates of the compounds of the invention 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, e.g. from 1 g to 100 g or from 5 g to 100 g per 100 kg of seed.

The invention therefore also relates to seed comprising a compound of the present invention, or an agriculturally useful salt thereof, as defined herein. The amount of the compound of the present invention or the agriculturally useful salt thereof will in general vary from 0.1 g to 10 kg per 100 kg of seed, preferably from 1 g to 5 kg per 100 kg of seed, in particular from 1 g to 1000 g per 100 kg of seed.

In the present invention, the compounds of the present invention may also be used for improv- ing the health of a plant. Therefore, the present invention also relates to a method for improving plant health by treating a rice plant, rice plant propagation material and/or the locus where the rice plant is growing or is to grow with an effective and non-phytotoxic amount of a compound of the present invention.

As used herein "an effective and non-phytotoxic amount" means that the compound is used in a quantity which allows to obtain the desired effect but which does not give rise to any phyto- toxic symptom on the treated plant or on the plant grown from the treated propagule or treated soil.

The terms "plant" and "plant propagation material" are defined above.

"Plant health" is defined as a condition of the plant and/or its products 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), quality (for example improved content or composition of certain ingredients or shelf life), plant vigour (for example improved plant growth and/or greener leaves ("greening effect"), tolerance to abiotic (for example drought) and/or biotic stress (for example disease) and production efficiency (for example, harvesting ef- ficiency, processability).

The above identified indicators for the health condition of a plant may be interdependent and may result from each other. Each indicator is defined in the art and can be determined by methods known to a skilled person.

Claims

Claims:

1 . A method of controlling rice pest invertebrates in rice, which method comprises applying to said rice pest invertebrates at least one pesticidally active pyrimidinium compound of formula (I)

wherein

R¹ is Ci-C4-alkyl, C3-C6-cycloalkyl, C2-C₄-alkenyl or benzyl, which groups may be partially or fully substituted with halogen, Ci-C₄-alkyl or Het;

Het is selected from D-1 , D-2 and D-3:

R^a is halogen, Ci-C₄-haloalkyl, CiC₄-alkoxy or Ci-C₄-alkylthio or phenyl, n is 0, 1 or 2, and

# denotes the bond in formula (I);

R^c is each independently hydrogen, Ci-C₄-alkyl, Ci-C₄-haloalkyl, C1-C6 cycloalkyl;

wherein two geminally bound groups R^bR^b, R^cR^b or R^CR^C together with the atom to which they are bound, may form a 3-, 4-, 5-, 6- or 7- membered saturated, partially unsaturated or aromatic carbo- or heterocyclic ring;

or a stereoisomer, tautomer, salt, or N-oxide thereof;

Method according to claim 1 or 2, wherein in the compound of formula I

R¹ is Ci-C₄-alkyl, C3-C6-cycloalkyl, C2-C₄-alkenyl, preferably wherein R¹ is Ci-C4-alkyl substituted with Het, preferably wherein

R¹ is methyl or ethyl, substituted with Het.

Method according to any of claims 1 to 3, wherein in the compound of formula I

R² is phenyl, pyridinyl or thiophene, which may be unsubstituted, partially, or fully substituted with R^2a; preferably wherein

R² is phenyl, which may be unsubstituted, partially, or fully substituted with R^2a; preferably wherein

R² is phenyl, which may be unsubstituted, partially, or fully substituted with halogen, Ci- C₄-alkyl or Ci-C3-haloalkyl; preferably wherein

R² is phenyl, which may be unsubstituted, partially, or fully substituted with trifluorome- thyl or halogen, preferably chloro; preferably wherein

R² is phenyl, 3,5-dichlorophenyl, 3-trifluoromethylphenyl.

Method according to any of claims 1 to 4, wherein in the compound of formula I

Het is selected from D-1 , D-2 and D-3, wherein

R^a is chloro,

n is 1 ;

preferably wherein

Het is D-1 a, D-2a and D-3a

preferably wherein

Het is D-2a.

Method according to any of claims 1 to 5, wherein the compound of formula I is one of the following compounds:

A method of controlling rice pest invertebrates in rice according to claim 1 , wherein the compound of formula (I) is dicloromezotiaz, which is a compound of formula (IB), in which R¹ is methyl substituted with 2-chloro-1 ,3-thiazol-5-yl)methyl; and

R² is 3,5-dichlorophenyl:

Method according to any of the preceding claims, in which the compound of formula I applied in mixture with at least one further pesticide.

Method according to any of the preceding claims, wherein the rice pest invertebrate is lected from the group of

Hemiptera:

brown planthopper - Nilaparvata lugens

small brown planthopper - Laodelphax striatellus

white-backed planthopper - Sogatella furcifera

white leafhopper - Cofana spectra green leafhopper - Nephotettix virescens, N. nigriceps, N. cincticeps, N. malayanus zig zag leafhopper - Recilia dorsalis

maize orange leafhopper - Cicadulina bipunctata

aster leafhopper - Macrosteles fascifrons

rice earhead bug, Leptocorisa orator/us, L. acuta

rice stink bugs - Nezara viridula, Pygomenida varipennis, Eysarcoris, Tibraca limba- triventris, Eysarcoris ventralis

small stink bug - Oebalus poecilus, O. pugnax

coreid bug - Eysarcoris sp

chinch bug - Blissus leucopterus leucopterus

rice mealybug, Brevennia rehi, Pseudococcus saccharicola

rice aphids, Rhopaiosiphum rufiabdominalis, Macrosiphum a venae, Hysteroneura setar- iae, Tetraneuro nigriabdominalis

bean root aphid - Smynthurodes betae

Lepidoptera:

rice skipper - Parnara guttata, Melanitis leda ismene

rice stalk borer - Chilotraea polychrysa

pink rice borer - Sesamia inferens

yellow rice borer - Tryporyza (=Scirpophaga) incertulas

white rice borer - Tryporyza innotata

rice leaf roller / leaf folder - Cnaphalocrocis medinalis, Marasmia patnalis, M. exigua rice ear-cutting caterpillar / armyworm- Pseudaletia separate

green caterpillar - Xanthodes transversa

green rice caterpillar - Narnaga aenescens

green horned caterpillars - Melanitis leda ismene, Mycalesis sp

fall army worm - Spodoptera frugiperda

cutworm - Mythimna separata

rice case worm - Nymphula depunctalis

black hairy caterpillar, Amata sp.

hairy caterpillar- Mods frugalis

yellow caterpillar, Psalis pennatula

rice semi-brown looper, Mods frugalis

rice semi-looper, Chrysodeixis chalcites

grass webworm - Herpetogramma licarsisalis

sugarcane borer - Diatraea saccharalis

corn stalk borer - Elasmopalpus lignosellus

striped grass looper - Mods latipes

european corn borer - Ostrinia nubilalis

Mexican rice borer - Eoreuma loftini Coleoptera:

water weevil - Lissorhopterus oryzophilus

rice plant weevil - Echinocnemus squamous

rice weevil - Oryzophagus oryzae

rice hi spa - Diclodispa armigera

rice leaf beetle - Oulema oryzae

rice blackbug - Scotinophora vermidulate, S. vermidulate, S. lurida, S. latiuscula rice flea beetle - Chaetocnima basalis

billbugs - Sphenophorus spp

grape colaspis - Colaspis brunnea, C. louisianae

rice pollen beetle, Chilolaba acuta Diptera:

stem maggot - Chlorops oryzae

leafminer - Agromyza oryzae

rice whorl maggot / rice stem maggot - Hydrellia sasakii

rice whorl maggot / small rice leafminer - Hydrellia griseola

rice gall midge - Orseolia (=Pachydip/osisJ oryzae

rice shoot fly- Atherigona oryzae

rice seed midge - Chironomus cavazzai, Chironomus spp, Cricotopus spp

Thysanoptera:

rice thrips- Chioethrips oryzae, Stenochaetothrips biformis, Perrisothrips sp., Hopiothrips sp.,

Orthoptera:

rice grasshoppers, Hierogiyphus banian, Hierogiyphus nigrorepietus, Catantops pinguis, Attractomorpha burri, A. crenuiate, A. psittacina psittacina, A. Bedeli, Oxya adenttata,

Oxya ebneri, Oxya hyla intricata, Acrida turricata

locusts - Locusta migratoria manilensis

mole cricket, Grylotalpa africana

field cricket: Gryllus bimaculatus, Teleogryllus occipitalis, Euscyrtus concinus katydid - Conocephalus longipennis

Isoptera:

termites - Macrotermes gilvus, Syntermes molestans Hymenoptera:

ants - Solenopsis geminata

rice white tip nematode - Aphelenchoides besseyi Acari:

rice panicle mite - Steotarsonemus pinki

Crustacea:

tadpole shrimp - Triops longicaudatus. T. cancriformis

rice crayfish - Procambarus clarkii, Orconectes virilis.

9. Method according to any of the preceding claims, wherein the rice pest invertebrate is from the order Hemiptera, Lepidoptera or Coleoptera;

preferably selected from hoppers,

or preferably selected from brown planthopper (Nilaparvata lugens), small brown planthopper {Laodelphax striatellus), white-backed planthopper {Sogatella furcifera), green leafhopper (Nephotettix virescens), rice stink bugs (Nezara viridula, Pygomenida varipennis, Eysarcoris, Tibraca limbatriventris, Eysarcoris ventralis), small stink bug (Oe- balus poecilus, O. pugnax), rice stem borer {Chilo suppressalis), yellow rice borer ( Trypo- ryza (=Scirpophaga) incertulas); rice leafroller / leaf folder (Cnaphalocrocis medinalis, Ma- rasmia patnalis, M. exigua), water weevil {Lissorhopterus oryzophilus), rice weevil (Ory- zophagus oryzae). 10. Method according to any of the preceding claims, wherein the method comprises granular application, seedling box application or foliar application.

1 1 . Method for increasing the health of rice plants, especially in paddy rice fields, comprising the treatment with at least one compound of formula (I) as defined in any of claims 1 to 8 or a mixture as defined in claim 9.

12. Method for increasing the yield of rice plants, comprising the treatment with at least one compound of formula (I) as defined in any of claims 1 to 8 or a mixture as defined in claim 9.

13. Method for protecting rice plants, using at least one compound of formula (I) as defined in any of claims 1 to 8 or a mixture as defined in claim 9.