CN117241668A - Microbiocidal quinoline/quinoxaline benzothiazine derivatives - Google Patents

Abstract

Compounds of formula (I) wherein the substituents are as defined in claim 1, are useful as pesticides, in particular as fungicides.

Description

Microbiocidal quinoline/quinoxaline benzothiazine derivatives

The present invention relates to microbiocidal quinoline/quinoxaline benzothiazine derivatives, for example as active ingredient, which have microbiocidal activity, in particular fungicidal activity. The invention also relates to the preparation of these quinoline/quinoxaline benzothiazine derivatives, to intermediates useful in the preparation of these quinoline/quinoxaline benzothiazine derivatives, to the preparation of these intermediates, to agrochemical compositions comprising at least one of these quinoline/quinoxaline benzothiazine derivatives, to the preparation of these compositions and to the use of these quinoline/quinoxaline benzothiazine derivatives or compositions in agriculture or horticulture for controlling or preventing infestation of plants, harvested food crops, seeds or non-living materials by phytopathogenic microorganisms, notably fungi.

Wheat is grass cultivated for its seeds, cereal grains that are staple food grains worldwide. Many species of wheat together constitute the wheat genus plant: the most widely cultivated is common wheat (t.aestivum). However, wheat cultivation presents a number of challenges. Wheat leaf blight (Septoria tritici blotch) is caused by the ascomycete fungus, globus graminearum (asexual stage: septoria tritici) and is one of the most important diseases of wheat, which is one of the most economically destructive diseases of this crop (currently the most economically relevant diseases in europe).

Thus, in particular, there is a continuing need to develop new methods to control or prevent infestation of cereal crops by fungal plant pathogens, such as, for example, infections of cereal grains, particularly wheat, by graminearum, particularly while retaining fungicidal activity, i.e., broad spectrum activity, against other fungal pathogens.

Certain fungicidal quinoline compounds are described in WO 2009/119089.

According to the present invention there is provided a compound having the formula (I):

wherein:

R ¹ is fluorine, chlorine, cyano or methyl;

R ² is hydrogen or fluorine;

R ³ is hydrogen, difluoromethyl or methyl.

R ⁴ Is C ₁ -C ₆ Alkyl, C ₁ -C ₆ Haloalkyl, C ₂ -C ₆ Alkenyl, C ₂ -C ₆ Alkynyl, C ₂ -C ₆ Haloalkenyl, C ₃ -C ₆ Cycloalkyl, C ₃ -C ₆ Cycloalkyl C ₁ -C ₂ Alkyl or heteroaryl C ₁ -C ₂ An alkyl group; wherein the heteroaryl is a 5-or 6-membered monocyclic aromatic ring containing 1, 2, 3 or 4 heteroatoms independently selected from N, O and S and optionally is substituted with 1, 2 or 3 heteroatoms independently selected from halogen, C ₁ -C ₃ Alkyl, C ₁ -C ₃ Substituents for alkoxy or cyano; and is also provided with

R ⁵ Is hydrogen or C ₁ -C ₄ An alkyl group; or (b)

R ⁴ And R is ⁵ Forming a cyclobutyl, cyclopentyl or cyclohexyl ring together with the attached carbon atom, wherein the ring structure is optionally substituted by 1, 2, 3 or 4 substituents independently selected from fluoro, cyano, methyl, methoxy;

R ⁶ Is chlorine, bromine, iodine, C ₁ -C ₄ Alkyl, C ₁ -C ₄ Haloalkyl, C ₂ -C ₄ Alkenyl, C ₂ -C ₄ Haloalkenyl, C ₂ -C ₄ Alkynyl, C ₁ -C ₄ Alkoxy, C ₁ -C ₄ Alkylthio, C ₃ -C ₅ Cycloalkoxy radicals C ₁ -C ₄ Haloalkoxy, cyano, C ₃ -C ₅ Cycloalkyl or CR ¹⁰ (＝NOR ⁸ ) The method comprises the steps of carrying out a first treatment on the surface of the And is also provided with

R ⁷ Is hydrogen, halogen, C ₁ -C ₄ Alkyl, C ₁ -C ₄ Haloalkyl or cyano, or

R ⁶ Is fluorine and R ⁷ Is halogen or C ₁ -C ₄ An alkyl group;

R ⁸ is C ₁ -C ₄ Alkyl, C ₁ -C ₄ Haloalkyl, C ₃ -C ₅ Alkenyl, C ₃ -C ₅ Haloalkenyl or C ₃ -C ₅ Alkynyl;

a is N or CR ⁹ ；

R ⁹ Hydrogen, difluoromethyl or methyl; and is also provided with

R ¹⁰ Is C ₁ -C ₄ An alkyl group; or (b)

An agronomically acceptable salt, enantiomer, S-oxide or N-oxide thereof.

Surprisingly, it has been found that for practical purposes the novel compounds of formula (I) have a very advantageous level of biological activity for protecting plants against diseases caused by fungi. In particular, this effect was observed for the spectrum of fungal pathogens, including sphaerella graminea (septoria tritici).

According to a second aspect of the present invention there is provided an agrochemical composition comprising a fungicidally effective amount of a compound of formula (I). Such agricultural compositions may further comprise at least one additional active ingredient and/or an agrochemically acceptable diluent or carrier.

According to a third aspect of the present invention there is provided a method of controlling or preventing infestation of useful plants by phytopathogenic microorganisms, wherein a fungicidally effective amount of a compound of formula (I), or a composition comprising such a compound as active ingredient, is applied to the plants, parts thereof or the locus thereof.

According to a fourth aspect of the present invention there is provided the use of a compound of formula (I) as a fungicide. According to this particular aspect of the invention, the use may not include methods of treating the human or animal body by surgery or therapy.

Where substituents are indicated as optionally substituted, this means that they may or may not bear one or more of the same or different substituents, for example one to four substituents. Typically, no more than three such optional substituents are present simultaneously. Preferably, no more than two such optional substituents are present at the same time (i.e., the group may optionally be substituted with one or two of the substituents indicated as "optional"). Where the "optional substituent" group is a larger group (e.g., cycloalkyl or phenyl), it is most preferred that only one such optional substituent is present. Where a group is indicated as being substituted with, for example, an alkyl group, this includes those groups that are part of other groups, for example, alkyl groups in alkylthio.

As used herein, the term "halogen" refers to fluorine (fluoro), chlorine (chloro), bromine (bromo) or iodine (iodine, iodo), preferably fluorine, chlorine or bromine.

As used herein, cyano means a —cn group.

As used herein, the term "C ₁ -C ₆ Alkyl "refers to a straight or branched hydrocarbon chain group consisting of only carbon and hydrogen atoms, free of unsaturation, having from one to six carbon atoms, and attached to the remainder of the molecule by a single bond. C (C) ₁ -C ₄ Alkyl groups should be construed accordingly. C (C) ₁ -C ₆ Examples of alkyl groups include, but are not limited to, methyl, ethyl, n-propyl, 1-methylethyl (isopropyl), n-butyl, and 1, 1-dimethylethyl (t-butyl).

As used herein, the term "C ₁ -C ₆ Haloalkyl "means C as defined generally above substituted with one or more halogen atoms which may be the same or different ₁ -C ₆ An alkyl group. C (C) ₁ -C ₄ Haloalkyl should be construed accordingly. C (C) ₁ -C ₆ Examples of haloalkyl include, but are not limited to, fluoromethyl, fluoroethyl, difluoromethyl, trifluoromethyl and 2, 2-trifluoroethyl.

As used herein, the term "C ₂ -C ₆ Alkenyl "refers to a straight or branched hydrocarbon chain group consisting of only carbon and hydrogen atoms, containing at least one double bond that may have an (E) -or (Z) -configuration, having from two to six carbon atoms, attached to the remainder of the molecule by a single bond. C (C) ₃ -C ₅ Alkenyl groups should be construed accordingly. C (C) ₂ -C ₆ Examples of alkenyl groups include, but are not limited to, vinyl (ethylene), prop-1-enyl, allyl (prop-2-enyl), and but-1-enyl.

As used herein, the term "C ₂ -C ₆ Haloalkenyl "means a quiltC as defined generally above substituted by one or more identical or different halogen atoms ₂ -C ₆ Alkenyl groups.

As used herein, the term "C ₂ -C ₆ Alkynyl "refers to a straight or branched hydrocarbon chain group consisting of only carbon and hydrogen atoms, containing at least one triple bond, having from two to six carbon atoms, and attached to the remainder of the molecule by a single bond. The term "C ₃ -C ₅ Alkynyl "should be construed accordingly. C (C) ₂ -C ₅ Examples of alkynyl groups include, but are not limited to, ethynyl, prop-1-ynyl, propargyl (prop-2-ynyl), and but-1-ynyl.

As used herein, the term "C ₃ -C ₆ Cycloalkyl "refers to a stable monocyclic group that is saturated and contains 3 to 6 carbon atoms. C (C) ₃ -C ₄ Cycloalkyl groups should be construed accordingly. C (C) ₃ -C ₆ Examples of cycloalkyl groups include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl.

As used herein, the term "C ₃ -C ₆ Cycloalkyl C ₁ -C ₂ Alkyl "means C as mentioned above ₃ -C ₆ Cycloalkyl through C ₁ -C ₂ The alkylene groups are bonded to the remainder of the molecule.

As used herein, the term "C ₁ -C ₄ Alkoxy "means having the formula R _a O-, wherein R _a Is C as defined above in general ₁ -C ₄ An alkyl group. C (C) ₁ -C ₄ Examples of alkoxy groups include, but are not limited to, methoxy, ethoxy, propoxy, isopropoxy.

As used herein, the term "C ₁ -C ₄ Haloalkoxy "means C as defined above substituted by one or more identical or different halogen atoms ₁ -C ₄ An alkoxy group. C (C) ₁ -C ₄ Examples of haloalkoxy groups include, but are not limited to, fluoromethoxy, difluoromethoxy, fluoroethoxy, trifluoromethoxy and trifluoroethoxy.

As used herein, the term "C ₁ -C ₄ Alkylthio processThe radical "means a radical of formula R _a S-wherein R is _a Is C as defined above in general ₁ -C ₄ An alkyl group. C (C) ₁ -C ₄ Examples of alkylthio groups include methylsulfanyl.

As used herein, the term "heteroaryl" refers to a 5-or 6-membered monocyclic aromatic ring group containing 1, 2, 3, or 4 heteroatoms independently selected from nitrogen, oxygen, and sulfur. Heteroaryl groups may be bonded to the remainder of the molecule through a carbon atom or heteroatom. Examples of heteroaryl groups include, but are not limited to, furyl, pyrrolyl, thienyl, pyrazolyl, imidazolyl, thiazolyl, isothiazolyl, oxazolyl, isoxazolyl, triazolyl, tetrazolyl, pyrazinyl, pyridazinyl, pyrimidinyl, and pyridyl.

As used herein, the term "heteroaryl C ₁ -C ₂ Alkyl "means heteroaryl as mentioned above through C ₁ -C ₂ The alkylene groups are bonded to the remainder of the molecule.

The presence of one or more possible asymmetric carbon atoms in the compound of formula (I) means that the compound can exist in optically isomeric form (i.e. in enantiomeric or diastereoisomeric form). Atropisomers may also be present as a result of limited rotation about a single bond. Formula (I) is intended to include all those possible isomeric forms and mixtures thereof. The present invention includes all those possible isomeric forms of the compounds having formula (I) and mixtures thereof. Likewise, formula (I) is intended to include all possible tautomers. The present invention includes all possible tautomeric forms of the compounds having formula (I).

In each case, the compounds according to the invention of formula (I) are in free form, oxidized form (as N-oxide or S-oxide), covalently hydrated form, or in salt form (for example agronomically usable or agronomically acceptable salt form).

The N-oxide is an oxidized form of a tertiary amine or an oxidized form of a nitrogen-containing heteroaromatic compound. Albini and S.Pietra are described, for example, in the publication of Bokaraton (Boca Raton) CRC Press by A.Albini and S.Pietra under the name "Heterocholic N-oxides [ Heterocyclic N-oxides ]".

The following list provides substituents R for compounds of formula (I) according to the invention ¹ 、R ² 、R ³ 、R ⁴ 、R ⁵ 、R ⁶ 、R ⁷ 、A、R ⁸ 、R ⁹ And R is ¹⁰ Including the preferred definitions. For any of these substituents, any definition given below may be combined with any definition of any other substituent given below or elsewhere in this document.

R ¹ Is fluorine, chlorine, cyano or methyl. Preferably, R ¹ Is fluorine.

R ² Is hydrogen or fluorine.

Preferably, when R ¹ When fluorine is used, R ² Is hydrogen or fluorine.

R ³ Is hydrogen, difluoromethyl or methyl. Preferably, R ³ Is hydrogen or methyl. More preferably, R ³ Is hydrogen.

R ⁴ Is C ₁ -C ₆ Alkyl, C ₁ -C ₆ Haloalkyl, C ₂ -C ₆ Alkenyl, C ₂ -C ₆ Alkynyl, C ₂ -C ₆ Haloalkenyl, C ₃ -C ₆ Cycloalkyl, C ₃ -C ₆ Cycloalkyl C ₁ -C ₂ Alkyl or heteroaryl C ₁ -C ₂ An alkyl group; wherein heteroaryl is a 5-or 6-membered monocyclic aromatic ring containing 1, 2, 3 or 4 heteroatoms independently selected from N, O and S and is optionally substituted with 1, 2 or 3 heteroatoms independently selected from halogen, C ₁ -C ₃ Alkyl, C ₁ -C ₃ Substituents for alkoxy or cyano groups. Preferably, R ⁴ Is C ₁ -C ₄ Alkyl, C ₁ -C ₄ Haloalkyl, C ₂ -C ₄ Alkenyl, C ₂ -C ₄ Alkynyl, C ₂ -C ₄ Haloalkenyl, C ₃ -C ₆ Cycloalkyl, C ₃ -C ₆ Cycloalkyl C ₁ -C ₂ Alkyl or heteroaryl C ₁ -C ₂ Alkyl, wherein heteroaryl is a compound comprising 1, 2, 3 or 4 groups independently selected from N, O and S A 5-or 6-membered monocyclic aromatic ring of heteroatoms and optionally substituted with 1 or 2 substituents independently selected from halogen, methyl, ethyl, methoxy, ethoxy or cyano. More preferably, R ⁴ Is C ₁ -C ₄ Alkyl, C ₁ -C ₄ Haloalkyl, C ₃ -C ₆ Cycloalkyl or heteroaryl C ₁ -C ₂ Alkyl, wherein heteroaryl is pyridinyl (pyridin-2-yl, pyridin-3-yl, pyridin-4-yl) optionally substituted with 1, 2 or 3 substituents independently selected from fluorine and chlorine. Even more preferably, R ⁴ Is C ₁ -C ₄ Alkyl, C ₁ -C ₄ Haloalkyl, C ₃ -C ₆ Cycloalkyl or (6-chloro-pyridin-3-yl) methyl. Most preferably, R ⁴ Is methyl, ethyl, difluoromethyl, trifluoromethyl, C ₄ -C ₅ Cycloalkyl or (6-chloro-pyridin-3-yl) methyl.

R ⁵ Is hydrogen or C ₁ -C ₄ An alkyl group. Preferably, R ⁵ Is hydrogen or methyl, and more preferably R ⁵ Is methyl.

Otherwise, R ⁴ And R is ⁵ Together with the attached carbon atoms, form a cyclobutyl, cyclopentyl or cyclohexyl ring, wherein the ring structure is optionally substituted by 1, 2, 3 or 4 substituents independently selected from fluoro, cyano, methyl, methoxy. Preferably, R ⁴ And R is ⁵ Together with the attached carbon atoms, form a cyclopentyl ring, wherein the ring structure is optionally substituted with 1 or 2 substituents independently selected from fluoro, cyano, methyl, methoxy.

⁶ In some embodiments of the invention (when R is not fluorine):

R ⁶ is chlorine, bromine, iodine, C ₁ -C ₄ Alkyl, C ₁ -C ₄ Haloalkyl, C ₂ -C ₄ Alkenyl, C ₂ -C ₄ Haloalkenyl, C ₂ -C ₄ Alkynyl, C ₁ -C ₄ Alkoxy, C ₁ -C ₄ Alkylthio, C ₃ -C ₅ Cycloalkoxy radicals C ₁ -C ₄ Alkoxy, cyano, C ₃ -C ₅ NaphtheneBase or CR ¹⁰ (＝NOR ⁸ ) The method comprises the steps of carrying out a first treatment on the surface of the And R is ⁷ Is hydrogen, halogen, C ₁ -C ₄ Alkyl, C ₁ -C ₄ Haloalkyl or cyano.

In these examples (when R ⁶ When not fluorine), preferably R ⁶ Is chlorine, bromine, iodine, C ₁ -C ₄ Alkyl, C ₁ -C ₄ Alkylthio, cyano, C ₁ -C ₄ Haloalkyl, C ₁ -C ₄ Alkoxy, C ₁ -C ₄ Alkoxy or C ₃ -C ₅ Cycloalkyl, more preferably R ⁶ Is chloro, bromo, iodo, methyl, ethyl, methylsulfanyl, cyano, difluoromethyl, trifluoromethyl, methoxy, ethoxy, cyclopropyl, cyclobutyl, and most preferably R ⁶ Is chloro, methyl, cyano, methylsulfanyl (e.g., chloro); and preferably R ⁷ Is hydrogen, chlorine or methyl.

⁶ In other embodiments of the invention (when R is fluorine):

R ⁶ is fluorine and R ⁷ Is halogen or C ₁ -C ₄ An alkyl group. Preferably, R ⁶ Is fluorine and R ⁷ Is chloro, methyl or ethyl. More preferably, R ⁶ Is fluorine and R ⁷ Is methyl.

R ⁸ Is C ₁ -C ₄ Alkyl, C ₁ -C ₄ Haloalkyl, C ₃ -C ₅ Alkenyl, C ₃ -C ₅ Haloalkenyl or C ₃ -C ₅ Alkynyl groups. Preferably, R ⁸ Is C ₁ -C ₄ Alkyl, C ₁ -C ₄ A fluoroalkyl group. More preferably, R ⁸ Is methyl or ethyl.

A is N or CR ⁹ . In some embodiments of the invention, a is N. In other embodiments of the invention, A is CR ⁹ Wherein R is ₉ Is hydrogen, difluoromethyl or methyl, and preferably hydrogen.

R ¹⁰ Is C ₁ -C ₄ Alkyl, and preferably, methyl or ethyl.

In a preferred embodiment of the invention, R ¹ And R is ² Is fluorine, or R ¹ Is fluorine and R ² Is hydrogen.

In a preferred embodiment of the invention, R ⁴ And R is ⁵ Is methyl.

In certain embodiments of the present invention, the compound having formula (I) may be selected from one of:

in examples (IA) and (IB), R ⁶ Can be chloro or methyl and R ⁷ Can be hydrogen or methyl, or R ⁶ Is fluorine and R ⁷ Is methyl.

Preferably, the compound having formula (I) is a compound selected from one of e.01 to e.25 in table E (below).

According to the present invention there is provided a method for controlling or preventing infestation of useful plants by phytopathogenic microorganisms, wherein a fungicidally effective amount of a compound according to the invention or a composition comprising such a compound as active ingredient is applied to the plants, parts thereof or to the locus thereof. Preferably, the phytopathogenic microorganism is (i) F.graminearum, (ii) F.niveum (F.niveum) or (iii) F.zeae (asexual: F.graminearum). Preferably, the useful plant is cereal, in particular wheat.

Specific examples of compounds having formula (I) are shown in the following tables A1 to A5:

table A1 provides 105 compounds of formula (I)

Wherein R is ¹ is-F, R ² And R is ³ is-H and A is-CH; and wherein R is ⁴ 、R ⁵ 、R ⁶ And R is ⁷ The values of (a) are as defined in table Z below:

table Z

Table A2There are provided 105 compounds of formula (I), wherein R ¹ is-F, R ² is-F, R ³ is-H, A is-CH; and wherein R is ⁴ 、R ⁵ 、R ⁶ And R is ⁷ The values of (a) are as defined in table Z above.

Table A3There are provided 105 compounds of formula (I), wherein R ¹ is-F, R ² is-H, R ³ is-CH ₃ A is-CH; and wherein R is ⁴ 、R ⁵ 、R ⁶ And R is ⁷ The values of (a) are as defined in table Z above.

Table A4There are provided 105 compounds of formula (I), wherein R ₁ is-F, R ₂ is-H, R ₃ is-H, A is-N; and wherein R is ⁴ 、R ⁵ 、R ⁶ And R is ⁷ The values of (a) are as defined in table Z above.

Table A5There are provided 105 compounds of formula (I), wherein R ₁ is-F, R ₂ is-F, R ₃ is-H, A is-N; and wherein R is ⁴ 、R ⁵ 、R ⁶ And R is ⁷ The values of (a) are as defined in table Z above.

The compounds of the present invention may be prepared as shown in schemes 1 to 5 below, wherein the definition of each variable is as defined above for compounds having formula (I), unless otherwise indicated.

The compounds of formula (I) may be prepared, for example, according to scheme 1.

Scheme 1:

carbonyl compounds of formula (IV) can be obtained by treating a heterocycle of formula (II) wherein X is bromine, chlorine or iodine and an aldehyde of formula (III), as described on pages 5080-5093 of European Journal of Organic Chemistry [ journal of european organic chemistry ] 2017. The thiophenol compound having the formula (VI) can be obtained by subjecting the carbonyl compound having the formula (IV) to the neoman-quardt rearrangement, followed by hydrolysis. Typical conditions involving the various steps of thiocarbamate formation, rearrangement and hydrolysis have been reviewed and described in Synthesis [ Synthesis ]2008, pages 661-689, org.lett. [ organic flash ]2018, pages 7483-7487 and WO 2002/092076.

As described in ACIEE 2018, pages 5350-5354, compounds having formula (I) can be prepared from thiophenols having formula (VI) by treatment with an ammonia source such as ammonia gas or bis (trimethylsilyl) amine in the presence of a dehydrating agent such as zinc chloride or titanium ethoxide to produce an imine having formula (VII). Such imines may be reacted with carbonyl compounds having the formula (VIII-a) or alternatives thereof, such as acetals having the formula (VIII-b) (wherein R) ²¹ Is C ₁ -C ₄ Alkyl) condensation. Closely related methods have been described in Tetrahedron]2001, pages 7501 to 7506.

The heterocyclic ring of formula (II) is readily available from inexpensive starting materials, as described in WO 2018/172133 or Tetrahedron [ Tetrahedron ]2017, pages 1618-1632. Aldehydes having the general formula (III) are readily prepared from commercially available materials by methods well known to those skilled in the art.

Alternatively, thiophenols of formula (VI) can be obtained by rearrangement of thioesters of formula (XI) by treatment with lewis acids such as aluminum trichloride in solvents such as nitrobenzene at temperatures between 100 ℃ and 210 ℃, as described in Bioorganic & Medicinal Chemistry [ Bioorganic chemistry and medicinal chemistry ]2007, pages 3505-3514. This is shown in scheme 2.

Scheme 2:

the thioesters of formula (XI) can be prepared by reacting a carboxylic acid derivative of formula (IX) (wherein R ²² OH, chlorine, bromine or iodine) with thiophenols having the formula (X). The conditions for such transformation are well known to those skilled in the art and are described in Bioorganic&Medicinal Chemistry Letters [ biological organic and pharmaceutical chemistry report ]]2015, pages 1509-1514.

Carboxylic acids having the general formula (IX) can be prepared from heterocycles having the formula (II) by interconversion of functional groups well known to those skilled in the art. Thiophenols having the formula (X) can be prepared from the corresponding disulfides, anilines, phenols or aryl halides by means of functional group interconversions by methods known to the person skilled in the art.

Alternatively, the imine of formula (VII) may be prepared from a nitrile of formula (XII) by treatment with thiophenol of formula (X) in the presence of a strong base such as n-butyllithium, as described in J.Heterochemistry Chem 1995, page 1683. Similarly, imines of formula (VII) may be obtained from heterocycles of formula (II) wherein X is bromine or iodine and nitriles of formula (XIII) in a solvent such as tetrahydrofuran in the presence of an organometallic reagent capable of halogen-metal exchange reactions such as lithium isopropylmagnesium chloride complex (turbo-Grignard). This is shown in scheme 3.

Scheme for the production of a semiconductor device3：

The compounds of formula (I) may also be prepared from heterocycles of formula (XVIII) (wherein R ²³ is-B (OH) ₂ 、-Bpin、-SO ₂ Na、SO ₂ CH ₂ CH＝CH ₂ -ZnBr or-Zn (O) ₂ CC(CH ₃ ) ₃ ) And an imine of formula (XVII) (wherein R ²⁴ Is chlorine, bromine, iodine or-OSO ₂ CF ₃ ) Ni-or Pd-catalysts such as 1,1' -bis (di-tert-butylphosphine) ferrocene supported on suitable phosphine ligands in an inert solvent such as THF or DMF and optionally a base such as K ₃ PO ₄ Prepared in the presence of a catalyst.

An imine of formula (XVII) (wherein R ²⁴ Is chlorine, bromine, iodine or-OSO ₂ CF ₃ ) From a compound of formula (XVI) in an inert solvent such as DCM or toluene in the presence of a suitable activator such as a Vilsmeier salt or trifluoromethanesulfonic anhydride and optionally a base such as 2, 6-lutidine. The compound of formula (XVI) is composed of thiophenol of formula (XV) and carbonyl compound of formula (VIII-a) or its substitute such as acetal of formula (VIII-b) (wherein R ²¹ Is C ₁ -C ₄ Alkyl) in the presence of an acidic catalyst such as p-toluene sulfonic acid, a dehydrating agent such as a molecular sieve, and optionally a nucleophilic amine catalyst such as pyrrolidine. This is shown in scheme 4.

Scheme 4:

thiophenols having the formula (XV) can be prepared by a variety of methods, a non-exhaustive description of a more preferred method being shown in scheme 5.

I. Thiophenols of the formula (XV) can be prepared from benzoic acids of the formula (XVI-a) by reacting with a strong base such as lithium diisopropylamide or sec-butyllithium and disulfides of the formula (XVII-a) (wherein R ²⁵ Is C ₁ -C ₁₄ Alkyl, phenyl C ₁ -C ₂ Alkyl or-CHCHSi (CH) ₃ ) ₃ ) Is treated to form a thioether having the formula (XVI-b). Functional group interconversion (acid to amide) by methods well known to those skilled in the art and by nucleophiles such as C ₁ -C ₁₄ The alkyl mercaptan is combined with a strong base such as sodium t-butoxide or passed through a fluoride source such as tetrabutylammonium fluoride (if R ²⁵ is-CHCHSi (CH) ₃ ) ₃ ) Removal of R ²⁵ The group converts the acid of formula (XVI-b) into thiophenol of formula (XV).

Thiophenols of the formula (XV) can be prepared from anthranilic acid derivatives of the formula (XVI-d) (wherein R ²⁷ Is H or C ₁ -C ₄ Alkyl) by treatment with a nitrosating agent such as sodium nitrite/HCl or isoamyl nitrite followed by a sulfur containing agent such as Na ₂ S ₂ Or sodium xanthate to give sulfides of formula (XVI-e) (wherein R ²⁶ Is H or-C (S) OCH ₂ CH ₃ ) Is prepared. This has been described in JP 2002053580 and US 2004/016734. The functional groups are interconverted (acid/ester to amide) by methods well known to those skilled in the art, followed by an optional cleavage step if R ²⁷ is-C (S) OCH ₂ CH ₃ The sulfide of formula (XVI-e) is converted to thiophenol of formula (XV) by treatment with an aqueous base.

Thiophenols having the formula (XV) can be prepared from the o-halobenzamides having the formula (XVI-f) wherein X is fluorine or chlorine by treatment with a sulfide source such as sodium sulfide in an inert solvent such as N-methyl-2-pyrrolidone.

Thiophenols having the formula (XV) can be prepared from an o-halobenzamide having the formula (XVI-f) wherein X is bromine or iodine by treatment with a sulfide source such as sulfur, sodium sulfide, thiourea or sodium thiosulfate in the presence of a suitable catalyst such as a Cu, ni or Pd salt stabilized by an amine-or phosphine-based carrier ligand. Examples are described in Tetrahedron Letters [ tetrahedral flash ]2011, pages 205-208; org.lett. [ organic flash report ],2009, pages 5250-5253 and JP 2017-095415.

Scheme 5:

methods for preparing benzoic acid having the formula (XVI-a), anthranilic acid derivatives having the formula (XVI-d) and benzamides having the formula (XVI-f) from readily available starting materials are well known to those skilled in the art.

Alternatively, the compound of formula (I) may be obtained by converting another closely related compound of formula (I) (or an analogue thereof) using standard synthetic techniques known to those skilled in the art. Non-exhaustive examples include oxidation, oxygenation, reduction, hydrogenation, hydrolysis, coupling, aromatic nucleophilic or electrophilic substitution, nucleophilic substitution, deoxofluorination, alkylation, free radical addition, nucleophilic addition, condensation, and halogenation.

Some of the intermediates described in the schemes above are novel and form another aspect of the invention as well.

The compounds of formula (I) may be used in the agricultural sector and related fields of use, for example as active ingredients for controlling plant pests or for use on non-living materials for controlling spoilage microorganisms or organisms potentially harmful to humans. These novel compounds are characterized by excellent activity at low application rates, good plant tolerance and environmental safety. They have very useful therapeutic, prophylactic and systemic properties and can be used to protect many cultivated plants. The compounds of formula (I) can be used to inhibit or destroy pests that occur on plants or plant parts (fruits, flowers, leaves, stems, tubers, roots) of different crops of useful plants, while also protecting those plant parts, which grow later, for example, from phytopathogenic microorganisms.

Compounds having formula (I) may also be used as fungicides. As used herein, the term "fungicide" means a compound that controls, alters, or prevents the growth of fungi. The term "fungicidally effective amount" means the amount of such a compound or combination of such compounds that is capable of affecting fungal growth. The effects of control or alteration include all deviations from natural development, such as killing, retardation, etc., and prevention includes forming a barrier or other defenses within or on the plant to prevent fungal infestation.

The compounds of formula (I) can also be used as seed dressing agents for treating plant propagation material, such as seeds (e.g. fruits, tubers, or grains), or plant cuttings (e.g. rice), for protecting against fungal infections as well as against phytopathogenic fungi present in the soil. The propagation material may be treated with a composition comprising a compound having the formula (I): for example, seeds may be dressed prior to sowing. The compounds of formula (I) may also be applied to the cereal grains (coating) by dipping the seeds in a liquid formulation or by coating them with a solid formulation. The composition may also be applied to the planting site at the time of planting the propagation material, such as to the furrow of the seed during sowing. The invention also relates to such a method of treating plant propagation material, and to plant propagation material so treated.

Furthermore, the compounds according to the invention can be used for controlling fungi in the relevant field, for example in the protection of industrial materials, including wood and industrial products related to wood, in food storage, in hygiene management.

Furthermore, the invention can be used to protect non-living materials (e.g., wood, wallboard, and paint) from fungal attack.

The compounds of formula (I) and fungicidal compositions containing them are useful for controlling plant diseases caused by a broad spectrum of fungal plant pathogens. They are effective in controlling a broad spectrum of plant diseases such as foliar pathogens of ornamental, turf, vegetable, field, cereal, and fruit crops.

These fungi and fungal vectors of diseases that can be controlled, along with phytopathogenic bacteria and viruses, are for example:

cephalosporium umbellatum, alternaria species, rhizopus species, cephalosporium species, aspergillus species (including Aspergillus flavus, aspergillus fumigatus, aspergillus nidulans, aspergillus niger, aspergillus terreus), aureobasidium species (including Aureobasidium pullulans), acremonium dermatitis, alternaria wheat, bremia lactucae (Bremia lactucae), portuga species (including Botrytis cinerea (B. Dothidea), vitis vinifera (B. Obtusa)), vitis species (including Botrytis cinerea (B. Cinerea)), candida species (including Candida albicans, candida glabrata (C. Glabra), candida krusei (C. Krusei), candida rugosa (C. Lusitana), candida parapsilosis (C. Paramatens), candida albicans (C. Licheniformis) candida tropicalis (c.tropicalis)), cephaloascus fragrans, coralloides species, cercospora species (including brown spot bacteria (c.arachidiocola)), late spot bacteria (Cercosporidium personatum), cladosporium species, ergot bacteria, macrosporium species, spiralis species, anthrax species (including banana anthracis (c.musae)), novel cryptococcus, mesotheca species (Diaporthe spp), hyposporium species, strawborium species, elcospora species, epidermomyces species, pyricularia, powdery mildew species (including powdery mildew (e.cichoricola), grape top blight bacteria (eutomyces patans), fusarium species (including fusarium, fusarium graminearum, fusarium, moniliforme, fusarium graminearum, fusarium solani, fusarium oxysporum, fusarium layering), fusarium wheat take-all (Gaeumannomyces graminis), saccharum sinensis Roxb (Gibberella fujikuroi), nicotiana tabacum (Gloeodes pomigena), pantoea banana (Gloeosporium musarum), colletotrichum apple (Glomerella cingulate), vitis vinifera (Guignardia bidwellii), fusarium sabanii (Gymnosporangium juniperi-virginianae), helminthosporum species, alternaria species, histoplasma species (including histoplasma capsulatum (H.capsule)), rhodotorula, leptographium lindbergi, capsicum frutescens (Leveillula taurica), pinus glabra (Lophodermium seditiosum), leucophyllum (Microdochium nivale), microsporum species, rhizoctonia species, mucor species, sphaericus species (including sphaericus, alternaria graminea, alternaria sphaericus photinia apple (m.pomi)), fusarium treponticum, picea, paracoccidiomycete species, penicillium species (including penicillium digitatum, penicillium italicum), truffle species, downy mildew species (including downy mildew of maize, downy mildew of Philippine and downy mildew of sorghum), downy mildew species, septoria glume, pachyrhizus, mulberry Huang Huo wood-needle porus (Phellinus igniarus), bottle mildew species, phoma species, phomopsis grape (Phomopsis viticola), phytophthora species (including phytophthora infestans), uniaxial mildew species (including downy mildew of holos, downy mildew of grape (p.virucicola)), gella species, the species of genus Leptosphaeria (including Leptosphaeria gracilis (P. Leucotrichia)), rhizoctonia cerealis (Polymyxa graminis), rhizoctonia cerealis (Polymyxa betae), rhizoctonia cerealis (Pseudocercosporella herpotrichoides), pseudomonas species, pseudoperonospora species (including Peronospora cucumeria, pseudoperonospora scandens), pseudopeziza tracheiphila, puccinia species (including Hortensis (P. Hordei), rhizopus oryzae (P. Recondta), puccinia strigosa (P. Striiformis), rhizoctonia cerealis (P. Triticina)), sclerotinia species, pyricularia species (including Pyricularia oryzae (P. Oryzae), pythium species (including Pythium ultimum), pythium species rhizoctonia species, rhizopus minutissima (Rhizomucor pusillus), rhizopus arrhizus, corallospora species, mycelial species (including cercospora spinosa and cercospora spinosa), calicheapest (Schizothyrium pomi), sclerotinia species, septoria species (including septoria nodorum (s. Nodorum), septoria tritici (s. Tritici)), erysiphe necator (Sphaerotheca macularis), monocystallium september (Sphaerotheca fusca) (cucumber powdery mildew (Sphaerotheca fuliginea)), sporotrichum species (sporothrix), cercospora nodorum (Stagonospora nodorum), leptospora species (stephylium spp), stereicospora (stereium hirsutum), rhizoctonia solani (Thanatephorus cucumeris), rhizoctonia solani (Thielaviopsis basicola), tilletia species, trichoderma species (including Trichoderma harzianum, trichoderma pseudokoningii, trichoderma viride), trichophyton species, ramaria species, uncaria vinifera, urocystis spp, utrichia species (Utrichia spp), armillariella species (including Margarella apple (V. Inaequalis)), verticillium species, and Xanthomonas species.

In particular, the compounds of formula (I) and fungicidal compositions containing them can be used for controlling plant diseases caused by a broad spectrum of fungal plant pathogens in the class Basidiomycetes, the class Zaomycetomycetes, the class Oomycetes and/or the class Deuteromycetes, the class Blastocodiomycete, the class Pot fungus, the class sacculus fungus (Glomeromycete) and/or the class Mucor fungus (Mucor) are disclosed.

These pathogens may include:

oomycetes, including phytophthora, such as those caused by phytophthora capsici, phytophthora infestans, phytophthora sojae, strawberry phytophthora (Phytophthora fragariae), phytophthora nicotianae (Phytophthora nicotianae), phytophthora camphorax (Phytophthora cinnamomi), phytophthora citrus (Phytophthora citricola), phytophthora citrus brown rot (Phytophthora citrophthora) and potato red rot germ (Phytophthora erythroseptica); saprophytic mildew, such as those caused by saprophytic mildew of melons, saprophytic mildew of Jiang Xiong (Pythium arrhenomanes), saprophytic mildew of gramineous, saprophytic mildew of abnormal (Pythium irregulare), and saprophytic mildew of ultimate; diseases caused by downy mildew orders such as downy mildew of welsh onion (Peronospora destructor), downy mildew of chinese cabbage, downy mildew of grape, downy mildew of sunflower, downy mildew of cucumber, white rust (Albugo candida), downy mildew of rice and downy mildew of lettuce; and others such as myceliophthora spiral, labyrinthula zosterae, gao Liangshuang dactylotheca (Peronosclerospora sorghi) and dactylotheca graminea (Sclerospora graminicola).

Ascomycetes, including leaf spot, blast or epidemic disease and/or rot, such as those caused by: gramineae such as Alternaria alliacea (Stemphylium solani), stagonospora tainanensis, cyclobalanomyces oleae (Setosphaeria turcica), pyrenochaeta lycoperisici, alternaria alternata, phoma tsutum (Phoma destructiva), phaeosphaeria herpotrichoides, phaeocryptocus gaeumannii, ophiosphaerella graminicola, wheat take-all (Ophiobolus graminis), cruciferae globalpina (Leptosphaeria maculans), fusarium (Hendersonia creberrima), cellularum ascaris (Helminthosporium triticirepentis), alternaria zeylanica (Setosphaeria turcica), helminthosporum sojae (Drechslera glycines), rhizoctonia solani (Didymella bryoniae), alternaria oleae (Cycloconium oleagineum), cladosporium polymorphum, leptosporum gramineum, pitaya black spot (Bipolaris cactivora), alternaria malis, rhizoctonia cerealis, rhizoctonia solani (Pyrenophora tritici-repentis), alternaria brassicae (Alternaria brassicicola), alternaria solani and Alternaria tomato (Alternaria tomatophila); the order of Aphanales (Capnodiales) such as Septoria tritici, septoria nodosa, septoria sojae (Septoria glycines), septoria arachnoides (Cercospora arachidicola), septoria sojae, septoria zeae, septoria Capsella (Cercosporella capsellae) and Mai She Baimei (Cercosporella herpotrichoides), cladosporium nectaricum (Cladosporium carpophilum), cladosporium fortunei (Cladosporium effusum), phaeolomyces fuscosum (Passalora furva), cladosporium oxysporum (Cladosporium oxysporum), dothistroma septosporum, botrytis cinerea (Isariopsis clavispora), leuconostoc banana black streak, graminearum (Mycosphaerella graminicola), leuconostoc mesporum (Mycovellosiella koepkeii), phaeoisariopsis bataticola, leuconostoc vitis (Pseudocercospora vitis), leuconostoc mesis, leucophyllum betanus, leucor (Ramularia collo-cygni); the Horseradish order includes Leptosphaeria species such as Leptosphaeria species, pyricularia oryzae (Magnaporthe grisea), pyricularia oryzae; the order of Gekkales, such as Hazelnut east fusarium wilt, apiognomonia errabunda, cytospora platani, soybean northern stem canker, botrytis cinerea (Discula destructiva), japanese strawberry (Gnomonia fructicola), kyoto, black-disc walnut (Melanconium juglandinum), phomopsis viticola (Phomopsis viticola), juglans regia (Sirococcus clavigignenti-juglandaceae), dongspori Tokyo (Tubakia drarina), dicarpella spp, apple tree rot (Valsa ceratosperma); and others such as Actinothyrium graminis, aschersonia pea, aspergillus flavus, aspergillus fumigatus, aspergillus nidulans, aspergillus papaya, phyllosphaera species (Blumeriella jaapii), candida species, soot germ (Capnodium ramosum), cephalosacut spp, alternaria leaf spot germ (Cephalosporium gramineum), coral shell (Ceratocystis paradoxa), chaetomium species, sphaera pseudowhite (Hymenoscyphus pseudoalbidus), coccidioides species, colporus (Cylindrosporium padi), bivalve (Diplocarpon malae), drepanopeziza campestris, elsino ampelina (elsino), epicoccum, epidermophyton species, grape top blight, geotrichum, cereal shell (Gibellina cerealis), septoria sorghum (Gloeocercospora sorghi), nicotiana species (Gloeodes pomigena), gloeosporium perennans; the fungus endophytic fungi (Gloeotinia temulenta), griphospaeria corticola, li Niqiu, myxospora (Leptographium microsporum), leptosphaerulinia crassiasca, harbouring (Lophodermium seditiosum), bisporus (Marssonina graminicola), trichoderma reesei (Microdochium nivale), cercospora schneideriana (Monilinia fructicola), rice cloudy (Monilinia fructicola), melon root rot (Monilinia fructicola), wire ring species (naemomyces spp.), new elminthium (ophioma novo-ulmi), paracoccidiosporium (Monilinia fructicola), penicillium expansum (Monilinia fructicola), rhodosporidium (Monilinia fructicola), rhodosporum (pezium) species (petrilidium spp), cercosporium species (Pezicula spp), soybean brown rot (Monilinia fructicola), black nevum (Monilinia fructicola), omum (Monilinia fructicola), trichoderma reesei (Monilinia fructicola), brassica pezizizizizizizium (Monilinia fructicola), brassica pezizizizizizizizium (Monilinia fructicola), brassica pezizizizizizium (Monilinia fructicola), brassica pezizizizium (Monilinia fructicola) and the fungus (Monilinia fructicola) of the fungus, and the fungus (sora spp) of the species of the genus brassica species (pezizophea (pezizopsis pinosus (Monilinia fructicola) Sclerotinia sclerotiorum (Sclerotinia minor); sclerotium spp, sclerotium (Typhula ishikariensis), mucor pulmonale (Seimatosporium mariae), lepteutypa cupressi, septocyta ruborum, rhizoctonia crocis (Sphaceloma perseae), sporonema phacidioides, rhizoctonia cerealis (Stigmina palmivora), tapesia yallundae, exocystia pyrifolia (Taphrina bulata), rhizoctonia gossypii (Thielviopsis basicola), trichoseptoria fructigena, and Lepidium meyenii (Zygophiala jamaicensis); powdery mildew, such as those caused by powdery mildew orders such as powdery mildew wheat, powdery mildew knotweed, grape hook shell, cucumber powdery mildew (Sphaerotheca fuligena), white fork wire single capsule shell, podospaera macularis, white sporopollen (Golovinomyces cichoracearum), leveillula taurica (Leveillula taurica), diffuse fork wire shell, oidiopsis gossypii, hazelnut shell (Phyllactinia guttata), oidium arachidis; mold, such as those caused by Botrytis cinerea such as Sphaerotheca gracilis (Dothiorella aromatica), dipterosporium seriata, bidevalia (Guignardia bidwellii), botrytis cinerea (Botrytis cinerea), sclerotinia (Botryotinia allii), sclerotinia fabae (Botryotinia fabae), clostridium amygdalina (Fusicoccum amygdali), pyricularia longan (Lasiodiplodia theobromae), phoma longifolia (Macrophoma theicola), fabricius phaseoloides, trimerella cucurbitaceae (Phyllosticta cucurbitacearum); anthracnose, such as those caused by small plexus shells (glommerelles) such as colletotrichum glomeratum, melon anthrax (Colletotrichum lagenarium), cotton anthrax, periclase, and colletotrichum graminearum; and fusarium or epidemic diseases, such as those caused by the order of the sarcoplasmales, such as, for example, acremonium straight, purple ergot, fusarium flavum, fusarium graminearum, soybean sudden death syndrome (Fusarium virguliforme), fusarium oxysporum, fusarium mucilaginosum, fusarium gulvulgare (Fusarium oxysporum f.sp.cube), gerlahia nivale, gibberella canescens, gibberella zeae, amycola species, verrucaria verrucosa, nectria ramulariae, trichoderma viride, leptospora rosea, and alligator root rot (Verticillium theobromae).

Basidiomycetes, including, for example, those caused by ustilaginoidea such as Ustilago oryzae (Ustilaginoidea virens), ustilago gracilis (Ustilago nuda), ustilago gracilis (Ustilago tritici), ustilago maydis (Ustilago zeae), rust such as those caused by cermeticulous fig (Cerotelium fici), picea spruce (Chrysomyxa arctostaphyli), sweet potato sheath rust (Coleosporium ipomoeae), camelina sativa (Hemileia vastatrix), cermetrella arachnoides (Puccinia arachidis), puccinia cacabata, puccinia graminis (Puccinia graminis), puccinia recondita (Puccinia recondita), puccinia sorghum (Puccinia sorghi), puccinia hordei (Puccinia hordei), puccinia barley stripe rust (Puccinia striiformis f.sp.hordei), cercinia tritici (Puccinia striiformis f.secalis), hazelnut (Pucciniastrum coryli); or rust orders such as those caused by rust pinus (Cronartium ribicola), rust sabina (Gymnosporangium juniperi-viginiana e), rust poplar (Melampsora medusae), rust pachyrhizus (Phakopsora pachyrhizi), rust polycephala (Phragmitis), physopella ampelosidis, rust tarabicum (Tranzschelia discolor), monospora faba (Uromyces vicae-fabae); and other rot and disease, such as those caused by cryptococcus species, chaetomium species, marasmiellus inoderma, kombucha species, head smut (Sphacelotheca reiliana), sclerotium snow rot (Typhula ishikariensis), nigella sativa (Urocystis agropyri), itersonilia perplexans, phanerochaete (corium sativum), phanerochaete (Laetisaria fuciformis), waita circineta, rhizoctonia solani, thanetephorus cucurmeris, phanerochaete dahliae (Entyloma dahlia), entylomella microspora, phanerochaete chrysalis (Neovossia moliniae), and phanerochaete aestivum (Tilletia caries).

The class Rhizopus, such as Arthropoda zeae (Physoderma maydis).

Mucorales, such as cucurbitaceae (Choanephora cucurbitarum); mucor species; rhizopus arrhizus (L.) Lindl,

along with diseases caused by other species and genera closely related to those listed above.

Any reference above and below to "sphaerella graminearum" or "aschersonia aestiva" should be understood as a reference to aschersonia aestiva (Zymoseptoria tritici) (the correct taxonomic designation).

Fusarium niveum (Rhizoctonia solani) is a fungal plant pathogen that attacks grains during all stages of development, causing various diseases such as seedling blight, snow rot, root rot, and scab, among others.

Gibberella zeae (asexual: fusarium graminearum) is a fungal plant pathogen that causes gibberellic disease (fusarium head blight) (destructive disease on wheat and barley). Fusarium yellow is also a pathogenic pathogen of fungal plant pathogens and seedling blight, root rot, scab, stem rot, common root rot, and other diseases of cereals, and is also a pathogenic pathogen of wheat scab. Wheat scab (FHB), also known as scab, is a fungal disease of small grain (including wheat, barley, oats, rye, corn, triticale, canary grass seeds, and some forage grasses).

In addition to their fungicidal activity, these compounds and compositions comprising them may also have activity against bacteria such as erwinia amylovora, erwinia soft rot (Erwinia caratovora), xanthomonas campestris, pseudomonas syringae, potato scab (Strptomyces scabies) and other related species, as well as certain protozoa.

Within the scope of the present invention, the target crop and/or useful plant to be protected typically includes perennial and annual crops, such as berry plants, e.g. blackberry, blueberry, cranberry, raspberry and strawberry; grains such as barley, corn, millet, oats, rice, rye, sorghum, triticale, and wheat; fiber plants, such as cotton, flax, hemp, jute, and sisal; field crops, such as sugar beet and fodder beet, coffee beans, hops, mustard, rape (canola), poppy, sugarcane, sunflower, tea and tobacco; fruit trees, such as apples, apricots, avocados, bananas, cherries, oranges, nectarines, peaches, pears, and plums; grass, such as bermuda grass, bluegrass, bunte grass, ciliate grass, nigella sativa, ryegrass, san-jose grass, zoysia japonica; herbs such as basil, borage, chives, coriander, lavender, angelicae pubescentis, peppermint, oregano, parsley, rosemary, sage and thyme; legumes such as beans, lentils, peas, and soybeans; nuts such as almonds, cashews, peanuts, hazelnuts, peanuts, pecans, pistachios, and walnuts; palm plants, such as oil palm; ornamental plants such as flowers, shrubs and trees; other trees such as cocoa, coconut, olive, and rubber trees; vegetables such as asparagus, eggplant, broccoli, cabbage, carrot, cucumber, garlic, lettuce, zucchini, melon, okra, onion, pepper, potato, pumpkin, rhubarb, spinach, and tomato; and grape vine, such as grape.

The useful plants and/or target crops according to the invention include conventional varieties which are treated in connection with genetic enhancement or genetic engineering, such as, for example, insect-resistant (e.g., bt. and VIP varieties) and disease-resistant, herbicide-resistant (e.g., glyphosate-resistant and glufosinate-resistant maize varieties, under the trade name RoundupAnd Liberty->Commercially available) and nematode tolerant varieties. Suitable genetically enhanced or engineered crop varieties include, by way of example, stoneville 5599BR cotton and Stoneville 4892BR cotton varieties.

The term "useful plants" and/or "target crops" is to be understood as also including useful plants which are resistant to herbicides like bromoxynil or classes of herbicides like for example HPPD inhibitors, ALS inhibitors like for example primisulfuron, prosulfuron and trifloxysulfuron, EPSPS (5-enol-pyruvyl-shikimate-3-phosphate-synthase) inhibitors, GS (glutamine synthetase) inhibitors or PPO (protoporphyrinogen-oxidase) inhibitors as a result of conventional breeding methods or genetic engineering methods. Has been caused by conventional breeding methods (mutagenesis)Examples of imidazolinone (e.g. imazethapyr) tolerant crops are Summer rape (canola). Examples of crops that have been rendered tolerant to herbicides or classes of herbicides by genetic engineering methods include glyphosate-and glufosinate-resistant maize varieties under the trade name Roundup->HerculexAnd Liberty->Are commercially available.

The term "useful plants" and/or "target crops" is understood to include those which are naturally or have rendered resistant to harmful insects. This includes plants transformed by using recombinant DNA techniques, for example, to synthesize one or more selectively acting toxins, as are known from, for example, toxin-producing bacteria. Examples of toxins that may be expressed include delta-endotoxins, vegetative insecticidal proteins (Vip), insecticidal proteins of bacterial colonizing nematodes, and toxins produced by scorpions, arachnids, wasps, and fungi. Examples of crops that have been modified to express Bacillus thuringiensis toxins are Bt mail(Syngenta Seeds). Examples of crops comprising more than one gene encoding insecticidal resistance and thereby expressing more than one toxin are +.>(seed of first-come). The crop or seed material thereof may also be resistant to multiple types of pests (so-called superposition transgenic events when produced by genetic modification). For example, the plant may have an expressed insecticidal egg Simultaneous herbicide tolerance, e.g. Herculex->(Tao Shiyi agricultural company (Dow Agrocciences), pioneer stock International (Piconeer Hi-Bred International)).

The term "useful plants" and/or "target crops" is to be understood as also including useful plants which have been transformed by using recombinant DNA techniques such that they are capable of synthesizing antipathogenic substances having selective activity, such as for example so-called "pathogenesis-related proteins" (PRP, see e.g. EP-a-0 392 225). Examples of such antipathogenic substances and transgenic plants capable of synthesizing such antipathogenic substances are known, for example, from EP-A-0 392 225, WO 95/33818 and EP-A-0 353 191. Methods of producing such transgenic plants are generally known to those skilled in the art and are described, for example, in the publications mentioned above.

Toxins that can be expressed by transgenic plants include, for example, insecticidal proteins from bacillus cereus or bacillus thuringiensis; or insecticidal proteins from bacillus thuringiensis, such as delta-endotoxins, e.g., cry1Ab, cry1Ac, cry1F, cry Fa2, cry2Ab, cry3A, cry Bb1 or Cry9C, or vegetative insecticidal proteins (Vip), e.g., vip1, vip2, vip3 or Vip3A; or insecticidal proteins of bacterial plant nematodes, such as Photorhabdus species (Photorhabdus spp.) or Xenorhabdus species (Xenorhabdus spp.), such as Xenorhabdus (Photorhabdus luminescens), xenorhabdus nematophilus (Xenorhabdus nematophilus); toxins produced by animals, such as scorpions, spider toxins, bee toxins, and other insect-specific neurotoxins; toxins produced by fungi, such as streptomycin, phytolectins, such as pea lectin, barley lectin or galanthamine lectin; lectins (agglutanins); protease inhibitors such as trypsin inhibitor, silk protease inhibitor, patatin, cystatin, papain inhibitor; ribosome Inactivating Proteins (RIP), such as ricin, maize-RIP, abrin, luffa seed protein, saporin or curcin; steroid metabolizing enzymes such as 3-hydroxysteroid oxidase, ecdysteroid-UDP-glycosyl-transferase, cholesterol oxidase, ecdysone inhibitor, HMG-COA-reductase, ion channel blockers such as sodium or calcium channel blockers, juvenile hormone esterase, diuretic hormone receptor, stilbene synthase, bibenzyl synthase, chitinase and glucanase.

Further, in the context of the present invention, delta-endotoxins (e.g., cry1Ab, cry1Ac, cry1F, cry Fa2, cry2Ab, cry3A, cry Bb1 or Cry 9C) or vegetative insecticidal proteins (Vip) (e.g., vip1, vip2, vip3 or Vip 3A) are understood to obviously also include mixed toxins, truncated toxins and modified toxins. Hybrid toxins are recombinantly produced by a new combination of different domains of those proteins (see, e.g., WO 02/15701). Truncated toxins, such as truncated Cry1 abs, are known. In the case of modified toxins, one or more amino acids of the naturally occurring toxin are replaced. In such amino acid substitutions, it is preferred to insert non-naturally occurring protease recognition sequences into the toxin, such as, for example, in the case of Cry3A055, cathepsin-G-recognition sequences into the Cry3A toxin (see WO 03/018810).

Further examples of such toxins or transgenic plants capable of synthesizing such toxins are disclosed, for example, in EP-A-0 374 753, WO 93/07278, WO 95/34656, EP-A-0 427 529, EP-A-451 878 and WO 03/052073.

Methods for preparing such transgenic plants are generally known to the person skilled in the art and are described, for example, in the publications mentioned above. CryI-type deoxyribonucleic acids and their preparation are known, for example, from WO 95/34656, EP-A-0 367 474, EP-A-0 401 979 and WO 90/13651.

Toxins included in transgenic plants render the plants tolerant to harmful insects. Such insects may be present in any insect taxa, but are particularly common in beetles (coleoptera), diptera insects (diptera), and moths (lepidoptera).

Transgenic plants containing one or more genes encoding insecticidal resistance and expressing one or more toxins are known and some are commercially available. Examples of such plants are:(maize variety, expressing Cry1Ab toxin); YIELdGard->(maize variety, expressing Cry3Bb1 toxin); YIELdGard(maize variety, expressing Cry1Ab and Cry3Bb1 toxins);(maize variety, expressing Cry9C toxin); herculex->(maize variety, expressing Cry1Fa2 toxin and the enzyme phosphinothricin N-acetyl transferase (PAT) to obtain tolerance to the herbicide glufosinate ammonium); nuCOTN->(cotton variety, expressing Cry1Ac toxin); bollgard->(cotton variety, expressing Cry1Ac toxin); bollgard->(cotton varieties expressing Cry1Ac and Cry2Ab toxins);(cotton variety, expressing Vip3A and Cry1Ab toxins);(potato variety, expressing Cry3A toxin);GT Advantage (GA 21 glyphosate resistance trait),CB Advantage (Bt 11 Corn Borer (CB) trait) >

Further examples of such transgenic crops are:

bt11 maize from Ezhengba seed Co., ltd., line Huo Bite (Chemin de l' Hobit) 27, F-31 790 st Su Weier (St. Sauveur), france accession number C/FR/96/05/10. Genetically modified maize is rendered resistant to attack by european corn borer (corn borer and cnaphalocrocis medinalis) by transgenic expression of truncated Cry1Ab toxins. Bt11 maize also transgenically expresses PAT enzyme to obtain tolerance to the herbicide glufosinate ammonium.

Bt176 corn from seed of Fangzha, huo Bite, line 27, F-31 790 san Su Weier, france accession number C/FR/96/05/10. Genetically modified maize, genetically expressed as a Cry1Ab toxin, is resistant to attack by european corn borers (corn borers and cnaphalocrocis medinalis). Bt176 maize also transgenically expresses the enzyme PAT to obtain tolerance to the herbicide glufosinate ammonium.

MIR604 corn from seed of Fangda, huo Bite, line 27, F-31 790, sheng Su Weier, france, accession number C/FR/96/05/10. Corn that has been rendered insect-resistant by transgenic expression of the modified Cry3A toxin. The toxin is Cry3A055 modified by insertion of a cathepsin-G-protease recognition sequence. The preparation of such transgenic maize plants is described in WO 03/018810.

MON 863 corn from Monsanto Europe S.A.) 270-272 Teflon (Avenue DE Tervuren), B-1150 Brussels, belgium, accession number C/DE/02/9.MON 863 expresses a Cry3Bb1 toxin and is resistant to certain coleopteran insects.

IPC 531 cotton from Mengshan European company 270-272 Teflon, B-1150 Brussels, belgium under accession number C/ES/96/02.

6.1507 maize, from pioneer overseas company (Pioneer Overseas Corporation), tedelsco, avenue Tedesco, 7B-1160 Brussels, belgium, accession number C/NL/00/10. Genetically modified maize, expressing the protein Cry1F to obtain resistance to certain lepidopteran insects, and PAT protein to obtain tolerance to the herbicide glufosinate ammonium.

NK603×MON 810 maize from Mengshan European company 270-272 Teflon, B-1150 Brussels, belgium under accession number C/GB/02/M3/03. By crossing the genetically modified varieties NK603 and MON 810, it is made up of a conventionally bred hybrid maize variety. NK603×MON 810 maize transgenically expresses the protein CP4 EPSPS obtained from Agrobacterium strain CP4, conferring herbicide resistance Tolerance (to glyphosate containing) and also expresses Cry1Ab toxins obtained from bacillus thuringiensis subspecies kurstaki, which confer tolerance to certain lepidopteran insects, including european corn borer.

As used herein, the term "locus" means a place in or on which plants are grown, or where seeds of cultivated plants are sown, or where seeds are to be placed in soil. It includes soil, seeds, and seedlings, along with established vegetation.

The term "plant" refers to all the tangible parts of a plant, including seeds, seedlings, saplings, roots, tubers, stems, stalks, leaves, and fruits.

The term "plant propagation material" is understood to mean reproductive parts of plants, such as seeds (which may be used for propagation of plants), as well as nutritional materials, such as cuttings or tubers (e.g. potatoes). Mention may be made, for example, of seeds (in the strict sense), roots, fruits, tubers, bulbs, rhizomes and parts of plants. Germinated plants and young plants to be transplanted after germination or after emergence can also be mentioned. These young plants may be protected prior to transplantation by being treated, either completely or partially, by dipping. Preferably, "plant propagation material" is understood to mean seeds.

The pesticides mentioned herein using their common names are, for example, known from "The Pesticide Manual [ handbook of pesticides ]", 15 th edition, british crop protection committee (British Crop Protection Council) 2009.

The compounds of formula (I) can be used in unmodified form or, preferably, together with adjuvants conventionally used in the field of formulation. For this purpose, they can be conveniently formulated in a known manner as emulsifiable concentrates, coatable pastes, directly sprayable or dilutable solutions or suspensions, diluted emulsions, wettable powders, soluble powders, dust powders, granules and also capsules (for example in polymeric substances). For the type of composition, the method of application is selected according to the intended purpose and the circumstances at the time, such as spraying, atomizing, dusting, broadcasting, painting or pouring. The composition may also contain further adjuvants, such as stabilizers, defoamers, viscosity modifiers, binders or tackifiers, together with fertilizers, micronutrient donors or other formulations for achieving special effects.

Suitable carriers and adjuvants, for example for agricultural use, may be solid or liquid and are substances useful in formulation technology, for example natural or regenerated mineral substances, solvents, dispersions, wetting agents, tackifiers, thickeners, binders or fertilisers. Such vectors are described, for example, in WO 97/33890.

Suspension concentrates are aqueous formulations in which finely divided solid particles of the active compound are suspended. Such formulations include anti-settling agents and dispersants, and may further include wetting agents to enhance activity, as well as defoamers and crystal growth inhibitors. In use, these concentrates are diluted in water and typically applied as a spray to the area to be treated. The amount of active ingredient may range from 0.5% to 95% of the concentrate.

Wettable powders are in the form of finely divided particles that disperse readily in water or other liquid carrier. These particles contain the active ingredient retained in a solid matrix. Typical solid matrices include fuller's earth, kaolin clays, silica and other readily wettable organic or inorganic solids. Wettable powders normally contain from 5% to 95% of the active ingredient plus a small amount of wetting, dispersing or emulsifying agents.

Emulsifiable concentrates are homogeneous liquid compositions dispersible in water or other liquids and may consist entirely of the active compound with a liquid or solid emulsifier, or may also contain liquid carriers such as xylene, heavy aromatic naphthas, isophorone and other non-volatile organic solvents. In use, these concentrates are dispersed in water or other liquid and are typically applied as a spray to the area to be treated. The amount of active ingredient may range from 0.5% to 95% of the concentrate.

The granule formulation includes both extrudates and coarser particles and is typically applied undiluted to the area to be treated. Typical carriers for particulate formulations include sand, fuller's earth, attapulgite clay, bentonite, montmorillonite, vermiculite, perlite, calcium carbonate, brick, pumice, pyrophyllite, kaolin, dolomite, stucco, wood flour, crushed corn cobs, crushed peanut shells, sugar, sodium chloride, sodium sulfate, sodium silicate, sodium borate, magnesium oxide, mica, iron oxide, zinc oxide, titanium oxide, antimony oxide, cryolite, gypsum, diatomaceous earth, calcium sulfate and other organic or inorganic absorbent active compounds or materials that may be coated with an active compound. Particle formulations typically contain from 5% to 25% of active ingredients which may include surfactants such as heavy aromatic naphthas, kerosene and other petroleum fractions, or vegetable oils; and/or an adhesive such as dextrin, glue or synthetic resin.

Dust powders are free-flowing mixtures of the active ingredient with finely divided solids such as talc, clay, flour and other organic and inorganic solids as dispersants and carriers.

Microcapsules are typically droplets or particles of an active ingredient enclosed within an inert porous shell that allows the enclosed material to escape to the environment at a controlled rate. The diameter of the encapsulated droplets is typically 1 to 50 microns. The encapsulated liquid typically comprises 50% to 95% by weight of the capsule and may include a solvent in addition to the active compound. The encapsulated particles are typically porous particles, wherein the porous membrane seals the particle orifice, retaining the active species in liquid form inside the particle pores. The diameter of the particles typically ranges from 1 mm to 1 cm and preferably from 1 mm to 2 mm. The particles are formed by extrusion, agglomeration or spheronization, or are naturally occurring. Examples of such materials are vermiculite, sintered clay, kaolin, attapulgite clay, sawdust and carbon fines. Shell or membrane materials include natural and synthetic rubbers, fibrous materials, styrene-butadiene copolymers, polyacrylonitriles, polyacrylates, polyesters, polyamides, polyureas, polyurethanes and starch xanthates.

Other useful formulations for agrochemical applications include simple solutions of the active ingredient in solvents such as acetone, alkylated naphthalenes, xylenes and other organic solvents in which the active ingredient is fully dissolved at the desired concentration. Pressurized sprays can also be used wherein the active ingredient is dispersed in finely divided form as a result of evaporation of the low boiling dispersant solvent carrier.

Suitable agricultural adjuvants and carriers useful in formulating the compositions of the invention in the above formulation types are well known to those skilled in the art.

Liquid carriers which may be used include, for example, water, toluene, xylene, naphtha, crop oil, acetone, methyl ethyl ketone, cyclohexanone, acetic anhydride, acetonitrile, acetophenone, amyl acetate, 2-butanone, chlorobenzene, cyclohexane, cyclohexanol, alkyl acetate, diacetone alcohol, 1, 2-dichloropropane, diethanolamine, p-diethylbenzene, diethylene glycol rosin acid, diethylene glycol butyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ether, N, N-dimethylformamide, dimethyl sulfoxide, 1, 4-dioxane, dipropylene glycol methyl ether, dipropylene glycol dibenzoate, dipropylene glycol (dipropylene glycol), alkylpyrrolidone, ethyl acetate, 2-ethylhexanol, ethylene carbonate, 1-trichloroethane, 2-heptanone, alpha-pinene, alpha-methyl ester, beta-ester, dipropylene glycol, beta-methyl ester, beta-ethyl ester, beta-pinene, beta-methyl ester, beta-pinene, beta-d-limonene, ethylene glycol butyl ether, ethylene glycol methyl ether, gamma-butyrolactone, glycerol diacetate, glycerol monoacetate, glycerol triacetate, hexadecane, hexylene glycol, isoamyl acetate, isobornyl acetate, isooctane, isophorone, cumene, isopropyl alcohol, ethyl alcohol, butyl alcohol, isopropyl alcohol, isopropyl myristate, lactic acid, laurylamine, mesityl oxide, methoxypropanol, methyl isovalerne, methyl isobutyl ketone, methyl laurate, methyl octanoate, methyl oleate, methylene chloride, m-xylene, N-hexane, N-octylamine, stearic acid, acetic acid Xin Anzhi, oleic acid, oleylamine, o-xylene, phenol, polyethylene glycol (PEG 400), propionic acid, propylene glycol monomethyl ether, p-xylene, toluene, triethyl phosphate, triethylene glycol, xylenesulfonic acid, paraffin, mineral oil, trichloroethylene, perchloroethylene, ethyl acetate, amyl acetate, butyl acetate, polyethylene glycol (PEG 400), propionic acid, propylene glycol monomethyl ether, p-xylene, toluene, triethyl phosphate, triethylene glycol, xylenesulfonic acid, paraffin, mineral oil, trichloroethylene, perchloroethylene, methanol, ethanol, isopropanol, and higher molecular weight alcohols (e.g., amyl alcohol, tetrahydrofurfuryl alcohol, hexyl alcohol, octyl alcohol, etc.), ethylene glycol, propylene glycol, glycerol, and N-methyl-2-pyrrolidone. Water is typically the carrier of choice for diluting the concentrate.

Suitable solid carriers include, for example, talc, titanium dioxide, pyrophyllite clay, silica, attapulgite clay, diatomaceous earth (kieselguhr), chalk, diatomaceous earth (diatomaxeous earth), lime, calcium carbonate, bentonite, fuller's earth, cotton seed hulls, wheat flour, soybean flour, pumice, wood flour, walnut hull flour, and lignin.

A wide range of surfactants are advantageously employed in the liquid and solid compositions, particularly those designed to be diluted with carrier prior to application. These agents, when used, generally comprise from 0.1% to 15% by weight of the formulation. They may be anionic, cationic, nonionic or polymeric in nature and may be employed as emulsifiers, wetting agents, suspending agents or for other purposes. Typical surfactants include alkyl sulfates such as diethanolammonium lauryl sulfate; alkylaryl sulfonates such as calcium dodecylbenzenesulfonate; alkylphenol-alkylene oxide addition products, e.g. nonylphenol-C ₁₈ An ethoxylate; alcohol-alkylene oxide addition products, e.g. tridecyl alcohol-C ₁₆ An ethoxylate; soaps, such as sodium stearate; alkyl naphthalene sulfonates such as sodium dibutyl naphthalene sulfonate; salts of dialkyl sulfosuccinates, such as sodium di (2-ethylhexyl) sulfosuccinate; mountain Sorbitol esters such as sorbitol oleate; quaternary amines such as lauryl trimethyl ammonium chloride; polyethylene glycol esters of fatty acids, such as polyethylene glycol stearate; block copolymers of ethylene oxide and propylene oxide; and salts of mono-and dialkyl phosphates.

Other adjuvants commonly used in agricultural compositions include crystallization inhibitors, viscosity modifiers, suspending agents, spray droplet modifiers, pigments, antioxidants, foaming agents, antifoams, opacifiers, compatibilizing agents, defoamers, masking agents, neutralizing agents and buffering agents, corrosion inhibitors, dyes, odorants, spreading agents, penetration aids, micronutrients, emollients, lubricants, and fixing agents.

Furthermore, further biocidal active ingredients or compositions may be combined with the compositions of the present invention and used in the methods of the present invention and administered simultaneously or sequentially with the compositions of the present invention. When administered simultaneously, these additional active ingredients may be formulated or mixed together with the compositions of the present invention, for example, in a spray can. These additional biocidal active ingredients can be fungicides, herbicides, insecticides, bactericides, acaricides, nematicides and/or plant growth regulators.

In addition, the compositions of the present invention may also be administered with one or more systemic acquired resistance inducers ("SAR" inducers). SAR inducers are known and described, for example, in US patent No. US 6,919,298 and include, for example, salicylates and the commercial SAR inducer alamic benzene-S-methyl.

The compounds of formula (I) are generally used in the form of compositions and can be applied simultaneously or sequentially with further compounds to the crop area or the plant to be treated. For example, these additional compounds may be fertilizers or micronutrient donors or other formulations that affect plant growth. They may also be selective or nonselective herbicides, together with insecticides, fungicides, bactericides, nematicides, molluscicides or mixtures of several of these preparations, if desired together with further carriers, surfactants or adjuvants which facilitate application, which are customarily used in the art of formulation.

The compounds of formula (I) may be used in the form of (fungicidal) compositions for controlling or protecting against phytopathogenic microorganisms, comprising at least one compound of formula (I) or at least one, preferably, various compounds as defined above as active ingredient (in free form or in agrochemically usable salt form), and at least one of the above-mentioned adjuvants.

The present invention therefore provides a composition, preferably a fungicidal composition, comprising at least one compound of formula (I) and an agriculturally acceptable carrier and optionally adjuvants. An agriculturally acceptable carrier is, for example, a carrier suitable for agricultural use. Agricultural vectors are well known in the art. Preferably, the composition may comprise, in addition to the compound of formula (I), at least one or more pesticidally active compounds, for example further fungicidally active ingredients.

The compound of formula (I) may be the only active ingredient of the composition or it may be admixed with one or more additional active ingredients such as pesticides, fungicides, synergists, herbicides or plant growth regulators, as appropriate. In some cases, additional active ingredients may produce unexpected synergistic activity.

Examples of suitable additional active ingredients include the following: 1,2, 4-thiadiazole, 2, 6-dinitroaniline, acylalanine, aliphatic nitrogen-containing compounds, amidines, aminopyrimidinols, anilines, anilinopyrimidines, anthraquinones, antibiotics, aryl-phenyl ketones, benzamides, benzene-sulfonamides, benzimidazoles, benzothiazoles, benzothiadiazoles, benzylcarbamates, butylamines, carbamates, formamides, cyclopropylamines, chloronitriles, cinnamides, copper-containing compounds, cyanoacetamides, cyanoacrylates, cyanoimidazoles, cyanomethylene-thiazolidines, dinitriles, dicarboximides, dimethylaminosulfonates, dinitrophenol carbonates, dinitrophenol dinitrophenyl crotonates, diphenyl phosphates, dithiino compounds, dithiocarbamates, dithioethers, dithiopentacyclic, ethyl-amino-thiazolecarboxamides, ethyl-phosphonates, furancarboxamides, glucopyranosyl groups, glucuronyl groups, glutaronitriles, guanidine, herbicides/plant growth regulators, hexopyranosyl antibiotics, hydroxy (2-amino) pyrimidines, hydroxyanilines, hydroxyisoxazoles, imidazoles, imidazolinones, pesticides/plant growth regulators, isobenzofuranones, isoxazolidinyl-pyridines, isoxazolines, maleimides, mandelic acid amides, pectin derivatives, morpholines, normorpholines, N-phenylcarbamates, organotin compounds, oxathiolane formamides, oxazoles, oxazolidinediones, phenol, phenoxyquinoline, phenyl-acetamide, phenylamide, phenylbenzamide, phenyl-oxo-ethyl-thiophene amide, phenylpyrrole, phenylurea, thiophosphate, phosphoric acid, phthalic acid, phthalimide, pyridine amide, piperazine, piperidine, plant extracts, polyoxin, propionamide, phthalimide, pyrazole-4-carboxamide, pyrazolone, pyridazinone, pyridine, pyridylcarboxamide, pyridinyl-ethylbenzamide, pyrimidamine, pyrimidine-amine, pyrimidone-hydrazone, pyrrolidine, pyrroloquinoline, quinazolinone, quinoline derivatives, quinoline-7-carboxylic acid, quinoxaline, spiroketal amine, strobilurin, sulfamoyl triazole, sulfonamide, tetrazolium oxime, thiadiazine carboxamide thiazole carboxamides, thiocyanates, thiophene carboxamides, toluamide, triazines, triazole benzothiazoles, triazoles, triazole-thiones, triazole-pyrimidine amines, valinamide carbamates, ammonium methylphosphonates, arsenic containing compounds, benzimidazole carbamates, carbonitriles, carboxanilides, carboxamide amides, carboxyanilides, diphenylpyridines, furanilides, hydrazinecarboxamides, imidazolinoacetates, isophthalates, isoxazolones, mercuric salts, organomercuric compounds, organic phosphates, oxazolidinediones, pentylsulfonylbenzene, phenylbenzamide, thiophosphonates, thiophosphates, pyridine carboxamides, pyridylfurfuryl ethers, pyridylmethyl ethers, SDHI, thiadiazinealkylthio ketones, thiazolidines.

Examples of suitable additional active ingredients also include the following: a compound selected from the group consisting of: petroleum oil, 1-bis (4-chlorophenyl) -2-ethoxyethanol, 2, 4-dichlorophenyl benzenesulfonate, 2-fluoro-N-methyl-N-1-naphthaleneacetamide, 4-chlorophenyl phenyl sulfone, acetylchlorfenapyr, aldicarb, racetrack, fruit-on-phosphorus, amine phosphorus, hydrogen oxalate amine phosphorus, amitraz, acaricide, arsenic trioxide, azobenzene, azophos, benomyl, benozhafos, benzyl benzoate, bixafen, deltamethrin, bromenoxadine, bromphos, fenpyroximate, buprofezin, butyl pyridaben calcium polysulfide, octachlorocamphene, chlorfenamate, phosphorus trithion, fenpicloram, chlorfenapyr hydrochloride, chlorfenapyr De-mite, ethyl ester acaricidal alcohol, chlormequat, propyl ester acaricidal alcohol, chlorfenpyr, fenprox I, fenprox II, fenprox, clofentezine, coumaphos, clomiphos, bap-thapyr, thiazate, chlorfenapyr, DCPM, DDT, trifluophos, phoxim-O, phoxim-S, varroa-methyl, varroa-O-methyl Neopril-S, neopril-S-methyl sulfone, dichlorvos (dichlorvos), benfuracarb, fenbucol (dinex), fenbucol (dinex-dichlexine), fenamic-4, fenamic-6, adjacent fenamic-0, nitron-pentyl, nitron-octyl, nitron-butyl, dichlorvos, sulfodiphenyl, alcohol-stopping sulfur, DNOC, fenacet (dofenapyn), dorametin, clofenacet, irinotecan, valinate, ethirimos, fenbuconazole, fenbutatin oxide, benfocarb, benomyl (fenpyrad), fenpyrad, flunifedipine (fenrifanil), flufenacet, flufenoxuron, bifenax, fluxapyroxad, FMC 1137, valicamidine hydrochloride, methomyl (formaranate), gamma-HCH, levalidine, benflumetofen, cetyl cyclopropanecarboxylate, fenpyrad, jasmine I, jasmine II, iodiphos, lindane, propargine, acephate, dithiphos, methifen, fenpyrad, brommethane, methomyl, monoctrofen, milbexime, propafenozide, profenofos, mevalicarb, mevalonate, dibromophosphorus (naja) d) 4-chloro-2- (2-chloro-2-methyl-propyl) -5- [ (6-iodo-3-pyridinyl) methoxy]Pyridazin-3-one, trifluralin, nikkomycin, penholder 1:1 zinc chloride complex, omethoate, ifolia, phoxim, phorate, pp' -DDT, parathion, permethrin, fenphos, phoxim, thiocyclophosphorus, phospham, turpentine chloride (polychloroeteres), acaricide (polynaphins), prochloraz, tick-borne, propoxur, ethionan, thiophos pyrethrin I, pyrethrin II, pyrethrin, pyridaphethione, azophoska, quinalphos, R-1492, glycilphos, rotenone, octamefhydrate captan, selametin, su Liu phosphorus, SSI-121, shu Feilun, flubendiamide, thiotepa, sulfur, flufenzine, tau-fluvalinate, TEPP, terbucarb, tetrachlorfon sulfone good acaricide, thiafenox, benfuracarb, monocrotophos, methyethophos, g-acaricide, threomycin, weifenphos, fenpropaphos, triazophos, triazuron, triclophos, trioxyphos, triazophos, triazuron, methimazole, chlorfenapyr, bethoxazin, copper dioctate, copper sulfate, cyclobutanediol, dichlornaphthaquinone, dichlorophenone, chlorphenamine, chlorphenate, polyacid, triphenyltin, slaked lime, zin, algicide, quinone, simazine, tin triphenylacetate, triphenyltin hydroxide, benfophos, piperazine, tolbutin, chloral candy, becphos, pyridin-4-amine, strychnine, 1-hydroxy-1H-pyridine-2-thione, 4- (quinoxalin-2-ylamino) benzenesulfonamide, 8-hydroxyquinoline sulfate, bromonitrol, copper hydroxide, cresol, pyrithione, doxycycline, sodium disultone, formaldehyde, mercuric oxide, kasugamycin hydrochloride hydrate, nickel bis (dimethyldithiocarbamate), trichloropicoline, xin Saitong, oxolinic acid, terramycin, potassium hydroxyquinoline sulfate, thiabendazole, streptomycin sesquisulfate, leaf blight phthalide, thimerosal, phaeodactylum gossypii GV, agrobacterium radiobacter, amblyseius species, aphania apiacea NPV, octopus wing small bee, aphis brachycarpa, aphis gossypii parasitic bee, aphid goiter, medicago silver noctuid NPV, bacillus sphaericus, beauveria brucei, phaeda viridis, cryptolipa mandshurica, coda malis GV, siberian hornet Aphis, pisum sinica, pisum sativum and She Yingji Aphis Aphis citrifolia, aphis citrina, heterodera grandis, aleurites maculata, aphis citrina NPV, metarhizium anisopliae, aleurus citrina, aleurites maculata, aleurites spinosa, aleurites, aphis citrina, and Metarhizium NPV and NPV of pine needle and pine needle of red head, plant bug, paecilomyces fumosoroseus, phytoseiulus wisgii, mao Wen nematode, plutella xylostella, noctuid, grignard, shangbi, leishmaniasis (Steinernema riobravis), gryllotalpa, rhizomys, and Rhizomys the genus Sphaeroides, the genus Trichocephalus, the genus Xiekola, the genus Verticillium, triazophos, bis (aziridine) methylaminophosphine sulfide, busulfan, dimetif, altretamine, hexamethophos, methylnasal, methylthionasal, methazolphoszine, infertility, fluvaluron, nasal, thiohexamethophos, thionasal, triadime, urethane imine, (E) -dec-5-en-1-yl acetate and (E) -dec-5-en-1-ol, (E) -tridec-4-en-1-yl acetate, (E) -6-methylhept-2-en-4-ol, Z) -tetradec-4, 10-dien-1-yl acetate, (Z) -dodeca-7-en-1-yl acetate, (Z) -hexadec-11-enal, (Z) -hexadec-11-en-1-yl acetate, (Z) -hexadeca-13-en-11-yn-1-yl acetate, (Z) -eicos-13-en-10-one, (Z) -tetradeca-7-en-1-al, (Z) -tetradeca-9-en-1-ol, (Z) -tetradeca-9-en-1-yl acetate, (7E, 9Z) -doc-7, 9-dien-1-yl acetate, (9Z, 11E) -tetradeca-9, 11-dien-1-yl acetate, (9Z, 12E) -tetradeca-9, 12-dien-1-yl acetate, 14-methyl octadeca-1-en, 4-methyl-nonen-5-ol with 4-methyl nonen-5-one, alpha-strin, silverson, dodiden, obtainable, lureone, epoxynonane, dodec-8-en-1-yl acetate, dodec-9-en-1-yl acetate, dodec-8, 10-dien-1-yl acetate, dode-1-yl acetate, lure-12E) -tetradeca-9, 12-dien-1-yl acetate, 14-methyl octadeca-5-ol, 4-methyl octadeca-ol, 4-one, tricyclam, 8-one, tricyclin, 8, siltsuzole, silvery, noctuid sex attractant, trapping ester, meng Tuome g acid (megatomoic acid) Insect-attracting ether, insect-attracting alkene, octadeca-2, 13-dien-1-yl acetate, octadeca-3, 13-dien-1-yl acetate, he Kangbi, coconut Rhinocerotis sinensis aggregation pheromone, felercanidine, triamcinolone, edible fungus methyl attractant alcohol, tetradec-11-en-1-yl acetate, mediterranean fruit fly attractant A, and Mediterranean fruit fly attractant B ₁ Mediterranean fruit fly attractant B ₂ The attractant C, trunc-call, 2- (octylthio) -ethanol, deet, butoxy (polypropylene glycol), dibutyl adipate, dibutyl phthalate, dibutyl succinate, deet, mosquito repellent, dimethyl phthalate, ethylhexyl glycol, hexylurea, mequintin, methyl neodecanoamide, oxamate, pacific, 1-dichloro-1-nitroethane, 1-dichloro-2, 2-bis (4-ethylphenyl) -ethane, 1, 2-dichloropropane and 1, 3-dichloropropene, 1-bromo-2-chloroethane, 2-trichloro-1- (3, 4-dichlorophenyl) ethyl acetate 2, 2-Dichloroethylene 2-ethylsulfinylethyl methyl phosphate, 2- (1, 3-dithiolan-2-yl) phenyldimethylcarbamate, 2- (2-butoxyethoxy) ethyl thiocyanate, 2- (4, 5-dimethyl-1, 3-dioxolan-2-yl) phenylmethylcarbamate, 2- (4-chloro-3, 5-xylyloxy) ethanol, 2-chlorovinyldiethyl phosphate, 2-imidazolidinone, 2-isovalerylindan-1, 3-dione, 2-methyl (prop-2-ynyl) aminophenylmethylcarbamate, 2-thiocyanoethyl laurate, 3-bromo-1-chloroprop-1-en, 3-methyl-1-phenylpyrazol-5-yl dimethyl-carbamate, 4-methyl (prop-2-ynyl) amino-3, 5-xylylmethyl carbamate, 5-dimethyl-3-oxocyclohex-1-enyl dimethyl carbamate, acephate, acrylonitrile, airy disk, alopecin, carbofuran, alpha-ecdysone, aluminum phosphide, methomyl, anabasine, methidathion (ath), picoline, bacillus thuringiensis delta-endotoxin, barium hexafluorosilicate, barium polysulfide, fumigating pyrethrin, bayer 22/190, bayer 22408, beta-cyhalothrin, pencycurthrin (bioethofenthrin), biochlorethrene, bis (2-chloroethyl) ether, borax, brombenfop, bromo-DDT, synthetic pesticide, worm, termitophos (buthiofos), butyl, arsenic calcium arsenate, Calcium cyanide, carbon disulfide, carbon tetrachloride, bardan hydrochloride, celebrity (cervadine), borneol, chlordane, decachloroketone, chloroform, chloropicrin, chlorpyrifos, chlorzophos, cis-bifenthrin (cis-resmethrin), cis-bifenthrin (cismethrin), fenvalerate (cloythrin), copper acetylarsenite, copper arsenate, copper oleate, livestock phosphorus (coumesilate), cryolite, CS 708, benzonitrile phosphorus, cartoneitrile, cyclosulfamethoxazole, d-tetramethrin, DAEP, dauron, desmethyl carbofuran, desmethyl, isochlorophosphorus, desmephos, dicresyl, cycloxaprin, dieldrin, diethyl 5-methylpyrazole-3-yl phosphate vinegar, coumestin (dior), tefram, permethrin, methoprene, methyl, dichlorvos, prochloraz Pentaquone, delpofol, benomyl, fruit and vegetable phosphorus, thiopyran phosphorus, DSP, ecdysterone, EI 1642, EMPC, EPBP, etaphos, ethionine, ethyl formate, dibromoethane, dichloroethane, ethylene oxide, EXD, cyromazine, ethylbenzene, fenitrothion, oxamidine (fenoxacrim), pyrifos-methyl, fenitrothion, ethylbecfos, fluclobinon (fluclofuron), fenbenfofos, fos-methyl, busulfan, furbenfuracarb, anti-pyrethrum, biguanide octone, biguanide octoate, sodium tetrathiocarbonate, benomyl, HCH, HEOD, heptachlorpyrifos, HHDN, hydrocyan, quinoline, IPSP, cloxazole, carbochlor-methyl, isoprothiolane, transplanting isoprothiolane, fenoxaprop-p, juvenile hormone I, juvenile hormone II, juvenile hormone III, chlorpyrifos, methoprene, lead arsenate, bromophenyl phosphorus, pyridalyl, fosthiazate, m-isopropylphenyl methyl carbamate, magnesium phosphide, azido phosphorus, methylparaben, aphos, pirimiphos, mercurous chloride, methylsulfoxide phosphorus, wilacre potassium salt, wilacre sodium salt, methylsulfonyl fluoride, butenyl phosphorus, methoprene, methothrin, methoxam, methyl isothiocyanate, methyl chloroform, methylene chloride, oxadiazon, miracle, nepropeptide phosphorus, naphthalene, NC-170, nicotine sulfate, nitrothiazine, orthonicotine, O-5-dichloro-4-iodophenyl O-ethyl thiophosphonate, O-diethyl O-4-methyl-2-oxo-2H-benzopyran-7-yl thiophosphonate, O-diethyl O-6-methyl-2-propylpyrimidin-4-yl thiophosphonate O, O, O, O ', O' -tetrapropyldithiopyrophosphate, oleic acid, p-dichlorobenzene, methylparathion, pentachlorophenol, pentachlorophenyl laurate, pH 60-38, fenthion, parathion, phosphine, methylphosphos, methamidophos, polychlorinated dicyclopentadiene isomers, potassium arsenite, potassium thiocyanate, precocin I, precocin II, precocin III, amidephyriphos, profluthrin, mevalonate, profluthrin, pirfenphos, antichlorethamate, quassia extract (quassia), quetiapine-methyl, tranin, iodisalazine, benfurthrin, rotenone, thienyl, rypsin, rimexosin, sabadilla, octamethyl, clarina, SI-0009, bupropion, sodium arsenite, sodium cyanide, sodium fluoride, sodium hexafluorosilicate, sodium pentachlorophenol, sodium selenate sodium thiocyanate, sulfometuron (sulfenuron), sulfometuron sodium salt (sulfenuron-sodium), sulfuryl fluoride, thiopropate, tar, thiodicarb, TDE, butyl pyrimidyl, dithiophosphate, cycloprothrin, tetrachloroethane, ticlophos, thiocyclam oxalate, benfot-butyl, monosultap, tetrabromothrin, permethrin, triazamate, isoprothioyl-3 (trichlorethos-3), chlorpyrifos, mixed carbofuran, triflumuron-methyl, chlorpyrifos, methoprene, veratrine, XMC, tamilin (zetamethrin), zinc phosphide, fenpyrad, and fluretofenprox, tetrafluoro-thrin, bis (tributyltin) oxide, bromoacetamide, ferric phosphate, niclosamide-ethanolamine, tributyltin oxide, pyrimorph, snail, 1, 2-dibromo-3-chloropropane, 1, 3-dichloropropene, 3, 4-dichlorotetrahydrothiophene 1, 1-dioxide, 3- (4-chlorophenyl) -5-methyl-rhodanine, 5-methyl-6-thio-1, 3, 5-thiadiazin-3-yl acetic acid, 6-isopentenyl aminopurine, 2-fluoro-N- (3-methoxyphenyl) -9H-purin-6-amine, hydrochlorothiazide, cytokinin, DCIP, furfural, isoamidophosphorus, kinetin Myrothecium verrucosum composition, tetrachlorothiophene, xylenol, zeatin, potassium ethylxanthate, alamic acid type benzene-S-methyl, giant knotweed extract, alpha-chlorohydrin, antoin, barium carbonate, bismurine urea, bromarone, chloromurine ketone, chloroindole hydrazide, cholecalciferol, chlororodenticide, crizophos, naphthacene, pyrimidyl, Dekk, thiabendazole, diphacin, calciferol, flumetline, fluoroacetamide, flumetsulam hydrochloride, moroxydine, duroman, phosphorus, trazodone, mevalonate, chives glucoside, sodium fluoroacetate, thallium sulfate, warfarin, 2- (2-butoxyethoxy) ethyl piperonate, 5- (1, 3-benzodioxol-5-yl) -3-hexylcyclohex-2-enone, farnesol with nerolidol, synergistic alkynylether, MGK 264, piperonyl butoxide, synergistic aldehyde, propyl isomer, S421, synergistic powder, sesamin, sulfoxide, anthraquinone, copper naphthenate, copper king, dicyclopentadiene, celen, zinc naphthenate, ziram, clothing Ma Ning, ribavirin, mercuric oxide, thiophanate, azaconazole, bitertanol, furfuryl azole, cyproconazole, difenoconazole diniconazole, epoxiconazole, fenbuconazole, fluquinconazole, flusilazole, flutriafol, furametpyr, hexaconazole, imazalil, imibenconazole, ipconazole, metconazole, myclobutanil, paclobutrazol, fenoxanil, penconazole, prothioconazole, pyribenzoxim (pyrifenox), prochloraz, propiconazole, cyproconazole, simeconazole, tebuconazole, trifluoperazole, triazolone, fluquinconazole, triticonazole, pyrimidol, chlorpyrimidol, fluben-zil, bupirimate (bupirimate), metidine (dimetirimol), ethirimol, dodine, fenpropidin, fenpropimorph, spiroxamine, tridemorph, cyprodinil, pyrimethanil (pyrimethadone), fenpyr-ethyl, fludioxonil, ben-methyl (pyrimethadone), furalaxyl (furalaxyl), metalaxyl, R-metalaxyl, furalamide, oxadixyl (oxadixyl), carbendazim, prochloraz (debacarb), corncob, thiabendazole, ethiprole (chlorozolate), sclerotium (dichlozole), myclobutanil (myclobutanil), procymidone (procymidone), ethephon (vinclozole), boscalid (boscalid), carboxin, formamide, fluoroamide (flutolanil), fenbuconazole, trifluralin (myclobutanil), trifluralin (prochloraz), trifluralin (trichlungin), trifluralin (ciclovil), trifluralin (ciclovir), triflumizoline (ciclovir), and the like the composition comprises metolachlor, carboxin oxide, penthiopyrad, thifluzamide, docusate, biguanide octyl amine, azoxystrobin, dimoxystrobin, enestroburin trifloxystrobin, fluoxastrobin, kresoxim-methyl, phenoxymycylamine, trifloxystrobin, orysastrobin, picoxystrobin, pyraclostrobin, thiram Mancozeb, metiram, zineb, captan, zofurben, folpet, dimetan, dichlormid, berdor, cupric oxide, mancozeb, quinocopper, phthalyl, kewen san, iprobenfos, clomiphos, tolclofos, dichlormid, benthiavalicarb, blasticidin (blast), triclopyr, chlorothalonil, cycloflufenamide, cymoxanil, cyclo Ding Fujun amine (cyclob), dicyclopyralid (dicycloset), pyridaben (dicyclomazine), chloranide (dicycloparan), diethofencarb, dimethomorph, dithianon (ethionamide), ethaboxam, hymexazol (etril), oxazamide, imidazolone (famefen) Pyricularia amide (fenoxanil), azoxystrobin (ferimzone), fluazinam (fluazinam), fluopyram (fluopiride), sulfenamide (fluvulfamide), fluxapyroxamide (fluazinam), cyproconazole, fosetyl-aluminum (fosetyl-aluminum), hymexazol (hymexazol), propineb, racetamide (cyazofamid), sulfenpyrad (metafurocarb), benomyl, pencycuron (pencycuron), phthalide, polyoxin (polyoxin), propamocarb (propamocarb), pyrifenoxaprop (fluquinconazole), fluquinconazole (pyroquindoxide), pyriflufenamide (pyrifenone), quintoxyl, pentachloronitrobenzene, thiazamide, imidazoxide, tricyclazole, oxazin, validamycin, valicarb, benomyl (flufenamid), flufenamid), flubeneteramide (Flubeneteram), isopyrazam, sedaxane (sedaxane), benzovindiflupyr, fluxazoxamide, 3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid (3 ',4',5' -trifluoro-biphenyl-2-yl) -amide, ifosfropylamine (isoflucypram), isothiabendamine, dipivemazine, 6-ethyl-5, 7-dioxo-pyrrolo [4,5 ] ][1,4]Dithiino [1,2-c ]]Isothiazole-3-carbonitrile, 2- (difluoromethyl) -N- [ 3-ethyl-1, 1-dimethyl-indan-4-yl]Pyridine-3-carboxamide, 4- (2, 6-difluorophenyl) -6-methyl-5-phenyl-pyridazine-3-carbonitrile, (R) -3- (difluoromethyl) -1-methyl-N- [1, 3-trimethylindan-4-yl]Pyrazole-4-carboxamide, 4- (2-bromo-4-fluoro-phenyl) -N- (2-chloro-6-fluoro-phenyl) -2, 5-dimethyl-pyrazol-3-amine, 4- (2-bromo-4-fluorophenyl) -N- (2-chloro-6-fluorophenyl) -1, 3-dimethyl-1H-pyrazole-5-amine, fludanazol (flupinaphyr), azoxystrobin (jiaxiangjunzhi), rithmidine (lvbenmixin), dichlorobenzothiazole (dichlobrazox), mandersbin (manderstrobin), 3- (4, 4-difluoro-3, 4-dihydro-3, 3-dimethylisoquinolin-1-yl) quinolone, 2- [ 2-fluoro-6- [ (8-fluoro-2-methyl-3-quinolinyl) oxy]Phenyl group]Propan-2-ol, thiapiprazole (oxathiapiprolin), N- [6- [ [ [ (1-methyltetrazol-5-yl) -phenyl-methylene]Amino group]Oxymethyl group]-2-pyridyl group]Tert-butyl carbamate, bixafen (pyraziflumid), fipronil (inpyrfluxam), tert-Luo Kapu (trolprocarb), penfluconazole, ipfentrifluoroazole (ipfentrifluoroazole), 2- (difluoromethyl) -N- [ (3R) -3-ethyl-1, 1-dimethyl-indan-4-yl ]Pyridine-3-carboxamide, N '- (2, 5-dimethyl-4-phenoxy-phenyl) -N-ethyl-N-methyl-carboxamide, N' - [4- (4, 5-dichlorothiazol-2-yl) oxy-2, 5-dimethyl-phenyl ]]-N-ethyl-N-methyl-formamidine, [2- [3- [2- [1- [2- [3, 5-bis (difluoromethyl) pyrazol-1-yl ]]Acetyl group]-4-piperidinyl]Thiazol-4-yl]-4, 5-dihydro-isoxazol-5-yl]-3-chloro-phenyl]Methanesulfonate, N- [6- [ [ (Z) - [ (1-methyltetrazol-5-yl) -phenyl-methylene]Amino group]Oxymethyl group]-2-pyridyl group]But-3-ynylcarbamate and N- [ [5- [4- (2, 4-dimethylphenyl) triazol-2-yl ]]-2-methyl-phenyl]Methyl group]Methyl carbamate, 3-chloro-6-methyl-5-phenyl-4- (2, 4, 6-trifluorophenyl) pyridazine, picolinic acid chloride (pyridamometyl), 3- (difluoromethyl) -1-methyl-N- [1, 3-trimethylindan-4-yl]Pyrazole-4-carboxamide, 1- [2- [ [1- (4-chlorophenyl) pyrazol-3-yl ]]Oxymethyl group]-3-methyl-phenyl]-4-methyl-tetrazol-5-one, 1-methyl-4- [ 3-methyl-2- [ [ 2-methyl-4- (3, 4, 5-trimethylpyrazol-1-yl) phenoxy ]]Methyl group]Phenyl group]Tetrazol-5-one, aminopyrafen (amipyrifen), zoxamide, amisulbrom, penflufen, (Z, 2E) -5- [1- (4-chlorophenyl) pyrazol-3-yl]oxy-2-methoxyimino-N, 3-dimethyl-pent-3-enamine, fluopicolide (floylpicolinamid), benomyl (fenicoxamid), iso Ding Yiyang quinoline, ifenfluquin (ipflufenoquin), quinine (quinofumelin), ipratropium, N- [2, 4-dichloro-phenoxy ]Phenyl group]-3- (difluoromethyl) -1-methyl-pyrazole-4-carboxamide, N- [2- [ 2-chloro-4- (trifluoromethyl) phenoxy ]]Phenyl group]-3- (difluoromethyl) -1-methyl-pyrazole-4-carboxamide, benzothiopheneEsters, myclobutanil, 5-amino-1, 3, 4-thiadiazole-2-thiol zinc salt (2:1), fluopyram, fluoxastrobin, fluoroether bacteria amide, pyriproxyfen (pyraproyne), piprazole (picarbazox), 2- (difluoromethyl) -N- (3-ethyl-1, 1-dimethyl-indan-4-yl) pyridine-3-carboxamide, 2- (difluoromethyl) -N- ((3R) -1, 3-trimethylindan-4-yl) pyridine-3-carboxamide, 4- [ [6- [2- (2, 4-difluorophenyl) -1, 1-difluoro-2-hydroxy-3- (1, 2, 4-triazol-1-yl) propyl]-3-pyridyl]Oxy group]Benzonitrile, formyltetraproline (Metylestraprole), 2- (difluoromethyl) -N- ((3R) -1, 3-trimethylindan-4-yl) pyridine-3-carboxamide, α - (1, 1-dimethylethyl) - α - [4'- (trifluoromethoxy) [1,1' -diphenyl]-4-yl]-5-pyrimidinecanol, fluoro Sha Puluo forest (fluoxaapipin), enestroburin (enoxarotrobin), 4- [ [6- [2- (2, 4-difluorophenyl) -1, 1-difluoro-2-hydroxy-3- (1, 2, 4-triazol-1-yl) propyl ]]-3-pyridyl]Oxy group]Benzonitrile, 4- [ [6- [2- (2, 4-difluorophenyl) -1, 1-difluoro-2-hydroxy-3- (5-sulfanyl-1, 2, 4-triazol-1-yl) propyl ] ]-3-pyridyl]Oxy group]Benzonitrile, 4- [ [6- [2- (2, 4-difluorophenyl) -1, 1-difluoro-2-hydroxy-3- (5-thio-4H-1, 2, 4-triazol-1-yl) propyl ]]-3-pyridyl]Oxy group]Benzonitrile, trinexapac-ethyl, coumoxystrobin, mesogenic, thiabendazole, zinc thiazole, a Mi Tuolin (amectotraction), iprodione, N-octyl-N' - [2- (octylamino) ethyl]Ethane-1, 2-diamine, N' - [ 5-bromo-2-methyl-6- [ (1S) -1-methyl-2-propoxy-ethoxy ]]-3-pyridyl]-N-ethyl-N-methyl-formamidine, N' - [ 5-bromo-2-methyl-6- [ (1R) -1-methyl-2-propoxy-ethoxy ]]-3-pyridyl]-N-ethyl-N-methyl-formamidine, N' - [ 5-bromo-2-methyl-6- (1-methyl-2-propoxy-ethoxy) -3-pyridinyl]-N-ethyl-N-methyl-formamidine, N' - [ 5-chloro-2-methyl-6- (1-methyl-2-propoxy-ethoxy) -3-pyridinyl]-N-ethyl-N-methyl-formamidine, N' - [ 5-bromo-2-methyl-6- (1-methyl-2-propoxy-ethoxy) -3-pyridinyl]-N-isopropyl-N-methyl-formamidine (these compounds may be prepared by the method described in WO 2015/155075); n' - [ 5-bromo-2-methyl-6- (2-propoxypropoxy) -3-pyridinyl]-N-ethyl-N-methyl-formamidine (this compound can be prepared by the method described in IPCOM 000249876D); N-isopropyl-N' - [ 5-methoxy-2-methyl-4- (2, 2-trifluoro-1-hydroxy-1-phenyl-ethyl) phenyl ]-N-methyl-formamidine, N' - [4- (1-cyclopropyl-2, 2-trifluoro- ]1-hydroxy-ethyl) -5-methoxy-2-methyl-phenyl]-N-isopropyl-N-methyl-formamidine (these compounds may be prepared by the methods described in WO 2018/228896); N-ethyl-N' - [ 5-methoxy-2-methyl-4- [ 2-trifluoromethyl) oxetan-2-yl]Phenyl group]-N-methyl-formamidine, N-ethyl-N' - [ 5-methoxy-2-methyl-4- [ 2-trifluoromethyl) tetrahydrofuran-2-yl]Phenyl group]-N-methyl-formamidine (these compounds may be prepared by the methods described in WO 2019/110427); n- [ (1R) -1-benzyl-3-chloro-1-methyl-but-3-enyl]-8-fluoro-quinoline-3-carboxamide, N- [ (1S) -1-benzyl-3-chloro-1-methyl-but-3-enyl]-8-fluoro-quinoline-3-carboxamide, N- [ (1R) -1-benzyl-3, 3-trifluoro-1-methyl-propyl]-8-fluoro-quinoline-3-carboxamide, N- [ (1S) -1-benzyl-3, 3-trifluoro-1-methyl-propyl]-8-fluoro-quinoline-3-carboxamide, N- [ (1R) -1-benzyl-1, 3-dimethyl-butyl]-7, 8-difluoro-quinoline-3-carboxamide, N- [ (1S) -1-benzyl-1, 3-dimethyl-butyl]-7, 8-difluoro-quinoline-3-carboxamide, 8-fluoro-N- [ (1R) -1- [ (3-fluorophenyl) methyl]-1, 3-dimethyl-butyl]Quinoline-3-carboxamide, 8-fluoro-N- [ (1S) -1- [ (3-fluorophenyl) methyl]-1, 3-dimethyl-butyl ]Quinoline-3-carboxamide, N- [ (1R) -1-benzyl-1, 3-dimethyl-butyl]-8-fluoro-quinoline-3-carboxamide, N- [ (1S) -1-benzyl-1, 3-dimethyl-butyl]-8-fluoro-quinoline-3-carboxamide, N- ((1R) -1-benzyl-3-chloro-1-methyl-but-3-enyl) -8-fluoro-quinoline-3-carboxamide, N- ((1S) -1-benzyl-3-chloro-1-methyl-but-3-enyl) -8-fluoro-quinoline-3-carboxamide (these compounds may be prepared by the methods described in WO 2017/153380); 1- (6, 7-dimethylpyrazolo [1, 5-a)]Pyridin-3-yl) -4, 5-trifluoro-3, 3-dimethyl-isoquinoline, 1- (6, 7-dimethylpyrazolo [1,5-a ]]Pyridin-3-yl) -4, 6-trifluoro-3, 3-dimethyl-isoquinoline, 4-difluoro-3, 3-dimethyl-1- (6-methylpyrazolo [1,5-a ]]Pyridin-3-yl) isoquinolines, 4-difluoro-3, 3-dimethyl-1- (7-methylpyrazolo [1, 5-a)]Pyridin-3-yl) isoquinolines, 1- (6-chloro-7-methyl-pyrazolo [1, 5-a)]Pyridin-3-yl) -4, 4-difluoro-3, 3-dimethyl-isoquinoline (these compounds may be prepared by the methods described in WO 2017/025510); 1- (4, 5-Dibenzoimidazol-1-yl) -4, 5-trifluoro-3, 3-dimethyl-isoquinoline, 1- (4, 5-Dibenzoimidazol-1-yl) -4, 4-difluoro-3, 3-dimethyl-isoquinoline, 6-chloro-4, 4-difluoro-3, 3-dimethyl-1- (4-methylbenzimidazol-1-yl) isoquinoline, 4-difluoro-room-energy conversion system 1- (5-fluoro-4-methyl-benzoimidazol-1-yl) -3, 3-dimethyl-isoquinoline, 3- (4, 4-difluoro-3, 3-dimethyl-1-isoquinolinyl) -7, 8-dihydro-6H-cyclopenta [ e ]]Benzimidazoles (these compounds may be prepared by the method described in WO 2016/156085); N-methoxy-N- [ [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl]Phenyl group]Methyl group]Cyclopropanecarboxamide, N, 2-dimethoxy-N- [ [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ]]Phenyl group]Methyl group]Propionamide, N-ethyl-2-methyl-N- [ [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ]]Phenyl group]Methyl group]Propionamide, 1-methoxy-3-methyl-1- [ [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ]]Phenyl group]Methyl group]Urea, 1, 3-dimethoxy-1- [ [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ]]Phenyl group]Methyl group]Urea, 3-ethyl-1-methoxy-1- [ [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ]]Phenyl group]Methyl group]Urea, N- [ [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl]Phenyl group]Methyl group]Propionamide, 4-dimethyl-2- [ [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ]]Phenyl group]Methyl group]Isoxazolidin-3-one, 5-dimethyl-2- [ [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ]]Phenyl group]Methyl group]Isoxazolidin-3-one, 1- [ [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ] ]Phenyl group]Methyl group]Pyrazole-4-carboxylic acid ethyl ester, N-dimethyl-1- [ [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ]]Phenyl group]Methyl group]-1,2, 4-triazol-3-amine (these compounds may be prepared by the methods described in WO 2017/055473, WO 2017/055469, WO 2017/093348 and WO 2017/118689); 2- [6- (4-chlorophenoxy) -2- (trifluoromethyl) -3-pyridyl]-1- (1, 2, 4-triazol-1-yl) propan-2-ol (this compound may be prepared by the method described in WO 2017/029179); 2- [6- (4-bromophenoxy) -2- (trifluoromethyl) -3-pyridinyl]-1- (1, 2, 4-triazol-1-yl) propan-2-ol (this compound may be prepared by the method described in WO 2017/029179); 3- [2- (1-chlorocyclopropyl) -3- (2-fluorophenyl) -2-hydroxy-propyl]Imidazole-4-carbonitrile (this compound may be prepared by the method described in WO 2016/156290); 3- [2- (1-chlorocyclopropyl) -3- (3-chloro-2-fluoro-phenyl) -2-hydroxy-propyl]Imidazole-4-carbonitrile (this compound may be prepared by the method described in WO 2016/156290); 2-amino-6-methyl-pyridine-3-carboxylic acid (4-phenoxyphenyl) methyl ester (this compound may be prepared by the method described in WO 2014/006945); 2, 6-dimethyl-1H, 5H- [1,4 ]]Dithiino [2,3-c:5,6-c ]']Dipyrrole-1, 3,5,7 (2H, 6H) -tetratones (this compound may be prepared by the method described in WO 2011/138281), N-methyl-4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ]Thiobenzamide; n-methyl-4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl]Benzamide; (Z, 2E) -5- [1- (2, 4-dichlorophenyl) pyrazol-3-yl]oxy-2-methoxyimino-N, 3-dimethyl-pent-3-enamine (this compound may be prepared by the method described in WO 2018/153707); n' - (2-chloro-5-methyl-4-phenoxy-phenyl) -N-ethyl-N-methyl-formamidine; n' - [ 2-chloro-4- (2-fluorophenoxy) -5-methyl-phenyl ]]-N-ethyl-N-methyl-formamidine (this compound may be prepared by the method described in WO 2016/202742); 2- (difluoromethyl) -N- [ (3S) -3-ethyl-1, 1-dimethyl-indan-4-yl]Pyridine-3-carboxamide (this compound may be prepared by the method described in WO 2014/095675); (5-methyl-2-pyridinyl) - [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ]]Phenyl group]Methanones, (3-methylisoxazol-5-yl) - [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ]]Phenyl group]Methanones (these compounds may be prepared by the methods described in WO 2017/220485); 2-oxo-N-propyl-2- [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl]Phenyl group]Acetamide (this compound may be prepared by the method described in WO 2018/065414); 1- [ [5- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl]-2-thienyl]Methyl group ]Pyrazole-4-carboxylic acid ethyl ester (this compound can be prepared by the method described in WO 2018/158365); 2, 2-difluoro-N-methyl-2- [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl]Phenyl group]Acetamide, N- [ (E) -methoxyiminomethyl]-4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl]Benzamide, N- [ (Z) -methoxyiminomethyl]-4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl]Benzamide, N- [ N-methoxy-C-methyl-carboximino]-4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl]Benzamide (these compounds may be prepared by the methods described in WO 2018/202428).

The compounds of the invention may also be used in combination with anthelmintic agents. Such anthelmintic agents include compounds selected from the group consisting of macrolides, such as ivermectin, abamectin, emamectin, eprinomectin, doramectin, selamectin, moxidectin, nemulin and milbemycin derivatives, as described in EP-357460, EP-444964 and EP-594291. Additional anthelmintic agents include semisynthetic and biosynthetic avermectin/milbemycin derivatives such as those described in U.S. Pat. No. 3,124, 9415944 and WO-9522552. Additional anthelmintic agents include benzimidazoles such as albendazole, candidazole, fenbendazole, flubendazole, mebendazole, oxfendazole, oxbendazole, pamidazole and other members of this class. Additional anthelmintic agents include imidazothiazoles and tetrahydropyrimidines such as tetraimidazole, levamisole, thiopyrimidine pamoate, octotel or morantel. Additional anthelmintic agents include flukicides (e.g., triclabendazole and closuluron) and tapecides (e.g., praziquantel and exenatide).

The compounds of the present invention may be used in combination with derivatives and analogues of the para Hao Kui amide/marcfortine anthelmintic agents, as well as antiparasitic oxazolines such as those disclosed in US-5478855, US-4639771 and DE-19520936.

The compounds of the invention may be used in combination with derivatives and analogues of the general class of dioxomorpholines antiparasitic agents (as described in WO 96/15121) and also with anthelmintically active cyclic depsipeptides (as described in WO 96/11945, WO 93/19053, WO 93/25543, EP 0 626 375, EP 0 382 173, WO 94/19334, EP 0 382 173 and EP 0 503 538).

The compounds of the invention may be used in combination with other ectoparasiticides; for example fipronil; a pyrethroid; an organic phosphate; insect growth regulators such as lufenuron; ecdysone agonists such as tebufenozide and the like; neonicotinoids such as imidacloprid and the like.

The compounds of the present invention may be used in combination with terpene alkaloids, such as those described in International patent application publication No. WO 95/19363 or WO 04/72086, in particular the compounds disclosed therein.

Other examples of such bioactive compounds that may be used in combination with the compounds of the present invention include, but are not limited to, the following:

Organic phosphate: acephate, methyl piroxicam, ethyl phoxim, methyl phoxim, bromphos, ethyl phoxim, thiophos, chlorpyrifos, clofenapyr, endo-phos, endo-S-methyl, endo-phos-p-S-methylsulfone, chlorimphos, diazinon, dichlorvos, baizhi, dimethoate, ethahos, ethion, acephate, oxypyriphos, valaphos, benfophos, fenitrothion, fenthion, pirfenphos, dinotefuran, amon, fos-methyl, heptene, chlorzophos, iprophos, isoxazole, malathion fenphos, methamidophos, methidathion, methylparathion, acephate, monocrotophos, dibromophosphorus, omethoate, methyl oxo-endophos, paraoxon, parathion, methylparathion, phenthoate, phoxim, iminophos, phosphamidon, phorate, oxime phophos, chlorfenphos-methyl, profenofos, proetamphos, propylthiophos, pyrazophos, pyridazinethion, quinophos, thiophos, temephos, terbufos, butyl pyrifos, setrofos, dimethos (thimeton), triazophos, trichlorfon, aphos.

Urethane: carbofuran, aldicarb, 2-sec-butylphenyl methyl carbamate, carbosulfan, carbaryl, carbosulfan, ethiprole, fenoxycarb, fentanyl, furacarb, HCN-801, isoprocarb, indoxacarb, methomyl, 5-methyl-m-isopropylbutachlor (methyl) carbamate, carbosulfan, pirimicarb, propoxur, thiodicarb, monocrotocarb, triazamate, UC-51717.

Pyrethroid: fluoroallethrin, allyl pyrethrin, cis-cypermethrin, 5-benzyl-3-furanmethyl (E) - (1R) -cis-2, 2-dimethyl-3- (2-oxothiolane-3-ylidenemethyl) cyclopropanecarboxylate, bifenthrin, beta-cyfluthrin, alpha-cyfluthrin, beta-cyfluthrin, bio-propethrin ((S) -cyclopentyl isomer), bio-bifenthrin, NCI-85193, beta-cythrin, lambda-cyhalothrin, cyphenothrin, deltamethrin cyhalothrin, fenvalerate, ethofenprox, pencythrin, fenpropathrin (D isomer), prallethrin, lambda-cyhalothrin, permethrin, phenothrin, propathrin, pyrethrin (natural product), bifenthrin, tetramethrin, tefluthrin, theta-cypermethrin, silafluothrin, t-cyhalothrin, tefluthrin, zeta-cypermethrin.

Arthropod growth regulator: a) Chitin synthesis inhibitor: benzoyl urea: chlorfluazuron, chlorpyrifos, flufenuron, triflumuron, chlorfenouron, diphenofluazuron, chlorfluazuron, buprofezin, fenpropiron, hexythiazox, etoxazole, clofentezine; b) Ecdysone antagonists: chlorantraniliprole, methoxyfenozide and tebufenozide; c) Juvenile hormone analogs: pyriproxyfen, methoprene (including S-methoprene), fenoxycarb; d) Lipid biosynthesis inhibitors: spirodiclofen.

Other antiparasitic agents: acarquinone, amitraz, AKD-1022, ANS-118, azadirachtin, bacillus thuringiensis, monosulfuron, bifenazate, lefenpyrad, fenisobromolate, BTG-504, BTG-505 toxafen, cartap, fenamate, acetamiprid, chlorfenapyr, chromafenozide, clothianidin, cyprodinil, diuron, chlorfenapyr DBI-3204, dipyr, dihydroxymethyl dihydroxypyrrolidine, diquat, captan, ethiprole, ethofenprox, fenazaquin, flufenzine (flumite), MTI-800, fenpyroximate, azoxystrobin, flufenpyrad, trifloxystrobin, flufenzine, trifluoperazone, benzyl fenpyrad (fluprofexyfen), benzyl fenpyrad (halofenprox), fenbucin (halofenox) Fluor-hydrazone, IKI-220, kenali, NC-196, mentha indicum (neem guard), nedinotefuran (nidinoterrestrran), nitenpyram, SD-35651, WL-108477, pyridalyl, propargite, protriafen, pymetrozine, pyridaben, pyriminobac-methyl, NC-1111, R-195, RH-0345, RH-2485, RYI-210, S-1283, S-1833, SI-8601, flusilate, silicon Luo Mating (silomadine), spinosad, tebufenpyrad, trichlorfon sulfone, tetramycin, thiacloprid, thiocyclam, tolfenpyrad, triazamate, triazophos, pyrifos, rotylen, YI-5301.

Biological agent: bacillus thuringiensis subtype Hua Yachong (Bacillus thuringiensis ssp aizawai), bacillus thuringiensis subspecies kurstaki (kurstaki), bacillus thuringiensis delta endotoxins, baculoviruses, entomopathogenic bacteria, viruses and fungi.

Bactericides: aureomycin, oxytetracycline, streptomycin.

Other biological agents: enrofloxacin, febantel, penoxsulam, meloxicam, cefalexin, kanamycin, piroxicam, clenbuterol, omeprazole, tiamulin, benazepril, pi Ruipu (pyriproxole), cefquinome, florfenicol, buserelin, ceftazidime, tolametin, ceftiofur (ceftiour), carprofen, metaflumizone, praziquantel, triclabendazole, fluoromethanesulfonm (fluxytioconazole), flufenoxadifam, mevalicarb Kang Mide (metacarpicoxamid).

The following mixtures of compounds of formula (I) with active ingredients are preferred. The abbreviation "TX" means one compound selected from the group consisting of the compounds as shown in tables A1 to A5 or table E (below), i.e. one of the compounds e.01 to e.25:

a compound selected from the group consisting of: petroleum oil+TX, 1-bis (4-chlorophenyl) -2-ethoxyethanol+TX, 2, 4-dichlorophenyl benzenesulfonate+TX, 2-fluoro-N-methyl-N-1-naphthylacetamide+TX, 4-chlorophenyl phenyl sulfone+TX, acetylfipronil+TX, aldicarb+TX, racetrack+TX, cyenophos+TX, amine phosphorus+TX, amine phosphorus oxalate+TX, amitraz+TX, acaricide+TX, arsenic trioxide+TX, azobenzene+TX, azo phosphorus+TX, benomyl+TX, feno Sha Lin (benoxafos) +TX, benzyl benzoate+TX, bipyramid+TX deltamethrin + TX, bromenamid + TX, bromthiophos + TX, bromacarb + TX, buprofezin + TX, butocarb + TX, calcium polysulfide + TX, octachlorocamphene + TX, chlorfenamic + TX, trithion + TX, acarb + TX, pyrifos + TX Dermatophagoides+TX, chlorfenapyr+TX, chlorfenamidine+TX, chlorfenapyr+TX, chlormeuron+TX, propyl ester acaricidal+TX, chlorfenapyr +TX, guathrin I+TX, guathrin II+TX, guathrin+TX, clomiphene+TX, coumaphos+TX, thiazate+TX, carprofen+TX, DCPM+TX, DDT+TX, tourette+TX, tourette-O+TX, tourette-S+TX, endophosphate-methyl+TX, endophosphate-O+TX, endophosphate-O-methyl+TX, endophosphate-S+TX, O-methyl the composition comprises a compound of the components of the composition, i.e. a combination of a endo-S-methyl+TX, an endo-S-methyl sulfone+TX, a bacteriostatic+TX, a dichlorvos+TX, a dicarboxyphosphite (dicyclophos) +TX, a acaricide+TX, a methophos+TX, a phenol (dinex) +TX, a phenol (dinex-dicylexine) +TX, a chlorpyrifos-4+TX, a chlorpyrifos-6+TX, a chlorpyrifos-0+TX, a nitropentyl+TX, a nitrooctyl+TX, a nitrobutyl+TX, a chlorpyrifos-0 Dephos+TX, sulfodiphenyl+TX, vinasse+TX, DNOC+TX, phenoxymite (dofenapyn) +TX, doramectin+TX, cloisonne+TX, irinotetin+TX, yithiophos+TX, ethirimphos+TX, anti-fenbuconazole+TX, benbutatin+TX, benfuracarb+TX, fenfuron+TX, fenfurazamide+TX, flufurazamide (fenfurafanil) +TX, flufuracart+TX, flufuracarmide+TX, flufuracard+TX, FMC 1137+TX, valicamidine+TX, valicamidine hydrochloride+TX, carboxin (formalanate) +tx, gamma-HCH+TX, levant+TX, benfurameter+TX, hexadecyl cyclopropanecarboxylate+TX, fenphos+water, jasmine I+TX, jasmine II+TX, iodothiophosphor+TX, lindane+TX, propargite+TX, aphphos+TX, dithiphos+TX, methifen+TX, fenpropaphos+TX, bromomethane+TX, methomyl+TX, carbofuran+TX, milbexime+TX, propylamine fluoride+TX, monocrotophos+TX, cyclobalm+TX, moxidectin+TX, dibromophosphorus (naled) +TX, 4-chloro-2- (2-chloro-2-methyl-propyl) -5- [ (6-iodo-3-pyridinyl) methoxy ]pyridazin-3-one+TX, fluoroformin+TX, nicotycin+TX, pentocyanamide+TX, pentocyanamide 1:1 zinc chloride complex+TX, omethoate+TX, isoison+TX, sulfonate+TX, pp' -DDT+TX, parathion+TX, permethrin+TX, fenthion+TX, fungicide+TX, thiocyclophosphorus+TX, phosphamide+TX, turpentine chloride (polychlorotethers) +TX, acaricide (polynaphins) +TX, propiono+TX, carpesium+TX, propoxur+TX, ethionine+TX, sulfenphos+TX, pyrethrin I+TX, pyrethrin II+TX, pyrethrin+TX, pyridazinethion+TX, pyrithione+TX, quinalphos) +, quinalphos (quintefos) +TX,R-1492+TX, glyciphos+TX, rotenone+TX, octamethiphos+TX, captan+TX, selametin+TX, su Liu phosphorus+TX, SSI-121+TX, shu Feilun +TX, flubendiamide+TX, thiotepa+TX, sulfur+TX, flufenzine+TX, tau-flufenthrinate+TX, TEPP+TX, terbucarb+TX, tetraclomite sulfone+TX, miticidal+TX, thiafenox+TX, indoxacarb+TX, monocrotocarb+TX, mevalinate+TX, kemite+TX, threomycin+TX, weifenphos+TX, benfurin+TX, triazophos+TX, triazuron+TX, trimethox, tolfenpyr (vaniliprole) +tx, bailout+benfurin+tx, trioxazin+copper, copper dioctade+copper sulfate, copper sulfate+octode+TX Cyclobutyronitrile (cybutryne) +TX, dichlorophenone+TX, bischlorophenol+TX, chlorphenamine+TX, triphenyltin+TX, slaked lime+TX, metin+TX, algicidal quinone+TX, quinodown+TX, simazine+TX, triphenyltin acetate+TX, triphenyltin hydroxide+TX, livestock phosphorus+TX, piperazine+TX, thiophanate+TX, chloral candy+TX, beclomethan+TX, pyridin-4-amine+TX, strychnine+TX, 1-hydroxy-1H-pyridine-2-thione+TX, 4- (quinoxalin-2-ylamino) benzenesulfonamide+TX, 8-hydroxyquinoline sulfate+TX, bromonitro+TX, copper hydroxide+TX, cresol+TX, dipyr+TX, sodium dixine+TX, TX, formaldehyde+TX, mercuric oxide+TX, kasugamycin+TX, kasugamycin hydrochloride hydrate+TX, nickel bis (dimethyldithiocarbamate) TX, trichloromethyl pyridine TX, xin Saitong TX, oxolinic acid TX, terramycin TX, potassium hydroxyquinoline sulfate TX, thiabendazole TX, streptomycin sesquisulfate TX, leaf blight TX, thimerosal TX, brown moth GV TX, agrobacterium radiobacter TX, amblyseius species TX, apices noctuid NPV TX, primordica ptera small bee TX, short-pitch aphid small bee TX, cotton aphid parasitic bee TX, aphid gall midge TX, alfalfa silver moth NPV TX, cotton bud noctuid NPV TX Bacillus sphaericus+TX, beauveria bassiana+TX, chrysopa falcata+TX, cryptocarya mansoni+TX, codling moth GV+TX, siberian cocoon bee+TX, pisum sativum She Yingji bee+TX, aphis livida+TX, aphis citri+TX, aphis suis and Aphis filifolia+TX, alternaria alternata+TX, alternaria tangutica+TX, aphis lygus+TX, cabbage looper NPV+TX, huang Kuobing flea bee+TX, metarhizium anisopliae+TX, metarhizium anisopliae variant+TX, NPV and npv+tx, stinkbug species+tx, paecilomyces fumosius+tx, zhili small phytoseiulus+tx, mao Wen nematode+tx, strongylosis+tx, noctuid+tx, grignard+tx, rubis+tx, rickettsia (Steinernema riobravis) +tx, mole cricket+tx, stinkbug species+tx, trichogramma species+tx, westernon's spider+tx, verticillium spp+tx, tsetse species+tx, verticillium spp+tx, verticillium lecanii+tx, oxaziridine+tx, bis (aziridine) methylaminophosphine sulfide+tx busulfan+TX, dimetifur+TX, altretamine+TX, hexamethylphosphorus+TX, methylalder+TX, methylthioalder+TX, methylphosphinazine+TX, infertility+TX, fluvaluron+TX, alder+TX, thiohexamethylphosphorus+TX, thioalder+TX, tritamine+TX, urethanimine+TX, (E) -dec-5-en-1-yl acetate and (E) -dec-5-en-1-ol+TX, (E) -tridec-4-en-1-yl acetate+TX, (E) -6-methylhept-2-en-4-ol+TX, (E), Z) -tetradec-4, 10-dien-1-yl acetate +TX, (Z) -dodeca-7-en-1-yl acetate +TX, (Z) -hexadec-11-enal +TX, (Z) -hexadec-11-en-1-yl acetate +TX, (Z) -hexadeca-13-en-11-yn-1-yl acetate+TX, (Z) -eicosa-13-en-10-one+TX, (Z) -tetradeca-7-en-1-al+TX, (Z) -tetradeca-9-en-1-ol+TX, (Z) -tetradeca-9-en-1-yl acetate+TX, (7E, 9Z) -dodeca-7, 9-dien-1-yl acetate+TX, (9Z, 11E) -tetradeca-9, 11-dien-1-yl acetate+TX, (9Z, 12E) -tetradeca-9, 12-dien-1-yl acetate+TX, 14-methyl octadeca-1-en+TX, 4-methyl-non-5-ol and 4-methyl-non-5-one+TX alpha-polylysine +TX, cethomson bark beetle aggregate pheromone +TX, dodecadienol +TX, obtainable Mongolian +TX, seduction +TX, epoxynonadecane +TX, dodeca-8-en-1-yl acetate +TX, dodeca-9-en-1-yl acetate +TX, dodeca-8 +TX, 10-dien-1-yl acetate + TX, dominicalure +TX, 4-methyl ethyl octoate +TX, eugenol +TX, southern pine bark beetle aggregate pheromone +TX, decoy-alkene-mixture I +TX, decoy-mixture II +TX, trap mixture III+TX, trap mixture IV+TX, trap mixture +TX, bark beetle dienol+TX, small celandiol+TX, chafer sex attractant +TX, trimethyldioxy tricyclic nonane+TX, noctuid attractant (litlure) +TX, noctuid sex attractant +TX, trap ester +TX, meng Tuome g acid (megatomoic aci) d) +TX, sequoyitol+TX, lure+TX, octadeca-2, 13-dien-1-yl acetate+TX, octadeca-3, 13-dien-1-yl acetate+TX, he Kangbi +TX, cocois Rhinocandin+TX, feverfew+TX, lure+TX, sordidin+TX, edible fungus methyl lure+TX, tetradeca-11-en-1-yl acetate+TX, mediterranean fly lure+TX, mediterranean fly lure A+TX, and Mediterranean fly lure B ₁ +TX, mediterranean fruit fly attractant B ₂ +TX, drosophila attractant C+TX, barbamate (trunk-call) +TX, 2- (octylthio) -ethanol+TX, mosquito-repellent ketone+TX, butoxy (polypropylene glycol) +TX, dibutyl adipate+TX, dibutyl phthalate+TX, dibutyl succinate+TX, mosquito-repellent amine+TX, mosquito-repellent+TX, dimethyl phthalate+TX, ethylhexyl glycol+TX, hexylurea+TX, mequintin+TX, methyl neodecanoamide+TX, oxamate+TX, paceridine+TX, 1-dichloro-1-nitroethane+TX, 1-dichloro-2, 2-bis (4-ethylphenyl) -ethane+TX, 1, 2-dichloropropane and 1, 3-dichloropropene+TX 1-bromo-2-chloroethane+TX, 2-trichloro-1- (3, 4-dichlorophenyl) ethyl acetate+TX, 2-dichloroethylene 2-ethylsulfinylethyl methyl phosphate+TX, 2- (1, 3-dithiolan-2-yl) phenyldimethylcarbamate+TX, 2- (2-butoxyethoxy) ethylthiocyanate+TX, 2- (4, 5-dimethyl-1, 3-dioxolan-2-yl) phenylmethylcarbamate+TX, 2- (4-chloro-3, 5-xylyloxy) ethanol+TX, 2-chlorovinyldiethyl phosphate+TX, 2-imidazolidinone+TX, 2-isovalerindan-1, 3-dione+TX, 2-methyl (prop-2-ynyl) aminophenylmethylcarbamate+tx, 2-thiocyanoethyl laurate+tx, 3-bromo-1-chloroprop-1-ene+tx, 3-methyl-1-phenylpyrazole-5-yldimethyl-carbamate+tx, 4-methyl (prop-2-ynyl) amino-3, 5-xylylmethylcarbamate+tx, 5-dimethyl-3-oxocyclohex-1-enyl dimethylcarbamate+tx, acephate+tx, acrylonitrile+tx, airy agent+tx, alomycin+tx, carbofuran+tx, alpha-ecdysone+tx, aluminum+tx, carbofuran+tx, neonicotine+tx, ethylphosphine (ath) +tx, picoline+tx, bacillus thuringiensis delta-endotoxin+tx, barium hexafluorosilicate+tx, barium polysulfide+tx, fumigating pyrethrin+bayer+22/190+bayer+08, beta-chlorohydrin+22408 Fenvalerate+tx, beta-cypermethrin+tx, pencythrin (bioethanomethrin) +tx, biothrin+tx, bis (2-chloroethyl) ether+tx, borax+tx, bromophenphosphorus+tx, bromo-ddt+tx, methomyl+tx, livestock carbofuran+tx, tertiophos (bustathiofos) +tx, butyl phosphorus+tx, calcium arsenate+tx, calcium cyanide+tx, carbon disulfide+tx, carbon tetrachloride+tx, bardan hydrochloride+tx, sevalidine (cevadine) +tx, borneol+tx, chlordan+tx, decachloroketone+tx, chloroform+tx, chloropicrin+tx, chlorfenphos (chlorpyrizophos) +tx, cis-resmethrin+tx, benfurin+tx, fensin+tx, fenvalerate (c acid+copper acetyl, acetyl acid+copper copper arsenate+tx, copper oleate+tx, livestock phosphorus (coumatite) +tx, cryolite+tx, CS 708+tx, cyanophos+tx, fenitrothion+tx, cyclofenpyr+tx, acephate+tx, d-tetramethrin+tx, daep+tx, daron+tx, desmethylcarbofuran+tx, detrainer+tx, isochlorophosphorus+tx, detrainer+tx, dicresyl+tx, cyclophosphazen+tx, dieldrin+tx, diethyl 5-methylpyrazol-3-yl phosphate+tx, asthma (dior) +tx, tetramethrin+tx, dimetretinyl+tx, benzyl pyrethrin+tx, methylparaben+tx, dichlorvow+tx, procyanin+tx, pentanitol+tx, delphin+tx, benzofuran+tx, vegetable phosphorus+tx, thiopyran+tx, dsp+tx, eiketone+1642, and the like, EMPC+TX, EPBP+TX, ethohos+TX, ethylthiodicarb+TX, ethyl formate+TX, dibromoethane+TX, dichloroethane+TX, ethylene oxide+TX, EXD+TX, dermatophagoides+TX, ethylbenzene+TX, fenitrothion+TX, oxamidin (fenoxacrim) +TX, pyrifos+TX, fenitrothion+TX, ethylthiophos+TX, fluclobine (fludrofen) +TX, butylthiophos+TX, phosphoarsine+TX, butylcyclophos+TX, furben+TX, indomethacin+TX, biguanide+TX, biguanide octaacetate+TX, flubendioctam tetrathiocarbonate+TX, benzyl acarb+TX, HCH+TX, HEOD+TX, heptachlor+TX, bisultap+TX, HHTN+TX, hydrogen cyanide+TX, quinolinyl+TX, IPSP+TX, cloxaprop+TX, carbochlor+TX, isoeuclidean+TX, iso Liu Lin +TX, transplanting agent+TX, isoprothiolane+TX, oxazachlor+TX, juvenile hormone I+TX, juvenile hormone II+TX, juvenile hormone III+TX, chlorovalerate+TX, nitenpyram+TX, lead arsenate+TX, bromophenyl+TX, pyridaphos+TX, thiazolium+TX, m-isopropylphenyl methyl amino methyl Acid ester+TX, magnesium phosphide+TX, azidothioate+TX, methylparaben+TX, aphis sulfide+TX, mercurous chloride+TX, methiothioate+TX, metam+TX, metam potassium salt+TX, metam sodium salt+TX, methylsulfonyl fluoride+TX, butenyl phosphate+TX, methoprene+TX, methothrin+TX, methodol+TX, methyl isothiocyanate+TX, methyl chloroform+TX, dichloromethane+TX, oxadiazon+TX, imazalil+TX, nepentylphosphine+TX, naphthalene+TX, NC-170+TX, nicotine+TX, nicotine sulfate+TX, nitrothiazine+TX, primordial nicotine+TX, O-5-dichloro-4-iodophenyl O-ethyl thiophosphonate+TX, O-diethyl O-4-methyl-2-oxo-2H-benzopyran-7-yl thiophosphonate+TX, O, O-diethyl O-6-methyl-2-propylpyrimidin-4-yl thiophosphonate +TX, O, O ', O' -tetrapropyldithiopyrophosphate +TX, oleic +TX, p-dichlorobenzyl +TX, methyl parathion +TX, pentachlorophenol +TX, lauric pentachlorophenyl +TX, PH 60-38+TX, fenthion +TX, p-chlorthion +TX, phosphine +TX, methyl octylthiophos +TX, methamidophos +TX, polychlorinated dicyclopentadiene isomers +TX, potassium arsenite +TX, potassium thiocyanate +TX, precocin I +TX, precocin II +TX, precocin III +TX, amidpyriphos +TX, profenothrin +TX, mevalonate +TX, propylthiophos +TX, piroxicam +TX, anticoccidial-tetramethrin +TX, the extract of ramulus Et folium Picrasmae (quassia) +TX, quetiapine-methyl+TX, traning phosphorus+TX, iodosal+TX, benfurin+TX, rotenone+TX, thienyl+TX, rypsin+TX, rimidine+TX, rimexodine+TX, sabadilla+TX, octamethyl phosphorus+TX, keline+TX, SI-0009+TX, thiapropionitrile+TX, sodium arsenite+TX, sodium cyanide+TX, sodium fluoride+TX, sodium hexafluorosilicate+TX, sodium pentachlorophenate+TX, sodium selenate+TX, sodium thiocyanate+TX, sulfophenyl (sulfenuron) +TX, sulfophenyl sodium sulfonate-sodium salt (sulfenuron-sodium) +TX, sulfuryl fluoride+TX, thiophosphoryl+TX Tar+TX, thiamethoxam+TX, TDE+TX, butylpyrimidyl phosphorus+TX, dithiophosphorus+TX, cyclopentenepropithrin+TX, tetrachloroethane+TX, thiacloprid+TX, thiocyclam+TX, thiocyclam oxalate+TX, tebufos+TX, monosultap+TX, tetrabromothrin+TX, antichlorethrin+TX, triazamate+TX, isoparaffin-3 (trichlorethophos-3) +TX, toxaphos+TX, mixed carbofuran+TX, triflumuron carboxin (tolprocarb) +TX, chlorpyrifos+TX, nitenpyram+TX, veratrine+TX, XMC+TX, Zetamilin (zetamethrin) +tx, zinc phosphide+tx, tolfenpyrad+tx, halothrin+tx, tetrafluorotetramethrin+tx, bis (tributyltin) oxide+tx, bromoacetamide+tx, ferric phosphate+tx, niclosamide-ethanolamine+tx, tributyltin oxide+tx, pyrimorph+tx, snail+tx, 1, 2-dibromo-3-chloropropane+tx, 1, 3-dichloropropene+tx, 3, 4-dichlorotetrahydrothiophene 1, 1-dioxide+tx, 3- (4-chlorophenyl) -5-methyl-rhodamine+tx, 5-methyl-6-thio-1, 3, 5-thiadiazin-3-ylacetic acid+tx, 6-isopentenylaminopurine+tx, 2-fluoro-N- (3-methoxyphenyl) -9H-purin-6-amine+tx, phenylchlorthalide+tx cytokinin+tx, dcip+tx, furfurol+tx, isoamidophosph+tx, kinetin+tx, verruca-plaque composition+tx, tetrachlorothiophene+tx, xylenol+tx, zeatin+tx, potassium ethylxanthate+tx, alac benzene+tx, alac benzene-S-methyl+tx, giant knotweed extract+tx, alpha-chlorohydrin+tx, anto+tx, barium carbonate+tx, bismurine urea+tx, bromomurine protuberance+tx, bromodiuron+tx, bromomurine amine+tx, chloromurine ketone+tx, cholecalciferol+tx, chloromouse+tx, cricotermin+tx, deracina+tx, garcina+tx, calciferol+tx, flunixin+tx, fluoroacetamide+tx, flunix, fluorating +TX, fluorating hydrochloride +TX, ratel +TX, dunaline +TX, phosphorus +TX, deraticide +TX, sea onion glycoside +TX, sodium fluoroacetate +TX, thallium sulfate +TX, deraticide +TX, 2- (2-butoxyethoxy) ethyl piperonate +TX, 5- (1, 3-benzodioxol-5-yl) -3-hexylcyclohex-2-enone +TX, farnesol +TX with nerolidol +TX, synergistic alkyne-ether +TX, MGK +TX, piperonyl-butoxide +TX, synergistic aldehyde +TX, propyl isomer +TX, S421+TX, synergistic powder +TX, sesamin +TX, sulfoxide +TX, anthraquinone +TX copper naphthenate+tx, copper king+tx, dicyclopentadiene+tx, columbium+tx, zinc naphthenate+tx, ziram+tx, clothes Ma Ning +tx, ribavirin+tx, mercuric oxide+tx, thiophanate-methyl+tx, azaconazole+tx, bitertanol+tx, furfuryl azole+tx, cyproconazole+tx, difenoconazole+tx, diniconazole+tx, epoxiconazole+tx, fenbuconazole+tx, fluquinconazole+tx, flusilazole+tx, tebuconazole+tx, furazolium+tx, hexaconazole+tx, imazalil+tx, ipconazole+tx, metconazole+tx, myclobutanil+tx, paclobutrazol+tx, pyrithione+tx, Penconazole+tx, prothioconazole+tx, pyriproxyfen oxime (pyrifenox) +tx, prochloraz+tx, propiconazole+tx, cyproconazole+tx, simeconazole (simeconazole) +tx, tebuconazole+tx, fluoroether+tx, triazolone+tx, fluconazole+tx, triticonazole+tx, pyrimidinone+tx, chloropyrimol+tx, fluorobenzomol+tx, bupirimate (bupirimate) +tx, methiodine (dimethirimol) +tx, ethirimol (ethirimol) +tx, dodecomorph+tx, fenpropidin (fenpropidin) +tx, fenpropimorph+tx, spiroxamine+tx, tridemorph+tx, cyprodinil+tx, azoxystrobin (pyrimethanil) +tx, fludioxonil+tx, benzodiazirine (pyrim) + furalaxyl (furalaxyl) +TX, metalaxyl+TX, R-metalaxyl+TX, furalamide+TX, oxadixyl (oxadixyl) +TX, carbendazim+TX, prochloraz (debacarb) +TX, fuberiberine+TX, thiabendazole+TX, ethiprole (chlorazolate) +TX, sclerotinia (dichloriline) +TX, methicillin (myclozoline) +TX, procymidone) +TX, vinylsclerotinia (vinclozoline) +TX boscalid (boscalid) +tx, carboxin+tx, formamide+tx, fluoroamide (flutolanil) +tx, fenamid+tx, carboxin+tx, pyriproxyfen (penthiopyrad) +tx, thifluzamide+tx, dorodine+tx, biguanide octylamine+tx, azoxystrobin+tx, dimoxystrobin+tx, enestroburin+tx, zoxamide+tx, fluoxystrobin+TX, fluoxastrobin+TX, kresoxim-methyl+TX, benoxamine+TX, trifloxystrobin+TX, picoxystrobin+TX, pyraclostrobin+TX, fenhexamid+TX, thiram+TX, metiram+TX, zineb+TX, dichlorm+TX, captan+TX, furazolium+TX, folpet+TX, p-metin+TX, poldocaine+TX, copper oxide+TX, mancozeb+TX, quinocopper+TX, phthalide+TX, kewen+TX, iprobenfos+TX, clophos+TX, methyl-p-n+TX, zineb+TX, benthiamine+TX, blasticidin+TX, triclopyr (TX), triclopyr+TX, triclopyr (chlorb+TX), triclopyr (62, flucycloxaprop (oxamid+TX), fluben+benzocaine (fluben), fluben (oxamid+TX, fluben+TX, fluben (oxamid+TX), fluben (triclopyr+TX ) +TX, ethaboxam (ethaboxam) +TX, ethaboxam (ethadiazole) +TX, oxazolone+TX, imidazolone (fenamidone) +TX, fenoxanil (fenoxanil) +TX, azoxystrobin (feramizone) +TX, fluazinam (fluazinam) +TX, fluopyram (fluopiolide) +TX, sulfenamide (flufluflufenamide) +TX, fluazolamide+TX, cycloxamide+TX, triethylammonium phosphonate (fosetyl-aluminum) +TX, hymexazol (hypoxazol) +TX, propineb+TX, triamcinolone+TX, thiodicarb (methiocarb) +TX, benzodone+TX, pencyfluron (pencycuron) +TX, phthalide+TX, polyoxin (polyoxin) +procyanide (pro) pirimicarb+TX, iodoquinoxalone (proquinazid) +TX, fluquinlone (pyroquinlon) +TX, nalidixic ketone (pyriofenone) +TX, quinoxyfen+TX, pentachloronitrobenzene+TX, tiadinil+TX, imidazoxide (triazoxide) +TX, tricyclazole+TX, oxazin+TX, validamycin+TX, valyl amine+TX, zoxamide) +TX, mandipyridyl amine (mandipalmid) +TX, fluorophenylamide (flubeneteram) +TX, isopyrazam) +TX, fluzoxamide (sedaxane) +TX, benzofluxazole+TX, fluxazole+TX, fluxazole hydroxylamine+TX, 3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid (3 ',4',5' -trifluoro-biphenyl-2-yl) -amide +TX, isofluorocyclopropylamine (isoflucypram) +TX, isothiabendazole+TX, dipivemethamate (dipymetrizole) +TX, 6-ethyl-5, 7-dioxo-pyrrolo [4,5 ] ][1,4]Dithiino [1,2-c ]]Isothiazole-3-carbonitrile +TX, 2- (difluoromethyl) -N- [ 3-ethyl-1, 1-dimethyl-indan-4-yl]Pyridine-3-carboxamide +tx, 4- (2, 6-difluorophenyl) -6-methyl-5-phenyl-pyridazine-3-carbonitrile +tx, (R) -3- (difluoromethyl) -1-methyl-N- [1, 3-trimethylindan-4-yl]Pyrazole-4-carboxamide +TX, 4- (2-bromo-4-fluoro-phenyl) -N- (2-chloro-6-fluoro-phenyl) -2, 5-dimethyl-pyrazol-3-amine +TX, 4- (2-bromo-4-fluorophenyl) -N- (2-chloro-6-fluorophenyl) -1, 3-dimethyl-1H-pyrazol-5-amine +TX, fludanazolamine (fluidapyr) +TX, azoxystrobin (jiaxigjunzhi) +TX, rituximab (lvben mianan) +TX, dichlorobenzothiazole (dichlobentazox) +TX, mandelimbine (manderobebin) +TX, 3- (4, 4-difluoro-3, 4-dihydro-3, 3-dimethylisoquinolin-1-yl) quinolone +TX, 2- [ 2-fluoro-6- [ (8-fluoro-2-methyl-3-quinolinyl) oxy]Phenyl group]propan-2-ol+TX, thiapiprazole (oxathiapiprolin) +TX, N- [6- [ [ [ (1-methyltetrazol-5-yl) -phenyl-methylene]Amino group]Oxy groupMethyl group]-2-pyridyl group]Tert-butyl carbamate+TX, bipyrazinyl amine (pyraziflumid) +TX, fipronil (inpyrfluxam) +TX, tert-Luo Kapu (trolprocarb) +TX, penoxsulam+TX, benzotriflumizole (ipfenobuconazole) +TX, 2- (difluoromethyl) -N- [ (3R) -3-ethyl-1, 1-dimethyl-indan-4-yl ]Pyridine-3-carboxamide +tx, N '- (2, 5-dimethyl-4-phenoxy-phenyl) -N-ethyl-N-methyl-carboxamide +tx, N' - [4- (4, 5-dichlorothiazol-2-yl) oxy-2, 5-dimethyl-phenyl]-N-ethyl-N-methyl-formamidine +TX, [2- [3- [2- [1- [2- [3, 5-bis (difluoromethyl) pyrazol-1-yl ]]Acetyl group]-4-piperidinyl]Thiazol-4-yl]-4, 5-dihydro-isoxazol-5-yl]-3-chloro-phenyl]Methanesulfonate +TX, N- [6- [ [ (Z) - [ (1-methyltetrazol-5-yl) -phenyl-methylene]Amino group]Oxymethyl group]-2-pyridyl group]But-3-ynyl carbamate + TX, N- [ [5- [4- (2, 4-dimethylphenyl) triazol-2-yl ]]-2-methyl-phenyl]Methyl group]Methyl carbamate+tx, 3-chloro-6-methyl-5-phenyl-4- (2, 4, 6-trifluorophenyl) pyridazine+tx, pyridine carbonyl chloride (pyridamethyl) +tx, 3- (difluoromethyl) -1-methyl-N- [1, 3-trimethylindan-4-yl]Pyrazole-4-carboxamide +TX and 1- [2- [ [1- (4-chlorophenyl) pyrazol-3-yl ]]Oxymethyl group]-3-methyl-phenyl]-4-methyl-tetrazol-5-one+tx, 1-methyl-4- [ 3-methyl-2- [ [ 2-methyl-4- (3, 4, 5-trimethylpyrazol-1-yl) phenoxy ]]Methyl group]Phenyl group]tetrazol-5-one+TX, aminopyrafen (aminopyrafen) +TX, zoxamide+TX, indazole-sulbactam+TX, fluxapyroxad+TX, (Z, 2E) -5- [1- (4-chlorophenyl) pyrazol-3-yl ]oxy-2-methoxyimino-N, 3-dimethyl-pent-3-enamine+TX, fluopicoxamid (florpicolamid) +TX, fenpiclamide (fenpiclamid) +TX, ison Ding Yiyang quinoline+TX, ifen quin (ipflufenoquin) +TX, quinine (quinofumelin) +TX, iprathiopyrad+TX, N- [2, 4-dichloro-phenoxy]Phenyl group]-3- (difluoromethyl) -1-methyl-pyrazole-4-carboxamide +tx, N- [2- [ 2-chloro-4- (trifluoromethyl) phenoxy ]]Phenyl group]-3- (difluoromethyl) -1-methyl-pyrazole-4-carboxamide +tx, benzothiostrobin +tx, cyanophenyl +tx, 5-amino-1, 3, 4-thiadiazole-2-thiol zinc salt (2:1) +tx, fluopyram +tx, fluothiazolazetidine +tx, fluoroether-carboxamide +tx, propyne (pyrepoyne) +tx, piprazole (picarbazox) +tx, 2- (difluoromethyl) -N- (3-ethyl-1, 1-dimethyl-indan-4-yl) pyridine-3-carboxamide +tx, 2- (difluoromethyl) -N- ((3R) -11, 3-trimethylindan-4-yl) pyridine-3-carboxamide +TX, 4- [ [6- [2- (2, 4-difluorophenyl) -1, 1-difluoro-2-hydroxy-3- (1, 2, 4-triazol-1-yl) propyl ]]-3-pyridyl]Oxy group]Benzonitrile+tx, formyltetraproline (methyltetraprole) +tx, 2- (difluoromethyl) -N- ((3R) -1, 3-trimethylindan-4-yl) pyridine-3-carboxamide+tx, α - (1, 1-dimethylethyl) - α - [4'- (trifluoromethoxy) [1,1' -diphenyl ]-4-yl]-5-pyrimidinecarbonyl +TX, fluoro Sha Puluo-lin (fluoroxyapipin) +TX, enestrobin (enoxyastrobin) +TX, 4- [ [6- [2- (2, 4-difluorophenyl) -1, 1-difluoro-2-hydroxy-3- (1, 2, 4-triazol-1-yl) propyl ]]-3-pyridyl]Oxy group]Benzonitrile +TX, 4- [ [6- [2- (2, 4-difluorophenyl) -1, 1-difluoro-2-hydroxy-3- (5-sulfanyl-1, 2, 4-triazol-1-yl) propyl ]]-3-pyridyl]Oxy group]Benzonitrile +TX, 4- [ [6- [2- (2, 4-difluorophenyl) -1, 1-difluoro-2-hydroxy-3- (5-thio-4H-1, 2, 4-triazol-1-yl) propyl ]]-3-pyridyl]Oxy group]Benzonitrile+tx, trinexapac-ethyl+tx, coumoxystrobin+tx, mesogenic+tx, thiabendazole+tx, thiazolium+tx, al Mi Tuolin (amecton) +tx, iprodione+tx, N-octyl-N' - [2- (octylamino) ethyl]Ethane-1, 2-diamine + TX; n' - [ 5-bromo-2-methyl-6- [ (1S) -1-methyl-2-propoxy-ethoxy ]]-3-pyridyl]-N-ethyl-N-methyl-formamidine +tx, N' - [ 5-bromo-2-methyl-6- [ (1R) -1-methyl-2-propoxy-ethoxy ]]-3-pyridyl]-N-ethyl-N-methyl-formamidine +tx, N' - [ 5-bromo-2-methyl-6- (1-methyl-2-propoxy-ethoxy) -3-pyridinyl]-N-ethyl-N-methyl-formamidine +tx, N' - [ 5-chloro-2-methyl-6- (1-methyl-2-propoxy-ethoxy) -3-pyridinyl]-N-ethyl-N-methyl-formamidine +tx, N' - [ 5-bromo-2-methyl-6- (1-methyl-2-propoxy-ethoxy) -3-pyridinyl ]-N-isopropyl-N-methyl-formamidine+tx (these compounds may be prepared by the methods described in WO 2015/155075); n' - [ 5-bromo-2-methyl-6- (2-propoxypropoxy) -3-pyridinyl]-N-ethyl-N-methyl-formamidine+tx (this compound can be prepared by the method described in IPCOM 000249876D); N-isopropyl-N' - [ 5-methoxy-2-methyl-4- (2, 2-trifluoro-1-hydroxy-1-phenyl-ethyl) phenyl]-N-methyl-formamidine +tx, N' - [4- (1-cyclopropyl-2, 2-trifluoro-1-hydroxy-ethyl) -5-methoxy-2-methyl-phenyl ]]-N-isopropyl-N-methyl-formamidine+tx (these compounds may be prepared by the methods described in WO 2018/228896); N-ethyl-N' - [ 5-methoxy-2-methyl-4- [ 2-trifluoro-methyl ]Radical) oxetan-2-yl radical]Phenyl group]-N-methyl-formamidine+tx, N-ethyl-N' - [ 5-methoxy-2-methyl-4- [ 2-trifluoromethyl) tetrahydrofuran-2-yl]Phenyl group]-N-methyl-formamidine+tx (these compounds can be prepared by the methods described in WO 2019/110427); n- [ (1R) -1-benzyl-3-chloro-1-methyl-but-3-enyl]-8-fluoro-quinoline-3-carboxamide +TX, N- [ (1S) -1-benzyl-3-chloro-1-methyl-but-3-enyl]-8-fluoro-quinoline-3-carboxamide +TX, N- [ (1R) -1-benzyl-3, 3-trifluoro-1-methyl-propyl]-8-fluoro-quinoline-3-carboxamide +TX, N- [ (1S) -1-benzyl-3, 3-trifluoro-1-methyl-propyl ]-8-fluoro-quinoline-3-carboxamide +TX, N- [ (1R) -1-benzyl-1, 3-dimethyl-butyl]-7, 8-difluoro-quinoline-3-carboxamide +tx, N- [ (1S) -1-benzyl-1, 3-dimethyl-butyl]-7, 8-difluoro-quinoline-3-carboxamide +TX, 8-fluoro-N- [ (1R) -1- [ (3-fluorophenyl) methyl]-1, 3-dimethyl-butyl]Quinoline-3-carboxamide +TX, 8-fluoro-N- [ (1S) -1- [ (3-fluorophenyl) methyl]-1, 3-dimethyl-butyl]Quinoline-3-carboxamide + TX, N- [ (1R) -1-benzyl-1, 3-dimethyl-butyl]-8-fluoro-quinoline-3-carboxamide +TX, N- [ (1S) -1-benzyl-1, 3-dimethyl-butyl]-8-fluoro-quinoline-3-carboxamide +tx, N- ((1R) -1-benzyl-3-chloro-1-methyl-but-3-enyl) -8-fluoro-quinoline-3-carboxamide +tx, N- ((1S) -1-benzyl-3-chloro-1-methyl-but-3-enyl) -8-fluoro-quinoline-3-carboxamide +tx (these compounds may be prepared by the methods described in WO 2017/153380);

1- (6, 7-dimethylpyrazolo [1,5-a ] pyridin-3-yl) -4, 5-trifluoro-3, 3-dimethyl-isoquinoline + TX, 1- (6, 7-dimethylpyrazolo [1,5-a ] pyridin-3-yl) -4, 6-trifluoro-3, 3-dimethyl-isoquinoline + TX, 4-difluoro-3, 3-dimethyl-1- (6-methylpyrazolo [1,5-a ] pyridin-3-yl) isoquinoline + TX, 4-difluoro-3, 3-dimethyl-1- (7-methylpyrazolo [1,5-a ] pyridin-3-yl) isoquinoline + TX, 1- (6-chloro-7-methyl-pyrazolo [1,5-a ] pyridin-3-yl) -4, 4-difluoro-3-dimethyl-isoquinoline + TX (these compounds may be prepared by the methods described in WO 2017/025510); 1- (4, 5-dimethylbenzimidazol-1-yl) -4, 5-trifluoro-3, 3-dimethyl-isoquinoline + TX, 1- (4, 5-dimethylbenzimidazol-1-yl) -4, 4-difluoro-3, 3-dimethyl-isoquinoline + TX, 6-chloro-4, 4-difluoro-3, 3-dimethyl-1- (4-methylbenzimidazol-1-yl) isoquinoline + TX, 4-difluoro-1- (5-fluoro-4-methyl-benzoimidazol-1-yl) -3, 3-dimethyl-isoquinoline + TX, 3- (4, 4-difluoro-3, 3-dimethyl-1-isoquinolyl) -7, 8-dihydro-6H-cyclopenta [ e ] benzimidazole + TX (these compounds may be prepared by the methods described in WO 2016/156085); N-methoxy-N- [ [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ] phenyl ] methyl ] cyclopropanecarboxamide+TX, N, 2-dimethoxy-N- [ [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ] phenyl ] methyl ] carboxamide+TX, N-ethyl-2-methyl-N- [ [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ] phenyl ] methyl ] carboxamide+TX, 1-methoxy-3-methyl-1- [ [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ] phenyl ] methyl ] urea+TX, 1, 3-dimethoxy-1- [ [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ] phenyl ] methyl ] urea+TX, 3-ethyl-1- [ [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ] phenyl ] methyl ] urea+TX, 1-methoxy-1- [ [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ] phenyl ] methyl ] carboxamide+TX, 1-methoxy-3- [ [4- [5- (trifluoromethyl) -3-methyl ] phenyl ] methyl ] carbamide 4, 4-dimethyl-2- [ [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ] phenyl ] methyl ] isoxazolidin-3-one+tx, 5-dimethyl-2- [ [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ] phenyl ] methyl ] isoxazolidin-3-one+tx, 1- [ [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ] phenyl ] methyl ] pyrazole-4-carboxylic acid ethyl ester+tx, N-dimethyl-1- [ [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ] phenyl ] methyl ] -1,2, 4-triazol-3-amine+tx. The compounds in this paragraph can be prepared by the methods described in WO 2017/055473, WO 2017/055469, WO 2017/093348 and WO 2017/118689; 2- [6- (4-chlorophenoxy) -2- (trifluoromethyl) -3-pyridinyl ] -1- (1, 2, 4-triazol-1-yl) propan-2-ol+tx (this compound may be prepared by the method described in WO 2017/029179); 2- [6- (4-bromophenoxy) -2- (trifluoromethyl) -3-pyridinyl ] -1- (1, 2, 4-triazol-1-yl) propan-2-ol+tx (this compound may be prepared by the method described in WO 2017/029179); 3- [2- (1-chlorocyclopropyl) -3- (2-fluorophenyl) -2-hydroxy-propyl ] imidazole-4-carbonitrile +tx (this compound may be prepared by the methods described in WO 2016/156290); 3- [2- (1-chlorocyclopropyl) -3- (3-chloro-2-fluoro-phenyl) -2-hydroxy-propyl ] imidazole-4-carbonitrile +tx (this compound may be prepared by the method described in WO 2016/156290); 2-amino-6-methyl-pyridine-3-carboxylic acid (4-phenoxyphenyl) methyl ester+tx (this compound may be prepared by the method described in WO 2014/006945); 2, 6-dimethyl-1H, 5H- [1,4] dithiino [2,3-c:5,6-c' ] bipyrrolidinyl-1, 3,5,7 (2H, 6H) -tetraone+TX (this compound can be prepared by the process described in WO 2011/138281); n-methyl-4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ] thiobenzamide+tx; n-methyl-4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ] benzamide + TX; (Z, 2E) -5- [1- (2, 4-dichlorophenyl) pyrazol-3-yl ] oxy-2-methoxyimino-N, 3-dimethyl-pent-3-enamine+tx (this compound can be prepared by the method described in WO 2018/153707); n' - (2-chloro-5-methyl-4-phenoxy-phenyl) -N-ethyl-N-methyl-formamidine+tx; n' - [ 2-chloro-4- (2-fluorophenoxy) -5-methyl-phenyl ] -N-ethyl-N-methyl-formamidine+tx (this compound may be prepared by the method described in WO 2016/202742); 2- (difluoromethyl) -N- [ (3S) -3-ethyl-1, 1-dimethyl-indan-4-yl ] pyridine-3-carboxamide + TX (this compound can be prepared by the method described in WO 2014/095675); (5-methyl-2-pyridinyl) - [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ] phenyl ] methanone+tx, (3-methylisoxazol-5-yl) - [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ] phenyl ] methanone+tx (these compounds may be prepared by the methods described in WO 2017/220485); 2-oxo-N-propyl-2- [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ] phenyl ] acetamide+tx (this compound can be prepared by the method described in WO 2018/065414); 1- [ [5- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ] -2-thienyl ] methyl ] pyrazole-4-carboxylic acid ethyl ester+tx (this compound can be prepared by the method described in WO 2018/158365); 2, 2-difluoro-N-methyl-2- [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ] phenyl ] acetamide+tx, N- [ (E) -methoxyiminomethyl ] -4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ] benzamide+tx, N- [ (Z) -methoxyiminomethyl ] -4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ] benzamide+tx, N- [ N-methoxy-C-methyl-carboimido ] -4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ] benzamide+tx (these compounds may be prepared by the methods described in WO 2018/202428), chloroindolylhydrazide+tx, fluoromethylsulphonm (flumidosulform) +, fluoxoconazole) +tx, flufenoxaoxazamide) +62, flufenoxaoxazamide) +panamide+tx.

Reference numerals in brackets after the active ingredient, e.g. [3878-19-1]Refers to chemical abstract accession numbers. The above-described hybrid formulations are known. When the active ingredients are included in "The Pesticide Manual [ handbook of pesticides ]]"[ The Pesticide Manual-AWorld Compendium [ handbook of pesticides-Global overview ]]The method comprises the steps of carrying out a first treatment on the surface of the 13 th edition; editing: c.d.s.tomlin; british crop protection Committee]In which they are described with the entry numbers given in parentheses above for the particular compound; for example, the compound "avermectin" is described by entry number (1). In "[ CCN]"in the case of the above addition to a specific compound, said compound is included in" Compendium of Pesticide Common Names [ pesticide general outline ]]"in, it can be on the internet [ a.wood;Compendium of Pesticide Common Names，Copyright1995-2004]obtaining; for example, the compound "acetylfipronil" is described in the internet address http:// www.alanwood.net/peticides/acetope.

Most of the above active ingredients are mentioned by the so-called "common names" above, the corresponding "ISO common names" or other "common names" being used in different situations. If the name is not a "common name", the name class used is instead given in parentheses for the particular compound; in this case, IUPAC names, IUPAC/chemical abstract names, "chemical names", "conventional names", "compound names", or "development codes" are used, or "aliases" are used if neither one of those names nor "common names" is used. "CAS registry number" means a chemical abstract registry number.

The active ingredient mixture of the compounds of formula (I) selected from one of the compounds shown in tables A1 to A5 or table E (below) is preferably in a mixing ratio from 100:1 to 1:6000, in particular in a ratio from 50:1 to 1:50, more in particular in a ratio from 20:1 to 1:20, even more in particular from 10:1 to 1:10, very in particular from 5:1 and 1:5, a ratio from 2:1 to 1:2 being given particularly preferred, and a ratio from 4:1 to 2:1 being likewise preferred, in particular in the following ratio: 1:1, or 5:1, or 5:2, or 5:3, or 5:4, or 4:1, or 4:2, or 4:3, or 3:1, or 3:2, or 2:1, or 1:5, or 2:5, or 3:5, or 4:5, or 1:4, or 2:4, or 3:4, or 1:3, or 2:3, or 1:2, or 1:600, or 1:300, or 1:150, or 1:35, or 2:35, or 4:35, or 1:75, or 2:75, or 4:75, or 1:6000, or 1:3000, or 1:1500, or 1:350, or 2:350, or 4:350, or 1:750, or 2:750, or 4:750. Those mixing ratios are by weight.

The mixture as described above may be used in a method for controlling pests, which comprises applying a composition comprising the mixture as described above to the pest or its environment, a method for treating the human or animal body by surgery or therapy, and a diagnostic method carried out on the human or animal body.

Mixtures comprising the compounds as shown in tables A1 to A5 or table E (below) and one or more active ingredients as described above can be applied, for example, in a single "water-admixed" form, in a combined spray mixture (which consists of separate formulations of the single active ingredient components), such as a "tank mix", and when applied in a sequential manner, i.e. one after the other, over a moderately short period of time, such as hours or days, in combination with a single active ingredient. The order of administration of the compounds as shown in tables A1 to A5 or table E (below) and one or more of the active ingredients as described above is not critical to the practice of the invention.

The compositions according to the invention may also comprise further solid or liquid adjuvants, such as stabilizers, for example non-epoxidized or epoxidized vegetable oils (for example epoxidized coconut oil, rapeseed oil or soybean oil), defoamers (for example silicone oils), preservatives, viscosity regulators, binders and/or adhesion promoters, fertilizers or other active ingredients for achieving a particular effect, for example bactericides, fungicides, nematicides, plant activators, molluscicides or herbicides.

The compositions according to the invention are prepared in a manner known per se, in the absence of auxiliaries, for example by grinding, sieving and/or compressing the solid active ingredients; and in the presence of at least one auxiliary, for example by intimately mixing the active ingredient with one or more auxiliary and/or grinding the active ingredient with one or more auxiliary. These processes for preparing the compositions and the use of the compounds (I) for preparing these compositions are also subjects of the invention.

Another aspect of the invention relates to the use of a fungicidal or insecticidal mixture comprising a compound of formula (I) or preferably of a variety of compounds as defined herein, a composition comprising at least one compound of formula (I) or at least one preferably of a variety of compounds as defined above, or at least one compound of formula (I) or at least one preferably of a variety of compounds as defined above, mixed with other fungicides or insecticides as described above, for controlling or preventing infestation of plants (e.g. useful plants (e.g. crop plants)), propagation material (e.g. seeds) thereof, harvested crops (e.g. harvested food crops), or non-living material by insects or phytopathogenic microorganisms (preferably fungal organisms).

Another aspect of the invention relates to a method of controlling or preventing infestation of plants, such as useful plants (e.g. crop plants), propagation material thereof (e.g. seeds), harvested crops (e.g. harvested food crops), or non-living material by phytopathogenic or spoilage microorganisms or organisms potentially harmful to humans, especially fungal organisms, which method comprises applying a compound of formula (I) or preferably various compounds as defined above as an active ingredient to the plants, to parts of the plants or to the locus thereof, to propagation material thereof, or to any part of the non-living material.

By controlling or preventing is meant reducing infestation by insects or phytopathogenic or spoilage microorganisms or organisms potentially harmful to humans, especially fungal organisms, to such a level that is demonstrated to be improved.

A preferred method of controlling or preventing infestation of crop plants by phytopathogenic microorganisms, especially fungal organisms, or insects is foliar application, which comprises applying a compound of formula (I), or an agrochemical composition comprising at least one of said compounds. The frequency and rate of application will depend on the risk of infestation by the corresponding pathogen or insect. However, the compounds of formula (I) can also penetrate plants via the soil through the root (systemic effect) by soaking the locus of the plant with a liquid formulation or by applying the compounds in solid form, for example in granular form, to the soil (soil application). In rice crops, such particles may be applied to irrigated rice fields. The compounds of formula (I) may also be applied to seeds (coatings) by impregnating the seeds or tubers with a liquid formulation of the fungicide or coating them with a solid formulation.

Formulations (e.g. compositions containing a compound of formula (I) and, if desired, a solid or liquid adjuvant or monomers for encapsulating a compound of formula (I)) may be prepared in a known manner, typically by intimately mixing and/or grinding the compound with extenders, e.g. solvents, solid carriers and optionally surface-active compounds (surfactants).

Methods of application of the compositions, i.e. methods of controlling pests of the above-mentioned type, such as spraying, atomizing, dusting, brushing, seed dressing, sowing or watering (which are selected to be suitable for the intended purpose of the environment at hand), and the use of the compositions for controlling pests of the above-mentioned type are further subjects of the invention. Typical concentration ratios are between 0.1 and 1000ppm, preferably between 0.1 and 500ppm, of active ingredient. The application rate per item is preferably from 1g to 2000g of active ingredient per item, more preferably from 10 to 1000g/ha, most preferably from 10 to 600g/ha. When used as a seed soaking agent, a suitable dosage is from 10mg to 1g of active substance per kg of seed.

When the combination according to the invention is used for treating seeds, a ratio of 0.001 to 50g of compound having formula (I) per kg of seeds, preferably from 0.01 to 10g/kg of seeds, is generally sufficient.

Suitably, the composition according to the invention comprising a compound of formula (I) is administered prophylactically (meaning before disease development) or therapeutically (meaning after disease development).

The compositions OF the invention can be used in any conventional form, for example, in the form OF a double-pack, dry seed-treating powder (DS), seed-treating Emulsion (ES), seed-treating flowable concentrate (FS), seed-treating solution (LS), seed-treating water-dispersible powder (WS), seed-treating capsule suspension (CF), seed-treating Gel (GF), emulsion Concentrate (EC), suspension Concentrate (SC), suspension Emulsion (SE), capsule Suspension (CS), water-dispersible particles (WG), emulsifiable particles (EG), water-in-oil Emulsion (EO), oil-in-water Emulsion (EW), microemulsion (ME), oil Dispersion (OD), oil suspension (OF), oil-soluble concentrate (OL), soluble concentrate (SL), ultra-low volume Suspension (SU), ultra-low volume liquid (UL), master drug (TK), dispersible Concentrate (DC), wettable Powder (WP) or any technically feasible formulation in combination with agriculturally acceptable adjuvants.

Such compositions can be produced in a conventional manner, for example by mixing the active ingredient with suitable formulation inert agents (diluents, solvents, fillers and optionally other formulation ingredients, such as surfactants, biocides, antifreeze agents, adhesion agents, thickeners and compounds which provide auxiliary effects). Conventional slow release formulations aimed at long lasting efficacy may also be used. In particular, formulations to be applied in spray form, such as water-dispersible concentrates (e.g. EC, SC, DC, OD, SE, EW, EO etc.), wettable powders and granules, may contain surfactants such as wetting and dispersing agents and other compounds which provide auxiliary effects, for example condensation products of formaldehyde with naphthalene sulfonates, alkylaryl sulfonates, lignin sulfonates, fatty alkyl sulfates and ethoxylated alkylphenols and ethoxylated fatty alcohols.

The seed dressing formulations are applied to the seeds in a manner known per se in the form of suitable seed dressing formulations, for example in the form of aqueous suspensions or dry powders which have good adhesion to the seeds, using the combinations and diluents of the invention. Such seed dressing formulations are known in the art. Seed dressing formulations may contain the individual active ingredients or combinations of active ingredients in encapsulated form, for example as slow release capsules or microcapsules.

Typically, the formulation comprises from 0.01 to 90% by weight of an active agent consisting of at least a compound of formula (I) together with components (B) and (C), and optionally other active agents (in particular microbiocides or preservatives etc.), from 0 to 20% of an agriculturally acceptable surfactant and from 10 to 99.99% of a solid or liquid formulation inert agent and one or more adjuvants. The concentrated form of the composition typically contains between about 2% and 80%, preferably between about 5% and 70% by weight of active agent. The formulation may for example contain from 0.01 to 20% by weight, preferably from 0.01 to 5% by weight, of active agent in the form of administration. However, commercial products will preferably be formulated as concentrates and the end user will typically use dilute formulations.

However, it is preferred that the commercial product is formulated as a concentrate and the end user will typically use a diluted formulation.

Examples

The following examples serve to illustrate the invention.

Certain compounds of the present invention may differ from known compounds in greater efficacy at low application rates, as demonstrated by one skilled in the art using the experimental procedures outlined in the examples, using lower application rates (if necessary), such as 50ppm, 12.5ppm, 6ppm, 3ppm, 1.5ppm, 0.8ppm, or 0.2 ppm.

The compounds having formula (I) may have a number of benefits, including in particular advantageous levels of biological activity for protecting plants from diseases caused by fungi or advantageous properties for use as agrochemical active ingredients (e.g. higher biological activity, advantageous activity profile, increased safety properties (including improved crop tolerance), improved physico-chemical properties, or increased biodegradability).

Throughout this specification, temperature is given in degrees celsius and "m.p." means melting point. LC/MS means liquid chromatography-mass spectrometry, and the description of the apparatus and method is described below.

Examples of formulations

The active ingredient is thoroughly mixed with the adjuvants and the mixture is thoroughly ground in a suitable mill to provide a wettable powder which can be diluted with water to give a suspension of the desired concentration.

The active ingredient is thoroughly mixed with the adjuvants and the mixture is thoroughly ground in a suitable mill to provide a powder that can be used directly for seed treatment.

Emulsifiable concentrate

Emulsions of any desired dilution that can be used in plant protection can be obtained from such concentrates by dilution with water.

A ready-to-use dust powder is obtained by mixing the active ingredient with a carrier and grinding the mixture in a suitable grinder. Such powders may also be used for dry dressing of seeds.

Extruder granule

The active ingredient is mixed with the auxiliary and ground, and the mixture is wetted with water. The mixture is extruded and then dried in an air stream.

Coated granule

Active ingredient [ Compound having formula (I) ] 8%

Polyethylene glycol (molecular weight 200) 3%

Kaolin 89%

The finely ground active ingredient is applied uniformly in a mixer to the kaolin wetted with polyethylene glycol. In this way dust-free coated granules are obtained.

Suspension concentrate

The finely ground active ingredient is intimately mixed with the adjuvants to give a suspension concentrate from which any desired dilution of the suspension can be obtained by dilution with water. With such dilutions, living plants can be treated together with plant propagation material and protected from infestation by microorganisms by spraying, watering or dipping.

Flowable concentrate for seed treatment

The finely ground active ingredient is intimately mixed with the adjuvants to give a suspension concentrate from which any desired dilution of the suspension can be obtained by dilution with water. With such dilutions, living plants can be treated together with plant propagation material and protected from infestation by microorganisms by spraying, watering or dipping.

Slowly releasing capsule suspension

28 parts of a combination of compounds of the formula (I) are mixed with 2 parts of an aromatic solvent and 7 parts of a toluene diisocyanate/polymethylene-polyphenyl isocyanate mixture (8:1). This mixture was emulsified in a mixture of 1.2 parts of polyvinyl alcohol, 0.05 parts of defoamer and 51.6 parts of water until the desired particle size was reached. To this emulsion was added a mixture of 2.8 parts of 1, 6-diaminohexane in 5.3 parts of water. The mixture was stirred until the polymerization was completed.

The capsule suspension obtained is stabilized by adding 0.25 parts of thickener and 3 parts of dispersant. The capsule suspension formulation contains 28% active ingredient. The diameter of the media capsule is 8-15 microns.

The resulting formulation is applied as an aqueous suspension to the seeds in a device suitable for this purpose.

List of abbreviations:

aq=aqueous solution

Ar=argon

br s=broad unimodal

CaSO ₄ =calcium sulfate

Cata CXium A Pd G3 = methanesulfonic acid [ (di (1-adamantyl) -n-butylphosphine) -2- (2 '-amino-1, 1' -biphenyl) ] palladium (II)

CDCl ₃ =chloroform-d

C = degrees celsius

Dcm=dichloromethane

dd = double doublet

DMF = dimethylformamide

d = double peak

EtOAc = ethyl acetate

equiv=equivalent

h=h

Hcl=hydrochloric acid

M=mole

m = multiple peaks

MgSO ₄ =magnesium sulfate

min = min

Mhz=megahertz

mp = melting point

NaHCO ₃ Sodium bicarbonate

NaOH = sodium hydroxide

NH ₄ Cl=ammonium chloride

PdCl ₂ (dtbpf) = [1,1' -bis (di-t-butylphosphino) ferrocene]Palladium dichloride (II)

ppm = parts per million

Rt=room temperature

Rt=retention time

s = single peak

t=triplet

Tbme=tert-butyl methyl ether

THF = tetrahydrofuran

LC/ms=liquid chromatography-mass spectrometry (descriptions of apparatus and methods for LC/MS analysis are given above)

Preparation example:

example A1:7, 8-dichloro-4- (8-fluoro-3-quinolinyl) -2, 2-dimethyl-1, 3-benzothiazine (Compound E.05)

Step 1：

A solution of 2-trimethylsilyl ethanethiol (0.50 g,3.72 mmol) in THF (35 mL) was treated with triethylamine (0.38 g,3.72 mmol) and p-toluenesulfonyl chloride (0.36 g,1.86 mmol) at 0deg.C to 5deg.C. The resulting mixture was stirred at 0 ℃ to 5 ℃ for 45 minutes, diluted with DCM, and washed with aqueous HCl (1M). The organic layer was treated with NaHCO ₃ Aqueous and brine washes over MgSO ₄ Dried, filtered and concentrated in vacuo. The residual oil was filtered through a short plug of silica gel (eluent: cyclohexane) to give trimethyl- [2- (2-trimethylsilylethyldisulfanyl) ethyl ] as a colourless liquid]A silane.

¹ H NMR(400MHz,CDCl ₃ )δppm:2.68-2.83(m,4H)0.86-1.07(m,4H)0.05(s,18H)。

Step 2:

to a solution of 3, 4-dichlorobenzoic acid (0.14 g,0.73 mmol) in tetrahydrofuran (4 mL) cooled at-70℃was added dropwise n-butyllithium (2.5 mol/L in hexane, 0.88mL,2.20 mmol) under argon. Trimethyl- [2- (2-Tri) in THF (5 mL) was addedMethylsilylethyldisulfanyl) ethyl]Prior to silane (0.39 g,1.47 mmol), the solution was stirred at-70℃for 2h. The reaction mixture was gradually warmed to RT over 4H, diluted with TBME and taken up with H ₂ And O extraction. The aqueous layer was acidified to pH 1 with HCl (2M) and extracted with TBME. The organic layer was washed with water, over MgSO ₄ Dried, filtered and concentrated under reduced pressure. The remaining solid was suspended in DCM, the undissolved solid was removed by filtration, and the filtrate was concentrated under reduced pressure to give 3, 4-dichloro-2- (2-trimethylsilylethylsulfanyl) benzoic acid as a white solid.

LC-MS (method G), rt=1.18 min, (M-H) =321.

¹ H NMR(400MHz,CDCl ₃ )δppm:8.06(d,1H),7.63(br d,1H),3.00-3.08(m,2H),0.85-0.94(m,2H),0.03(s,9H)。

Step 3:

to a solution of 3, 4-dichloro-2- (2-trimethylsilylethylsulfanyl) benzoic acid (0.18 g,0.56 mmol) in toluene (1 mL) at RT was added one drop of DMF and thionyl chloride (0.09 mL,1.22 mmol). The reaction mixture was warmed to 70 ℃ and aged at this temperature for 2h. All volatiles were then removed under reduced pressure, the residue was taken up in dioxane (0.6 mL) and ammonia (25% in water) was slowly added at RT (0.52 mL,7.23 mmol). The reaction mixture was stirred at RT for 45min, diluted with water and extracted with EtOAc. The organic phase was washed with brine, over MgSO ₄ Dried, filtered and concentrated. The residue was purified by flash chromatography (silica gel, cyclohexane: etOAc) to give 3, 4-dichloro-2- (2-trimethylsilylethylsulfanyl) benzamide as a beige solid.

LC-MS (method G), rt=1.10 min.

¹ H NMR(400MHz,CDCl ₃ )δppm:7.67(d,1H),7.53(d,1H),7.10(br s,1H),5.89(br s,1H),2.91-3.09(m,2H),0.82-0.92(m,2H),0.02(s,9H)。

Step 4:

to 3, 4-dichloro-2- (2-trimethylsilylethylsulfanyl) benzamide (0.08 g,0.25 at RTTo a solution of mmol) in THF (1 mL) was added tetrabutylammonium fluoride (1M in THF, 0.74mL,0.74 mmol). The solution was stirred for 20min at RT and then diluted with aqueous HCl (1M). The mixture was extracted with EtOAc, and the organic phase was washed with brine, over MgSO ₄ Drying, filtering and concentrating. The residue was purified by flash chromatography (silica gel, cyclohexane: etOAc) to give 3, 4-dichloro-2-sulfanyl-benzamide as an orange solid.

LC-MS (method G), R _t ＝0.82min，(M+H)＝222。

¹ H NMR(400MHz,CDCl ₃ )δppm＝7.41(d,1H),7.31(d,1H),6.22(s,1H),5.72(br s,2H)。

Step 5:

3, 4-dichloro-2-sulfanyl-benzamide (0.03 g,0.14 mmol), 2-dimethoxypropane (0.03 mL,0.27 mmol), p-toluenesulfonic acid (1 small crystal) anda suspension of molecular sieves in toluene (0.5 mL) was stirred at 80℃for 18h. The reaction mixture was cooled to RT, diluted with EtOAc, and the solids were removed by filtration. The filtrate was washed with water and brine, over MgSO ₄ Dried, filtered and concentrated under reduced pressure. The residue was purified by flash chromatography (silica gel, cyclohexane: etOAc) to give 7, 8-dichloro-2, 2-dimethyl-3H-1, 3-benzothiazin-4-one as an orange gum.

LC-MS (method G), R _t ＝0.99min，(M+H)＝262。

¹ H NMR(400MHz,CDCl ₃ )δppm＝8.06(d,1H),7.39(d,1H),6.17(br s,1H),1.77(s,6H)。

Step 6:

a solution of DMF (0.02 mL,0.23 mmol) in DCM (0.2 mL) at 0deg.C was treated with oxalyl chloride (0.014 mL,0.15 mmol) and the resulting white suspension was stirred at 0deg.C for 1h. A solution of 7, 8-dichloro-2, 2-dimethyl-3H-1, 3-benzothiazin-4-one (0.02 g,0.076 mmol) in DCM (0.2 mL) was then added to the suspension and the reaction mixture warmed to RT. After 40min, LC-MS indicated complete conversion. The reaction mixture was diluted with DCM and poured onto ice and NaHCO ₃ On a mixture of aqueous solutions. The mixture was extracted with DCM and the organic phase was taken over MgSO ₄ Drying, filtering and concentrating under reduced pressure to obtain 4,7, 8-trichloro-2, 2-dimethyl-1, 3-benzothiazine (LC-MS (method G), R _t =1.25 min, (m+h) =282), which was used as is for the coupling reaction.

To a degassed solution of 8-fluoro-3- (4, 5-tetramethyl-1, 3, 2-dioxaborolan-2-yl) quinoline (0.027 g,0.09mmol,1.1 equiv.) and 4,7, 8-trichloro-2, 2-dimethyl-1, 3-benzothiazine (0.02 g,0.089 mmol) in DMF (0.4 mL) was added K ₃ PO ₄ (0.06G, 0.27 mmol) and CataCXiumA Pd G3 (0.0070G, 0.009 mmol). The resulting mixture was warmed to 60 ℃ and stirred at this temperature for 20min. The reaction mixture was cooled to RT, diluted with EtOAc, and quenched with NH ₄ The aqueous Cl solution was washed. The organic phase was washed with brine, over MgSO ₄ Dried, filtered and concentrated in vacuo. The residue was purified by flash chromatography (silica gel, cyclohexane: etOAc) to give 7, 8-dichloro-4- (8-fluoro-3-quinolinyl) -2, 2-dimethyl-1, 3-benzothiazine as an orange solid.

LC-MS (method G), rt=1.25 min, (m+h) =391.

¹ H NMR(400MHz,CDCl ₃ )δppm: ¹ H NMR( ₁ -CDCl ₃ )δ:9.07(d,1H),8.33(t,1H),7.69(d,1H),7.40-7.61(m,2H),7.27(d,1H),7.16(d,1H),1.75(s,6H)。

¹⁹ F NMR( ₁ -CDCl ₃ )δ:-124.91(s)。

Example A2:8-chloro-4- (8-fluoro-3-quinolinyl) -2, 2-dimethyl-1, 3-benzothiazine (Compound E.02).

Step 1:

to an ice-cooled solution of 2, 3-dichlorobenzonitrile (3.0 g,17.44 mmol) in DMSO (15 mL) was added K ₂ CO ₃ (0.49 g,3.49 mmol) and H ₂ O ₂ (at H ₂ 30% in O, 2.7mL,26.16 mmol). The reaction mixture was gradually warmed to RT and stirred at this temperature for 2h. However, the method is thatIce cold water was then added and the precipitate was collected by filtration. Drying under reduced pressure to obtain 2, 3-dichlorobenzamide.

LC-MS (method G1), R _t ＝0.84min，(M+H)＝190。

¹ H NMR(400MHz,DMSO)δppm＝7.98(br s,1H),7.70-7.76(m,1H),7.61-7.69(m,1H),7.36-7.43(m,2H)。

Step 2:

a solution of sodium sulfide (2.49 g,31.6 mmol) in 1-methyl-2-pyrrolidine (150 mL) was aged under a gentle stream of nitrogen at 190℃for 2h. The resulting solution was cooled to 130 ℃, 3-chloro-2-sulfanyl-benzamide (5.0 g,26.3 mmol) was added, the mixture was warmed to 175 ℃ and aged at this temperature for 4h. The mixture was then cooled to 70 ℃ and MgSO was added ₄ (3.23 g,26.3 mmol), p-toluenesulfonic acid (5.50 g,28.9 mmol) and 2, 2-dimethoxypropane (17 mL,131 mmol). The resulting suspension was warmed to 100 ℃ and stirred at this temperature for 16h. The reaction mixture was cooled to RT, water was added and the mixture was acidified with aqueous HCl (2M). The resulting emulsion was extracted with EtOAc and the organic phase was washed with brine over MgSO ₄ Dried, filtered and concentrated in vacuo. The residue was purified by flash chromatography (silica gel, cyclohexane: etOAc) to give 8-chloro-2, 2-dimethyl-3H-1, 3-benzothiazin-4-one as a yellow solid.

LC-MS (method G1), R _t ＝1.02min，(M+H)＝228。

¹ H NMR(400MHz,CDCl ₃ )δppm:8.1(dd,1H),7.51(dd,1H),7.22(t,1H),6.91(br s,1H),1.75(s,6H)。

Step 3:

a solution of DMF (0.06 mL,0.79 mmol) in DCM (1.5 mL) at 0deg.C was treated with oxalyl chloride (0.07 mL,0.79 mmol). The resulting white suspension was stirred at 0℃for 1h. A solution of 8-chloro-2, 2-dimethyl-3H-1, 3-benzothiazin-4-one (0.100 g,0.44 mmol) in DCM (1 mL) was then added to the suspension at 0deg.C and the mixture was gradually warmed to RT. After 2h, LC-MS indicated complete conversion. The reaction mixture was diluted with DCM and poured onto ice and NaHCO ₃ Aqueous solutionIs a mixture of (a) and (b). The mixture was extracted with DCM and the organic phase was taken over MgSO ₄ Dried, filtered and concentrated under reduced pressure to give 4, 8-dichloro-2, 2-dimethyl-1, 3-benzothiazine (LC-MS (method G1), R _t =1.26 min, (m+h) =246), which was used as is for the coupling reaction.

To a degassed solution of (8-fluoro-3-quinolinyl) boronic acid (0.10 g,0.53 mmol) and 4, 8-dichloro-2, 2-dimethyl-1, 3-benzothiazine (0.118 g,0.44 mmol) in DMF (2 mL) was added K ₃ PO ₄ (0.31 g,1.44 mmol) and PdCl ₂ (dtbpf) (0.016 g,0.024 mmol). The resulting mixture was warmed to 60 ℃ and stirred at this temperature for 1h. The reaction mixture was cooled to RT and partitioned between ice water and EtOAc. The organic phase was washed with brine, over MgSO ₄ Dried, filtered and concentrated under reduced pressure. The residue was purified by flash chromatography (silica gel, cyclohexane: etOAc) to give 8-chloro-4- (8-fluoro-3-quinolinyl) -2, 2-dimethyl-1, 3-benzothiazine as a beige solid.

LC-MS (method), R _t ＝1.27min，(M+H)＝357。

¹ H NMR(400MHz,CDCl ₃ )δppm：9.07(d,1H),8.35(t,1H),7.69(d,1H),7.48-7.60(m,3H),7.20(dd,1H),7.11(t,1H),1.75(s,6H)。

¹⁹ F NMR( ₁ -CDCl ₃ )δ:-125.08(s)。

Analysis method

Method G:

spectra were recorded on a mass spectrometer (SQD, SQDII single quadrupole mass spectrometer) from Waters, which was equipped with electrospray sources (polarity: positive and negative ions), capillary voltages: 3.00kV, taper hole scope: 30V, extractor: 2.00V, source temperature: desolvation temperature at 150 ℃): 350 ℃, taper hole gas flow: 50l/h, desolvation gas flow: 650l/h, mass range: 100Da to 900 Da) and Acquity UPLC from waters company: binary pumps, heated column chambers, diode array detectors, and ELSD detectors. Column: waters UPLC HSS T3,1.8 μm, 30X 2.1mm, temperature: 60 ℃, DAD wavelength range (nm): 210 to 500, solvent gradient: a=water+5% meoh+0.05% HCOOH, b=acetonitrile+0.05% HCOOH; gradient: 10% -100% B, within 1.2 min; the flow rate (mL/min) was 0.85.

Method G1:

spectra were recorded on a mass spectrometer from waters (SQD, SQDII single quadrupole mass spectrometer) equipped with electrospray sources (polarity: positive and negative ions), capillary voltage: 0.8kV, taper hole range: 25V, source temperature: desolvation temperature at 120 ℃): 600 ℃, taper hole gas flow: 50l/h, desolvation gas flow: 1000l/h, mass range: 110Da to 850 Da) and the Acquity UPLC from waters company: binary pumps, heated column chambers, diode array detectors, and ELSD detectors. Column: waters UPLC HSS T3C 18,1.8 μm, 30X 2.1mm, temperature: 40 ℃, DAD wavelength range (nm): 230 to 400, solvent gradient: a=water+0.05% HCOOH, b=acetonitrile+0.05% HCOOH: gradient: 10% -100% B, within 1.6 min; the flow rate (mL/min) was 0.60.

Method H1:

at SFC Waters Acquity UPC ² The spectrum was recorded on/QDa, where it was recorded on PDA detector Waters Acquity UPC ² And (5) detecting. Column: daicel SFCIE,3mm,0.3 cm. Times.10 cm, mobile phase at 40 ℃): a: CO ₂ B: 2-propanol, no gradient: 15% B, ABPR in 4.8 min: 1800psi, flow rate: 2.0ml/min, detection: 240nm, sample concentration: 1mg/mL in methanol/2-propanol, injection: 2. Mu.L.

Table E:melting point (mp) and/or LC/MS data (retention time (R) _t ))：

Fabricius graminearum (septoria tritici)/preventive on wheat

Wheat plant cultivar Riband, 2 weeks old, was sprayed with the formulated test compound diluted in water in a spray booth. One day after spray application, the test plants were inoculated by spraying a spore suspension thereon, and then kept in a greenhouse at 22 ℃/21 ℃ (day/night). Disease damage was directly assessed when appropriate levels of disease were present on untreated control plants and compared to untreated controls to calculate efficacy (16 to 19 days post application).

The following compounds listed in table E (above) gave at least 80% control of c.graminearum at 60ppm when compared to untreated controls that showed extensive disease development under the same conditions.

E.01、E.02、E.03、E.05、E.08、E.11、E.12、E.13、E.14、E.16、E.25。

Fusarium yellow liquid culture (scab)

Fungal conidia from frozen storage are directly mixed into the nutrient broth (PDB-potato dextrose broth). After placing the (DMSO) solution of the test compound in a microtiter plate (96-well format), the nutrient broth containing the fungal spores is added. The test plates were incubated at 24 ℃ and inhibition of growth was determined photometrically 3 to 4 days after application.

The following compounds in table E (above) gave at least 80% control of fusarium yellow at 20ppm when compared to untreated controls that showed extensive disease development under the same conditions:

E.03、E.04、E.05、E.06、E.07、E.08、E.09、E.10、E.11、E.12、E.13、E.14、E.15、E.16、E.17、E.19、E.21、E.23、E.24、E.25。

fusarium yellow/wheat/spike preventive (scab)

Wheat ear cultivar Monsun was placed on agar in multiwell plates (24-well format) and sprayed with formulated test compound diluted in water. The spikelets were inoculated with a spore suspension of the fungus 1 day after application. The inoculated spikelets were incubated at 20 ℃ and 60% relative humidity in a climatic chamber under a light regimen of 72h semi-darkness followed by 12h light/12 h darkness, and when appropriate levels of disease damage occurred on untreated, comparative spikelets (6-8 days after application), the activity of the compounds was assessed as percent disease control when compared to untreated.

The following compounds in table E (above) gave at least 80% control of fusarium yellow at 200ppm when compared to untreated controls that showed extensive disease development under the same conditions:

E.05、E.06、E.08、E.14、E.15、E.19。

clostridium snow rot (Rhizoctonia solani)/liquid culture (cereal root rot)

Fungal conidia from frozen storage are directly mixed into the nutrient broth (PDB-potato dextrose broth). After placing the (DMSO) solution of the test compound in a microtiter plate (96-well format), the nutrient broth containing the fungal spores is added. The test plates were incubated at 24 ℃ and inhibition of growth was determined photometrically 4 to 5 days after application.

The following compounds in table E (above) gave at least 80% control of clostridium snow rotundum at 20ppm when compared to untreated controls that showed extensive disease development under the same conditions:

E.03、E.04、E.05、E.06、E.07、E.08、E.09、E.11、E.12、E.13、E.14、E.15、E.16、E.17、E.18、E.19、E.20、E.21、E.23、E.24。

botrytis cinerea (Botryotinia fuckeliana or Botrytis cinerea)/liquid culture (Botrytis cinerea)

Fungal conidia from frozen storage are directly mixed into a nutrient broth (Vogels) broth. After placing the (DMSO) solution of the test compound in a microtiter plate (96-well format), the nutrient broth containing the fungal spores is added. The test plates were incubated at 24 ℃ and inhibition of growth was determined photometrically 3-4 days after application.

The following compounds gave at least 80% control of botrytis cinerea at 20ppm when compared to untreated controls that showed extensive disease development under the same conditions:

E.01、E.02、E.03、E.04、E.05、E.06、E.07、E.08、E.09、E.10、E.11、E.12、E.13、E.14、E.15、E.16、E.17、E.18、E.19、E.20、E.21、E.22、E.23、E.24、E.25。

sphaeromyces cucumeris (Glomerella lagenarium) (Colletotrichum) lagenarium))/liquid culture (anthracnose)

Fungal conidia from frozen storage are directly mixed into the nutrient broth (PDB-potato dextrose broth). After placing the (DMSO) solution of the test compound in a microtiter plate (96-well format), the nutrient broth containing the fungal spores is added. The test plates were incubated at 24 ℃ and inhibition of growth was measured photometrically 3-4 days after application.

The following compounds gave at least 80% control of chaetomium cucumerinum at 20ppm when compared to untreated controls that showed extensive disease development under the same conditions:

E.01、E.02、E.03、E.04、E.05、E.06、E.07、E.08、E.09、E.11、E.12、E.13、E.14、E.15、E.17、E.18、E.19、E.20、E.25。

comparative example

Fabricius graminearum (septoria tritici)/preventive on wheat

In the spray chamber, wheat plant cultivar Riband, 2 weeks old, was sprayed with test compound formulated as emulsifiable concentrate diluted in water. One day after application, the test plants were inoculated by spraying a spore suspension thereon, and then kept in a greenhouse at 22 ℃/21 ℃ (day/night). Disease damage was directly assessed when appropriate levels of disease were present on untreated control plants and compared to untreated controls to calculate efficacy (16 to 19 days post application).

Botrytis cinerea/tomato/preventive (Botrytis cinerea on tomato)

Tomato plants of 4 weeks old were spray treated with test compounds formulated as emulsifiable concentrates diluted in water in a spray chamber. Two days after application, the test plants were inoculated by spraying them with a spore suspension. Inoculated test plants were grown in a greenhouse at 20 ℃ and 95% relative humidity, and when an appropriate level of disease appeared on untreated comparative plants (5-6 days after application), the percentage of leaf area covered by the disease was assessed.

Cladosporium cucumerinum/apple/preventive (scab on apple)

Apple seedlings of 3 weeks old were sprayed with test compound formulated as emulsifiable concentrate diluted in water in a spray chamber. 1 day after application, test plants were inoculated by spraying them with a spore suspension. After a 2 day incubation period at 20 ℃ and 95% relative humidity, the inoculated test plants were placed in the greenhouse at 20 ℃/19 ℃ (day/night) and 60% relative humidity. When an appropriate level of disease appears on untreated control plants (11-13 days after application), the percentage of leaf area covered by the disease is assessed.

Melon anthrax/cucumber/preventive (anthracnose)

In the spray booth, the 1 week old cucumber plant cultivar Wisconsin was sprayed with the test compound formulated as emulsifiable concentrate diluted in water. One day after application, the test plants were inoculated by spraying them with a spore suspension. After a incubation period of 30h in the dark at 23 ℃ and 100% relative humidity, the inoculated test plants were kept in the greenhouse at 23 ℃/21 ℃ (day/night) and 70% relative humidity. When an appropriate level of disease appears on untreated control plants (6-8 days after application), the percentage of leaf area covered by the disease is assessed.

In the comparative experimental examples above, it was shown that the control of the selected compounds according to the invention on the species sphaericus (septoria graminea) was significantly better than the compounds of the prior art (WO 2009/119089).

Furthermore, in the above comparative examples, it was demonstrated that the compounds according to the invention exhibit excellent control of the species sphaericus (septoria graminea) without impairing the scope of other diseases controlled by the compounds of the prior art.

Claims (15)

1. A compound having the formula (I):

wherein:

R ¹ is fluorine, chlorine, cyano or methyl;

R ² is hydrogen or fluorine;

R ³ hydrogen, difluoromethyl or methyl;

R ⁴ is C ₁ -C ₆ Alkyl, C ₁ -C ₆ Haloalkyl, C ₂ -C ₆ Alkenyl, C ₂ -C ₆ Alkynyl, C ₂ -C ₆ Haloalkenyl, C ₃ -C ₆ Cycloalkyl, C ₃ -C ₆ Cycloalkyl C ₁ -C ₂ Alkyl or heteroaryl C ₁ -C ₂ An alkyl group; wherein the heteroaryl is a 5-or 6-membered monocyclic aromatic ring containing 1, 2, 3 or 4 heteroatoms independently selected from N, O and S and optionally is substituted with 1, 2 or 3 heteroatoms independently selected from halogen, C ₁ -C ₃ Alkyl, C ₁ -C ₃ Substituents for alkoxy or cyano; and is also provided with

R ⁵ Is hydrogen or C ₁ -C ₄ An alkyl group; or (b)

R ⁴ And R is ⁵ Forming a cyclobutyl, cyclopentyl or cyclohexyl ring together with the attached carbon atom, wherein the ring structure is optionally substituted by 1, 2, 3 or 4 substituents independently selected from fluoro, cyano, methyl, methoxy;

R ⁶ Is chlorine, bromine, iodine, C ₁ -C ₄ Alkyl, C ₁ -C ₄ Haloalkyl, C ₂ -C ₄ Alkenyl, C ₂ -C ₄ Haloalkenyl, C ₂ -C ₄ Alkynyl, C ₁ -C ₄ Alkoxy, C ₁ -C ₄ Alkylthio, C ₃ -C ₅ Cycloalkoxy radicals C ₁ -C ₄ Haloalkoxy, cyano, C ₃ -C ₅ Cycloalkyl or CR ¹⁰ (＝NOR ⁸ ) The method comprises the steps of carrying out a first treatment on the surface of the And is also provided with

R ⁷ Is hydrogen, halogen,C ₁ -C ₄ Alkyl, C ₁ -C ₄ Haloalkyl or cyano, or

R ⁶ Is fluorine and R ⁷ Is halogen or C ₁ -C ₄ An alkyl group;

R ⁸ is C ₁ -C ₄ Alkyl, C ₁ -C ₄ Haloalkyl, C ₃ -C ₅ Alkenyl, C ₃ -C ₅ Haloalkenyl or C ₃ -C ₅ Alkynyl;

a is N or CR ⁹ ；

R ⁹ Hydrogen, difluoromethyl or methyl; and is also provided with

R ¹⁰ Is C ₁ -C ₄ An alkyl group; or (b)

An agronomically acceptable salt, N-oxide and/or S-oxide or stereoisomer thereof.

2. The compound of claim 1, wherein R ¹ Is fluorine.

3. A compound according to claim 1 or claim 2, wherein R ³ Is hydrogen or methyl.

4. A compound according to any one of claims 1 to 3, wherein R ⁴ Is C ₁ -C ₄ Alkyl, C ₁ -C ₄ Haloalkyl, C ₃ -C ₆ Cycloalkyl or (6-chloro-pyridin-3-yl) methyl.

5. The compound of any one of claims 1 to 4, wherein R ⁵ Is hydrogen or methyl.

6. A compound according to any one of claims 1 to 3, wherein R ⁴ And R is ⁵ Together with the attached carbon atoms, form a cyclopentyl ring, wherein the ring structure is optionally substituted with 1 or 2 substituents independently selected from fluoro, cyano, methyl, methoxy.

7. The compound of any one of claims 1 to 6, wherein R ⁶ Is chlorine, bromine, iodine, C ₁ -C ₄ Alkyl, C ₁ -C ₄ Alkylthio, cyano, C ₁ -C ₄ Haloalkyl, C ₁ -C ₄ Alkoxy, C ₁ -C ₄ Alkoxy or C ₃ -C ₅ Cycloalkyl, and preferably R ⁶ Is chloro, methyl, cyano, methylsulfanyl.

8. The compound of any one of claims 1 to 7, wherein R ⁶ Is chloro, bromo, iodo, methyl, ethyl, methylsulfanyl, cyano, difluoromethyl, trifluoromethyl, methoxy, ethoxy, cyclopropyl, cyclobutyl, and R ⁷ Is hydrogen, chlorine or methyl.

9. The compound of any one of claims 1 to 6, wherein R ⁶ Is fluorine and R ⁷ Is methyl.

10. The compound of any one of claims 1 to 9, wherein a is CR ⁹ And wherein R is ⁹ Is hydrogen.

11. An agrochemical composition comprising a fungicidally effective amount of a compound according to any one of claims 1 to 10.

12. The composition of claim 11, further comprising at least one additional active ingredient and/or an agrochemically acceptable diluent or carrier.

13. A method for controlling or preventing infestation of useful plants by phytopathogenic microorganisms, wherein a fungicidally effective amount of a compound according to any one of claims 1 to 10, or a composition comprising the compound as active ingredient, is applied to the plants, parts thereof or the locus thereof.

14. The method according to claim 13, wherein the phytopathogenic microorganism is a globus gramineus and the useful plant is a cereal, in particular wheat.

15. Use of a compound according to any one of claims 1 to 10 as a fungicide.