CN112020503A - Microbicidal oxadiazole derivatives - Google Patents

Abstract

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

Description

Microbicidal oxadiazole derivatives

The present invention relates to microbicidal oxadiazole derivatives, for example as active ingredients, which have microbicidal, in particular fungicidal, activity. The invention also relates to agrochemical compositions comprising at least one of these oxadiazole derivatives, to processes for the preparation of these compounds, and to the use of these oxadiazole 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, preferably fungi.

EP 0276432 and WO 2015/185485 describe the use of substituted oxadiazoles for combating phytopathogenic fungi.

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

wherein

A is A-1, A-2, A-3, or A-4;

and A-1, A-2, A-3, or A-4 is optionally substituted with one or two independently selected halogen groups;

R¹and R²Independently selected from hydrogen, methyl and cyano; or

R¹And R²Together with the carbon atom to which they are bonded form a cyclopropyl ring;

R³is hydroxy, C_1-4Alkoxy or C_1-3A haloalkoxy group;

z is R⁴Wherein R is⁴Is C_3-6Cycloalkyl or heterocyclyl, wherein the heterocyclyl moiety is a 4-to 6-membered non-aromatic ring, said ring comprising 1 or 2 rings independently selected from N, NR⁵Heteroatoms or groups of O and S; wherein said cycloalkyl or heterocyclyl is optionally substituted by 1 or 2 substituents selected from R⁶May be the same or different;

R⁶is a cyano group,Halogen, hydroxy, amino, methyl, ethyl, propyl, cyclopropyl, prop-2-enyl, prop-2-ynyl, difluoromethyl, trifluoromethyl, methoxy, ethoxy, difluoromethoxy, prop-2-enyloxy, prop-2-ynyloxy, N-methylamino, N-dimethylamino, methylcarbonyl, methoxycarbonyl, formylamino, N-methylaminocarbonyl, N-dimethylaminocarbonyl or methoxycarbonylamino; and wherein Z may optionally contain 1 atom selected from C (O) or S (O)₂A group of (a); and is

R⁵Represents hydrogen, methyl, methoxy, formyl or acyl;

or

R³And Z together with the-N-C (═ S) -group to which they are bonded form a 4-to 7-membered non-aromatic heterocyclyl ring, wherein said heterocyclyl optionally comprises 1 or 2 substituents independently selected from N, O, S, C (O) and S (O)₂Provided that said heterocyclyl ring does not contain 2 adjacent atoms selected from O and S, and said heterocyclyl is optionally substituted with 1 or 2 substituents, which may be the same or different, selected from: cyano, halogen, hydroxy, amino, C_1-4Alkyl radical, C_1-4Haloalkyl and C_1-4An alkoxy group; or the group R³And Z is a heterocyclic radical formed by C_3-6Cycloalkyl substituted to form a spiro ring;

or a salt 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.

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 having formula (I) as a fungicide. According to this particular aspect of the invention, the use may not include a method of treatment of the human or animal body by surgery or therapy.

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

As used herein, cyano means a-CN group.

As used herein, the term "hydroxyl" means an — OH group.

As used herein, amino means-NH₂A group.

As used herein, acyl means-C (O) CH₃A group.

As used herein, formyl means a-C (O) H group.

As used herein, the term "C_1-4Alkyl "refers to a straight or branched hydrocarbon chain group consisting only of carbon and hydrogen atoms, which is free of unsaturation, has from one to four carbon atoms, and is attached to the rest of the molecule by a single bond. C_1-3Alkyl and C_1-2Alkyl groups should be construed accordingly. C_1-4Examples of alkyl groups include, but are not limited to, methyl, ethyl, n-propyl, 1-methylethyl (isopropyl), n-butyl, and 1-dimethylethyl (tert-butyl). "C_1-2Alkylene "radical means C_1-2Alkyl groups are defined accordingly, except that such groups are attached to the rest of the molecule by two single bonds. C_1-2An example of alkylene is-CH₂-and-CH₂CH₂-。

As used herein, the term "C_1-4Alkoxy "means having the formula R_aA group of O-wherein R_aIs C as generally defined above_1-4An alkyl group. Term C_1-3Alkoxy and C_1-2Alkoxy radicalThe radicals should be interpreted accordingly. C_1-4Examples of alkoxy groups include, but are not limited to, methoxy, ethoxy, propoxy, isopropoxy, and tert-butoxy.

As used herein, the term "C_1-2Haloalkoxy "means C as defined above substituted by one or more of the same or different halogen atoms_1-2An alkoxy group. C_1-2Examples of haloalkoxy include, but are not limited to, fluoromethoxy, difluoromethoxy, fluoroethoxy, trifluoromethoxy, and trifluoroethoxy.

As used herein, the term "C_3-6Cycloalkyl "refers to a stable monocyclic group that is saturated or partially unsaturated and contains 3 to 6 carbon atoms. C_3-5Cycloalkyl and C_3-4Cycloalkyl groups should be interpreted accordingly. C_3-6Examples of cycloalkyl groups include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclopenten-1-yl, cyclopenten-3-yl, and cyclohexen-3-yl.

As used herein, the term "heterocyclyl" or "heterocyclic" generally refers to a stable, saturated or partially saturated 4-to 6-membered non-aromatic monocyclic ring containing 1 or 2 heteroatoms independently selected from nitrogen, oxygen, and sulfur. The heterocyclyl group may be bonded to the remainder of the molecule via a carbon atom or heteroatom. Examples of heterocyclyl groups include, but are not limited to, azetidinyl, oxetanyl, pyrrolidinyl, tetrahydrofuranyl, tetrahydrothienyl, tetrahydrothiopyranyl, piperidinyl, piperazinyl, tetrahydropyranyl, dioxolanyl, and morpholinyl.

The presence of one or more possible asymmetric carbon atoms in the compound having formula (I) means that the compound can exist in chiral isomeric forms, i.e. enantiomeric or diastereomeric forms. Atropisomers may also be present as a result of restricted rotation about a single bond. The compounds of formula (I) are 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, compounds having formula (I) are intended to include all possible tautomers (including lactam-lactam tautomerism and keto-enol tautomerism), when present. The present invention includes all possible tautomeric forms of the compounds having formula (I).

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

N-oxides are oxidized forms of tertiary amines or oxidized forms of nitrogen-containing heteroaromatic compounds. For example, a. albini and s.pietra described them in a book entitled "Heterocyclic N-oxides" published in 1991 by bocardon (Boca Raton) CRC press.

The following list provides substituents A (including A-1, A-2, A-3, or A-4), Z, R for the compounds of the invention having formula (I)¹、R²、R³、R⁴、R⁵And R⁶The definition of (1) includes preferred definitions. For any of these substituents, any of the definitions given below may be combined with any of the definitions given below or any other substituent given elsewhere in this document.

A is A-1, A-2, A-3, or A-4,

wherein A-1, A-2, A-3, or A-4 is optionally substituted with 1 or 2 independently selected halogen groups. Preferably, the halogen is chlorine or fluorine, and most preferably is fluorine.

In some embodiments of the invention, A is A-1.

In some embodiments of the invention, A is A-2.

In some embodiments of the invention, A is A-3.

In some embodiments of the invention, A is A-4.

Preferably, A is A-1 optionally substituted with 1 or 2 fluoro groups, or A is unsubstituted A-4. More preferably, A is unsubstituted A-1(1, 4-phenylene) or unsubstituted A-4(2, 5-thienylene).

R¹And R²Independently selected from hydrogen, methyl and cyano; or R¹And R²Together with the carbon atom to which they are bonded form a cyclopropyl ring. Preferably, R¹And R²Independently selected from hydrogen and methyl (e.g., R)¹Is hydrogen and R²Is methyl) and more preferably, R¹And R²Is hydrogen.

R³Is hydroxy, C_1-4Alkoxy or C_1-3A haloalkoxy group. Preferably, R³Is C_1-4Alkoxy or C_1-2Fluoroalkoxy, and more preferably, R³Is methoxy, ethoxy or 2, 2-difluoroethoxy.

Z is R⁴Wherein R is⁴Is C_3-6Cycloalkyl or heterocyclyl, wherein the heterocyclyl moiety is a 4-to 6-membered non-aromatic ring, said ring comprising 1 or 2 rings independently selected from N, NR⁵Heteroatoms or groups of O and S; wherein said cycloalkyl or heterocyclyl is optionally substituted by 1 or 2 substituents selected from R⁶May be the same or different.

Preferably, R⁴Is C_3-6Cycloalkyl optionally substituted by 1 or 2 radicals selected from R⁶May be the same or different. More preferably, R⁴Is C_3-4Cycloalkyl optionally substituted by 1 or 2 radicals selected from R⁶May be the same or different. Even more preferably, R⁴Is C_3-4Cycloalkyl, optionally substituted with 1 or 2 substituents, which may be the same or different, selected from: cyano, halogen, hydroxy, amino, methyl, ethyl and propyl. Still more preferably, R⁴Is cyclopropyl optionally substituted by 1R⁶Wherein R is⁶Selected from cyano, halogen, hydroxy, amino, methyl, ethyl, n-propyl and isopropyl.

R⁶Is cyano, halogen, hydroxy, amino, methyl, ethyl, n-propyl, isopropyl, cyclopropyl, prop-2-enyl, prop-2-ynyl, difluoromethyl, trifluoromethylMethoxy, ethoxy, difluoromethoxy, prop-2-enyloxy, prop-2-ynyloxy, N-methylamino, N-dimethylamino, methylcarbonyl, methoxycarbonyl, formylamino, N-methylaminocarbonyl, N-dimethylaminocarbonyl or methoxycarbonylamino.

Z may optionally contain 1 element selected from C (O) or S (O)₂A group of (1).

R⁵Represents hydrogen, methyl, methoxy, formyl or acyl.

In other embodiments of the invention, in the compounds having formula (I), R³And Z together with the-N-C (═ S) -group to which they are bonded may form a 4-to 7-membered non-aromatic heterocyclyl ring, wherein said heterocyclyl optionally comprises 1 or 2 substituents independently selected from N, O, S, C (O) and S (O)₂Provided that said heterocyclyl ring does not contain 2 adjacent atoms selected from O and S, and said heterocyclyl is optionally substituted with 1 or 2 substituents, which may be the same or different, selected from: cyano, halogen, hydroxy, amino, C_1-4Alkyl radical, C_1-4Haloalkyl and C_1-4Alkoxy, or said from R³And Z is a heterocyclic radical formed by C_3-6Cycloalkyl groups are substituted to form spiro rings.

Preferably, R³And Z together with the-N-C (═ S) -group to which they are bonded form a group selected from:

wherein X₁And X₂is-CH₂-or-O-and each group is optionally substituted with 1 or 2 substituents which may be the same or different selected from: cyano, halogen, hydroxy, amino, C_1-4Alkyl radical, C_1-4Haloalkyl and C_1-4Alkoxy, and more preferably, optionally substituted with 1 or 2 substituents which may be the same or different selected from: cyano, halogen, hydroxy, amino, methyl, ethyl, C_1-2Fluoroalkyl, methoxy and ethoxy, and even more preferably, it isOptionally substituted with 1 or 2 substituents which may be the same or different selected from: halogen, methyl, ethyl and methoxy.

Preferably, the compound according to formula (I) is selected from compounds 1.1 to 1.6 listed in table T1 (below).

Preferably, in the compounds according to formula (I) of the present invention:

a is A-1 or A-4 optionally substituted with 1 or 2 fluoro groups;

R¹and R²Independently selected from hydrogen and methyl;

R³is C_1-2Alkoxy or C_1-2A fluoroalkoxy group; and is

R⁴Is C_3-4Cycloalkyl optionally substituted by 1 or 2 radicals selected from R⁶May be the same or different.

More preferably still, the first and second liquid crystal compositions are,

a is A-1 or A-4 optionally substituted with 1 or 2 fluoro groups;

R¹and R²Is hydrogen;

R³is methoxy, ethoxy or 2, 2-difluoroethoxy; and is

R⁴Is C_3-4Cycloalkyl optionally substituted by 1 or 2 radicals selected from R⁶May be the same or different, wherein R is⁶Selected from cyano, halogen, hydroxy, amino, methyl, ethyl and propyl.

Even more preferably still, the first and second substrates are,

a is unsubstituted A-1 or unsubstituted A-4;

R¹and R²Is hydrogen;

R³is a methoxy group; and is

R⁴Is cyclopropyl optionally substituted by 1R⁶Wherein R is⁶Selected from cyano, halogen, hydroxy, amino, methyl, ethyl, n-propyl and isopropyl.

Preferably, in the compounds according to formula (I) of the present invention:

a is A-1 or A-4 optionally substituted with 1 or 2 fluoro groups;

R¹and R²Independently selected from hydrogen and methyl; and is

R³And Z together with the-N-C (═ S) -group to which they are bonded form a group selected from:

wherein X₁And X₂is-CH₂-or-O-and each group is optionally substituted with 1 or 2 substituents which may be the same or different selected from: cyano, halogen, hydroxy, amino, C_1-4Alkyl radical, C_1-4Haloalkyl and C_1-4An alkoxy group.

More preferably still, the first and second liquid crystal compositions are,

a is unsubstituted A-1 or unsubstituted A-4;

R¹and R²Independently selected from hydrogen and methyl; and is

R³And Z together with the-N-C (═ S) -group to which they are bonded form a group selected from:

wherein X₁And X₂is-CH₂-or-O-and each group is optionally substituted by 1 or 2 substituents selected from C_1-4Alkyl groups (e.g., methyl) may be substituted with the same or different substituents.

The compounds of formula (I) are characterized by a thiocarbonyl moiety and are believed to act in vivo under suitable conditions (e.g., metabolic processes or biosynthetic transformations) as precursors (procides) to compounds of formula (II) characterized by a carbonyl moiety (e.g., an amide or a urea).

The compounds of the invention may be of the formulaAn enantiomer of a compound of formula (I) represented by formula (Ia) or formula (Ib), wherein R¹And R²Are different substituents.

It will be appreciated that the compounds of formula (I) according to the invention may be present in CF when in an aqueous medium₃The reversible equilibrium of the corresponding covalently hydrated forms at the oxadiazole motif (i.e. the compounds of formula (I-I) and (I-II) shown below, which may exist as tautomers as compounds of formula (I-Ib) and (I-IIb)). This dynamic equilibrium may be important for the biological activity of the compound having formula (I).

A (including A-1, A-2, A-3, or A-4), R for the compounds of formula (I) of the invention¹、R²、R³、Z、R⁴And R⁵The designations of (A) and (B) generally apply to compounds having the formula (I-I) and (I-II), and to A (including A-1, A-2, A-3, or A-4), R¹、R²、R³、Z、R⁴And R⁵As shown in table 1.1 to table 1.11, table 2.1 to table 2.10, or compounds 1.1 to 1.6 according to the invention as listed in table T1 (below).

The compounds of the invention may be prepared as shown in schemes 1 to 14 below, wherein (unless otherwise specified) the definition of each variable is as defined above for the compounds of formula (I).

The compound of formula (I) can be prepared from the compound of formula (II) by reacting in an acceptable solvent (e.g., toluene, CH)₂Cl₂、CHCl₃Tetrahydrofuran, tert-butyl methyl ether) at a temperature of between 0 ℃ and 100 ℃ with a suitable source of sulphur [ e.g. elemental sulphur (S)₈) Lawson's reagent (L)awesson's reagent), or P₂S₅]The reaction of (1). For related examples, see Hermant, F. et al Organometallics [ organometallic ]](2014),33,5643; heyde, c, et al e.j.org.chem. [ european journal of organic chemistry](2000),19,3273. This reaction is shown in scheme 1.

Scheme 1

A compound having the formula (III) (wherein Z^aIs hydrogen, C (O) R⁴、C(S)R⁴Or R is³And Z^aTogether with the nitrogen atom to which they are bonded to form a 4-to 7-membered non-aromatic heterocyclyl ring containing 1 or 2 groups selected from C (O) or C (S) may be prepared from a compound of formula (V) wherein X is OH, OSO₂Me, Cl, Br, or I, preferably Br or I), by reaction optionally in the presence of a base (e.g. triethylamine, N-diisopropylethylamine, K₂CO₃、NaHCO₃Or Na₂CO₃) With a compound of formula (IV) in a suitable solvent (e.g. dimethylacetamide, tetrahydrofuran, 2-methyltetrahydrofuran, acetone, toluene, or acetonitrile) at a temperature between 25 ℃ and 110 ℃. In some cases, by using a catalyst (e.g., Bu)₄NHSO₄、Bu₄NBr、Bu₄NI, NaI or 4-dimethylaminopyridine) and optionally under microwave irradiation. For related examples, see: WO 1995/9518122 and jpn. kokai Tokkyo Koho, (1993), 05286936; heterocycles [ Heterocycles ] Miyawaki, K](2001) 54,887; WO 2003/028729; WO 2013/066839; and WO 2017/055473. This reaction is shown in scheme 2.

Scheme 2

Alternatively, the compound of formula (I) may be obtained by coupling conversion of a compound of formula (VI) and a compound of formula (VII) in a suitable solvent (e.g. dimethylformamide, dichloromethane or tetrahydrofuran) at a temperature between 0 ℃ and 100 ℃ and optionally in the presence of a base such as triethylamine. See, for example, WO 2004/046162. Compounds having formula (VI) are commercially available. This reaction is shown in scheme 3.

Scheme 3

In addition, compounds having formula (I) can be prepared from compounds having formula (VIII) by reaction with trifluoroacetic acid, a trifluoroacetate ester (e.g., methyl or ethyl trifluoroacetate), trifluoroacetic anhydride, or a trifluoroacetyl halide (including trifluoroacetyl fluoride, trifluoroacetyl chloride, and trifluoroacetyl bromide), optionally in the presence of a base (e.g., pyridine or 4-dimethylaminopyridine) in a suitable solvent (e.g., toluene, ethyl acetate, tetrahydrofuran, 2-methyltetrahydrofuran, or ethanol) at a temperature between 0 ℃ and 75 ℃. For related examples, see WO 2003/028729, WO 2017/055473, and WO 2010/045251. This reaction is shown in scheme 4.

Scheme 4

The compound of formula (VIII) can be prepared from the compound of formula (IX) by reaction with hydroxylamine hydrochloride or an aqueous hydroxylamine solution in the presence of a base such as triethylamine or potassium carbonate in a suitable solvent such as methanol or ethanol at a temperature between 0 ℃ and 80 ℃. In some cases better reaction performance can be obtained from the use of a catalyst (e.g. 8-hydroxyquinoline). For related examples, see Kitamura, s, et al chem.pharm.bull. [ chemical and pharmaceutical bulletin ] (2001),49,268, WO 2017/055473, and WO 2013/066838. This reaction is shown in scheme 5.

Scheme 5

The compound of formula (IX) can be prepared from a compound of formula (X) wherein Y is formyl, Cl, Br, or I, by reacting with a cyanide reagent (such as acetone cyanohydrin, dimethyl malononitrile, K) in a suitable solvent (e.g., dimethylformamide or N-methylpyrrolidinone) at an elevated temperature between 80 ℃ and 120 ℃ and optionally in the presence of a metal catalyst (e.g., Pd or Ni), organomagnesium, or organolithium reagent₄[Fe(CN)₆]、Zn(CN)₂NaCN, or CuCN). For related examples, see Reeves, j.t. et al j.am.chem.soc. [ society of american chemical society](2015) 137,9481; ushijima, s., Togo, h.synlett [ quick synthesis report ]](2010), 1067; US 2007/0155739, WO 2017/055473, and WO 2009/022746. This reaction is shown in scheme 6.

Alternatively, the compound having formula (IX) may be prepared from a compound having formula (X) (wherein Y is NH₂) By using a suitable nitrite source (e.g., NaNO) in an acceptable solvent (e.g., aqueous acetonitrile) at a temperature between 0 ℃ and 100 ℃₂Or isoamyl nitrite), a suitable acid (e.g., hydrochloric acid or HBF₄) And radical-nucleophilic aromatic substitution of a copper source (e.g., CuCN). For a related example, see Wen, Q, et al, Tet.Lett. [ tetrahedron letters](2014),55,1271. This reaction is shown in scheme 6.

Scheme 6

Compounds having the formula (X) (wherein Y is CN, NH)₂Cl, Br, or I) can be prepared from compounds having formula (XI) by reaction in an acceptable solvent (e.g., CH)₂Cl₂Tetrahydrofuran, tert-butyl methyl ether) at a temperature between 0 ℃ and 100 ℃ with a suitable source of sulfur [ e.g. elemental sulfur (S)₈) Lawson's reagent, or P₂S₅]The reaction of (1). For related examples, see Hermant, FOrganometallics](2014),33,5643; heyde, c, et al e.j.org.chem. [ european journal of organic chemistry](2000),19,3273. This reaction is shown in scheme 7.

Scheme 7

Compounds of formula (X) wherein Y is formyl, CN, Cl, Br, or I may be obtained by coupling conversion of a compound of formula (VI) and a compound of formula (XII) in a suitable solvent (e.g. dimethylformamide, dichloromethane or tetrahydrofuran) at a temperature between 0 ℃ and 100 ℃ and optionally in the presence of a base such as triethylamine. See, for example, WO 2004/046162. Compounds having formula (VI) are commercially available. This reaction is shown in scheme 8.

Scheme 8

A compound having formula (XIII) (wherein Y is CN, Cl, Br, or I, and Z^aIs hydrogen, C (O) R⁴、C(S)R⁴Or R is³And Z^aTogether with the nitrogen atom to which they are bonded to form a 4-to 7-membered non-aromatic heterocyclyl ring containing 1 or 2 groups selected from C (O) or C (S) may be prepared from a compound of formula (XIV) wherein X is OH, OSO₂Me, Cl, Br, or I, preferably Br or I) by reaction optionally in the presence of a base (e.g., triethylamine, N-diisopropylethylamine, K₂CO₃、NaHCO₃Or Na₂CO₃) With a suitable compound of formula (IV) in a suitable solvent (e.g. dimethylacetamide, tetrahydrofuran, 2-methyltetrahydrofuran, acetone, toluene, or acetonitrile) at a temperature between 25 ℃ and 110 ℃. In some cases, by catalyst use (e.g., Bu)₄NHSO₄、Bu₄NBr、Bu₄NI, NaI, or 4-dimethylaminopyridine), optionally under microwave irradiationBetter reaction performance is obtained. For related examples, see: WO 1995/9518122 and jpn. kokai Tokkyo Koho, (1993), 05286936; heterocycles [ Heterocycles ] Miyawaki, K](2001) 54,887; WO 2003/028729; WO 2013/066839; and WO 2017/055473. This reaction is shown in scheme 9.

Scheme 9

Compounds of formula (V) wherein X is Cl or Br can be prepared from compounds of formula (XV) by reaction with a suitable halogen source (e.g., N-bromosuccinimide (NBS) or N-chlorosuccinimide (NCS)) and a free radical initiator (e.g., (PhCO @) in a suitable solvent (e.g., tetrachloromethane) at a temperature between 55 ℃ and 100 ℃, optionally in the presence of ultraviolet light₂)₂Or Azobisisobutyronitrile (AIBN)). For related examples, see WO 2017/055473; liu, S, et al Synthesis](2001) 14,2078; and Kompella, a. et al org.proc.res.dev. [ organic processing research and development](2012) 16,1794, and WO 2017/055473. This reaction is shown in scheme 10.

Scheme 10

Alternatively, a compound having formula (V) (wherein X is OH, OSO)₂Me, Cl, Br, or I, preferably OH) can be prepared from a compound having formula (XVI) by reaction with trifluoroacetic acid, a trifluoroacetate ester (e.g., methyl or ethyl trifluoroacetate), trifluoroacetic anhydride, or a trifluoroacetyl halide (including trifluoroacetyl fluoride, trifluoroacetyl chloride, and trifluoroacetyl bromide), optionally in the presence of a base (e.g., pyridine or 4-dimethylaminopyridine), in a suitable solvent (e.g., toluene, ethyl acetate, tetrahydrofuran, 2-methyltetrahydrofuran, or ethanol) at a temperature between 0 ℃ and 75 ℃. For related examples, see WO 2003/028729, WO 2017/055473, and WO 2010/045251. This reaction is shown inScheme 11.

Scheme 11

A compound having the formula (XVI) (wherein X is OH, OSO)₂Me, Cl, Br, or I, preferably OH) can be prepared from a compound having formula (XVII) by reaction with hydroxylamine hydrochloride or an aqueous hydroxylamine solution, optionally in the presence of a base such as triethylamine or potassium carbonate, in a suitable solvent such as methanol or ethanol at a temperature between 0 ℃ and 80 ℃. In some cases better reaction performance can be obtained from the use of a catalyst (e.g. 8-hydroxyquinoline). For related examples, see Kitamura, s, et al chem.pharm.bull [ chemical and pharmaceutical bulletins](2001) 49,268, WO 2017/055473 and WO 2013/066838. This reaction is shown in scheme 12.

Scheme 12

A compound having the formula (XVII) (wherein X is OH, OSO)₂Me, Cl, Br, or I) is commercially available or can be prepared from compounds of formula (XVIII) wherein Y is formyl, Cl, Br, or I by reaction with cyanide reagents (such as acetone cyanohydrin, dimethyl malononitrile, K) in a suitable solvent (e.g., dimethylformamide or N-methylpyrrolidone) at elevated temperatures between 80 ℃ and 120 ℃ and optionally in the presence of a metal catalyst (e.g., Pd or Ni), organomagnesium, or organolithium reagent₄[Fe(CN)₆]、Zn(CN)₂NaCN, or CuCN). For related examples, see Reeves, j.t. et al j.am.chem.soc. [ society of american chemical society](2015) 137,9481; ushijima, s., Togo, h.synlett [ quick synthesis report ]](2010), 1067; US 2007/0155739; WO 2017/055473; and WO 2009/022746. This reaction is shown in scheme 13.

Alternatively, a compound having formula (XVII) (wherein X is OH, OSO)₂Me, Cl, Br, or I) canBy a compound of formula (XVIII) (wherein Y is NH)₂) By reaction with a suitable nitrite source (e.g., NaNO) in an acceptable solvent system (e.g., acetonitrile and water) at a temperature between 0 ℃ and 100 ℃₂Or isoamyl nitrite), a suitable acid (e.g., hydrochloric acid or HBF₄) And radical-nucleophilic aromatic substitution of a copper source (e.g., CuCN). For a related example, see Wen, Q, et al, Tet.Lett. [ tetrahedron letters](2014),55,1271. This reaction is shown in scheme 13.

Scheme 13

Alternatively, a compound having formula (XVIII) (wherein X is Cl, Br, I, or OSO)₂Me, and Y is formyl, NH₂Cl, Br, I, CN, or 5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl) are commercially available or can be prepared from compounds having formula (XIX) in the following manner: with a suitable acid source (e.g., hydrochloric, hydrobromic, or hydroiodic acid) or a suitable halogen source (e.g., tetrabromomethane, tetrachloromethane, or iodine) in the presence of triphenylphosphine, or with methanesulfonyl chloride (ClSO)₂Me) (in a suitable solvent (e.g. dichloromethane), optionally in the presence of a base (e.g. triethylamine) at a temperature between 0 ℃ and 100 ℃). See Liu, h, et al bioorg.med.chem. [ bio-organic and pharmaceutical chemistry, for relevant examples](2008) 16,10013, WO 2014/020350 and Kompella, A. et al, bioorg.Med.chem.Lett [ Rapid report on bioorganic and pharmaceutical chemistry ]](2001),1,3161. Compounds having formula (XIX) are commercially available or can be prepared using known methods. This reaction is shown in scheme 14.

Scheme 14

As already indicated, surprisingly, it has now been found that, for practical purposes, the compounds of the invention having formula (I) have a very advantageous level of biological activity for protecting plants from diseases caused by fungi.

The compounds of formula (I) can be used in the agricultural sector and in the relevant fields of use, for example, as active ingredients for controlling plant pests, or on non-living materials for controlling spoilage microorganisms or organisms potentially harmful to humans. These novel compounds are distinguished by excellent activity at low application rates, good plant tolerance and no environmental hazard. 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 which occur on plants or plant parts (fruits, flowers, leaves, stems, tubers, roots) of a wide variety of different crops of useful plants, while also protecting, for example, those plant parts which grow later, from phytopathogenic microorganisms.

The present invention further relates to a method for controlling or preventing infestation of plants or plant propagation material susceptible to microbial attack and/or harvested food crops by treating the plants or plant propagation material and/or harvested food crops, wherein an effective amount of a compound of formula (I) is applied to the plants, parts thereof or the locus thereof.

It is also possible to use compounds of the formula (I) as fungicides. As used herein, the term "fungicide" means a compound that controls, modifies, or prevents the growth of fungi. The term "fungicidally effective amount" when used means the amount of such a compound or combination of such compounds that is capable of effecting fungal growth. The effects of control or modification include all deviations from natural development, such as killing, retardation, etc., and prevention includes barrier or other defense constructs in or on the plant to prevent fungal infection.

It is also possible to use the compounds of the formula (I) as seed dressings for the treatment of plant propagation material (e.g. seeds, such as fruits, tubers or grains) or plant cuttings for the protection 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 formula (I): for example, the seeds may be dressed prior to sowing. The active compounds of formula (I) can also be applied to the cereals (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, for example to the furrow of the seed during sowing. The invention also relates to such a method of treating plant propagation material, and to the plant propagation material so treated.

Furthermore, the compounds of formula (I) may be used in the relevant field for controlling fungi, for example for the protection of industrial materials, including wood and wood-related industrial products, food storage, hygiene management.

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

The compounds of formula (I) are effective, for example, against disease-causing fungi and fungal vectors as well as phytopathogenic bacteria and viruses. Fungi and fungal vectors for these diseases and phytopathogenic bacteria and viruses are for example:

head of Amycota pyrifera (Absidia coreybifera), Alternaria species (Alternaria spp), Saccharomyces species (Aphanomyces spp), Ascocystus species (Ascochyta spp), Aspergillus species (Aspergillus spp) (including Aspergillus flavus (A.flavus), Aspergillus fumigatus (A.fumigatus), Aspergillus nidulans (A.nidulans), Aspergillus niger (A.niger), Aspergillus terreus (A.terreus), Aureobasidium species (Aureobasidium spp) (including Aureobasidium pullulans), Blastomyces dermatitidis (A.pustulatus), Blastomyces dermatitidis (Blastomyces), Blastomyces tritici (Blumeae), Bremia lactucae (Bremia lactucae), Acidospora vitis species (Botyomyces sp) (including Staphylococcus ulcer (B.licheniformis), Micromyces vitis (B.sp.), Candida albicans (Candida), Candida albicans (C) Candida albicans (C.lucitania), Candida parapsilosis (C.paradoxusisis), Candida tropicalis (C.tropicalis)), Cephalaspora fragrans, Cercospora species (Ceratosystis spp), Cercospora spp (including Fusarium oxysporum (C.arachidicola)), Cercospora late (Cercospora personatum), Cladosporium spp (Cladosporium spp), Claviceps purpurea (Claviceps purpurea), Coccidioides immitis, Cochlospora sp (Cochliobolus spp), Colletotrichum spp (including Paralichia amylovora (C.mace)), Cryptococcus neotype (Cryptococcus neospora), Sphaerotheca (Hypocrea), Microcystis spp (including Pseudomonas sp), Micrococcus spp (Microcystis sp), Micrococcus spp (Micrococcus sp), Micrococcus sp (including Pseudomonas sp), Micrococcus sp (Micrococcus sp), Micrococcus sp, Microsporum sp, Micrococcus sp, grape crown blight (Eutypa lata), Fusarium species (Fusarium spp) (including Fusarium culmorum (F.culmorum), Fusarium graminearum (F.graminearum), F.langsethie, Fusarium moniliforme (F.moniliforme), Fusarium collosporum (F.oxysporum), Fusarium solani (F.proliferum), Fusarium oxysporum (F.subgluteanum), Fusarium exserosum (F.solaani), Fusarium graminearum (F.sourea), Fusarium graminearum (Gibberella fujikurourea), Fusarium anthracis (Gloeodens pomagena), Fusarium colletotrichum (Gloenoporus collectinatum), Fusarium (Gloenophytrium solani), Fusarium solani (Lepidium capsulatum), Fusarium solanum species (Lepidium), Fusarium solanum serohilum), Fusarium sporophyceae (Lepidium), Fusarium species (Lepidium), Fusarium oxysporium), Fusarium species (Lepidium), Fusarium oxysporium), Fusarium (Lepidium) and Fusarium sp. purpurum) including Lepidium sp. purpurum) and Fusarium (Lepidium sp Rhizoctonia solani (Microdochium nivale), Microsporum species (Microsporum spp), streptozoctonia species (Monilinia spp), Mucor species (Mucor spp), sphacelotheca species (Mycosphaerella spp) (including Mycosphaerella graminicola (m.graminicola), alternaria mali (m.pomi)), ramaria arborescens (Oncobasidium theobroma), picea spruce (ophytosma picea), paracoccus species (Paracoccidioides spp) (including Penicillium digitatum (p.digitatum), Penicillium (p.italicum), myceliophthora species (Penicillium sp), phytophthora speciosa (phytophthora sphaerica), phytophthora spp (phytophthora capsici spp), phytophthora sp (phytophthora capsici (p.m), phytophthora capsici (phytophthora sp.sp.), phytophthora sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.p.sp.sp.sp.sp.sp.p.sp.sp.p.), phytophthora sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp., Phoma species (Phoma Spp), Phomopsis viticola (Phomopsis viticola), Phytophthora species (Phytophthora Spp), including Phytophthora infestans (P.infestans), Plasmopara species (Plasmopara Spp), including Holotrichia (P.halstein), Plasmopara viticola (P.viticola), Pyrenophora species (Pleospora Spp), Sporosphaerella pusilla species (Podosphaera Spp), including Sporosphaera leucotrichum (P.leucotricha), Populomyia graminis (Polymyxas graminis), Polymyxoma betanus (Polymyxa betae), Triticum tritici (Psorospora thermophila) and Pseudomonas Pseudoperonospora (P.pseudoperonospora), Pseudomonas sp, Pseudoperonospora Pseudoperonospora (P), Pseudoperonospora Pseudoperonospora scabra), Pseudoperonospora Pseudoperonospora (P), Pseudoperonospora Pseudoperonospora p (P), Pseudoperonospora Pseudoperonospora p (P) Rhizoctonia species (pyrenosphaza spp), Pyrenophora species (Pyrenophora spp), Pyricularia spp including rice blast (p.oryzae), Pythium species (Pythium spp) including Pythium ultimum (p.ultimum), stylobacillus species (Ramularia spp), Rhizoctonia species (Rhizoctonia spp), Rhizomucor pusillus (Rhizopus arrhizus), Rhizoctonia species (Rhizoctonia spp), Rhizopus species (Rhizoctonia spp) including Rhizopus oxysporus (s.apiosporium) and Rhizopus polyspora (s proliponficus), schencotium (canothothyromyces), sclerotium species (sclerotiorhium, Rhizoctonia spp) including Rhizopus sporum (s.apiaria), Rhizoctonia solani (sporulopsis spp), Rhizoctonia solani (sporulopsis sp), Rhizopus (sporulopsis spp), Rhizopus sporulopsis sp) Chitin glumae (Stagonospora nodorum), Stemphylium species (stemphyllum), phloem (Stereum hirsutum), rhizoctonia solani (thanephorus cusieris), moniliforme (Thielaviopsis basicola), triticale, trichoderma species (including trichoderma harzianum), trichoderma pseudokoningii, trichoderma viride), trichophyton species, phellopteruma species, rhynchophyllum, ustilagopus (urospora) species, ustilagopus (Ustilago) species, venturia species (including venturia inaequalis), verticillium species, and xanthomonas species.

The compounds of formula (I) may be used, for example, in lawns, ornamentals such as flowers, shrubs, broad-leaved trees or evergreens, e.g., conifers, as well as tree injection, pest management, and the like.

Within the scope of the present invention, the target crops and/or useful plants to be protected typically include perennial and annual crops, such as berry plants, e.g. blackberry, blueberry, cranberry, raspberry and strawberry; cereals, such as barley, maize, millet, oats, rice, rye, sorghum, triticale and wheat; fiber plants such as cotton, flax, hemp, jute, and sisal; field crops such as sugar and feed beet, coffee beans, hops, mustard, oilseed rape (canola), poppy, sugar cane, sunflower, tea and tobacco; fruit trees, such as apple, apricot, avocado, banana, cherry, citrus, nectarine, peach, pear, and plum; grasses, such as bermuda grass, bluegrass, bentgrass, ciliate grass, beefwood, lolium, saint augustum, and zoysia; herbs such as basil, borage, chives, coriander, lavender, lemongrass, 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 cacao, 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 grapevines, such as grapes.

The term "useful plants" is to be understood as also including useful plants which, as a result of conventional breeding methods or genetic engineering, are rendered tolerant to herbicides like bromoxynil or to herbicides like for example HPPD inhibitors, ALS inhibitors like for example primisulfuron, prosulfuron and trifloxysulfuron, EPSPS (5-enol-acetone-shikimate-3-phosphate-synthase) inhibitors, GS (glutamine synthetase) inhibitors or PPO (protoporphyrinogen oxidase) inhibitors. An example of a crop which has been rendered tolerant to imidazolinones, such as imazethapyr, by conventional breeding methods (mutagenesis) is

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 corn varieties, among others

Herculex

And

commercially available under the trade name.

The term "useful plants" is to be understood as also including useful plants which have been so transformed, by using recombinant DNA techniques, that they are capable of synthesising one or more selectively acting toxins, such as are known, for example, from toxin-producing bacteria, in particular of the genus bacillus.

Examples of such plants are:

(Jade)Rice variety, expressing cryia (b) toxin); YieldGard

(maize variety, expressing CryIIIB (b1) toxin); YieldGard

(maize variety, expressing cryia (b) and CryIIIB (b1) toxins);

(maize variety, expressing Cry9(c) toxin); herculex

(maize variety, expressing the CryIF (a2) toxin and the enzyme phosphinothricin N-acetyltransferase (PAT) which acquired salt tolerance to the herbicide glufosinate); nucotn

(cotton variety, expressing CryIA (c) toxin); bollgard

(cotton variety, expressing CryIA (c) toxin); bollgard

(cotton variety, expressing CryIA (c) and CryIIA (b) toxins);

(cotton variety, expressing VIP toxin);

(potato variety, expressing CryIIIA toxin);

GT Advantage (GA21 glyphosate tolerant trait),

CB Advantage (Bt11 Corn Borer (CB) character),

RW (corn rootworm trait) and

the term "crop plant" is to be understood as also including crop plants which have been so transformed, by using recombinant DNA techniques, that they are capable of synthesising one or more selectively acting toxins, as are known, for example, from toxin-producing bacteria, especially those of the genus bacillus.

Toxins that can be expressed by such transgenic plants include, for example, insecticidal proteins from bacillus cereus or bacillus popilliae; or insecticidal proteins from bacillus thuringiensis, such as-endotoxins, for example Cry1Ab, Cry1Ac, Cry1F, Cry1Fa2, Cry2Ab, Cry3A, Cry3Bb1 or Cry9C, or vegetative insecticidal proteins (Vip), for example Vip1, Vip2, Vip3 or Vip 3A; or insecticidal proteins of bacteria colonizing the nematodes, such as Photorhabdus species (spp.) or Xenorhabdus species (spp.), such as Photorhabdus luminescens (Luminoscens), Xenorhabdus nematophilus (Xenorhabdus nematophilus); toxins produced by animals, such as scorpion toxin, spider toxin, bee toxin, and other insect-specific neurotoxins; toxins produced by fungi, such as streptomycete toxins, phytolectins (lectins), such as pea lectins, barley lectins or snowdrop lectins; lectin (agglutinin); protease inhibitors such as trypsin inhibitors, serine protease inhibitors, patatin, cystatin, papain inhibitors; ribosome Inactivating Proteins (RIPs), such as ricin, maize-RIP, abrin, luffa seed toxin protein, saporin protein or bryodin; 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 receptors, stilbene synthase, bibenzyl synthase, chitinase, and glucanase.

Further, in the context of the present invention, endotoxins (e.g. Cry1Ab, Cry1Ac, Cry1F, Cry1Fa2, Cry2Ab, Cry3A, Cry3Bb1, or Cry9C) or vegetative insecticidal proteins (Vip) (e.g. Vip1, Vip2, Vip3, or Vip3A) are to be understood as obviously also including mixed toxins, truncated toxins and modified toxins. Hybrid toxins are recombinantly produced by a novel combination of the different domains of those proteins (see, e.g., WO 02/15701). Truncated toxins, such as truncated Cry1Ab, 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 a non-naturally occurring protease recognition sequence into the toxin, for example as in the case of Cry3a055, a cathepsin-G-recognition sequence is inserted into the Cry3A toxin (see WO 03/018810).

Examples of such toxins or transgenic plants capable of synthesizing such toxins are disclosed in, for example, EP-A-0374753, WO 93/07278, WO 95/34656, EP-A-0427529, EP-A-451878 and WO 03/052073.

Methods for the preparation of 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-0367474, EP-A-0401979 and WO 90/13651.

The toxins included in the transgenic plants render the plants tolerant to harmful insects. Such insects may be present in any taxonomic group of insects, but are particularly common to beetles (coleoptera), diptera (diptera) and moths (lepidoptera).

Transgenic plants comprising one or more genes encoding insecticide resistance and expressing one or more toxins are known and some of them are commercially available. Such asExamples of 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-acetyltransferase (PAT) that acquired salt tolerance to the herbicide glufosinate); nucotn

(cotton variety, expressing Cry1Ac toxin);

(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 (GA21 glyphosate tolerant trait),

CB Advantage (Bt11 Zea maydis (CB) trait) and

further examples of such transgenic crops are:

bt11 maize, from Syngenta Seeds (Syngenta Seeds SAS), Hodby road (Chemin de l' Hobit)27, F-31790 Saussurel (St. Sauveur), France, accession number C/FR/96/05/10. Genetically modified maize is made resistant to attack by european corn borers (corn borers and pink stem borers) by transgenic expression of a truncated Cry1Ab toxin. Bt11 maize also transgenically expresses the PAT enzyme to gain tolerance to the herbicide glufosinate ammonium.

Bt176 maize from Syngenta seeds, Hollyroad 27, F-31790 san Suvier, France, accession number C/FR/96/05/10. Genetically modified maize is capable of resisting the invasion of European corn borers (corn borers and pink stem borers) by transgenically expressing Cry1Ab toxin. Bt176 maize also transgenically expresses the enzyme PAT to gain tolerance to the herbicide glufosinate ammonium.

MIR604 maize from Synindac seed company, Hollyroad 27, F-31790 san Suvier, France, accession number C/FR/96/05/10. Maize that is rendered insect resistant by transgenic expression of a modified Cry3A toxin. This 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 European S.A., 270-272 Tefreund Dawley (Avenue DE Tervuren), B-1150 Brussel, Belgium, accession number C/DE/02/9. MON 863 expresses Cry3Bb1 toxin and is resistant to certain coleopteran insects.

IPC 531 Cotton from European, Monsanto, 270-272 Teverun Daizhou, B-1150 Brussel, Belgium, accession number C/ES/96/02.

6.1507 corn, from Pioneer Overseas Corporation, Texasco Dawley (Avenue Tedesco), 7B-1160 Brussel, Belgium, accession number C/NL/00/10. Genetically modified maize, expressing the protein Cry1F to obtain resistance to certain lepidopteran insects, and expressing the PAT protein to obtain tolerance to the herbicide glufosinate-ammonium.

NK603 XMON 810 maize, from Monsanto European 270-272 Tefreund David, B-1150 Brussel, Belgium, accession number C/GB/02/M3/03. Consists of a conventionally bred hybrid maize variety by crossing the genetically modified varieties NK603 and MON 810. NK603 XMON 810 maize transgenically expresses protein CP4 EPSPS obtained from Agrobacterium strain CP4 to make it herbicide tolerant

(containing glyphosate), and also Cry1Ab toxin obtained from Bacillus thuringiensis Coxifraga subspecies, rendering it resistant to certain lepidopteran insects, including European corn borer.

The compounds of formula (I) are useful for controlling or preventing phytopathogenic diseases, especially phytopathogenic fungi on soybean plants (such as phakopsora pachyrhizi).

In particular, transgenic soybean plants expressing toxins such as insecticidal proteins such as-endotoxins (e.g., Cry1Ac (Cry1Ac Bt protein)). Thus, this may include inclusion of event MON87701 (see U.S. patent No. 8,049,071 and related applications and patents, and WO 2014/170327 a1 (see, e.g., the reference Intacta RR2 PRO^TMParagraph [008 ] of Soybean]) Event MON87751 (U.S. patent application publication No. 2014/0373191), or event DAS-81419 (U.S. patent No. 8632978 and related applications and patents)A transgenic soybean plant.

Other transgenic soybean plants may comprise event SYHT0H2-HPPD tolerance (U.S. patent application publication No. 2014/0201860 and related applications and patents), event MON 89788-glyphosate tolerance (U.S. patent application publication No. 7,632,985 and related applications and patents), event MON 87708-dicamba tolerance (U.S. patent application publication No. US 2011/0067134 and related applications and patents), event DP-356043-5-glyphosate and ALS tolerance (U.S. patent application publication No. US 2010/0184079 and related applications and patents), event a 2704-12-glufosinate tolerance (U.S. patent application publication No. US 2008/0320616 and related applications and patents), event DP-305423-1-ALS tolerance (U.S. patent application publication No. US 2008/0312082 and related applications and patents), Event A5547-127-glufosinate tolerance (U.S. patent application publication No. US 2008/0196127 and related applications and patents), event DAS-40278-9-tolerance to 2, 4-dichlorophenoxyacetic acid and aryloxyphenoxypropionate (see WO 2011/022469, WO 2011/022470, WO 2011/022471, and related applications and patents), event 127-ALS tolerance (WO 2010/080829 and related applications and patents), event GTS 40-3-2-glyphosate tolerance, event DAS-68416-4-2, 4-dichlorophenoxyacetic acid and glufosinate tolerance, event FG 72-glyphosate and isoxaflutole tolerance, event BPS-CV127-9-ALS tolerance and GU 262-glufosinate tolerance or event SYHT04R-HPPD tolerance.

The compounds of formula (I) are useful for controlling or preventing phytopathogenic diseases, especially phytopathogenic fungi on soybean plants (such as phakopsora pachyrhizi). In particular, there are certain elite Soybean Plant varieties known in the scientific literature in which R gene stacks conferring a degree of immunity or resistance to a particular phakopsora pachyrhizi have been introgressed into the Plant genome, see, e.g., "lighting Asian Soybean Rust [ fight against Asian Soybean Rust ]", Langenbach C et al, Front Plant Science [ Plant Science Front ]7(797) 2016).

A elite plant is any plant from the elite line, and thus a elite plant is a representative plant from the elite variety. Non-limiting examples of superior soybean varieties commercially available to farmers or soybean breeders include: AG00802, a0868, AG0902, a1923, AG2403, a2824, a3704, a4324, a5404, AG5903, AG6202, AG 0934; AG 1435; AG 2031; AG 2035; AG 2433; AG 2733; AG 2933; AG 3334; AG 3832; AG 4135; AG 4632; AG 4934; AG 5831; AG 6534; and AG7231 (asgro Seeds, demelein (Des Moines), iowa, usa); BPR0144RR, BPR 4077NRR, and BPR 4390NRR (Bio Plant Research), Camp Point (Camp Point), il, usa); DKB17-51 and DKB37-51 (Decalb Genetics, Decalb, Ill., USA); DP 4546RR, and DP 7870RR (Delta & Pine Land Company, lubock, texas, usa); JG 03R501, JG 32R606C ADD, and JG 55R503C (JGL Inc., greenkasle, indiana, usa); NKS 13-K2 (NK Division of Syngenta Seeds, Inc. (NK Division of Syngenta Seeds), gold Valley (Golden Valley), Minnesota (Minnesota), USA); 90M01, 91M30, 92M33, 93M11, 94M30, 95M30, 97B52, P008T22R 2; P16T17R 2; P22T 69R; P25T 51R; P34T07R 2; P35T 58R; P39T 67R; P47T 36R; P46T 21R; and P56T03R2 (Pioneer International, Inc. (Pioneer Hi-Bred International), Manchurn (Johnston), Iowa, USA); SG4771NRR and SG5161NRR/STS (Soygenetics, LLC, Lafaytte, Ind. Naa, USA); S00-K5, S11-L2, S28-Y2, S43-B1, S53-A1, S76-L9, S78-G6 and S0009-M2; S007-Y4; S04-D3; S14-A6; S20-T6; S21-M7; S26-P3; S28-N6; S30-V6; S35-C3; S36-Y6; S39-C4; S47-K5; S48-D9; S52-Y2; S58-Z4; S67-R6; S73-S8; and S78-G6 (hengda seed company, Henderson, kentucky, usa); richer (north star Seed Ltd.), Alberta (Alberta), canada); 14RD62 (Stine Seed Co., Stine Seed Co., Iowa, USA); or Armor 4744 (Armor Seed LLC, alaska, usa).

Thus, in another preferred embodiment, compounds having formula (I) are used to control phakopsora pachyrhizi (including its fungicidally resistant strains, as described below) on elite soybean plant varieties, wherein the R gene stack that confers a degree of immunity or resistance to a particular phakopsora pachyrhizi has been introgressed into the plant genome. Many benefits are expected from such uses, such as improved biological activity, a favorable or broader spectrum of activity (including sensitive and resistant strains of phakopsora pachyrhizi), increased safety, improved crop tolerance, synergistic interactions or enhanced properties, improved onset or longer lasting residual activity, reduced number of applications and/or reduced application rates of compounds and compositions required for effective control of phytopathogens (phakopsora pachyrhizi), thereby achieving beneficial resistance-management practices, reduced environmental impact and reduced operator exposure.

Fungicidal resistant strains of phakopsora pachyrhizi have been reported in the scientific literature, wherein strains are observed that are resistant to one or more fungicides from at least each of the following classes of fungicidal modes of action: sterol demethylation inhibitors (DMI), quinone outside inhibitors (QoI) and succinate dehydrogenase inhibitors (SDHI). See, for example: "Sensitivity of Phakopsora pachyrhizi toxins in their quinone-outer-inhibitors and methylation-inhibitors, and related resistance mechanisms]"Schmitz HK et al, Pest Manag Sci [ Pest Manag science of Pest](2014)70: 378-; "First detection of a SDH variant with reduced SDHI sensitivity in Phakopsora pachyrhizi [ SDH variants with reduced SDHI sensitivity were First detected in T.pachyrhizi]”

K et al, J Plant Dis Prot [ journal of Plant disease protection ]](2018)125: 21-2; "Competitive fitness of Competitive fixness of Phakopsora pachyrhizi isolates with mutations in the CYP51 and CYTB genes [ Competitive fitness of Phoma pachyrhizi isolates with mutations in CYP51 and CYTB genes]"Kloowski AC et al,phytopathology](2016)106: 1278-1284; detection of the mutation F129L in the cytochrome b gene of Phakopsora pachyrhizi (Phakopsora pachyrhizi) by "Detection of the F129L mutation in the cytochrome b gene of the Phakopsora pachyrhizi]"Kloowski AC et al, Pest Manag Sci [ Pest management science](2016)72:1211-1215。

Thus, in a preferred embodiment, compounds having formula (I) can be used to control phakopsora pachyrhizi that is resistant to one or more fungicides from any of the following fungicidal MoA classes: sterol demethylation inhibitors (DMI), quinone outside inhibitors (QoI) and succinate dehydrogenase inhibitors (SDHI).

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

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

The term "plant propagation material" is to be understood as meaning the reproductive parts of plants, such as seeds, which parts can be used for the propagation of plants, and vegetative material, 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. Mention may also be made of germinated plants and young plants which are to be transplanted after germination or after ground breaking. These young plants can be protected prior to transplantation by being treated in whole or in part by immersion. Preferably, "plant propagation material" is understood to mean seeds.

The compounds of formula (I) can be used in unmodified form or, preferably, together with adjuvants conventionally used in the art of formulation. For this purpose, they can be conveniently formulated in known manner as emulsifiable concentrates, coatable pastes, directly sprayable or dilutable solutions or suspensions, dilute emulsions, wettable powders, soluble powders, dusts, granules and also encapsulants, for example in polymeric substances. The type of composition, the method of application, such as spraying, atomizing, dusting, spreading, coating or pouring, is selected according to the intended purpose and the prevailing circumstances. The compositions may also contain additional adjuvants, such as stabilizers, defoamers, viscosity modifiers, binders or tackifiers, as well as fertilizers, micronutrient donors or other formulations for achieving a particular effect.

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 fertilizers. Such vectors are described, for example, in WO 97/33890.

Suspension concentrates are aqueous formulations in which highly dispersed 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 anti-foaming agents and crystal growth inhibitors. In use, these concentrates are diluted in water and applied to the area to be treated, usually as a spray. The amount of active ingredient may range from 0.5% to 95% of the concentrate.

Wettable powders are in the form of highly dispersible granules which are readily dispersible in water or other liquid carriers. These particles contain the active ingredient held in a solid matrix. Typical solid substrates include fuller's earth, kaolin clays, silicas and other readily wettable organic or inorganic solids. Wettable powders usually contain from 5% to 95% of the active ingredient plus a small amount of wetting, dispersing or emulsifying agent.

Emulsifiable concentrates are homogeneous liquid compositions that are dispersible in water or other liquids and may consist entirely of the active compound with liquid or solid emulsifiers 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.

Particulate formulations include both extrudates and coarser particles and are typically applied undiluted to the area in need of treatment. Typical carriers for granular formulations include sand, fuller's earth, attapulgite clay, bentonite clay, montmorillonite clay, vermiculite, perlite, calcium carbonate, brick, pumice, pyrophyllite, kaolin, dolomite, stucco, wood flour, ground corn cobs, ground peanut hulls, 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 active absorbing or active compound-coated materials. Granular formulations typically contain 5% to 25% active ingredient, which may include surfactants such as heavy aromatic essential oils, kerosene and other petroleum fractions, or vegetable oils; and/or adhesives such as dextrins, glues or synthetic resins.

Dusty powders are free-flowing mixtures of the active ingredient with highly dispersed solids such as talc, clays, flours and other organic and inorganic solids as dispersants and carriers.

Microcapsules are typically droplets or particles of the active ingredient encapsulated within an inert porous shell that allows the encapsulated material to escape to the environment at a controlled rate. The encapsulated droplets typically have a diameter of 1 micron to 50 microns. The encapsulated liquid typically constitutes 50% to 95% of the weight of the capsule and may include a solvent in addition to the active compound. Encapsulated particles are typically porous particles in which a porous membrane seals the particle pores, thereby retaining the active species in liquid form inside the particle pores. The diameter of the particles typically ranges from 1mm to 1 cm and preferably 1mm 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 granules. 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 (e.g., acetone, alkylated naphthalenes, xylene, and other organic solvents) in which the active ingredient is completely dissolved at the desired concentration. Pressurized sprays may also be used in which the active ingredient is dispersed in a highly dispersed 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 present invention in the above formulation types are well known to those of ordinary skill in the art.

Liquid carriers that may be utilized 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 abietate, diethylene glycol butyl ether, diethylene glycol ethyl ether, diethylene glycol methyl ether, N-dimethylformamide, dimethyl sulfoxide, 1, 4-dioxane, dipropylene glycol methyl ether, dipropylene glycol dibenzoate, dipropylene glycol (diproxitol), alkylpyrrolidones, ethyl acetate, 2-ethylhexanol, ethylene carbonate, 1,1, 1-trichloroethane, 2-heptanone, alpha-pinene, d-limonene, di (proxytol), alkyl pyrrolidones, ethyl acetate, 2-ethylhexanol, ethylene carbonate, 1, 1-trichloroethane, 2-heptanone, alpha-pinene, d-limonene, methyl alcohol, 1,2, Ethylene glycol, 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 myristate, lactic acid, laurylamine, mesityl oxide, methoxypropanol, methyl isoamyl ketone, methyl laurate, methyl caprylate, methyl oleate, methylene chloride, m-xylene, n-hexane, n-octylamine, octadecanoic acid, octylamine acetate, oleic acid, oleyl amine, o-xylene, phenol, polyethylene glycol (PEG400), propionic acid, propylene glycol monomethyl ether, p-xylene, toluene, triethyl phosphate, triethylene glycol, xylene sulfonic acid, paraffin, mineral oil, trichloroethylene, perchloroethylene, ethyl acetate, amyl acetate, butyl acetate, Methanol, ethanol, isopropanol, and higher molecular weight alcohols such as pentanol, tetrahydrofurfuryl alcohol, hexanol, octanol, and the like, ethylene glycol, propylene glycol, glycerol, and N-methyl-2-pyrrolidone. Water is generally the vehicle of choice for diluting the concentrate.

Suitable solid carriers include, for example, talc, titanium dioxide, pyrophyllite clay, silica, attapulgite clay, sandy 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 shell flour, and lignin.

A wide range of surfactants can be advantageously employed in the liquid and solid compositions, especially those designed to be dilutable with a carrier prior to administration. These agents, when used, typically constitute 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 emulsifying agents, wetting agents, suspending agents or for other purposes. Typical surfactants include alkyl sulfates such as diethanolammonium lauryl sulfate; alkyl aryl sulfonates such as calcium dodecylbenzenesulfonate; alkylphenol/alkylene oxide addition products, such as nonylphenol-c.sub.18 ethoxylates; alcohol-alkylene oxide addition products, such as tridecyl alcohol-C.sub.16 ethoxylate; soaps, such as sodium stearate; alkyl naphthalene sulfonates such as sodium dibutylnaphthalene sulfonate; salts of dialkyl sulfosuccinates, such as sodium bis (2-ethylhexyl) sulfosuccinate; sorbitol esters, such as sorbitol oleate; quaternary amines, such as lauryl trimethyl ammonium chloride; polyoxyethylene 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 crystallisation inhibitors, viscosity modifiers, suspending agents, spray droplet modifiers, pigments, antioxidants, foaming agents, antifoaming agents, opacifiers, compatibilizing agents, antifoam agents, masking agents, neutralising and buffering agents, corrosion inhibitors, dyes, flavour enhancers, spreading agents, penetration aids, micronutrients, emollients, lubricants and fixing agents.

Furthermore, further, other 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 applied 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 in, for example, a spray can. These further biocidal active ingredients may be fungicides, herbicides, insecticides, bactericides, acaricides, nematicides and/or plant growth regulators.

Pesticides using their common names mentioned herein are known, for example, from The Pesticide Manual, 15 th edition, British Crop Protection Council 2009.

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 acibenzol-S-methyl.

The compounds of formula (I) are generally used in the form of agrochemical compositions and can be applied to the crop area or to the crop to be treated simultaneously or sequentially with further compounds. For example, these additional compounds may be fertilizers or micronutrient donors or other preparations that affect plant growth. They may also be selective herbicides 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 application-promoting adjuvants customarily employed in the art of formulation.

The compounds of formula (I) may be used in the form of (fungicidal) compositions for the control or protection against phytopathogenic microorganisms, comprising, as active ingredient, at least one compound of formula (I) or at least one preferred individual compound as defined herein, in free form or in agrochemically usable salt form, and at least one of the aforementioned adjuvants.

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

The compound of formula (I) may be the sole active ingredient of the composition or it may be mixed with one or more additional active ingredients (such as a pesticide, fungicide, synergist, herbicide or plant growth regulator) as appropriate. In some cases, the additional active ingredients may result in unexpected synergistic activity.

Examples of suitable additional active ingredients include the following: acyclic amino acid (acycloamino acid) fungicides, aliphatic nitrogen fungicides, amide fungicides, aniline fungicides, antibiotic fungicides, aromatic fungicides, arsenic-containing fungicides, aryl phenyl ketone fungicides, benzamide fungicides, benzanilide fungicides, benzimidazole fungicides, benzothiazole fungicides, plant fungicides, bridging biphenyl fungicides, carbamate fungicides, carbanilate fungicides, conazole fungicides, copper fungicides, dicarboximide fungicides, dinitrophenol fungicides, dithiocarbamate fungicides, dithiolane fungicides, furoamide fungicides, furanilide fungicides, hydrazide fungicides, imidazole fungicides, mercury fungicides, morpholine fungicides, organophosphate fungicides, organotin fungicides, and the like, Oxathiin fungicides, oxazole fungicides, thiophenamide fungicides, polysulfide fungicides, pyrazole fungicides, pyridine fungicides, pyrimidine fungicides, pyrrole fungicides, quaternary ammonium fungicides, quinoline fungicides, quinone fungicides, quinoxaline fungicides, strobilurin fungicides, sulfonanilide (sulfonanilide) fungicides, thiadiazole fungicides, thiazole fungicides, thiazolidine fungicides, thiocarbamate fungicides, thiophene fungicides, triazine fungicides, triazole fungicides, triazolopyrimidine fungicides, urea fungicides, valiamide (valinamide) fungicides, and zinc fungicides.

Examples of suitable additional active ingredients also include the following: 3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid (9-dichloromethylene-1, 2,3, 4-tetrahydro-1, 4-methano-naphthalen-5-yl) -amide, 3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid methoxy- [ 1-methyl-2- (2,4, 6-trichlorophenyl) -ethyl ] -amide, 1-methyl-3-difluoromethyl-1H-pyrazole-4-carboxylic acid (2-dichloromethylene-3-ethyl-1-methyl-indan-4-yl) -amide (1072957-71-1), 1-methyl-3-difluoromethyl-1H-pyrazole-4-carboxylic acid (4' -methylsulfanyl-biphenyl-2-yl) -amide, 1-methyl-3-difluoromethyl-4H-pyrazole-4-carboxylic acid [2- (2, 4-dichloro-phenyl) -2-methoxy-1-methyl-ethyl ] -amide, (5-chloro-2, 4-dimethyl-pyridin-3-yl) - (2,3, 4-trimethoxy-6-methyl-phenyl) -methanone, (5-bromo-4-chloro-2-methoxy-pyridin-3-yl) - (2,3, 4-trimethoxy-6-methyl-phenyl) -methanone, 2- {2- [ (E) -3- (2, 6-dichloro-phenyl) -1-methyl-prop-2-ene- (E) -ylideneaminooxymethyl ] -phenyl } -2- [ (Z) -methoxyimino ] -N-methyl-acetamide, 3- [5- (4-chloro-phenyl) -2, 3-dimethyl-isoxazolidin-3-yl ] -pyridine, (E) -N-methyl-2- [2- (2, 5-dimethylphenoxymethyl) phenyl ] -2-methoxy-iminoacetamide, processes for their preparation, pharmaceutical compositions containing them and their use, 4-bromo-2-cyano-N, N-dimethyl-6-trifluoromethylbenzimidazole-1-sulfonamide, α - [ N- (3-chloro-2, 6-xylyl) -2-methoxyacetamido ] -y-butyrolactone, 4-chloro-2-cyano-N, N-dimethyl-5-p-tolylimidazole-1-sulfonamide, N-allyl-4, 5-dimethyl-2-trimethylsilylthiophene-3-carboxamide, N- (l-cyano-1, 2-dimethylpropyl) -2- (2, 4-dichlorophenoxy) propionamide, N- (2-methoxy-5-pyridyl) -cyclopropanecarboxamide, N- (3-chloro-2, 6-xylyl) -2-methoxyacetylamino-butyronitrile, N- (2-chloro-5-pyridyl) -2-butyronitrile-amide, and mixtures thereof, (. + -) cis-1- (4-chlorophenyl) -2- (1H-1,2, 4-triazol-1-yl) -cycloheptanol, 2- (1-tert-butyl) -1- (2-chlorophenyl) -3- (1,2, 4-triazol-1-yl) -propan-2-ol, 2',6' -dibromo-2-methyl-4-trifluoromethoxy-4 '-trifluoromethyl-1, 3-thiazole-5-carboxanilide, 1-imidazolyl-1- (4' -chlorophenoxy) -3, 3-dimethylbut-2-one, (E) -2- [2- [6- (2-cyanophenoxy) pyrimidine-4- Aryloxy ] phenyl ] 3-methoxyacrylate methyl ester, (E) -2- [2- [6- (2-sulfanylaminophenoxy) pyrimidin-4-yloxy ] phenyl ] -3-methoxyacrylate methyl ester, (E) -2- [2- [6- (2-fluorophenoxy) pyrimidin-4-yloxy ] phenyl ] -3-methoxyacrylate methyl ester, (E) -2- [2- [6- (2, 6-difluorophenoxy) pyrimidin-4-yloxy ] phenyl ] -3-methoxyacrylate methyl ester, (E) -2- [2- [3- (pyrimidin-2-yloxy) phenoxy ] phenyl ] -3-methoxyacrylate methyl ester, methyl ester, (E) -methyl 2- [2- [3- (5-methylpyrimidin-2-yloxy) -phenoxy ] phenyl ] -3-methoxyacrylate, methyl (E) -2- [2- [3- (phenyl-sulfonyloxy) phenoxy ] phenyl-3-methoxyacrylate, methyl (E) -2- [2- [3- (4-nitrophenoxy) phenoxy ] phenyl ] -3-methoxyacrylate, methyl (E) -2- [ 2-phenoxyphenyl ] -3-methoxyacrylate, methyl (E) -2- [2- (3, 5-dimethyl-benzoyl) pyrrol-1-yl ] -3-methoxyacrylate, (E) -methyl 2- [2- (3-methoxyphenoxy) phenyl ] -3-methoxyacrylate, (E) -methyl 2- [2- (2-phenylethen-1-yl) -phenyl ] -3-methoxyacrylate, (E) -methyl 2- [2- (3, 5-dichlorophenoxy) pyridin-3-yl ] -3-methoxyacrylate, (E) -methyl 2- (2- (3- (1,1,2, 2-tetrafluoroethoxy) phenoxy) phenyl) -3-methoxyacrylate, (E) -methyl 2- (2- [3- (. alpha. -hydroxybenzyl) phenoxy ] phenyl) -3-methoxyacrylate, methyl (E) -2- [3- (. alpha. -hydroxybenzyl) phenoxy ] phenyl ] -3-methoxyacrylate, (E) -methyl 2- (2- (4-phenoxypyridin-2-yloxy) phenyl) -3-methoxyacrylate, methyl (E) -2- [2- (3-n-propyloxy-phenoxy) phenyl ] 3-methoxyacrylate, methyl (E) -2- [2- (3-isopropyloxyphenoxy) phenyl ] -3-methoxyacrylate, methyl (E) -2- [2- [3- (2-fluorophenoxy) phenoxy ] phenyl ] -3-methoxyacrylate, methyl (E) -2- [2- (3-ethoxyphenoxy) phenyl ] -3-methoxyacrylate, methyl (E) -2- [2- (4-tert-butyl-pyridin-2-yloxy) Methyl phenyl ] -3-methoxyacrylate, methyl (E) -2- [2- [3- (3-cyanophenoxy) phenoxy ] phenyl ] -3-methoxyacrylate, methyl (E) -2- [2- [ (3-methyl-pyridin-2-yloxymethyl) phenyl ] -3-methoxyacrylate, methyl (E) -2- [2- [6- (2-methyl-phenoxy) pyrimidin-4-yloxy ] phenyl ] -3-methoxyacrylate, methyl (E) -2- [2- (5-bromo-pyridin-2-yloxymethyl) phenyl ] -3-methoxyacrylate, (E) -methyl 2- [2- (3- (3-iodopyridin-2-yloxy) phenoxy) phenyl ] -3-methoxyacrylate, methyl (E) -2- [2- [6- (2-chloropyridin-3-yloxy) pyrimidin-4-yloxy ] phenyl ] -3-methoxyacrylate, methyl (E), (E) -2- [2- (5, 6-dimethylpyrazin-2-ylmethyloximomethyl) phenyl ] -3-methoxyacrylate, methyl (E) -2- {2- [6- (6-methylpyridin-2-yloxy) pyrimidin-4-yloxy ] phenyl } -3-methoxy-acrylate, methyl (E) -2- [2- (6-methylpyridin-2-yloxy) pyrimidin-4-yloxy) phenyl ] -n-3-methoxyacrylate, methyl (E) -n-butyl (E) -n-, (E) (E) -2- {2- (3-methoxyphenyl) methyloxidomethyl ] -phenyl } -3-methoxyacrylate methyl ester, (E) -2- {2- (6- (2-azidophenoxy) -pyrimidin-4-yloxy ] phenyl } -3-methoxyacrylate methyl ester, (E) -2- {2- [ 6-phenylpyrimidin-4-yl) -methyloxidomethyl ] phenyl } -3-methoxyacrylate methyl ester, (E) -2- {2- [ (4-chlorophenyl) -methyloxidomethyl ] -phenyl } -3-methoxyacrylate methyl ester, (E) -2- {2- [6- (2-n-propylphenoxy) -1 Methyl 3, 5-triazin-4-yloxy ] phenyl } -3-methoxyacrylate, (E) -2- {2- [ (3-nitrophenyl) methyloximinomethyl ] phenyl } -3-methoxyacrylate, 3-chloro-7- (2-aza-2, 7, 7-trimethyl-oct-3-en-5-yne), 2, 6-dichloro-N- (4-trifluoromethylbenzyl) -benzamide, 3-iodo-2-propinol, 4-chlorophenyl-3-iodopropargyl formal, 3-bromo-2, 3-diiodo-2-propenylethylcarbamate, methyl (E) -2- {2- [ (3-nitrophenyl) methyloximinomethyl ] phenyl } -3-methoxyacrylate, methyl (E) -2, 6-dichloro-N- (4-trifluoromethylbenzyl) -benzamide, 3-iodo-2-propiolic alcohol, 2,3, 3-triiodoallyl alcohol, 3-bromo-2, 3-diiodo-2-propenyl alcohol, 3-iodo-2-propynyl n-butyl carbamate, 3-iodo-2-propynyl n-hexyl carbamate, 3-iodo-2-propynyl cyclohexyl carbamate, 3-iodo-2-propynyl phenyl carbamate; phenol derivatives such as tribromophenol, tetrachlorophenol, 3-methyl-4-chlorophenol, 3, 5-dimethyl-4-chlorophenol, phenoxyethanol, dichlorophen, o-phenylphenol, m-phenylphenol, p-phenylphenol, 2-benzyl-4-chlorophenol, 5-hydroxy-2 (5H) -furanone; 4, 5-dichlorodithiazolinone, 4, 5-benzodithiazolone, 4, 5-trimethylenedithiazolone, 4, 5-dichloro- (3H) -1, 2-dithio-3-one, 3, 5-dimethyl-tetrahydro-1, 3, 5-thiadiazin-2-thione, N- (2-p-chlorobenzoylethyl) -hexamethylenetetramine chloride, aragonic acid benzene, octaninety-mixed acid (acetyltetracos), gossypol, albendazole, cartap (aldimorph), allicin, allyl alcohol, ametoctradin, amisulam, amobam, aminopropyl phosphonic acid (ampropylfos), benazolin, arsenic (asomate), aureofungin, azaconazole, azafendine (azafendin), thiram oxide (azithiiram), azoxystrobin, Barium polysulfide, benalaxyl-M, mefenoxanil (benodanil), benomyl, fenazone, metouron (bentaluron), benthiavalicarb, thiocyan, benzalkonium chloride, festoonic acid (benzamacril), benzomorph (benzamorf), benzohydroxamic acid, benzovindiflupyr (benzovindifluppy), berberine, benoxacor (bethoxazin), bitertanol (biloxzol), binapacryl, biphenyl, bitertanol, bixafen (bixafen), blastin, boscalid, bromothalonil, bromuconazole, bupirimate, buthionine, buthionate, captate, captafol, morcarb, carbendazim hydrochloride, propranol, carvone, CGA41396, chlozoan (fenchloraz), chlorazol, fenchol, fenchlorazol, fenchol, fenpicloran, fenchlorazol, fenpyrone, chlon (fencholrozine), chlozolone, chlozolol (fencholrozolol), cloxacarb, chlozolol, Climbazole, clotrimazole, clarithron (clozylacon), copper-containing compounds such as copper acetate, copper carbonate, copper hydroxide, copper naphthenate, copper oleate, copper oxychloride, copper oxyquinoline, copper silicate, copper sulfate, copper resinate, copper zinc chromate and Bordeaux mixture, cresol, thiabendazole, copper thiram (cuprobam), cuprous oxide, cetrimide, cyclamamide (cycloflunomid), cycloheximide, cyflufenamide, cymoxanil, cyazofamid (cybendazole), cyproconazole, cyprodinil, dazomethane, diclofen, bensulide, chlorotriazole, diethofencarbazide, difenoconazole, O-dibenzylisopropyl-thiopropionate, O-dibenzyl-S-benzyl-thiophosphate, copper chloride, copper oxide, copper hydroxide, copper naphthenate, copper oleate, copper oxychloride, copper (cupronide), copper oxide, cyclobutamide, cyclomethionate, cycloheximide, cyclomethicone, cycloate, cyclobutamol, cyhalonil, cycloheximide, cyhalonil, prochlor, Dimefluzole (dimefluzole), dimethomorph, dimeticonazole (dimeticonazole), dimethomorph, metconazole, diniconazole-M, dinotefuran, dinocap, clofenamate, nitryl (dinopenton), nitrooctyl ester acaricide, nitrobutyl ester (dinoterbon), diphenylamine, dipyridamole, disulfotol, dimethos (dithimafos), dithianon, disulfide, dodecyl dimethyl ammonium chloride, dodecacyclomorpholine, dodine, dodecol, dodecylguanidineacetate, diketene, distemper, enestroburin, epoxiconazole, ethiconazole, thienam (ethaboxam), ethaboxam, ethirimol, ethoxyquin, ethylicin (ethionin), (Z) -N-benzyl-N ([ methyl (methyl-thioethylaminoxy carbonyl) amino ] thio) -beta-alanine ethyl ester, terrazole, famoxadone, fenamidone, Diuron, fenacet, fenarimol, fenbuconazole, metrafluoride, fenhexamid, pyrimethanil, pyricularia, fenpiclonil, fenpyrad, fenpropidin, fenpropimorph, fenpyrazamine, fentin acetate, triphenyltin hydroxide, ferbamate, pyribenzozone, fluazinam, fludioxonil, flumetol, flumorph, fluopicolide (fluulide), fluopyram, furflufen, triflumizole (fluflumizole), fluoxastrobin, fluquinconazole, flusilazole, flusulfamide, fluthianil, flutole, flutriafol, formaldehyde, triethylphos, fuberidazole, furalaxyl, furflupyrad, difenoconazole, furazolidone, fludioxonil, flutolmeturon, glyburide, griseofulvin, bixin, quinolinyl acrylate, hexaflufen (hexachlorophene), hexachlorophene (thion), hexachlorophene, Amalgafen (hydrargaphen), hydroxyisoxazole, hymexazol, imazalil sulfate, imibenconazole, iminoctadine triacetate, cumquat (inezin), iodopropynyl butylcarbamate (iodocarb), ipconazole, ipfentrifiullunazole, iprobenfos, iprodione, propineb, isopropylbutylcarbamate, isoprothiolane, isopyrazamide, isothiopyrad, fenamidone (isovaledione), phorate (izopamfos), kasugamycin, kresoxim-methyl, LY186054, LY211795, LY248908, mancozeb, mandipropamid, maneb, anthranilamide, mecarbazid (mecarbazid), metalaxyl, fluroxypyr, meperfusal, mepanipyrimethanil, mefenpyr, mechloraz, mercuric chloride, thiuron chloride, dinotefuran, dinafop (meptyldinocap), meptyl, metyl, metoclopramide, Metiram, metiram-zinc, metominostrobin, metrafenone, tiadinil, metiram ring (milneb), moroxydine (moroxydine), myclobutanil (myclozolin), metiram (nabam), natamycin, tianan, thiram, nitrostyrene, phthalazinone, fluoropyrimidinol, octreone, furosemide, organomercurides, orysastrobin, osthol (othol), oxadixyl, rimsulfuron methyl, thifluzaquin (oxaapaprolin), oxine-copper (oxine-copper), oxolinic acid, ipconazole (oxypoconazole), oxycarboxin, piridol (paradol), pefurazoate, penconazole, pencycuron, fluxafen, penoxsulfen-sodium pentachlorophenate, penthiopyrad, pyraclostrobin, cyhalonil, dicofofos, dichlorophosphonium (phosphodiphenoxylate), Al-carbendazim, polyoxin, carbendazim (polyoxin), carbendazim, polyoxin (metoclopramide, carbendazim, pyraclostrobin (metoclopramide), pyraclostrobin (metocloprid), pyraclostrobin (metoclopramide), metoclopramide, metoclopr, Metiram, thiabendazole, prochloraz, procymidone, prochloraz, propamocarb, propiconazole, propineb, propionic acid, iodoquinazolinone, thiophanate (prothiocarb), prothioconazole, pyraclostrobin (pydiflumetofen), bisoprofen, pyraclostrobin (pyrametostrobin), pyraoxystrobin, pyraclostrobin, pyribenzocarb, pyridecarbonitrile (pyridinitril), pyribenzoxim, pyrimethanil, pyridinofen (pyroxene), pyroquilon, prochloraz (pyroxychlorine), pyriflufen, pyroxylin, pyroquilin, quaternary ammonium compound, hydroxyquinolyl (quinacetol), benzoquinone (quinazazolizone), quinconazole (quinconazole), fenchlorazol, quinconazole (quinconazole), quinconazole (propiconazole), fendone (fenchlorazol), fenthiflufen), fenpyroximate (fenpropiconazole), fenpropiconazole (fenpyr), fenpyraclostrobin (fenpyroxafen), fenpropiconazole (fenpyroxim), fenpropiconazole (fenpyr), fenpyraclostrobin (fenpropiconazole), fenpropiconazole (fenpropiconazole), fenpropiconazole (fenpropi, Isobutoxyquinoline (tebfloquin), bismerthiazol, tetrachloronitrobenzene, fop-butyl sulfide, tetraconazole, thiabendazole, thiadifloro (thiadifluor), thiabendazole (thiazofenon), thifluzamide, 2- (thiocyanomethylthio) benzothiazole, thiophanate-methyl, dicofox (thioquinox), salen, tiadinil, imibenconazole (timenconazole), thiocyanobenzamide (tioxymid), tolclofos-methyl, tolylfluanid, triadimefon, triadimenol, fenbuconazole (triamamphophos), pyrimethanol (triarim), butriazole, imidazole, tricyclazole, tridemorph, trifloxystrobin, acetamiprid (triflumazole), triforine, triflumizole, uniconazole, thiram, fluvalidamide, validamide, valicarb, pyrimethanil, fenpyrad, and zineb (fenzamide), zinc difenozide.

The compounds of the present invention may also be used in combination with anthelmintic agents. Such anthelmintic agents include compounds selected from the macrolide class of compounds, such as ivermectin, abamectin, emamectin, eprinomectin, doramectin, selamectin, moxidectin, nemadectin and milbemycin derivatives, as described in EP-357460, EP-444964 and EP-594291. Additional anthelmintic agents include semi-synthetic and biosynthetic avermectins/milbemycin derivatives, such as those described in US-5015630, WO-9415944 and WO-9522552. Additional anthelmintic agents include benzimidazoles such as albendazole, canabendazole, fenbendazole, flubendazole, mebendazole, oxfendazole, oxibendazole, parbendazole, and other members of the classes. Additional anthelmintic agents include imidazothiazoles and tetrahydropyrimidines, such as tetraimidazole, levamisole, pyrantel pamoate, octopine or morantel. Additional anthelmintic agents include flukicides (e.g., triclabendazole and clorsulon) and tapecides (e.g., praziquantel and epsiprantel).

The compounds of the invention may be used in combination with derivatives and analogues of anthelmintic agents of the paraherquamide/marcfortine class and with antiparasitic oxazolines as 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 dioxomorpholine antiparasitic agents as described in WO 96/15121 and also with anthelmintically active cyclic depsipeptides such as those described in WO 96/11945, WO 93/19053, WO 93/25543, EP 0626375, EP 0382173, WO 94/19334, EP 0382173 and EP 0503538.

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

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, particularly the compounds disclosed therein.

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

organic phosphoric acid ester: acephate, methyl pyroxaphos, ethyl valefos, methyl valefos, bromophos, ethyl bromophos, cadusafos, chlorethophos (chlorethoxyphos), chlorpyrifos, chlorophenoxyphos, chlorophosphorus chloride, systemic phosphorus-S-methyl sulfone, chloroformithion, diazinon, dichlorvos, butylperoxy, dimethoate, fosetyl, ethiofen, fenamiphos, oxypyrimidine, vazaphosphor, fenamiphos, fenthion, phos, phosmet, fenphos, pyrazofos, difenofos, fosthiazate, heptenophos, clozaphosphor, isoprofos, isoxazolophos, malathion, chlorfenphos, methamidophos, methidathion, methyl parathion, monocrotophos, triazophos, dibromophos, omethoate, methyl oxophos, paraoxon, parathion, methyl parathion, fenphos, thiocarb, thiocyanoto, Phosmet, phosphamidon, phorate, phoxim, chlorfenap, chlorfenapyr-methyl, profenofos, propaphos, proethamphos, profenofos, pyrazofos, pyridaphethione, quinalphos, thiofenamiphos, temephos, terbufos, butylpyrimidine phosphate, sethion, disulfoton (thimeton), triazophos, trichlorfon, and phosmet.

Carbamate ester: cotton boll-weevil, aldicarb, 2-butyphenyl methyl carbamate, benfuracarb, carbaryl, carbofuran, carbosulfan, bendiocarb, ethiofencarb, fenoxycarb, fenthiok, furacarb, HCN-801, isoprocarb, indoxacarb, methiocarb, methomyl, 5-methyl-m-cumyl butynyl (methyl) carbamate, oxamyl, pirimicarb, propoxur, thiodicarb, monocarb, triazamate, UC-51717.

Pyrethroid: fluthrin, allethrin, alpha-cypermethrin, 5-benzyl-3-furylmethyl (E) - (1R) -cis-2, 2-dimethyl-3- (2-oxothiolane-3-ylidenemethyl) cyclopropanecarboxylate, bifenthrin, beta-cyfluthrin, alpha-cypermethrin, beta-cypermethrin, bioallethrin ((S) -cyclopentyl isomer), bioresmethrin, bifenthrin, NCI-85193, cycloprothrin, cyfluthrin, cypermethrin, deltamethrin, empenthrin, esfenvalerate, etofenprox, fenpropathrin, fenvalerate, flucythrinate, flumethrin, cyfluthrin (D isomer), Prallethrin, cyfluthrin, lambda-cyhalothrin, permethrin, phenothrin, prallethrin, pyrethrin (natural product), resmethrin, tetramethrin, transfluthrin, theta-cypermethrin, silafluothrin, t-tau-fluvalinate, tefluthrin, tetrabromthrin, zeta-cypermethrin.

Arthropod growth regulator: a) chitin synthesis inhibitors: benzoyl urea: chlorfluazuron, diflubenzuron, flucycloxuron, flufenoxuron, hexaflumuron, lufenuron, novaluron, teflubenzuron, chlorfluazuron, buprofezin, phenthoate, hexythiazox, etoxazole, clofentezine (chlorpfendazine); b) ecdysone antagonists: chlorfenozide, methoxyfenozide, tebufenozide; c) juvenile hormone analogs: pyriproxyfen, methoprene (including S-methoprene), fenoxycarb; d) lipid biosynthesis inhibitors: spirodiclofen.

Other antiparasitic agents: fenaminoquinone, amitraz, AKD-1022, ANS-118, azadirachtin, Bacillus thuringiensis, sulfothiobac, bifenazate, binazate, bromopropylate, BTG-504, BTG-505, toxaphene, cartap, fenaminostrobin, chlordimeform, chlorfenapyr, chromafenozide, clothianidin, cyromazine, difloron (deacloden), chlordiazuron, DBI-3204, diethofencarb, dihydroxymethyl dihydroxy pyrrolidine, dinosaur, dinocap, endosulfan, ethiprole, ethofenprox, fenazaquin, flufenzine (flokite), MTI-800, fenpyroximate, pyrimidifen, flutriathia, bromofluthrin, flufenzine, trifluofen, benzoxyfen (fluroxyfen), benzoxyfen (halofenprox), hydramethylhydrazone, I-220, sodium hydrosilicate, NC-196, Indian mint (nereid), dinotefuran-10825, dinotefuran-2, dinotefuran, Pyridalyl, propargite, Profenofibrate (procifenbute), pymetrozine, pyridaben, pyriminostrobin, NC-1111, R-195, RH-0345, RH-2485, RYI-210, S-1283, S-1833, SI-8601, silafluofen, silomastin (silomadine), pleocidin, tebufenpyrad, trichlorfone, tetraantibiotic, thiacloprid, thiocyclam, thiamethoxam, tolfenpyrad, triazamate, triethylpleocidin, tretinoin, propargyl ether, bolacre (vertalelect), YI-5301.

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

A bactericide: chlortetracycline, oxytetracycline, streptomycin.

Other biological agents: enrofloxacin, febantel, penethamate, meloxicam, cephalexin, kanamycin, pimobendan, clenbuterol, omeprazole, thiamerin, benazepril, piriprep (pyriprole), cefquinome, florfenicol, buserelin, cefuroxime, tolacin, ceftiofur, carprofen, meflozone, praziquantel, triclabendazole.

The following mixtures of compounds having formula (I) with active ingredients are preferred. The abbreviation "TX" means a composition selected from the group consisting of: compounds as shown in tables 1.1 to 1.11, tables 2.1 to 2.10, or compounds 1.1 to 1.6 according to the invention as listed in table T1 (below):

an adjuvant selected from the group consisting of: petroleum (alias) (628) + TX;

an acaricide selected from the group consisting of: 1, 1-bis (4-chlorophenyl) -2-ethoxyethanol (IUPAC name) (910) + TX, 2, 4-dichlorophenyl benzenesulfonate (IUPAC/chemical abstracts name) (1059) + TX, 2-fluoro-N-methyl-N-1-naphthaleneacetamide (IUPAC name) (1295) + TX, 4-chlorophenyl phenylsulfone (IUPAC name) (981) + TX, abamectin (1) + TX, fenaminoquin (3) + TX, acetofenacet [ CCN ] + TX, flupropathrin (9) + TX, aldicarb (16) + TX, aldicarb (863) + α -cypermethrin (202) + TX, thiothiuron (870) + TX, sulfamite ester [ CCN ] + TX, aminothionate (872) + TX, phosphamidooxalate (TX), phosphamidooxalate (875) + methimamidine (24) + TX, Dicofol (881) + TX, arsenic trioxide (882) + TX, AVI 382 (compound code) + TX, AZ 60541 (compound code) + TX, benfop (44) + TX, bazophos (azinphos-methyl) (45) + TX, azobenzene (IUPAC name) (888) + TX, azocyclotin (azacyclotin) (46) + TX, azophos (azothoate) (889) + TX, benomyl (62) + TX, benoxafos (Benoxafos) (alias) [ CCN ] + TX, benoxamate (benzoximate) (71) + TX, benzyl benzoate (IUPAC name) [ CCN ] + TX, bifenazate (74) + TX, bifenthrin (76) + TX), dicofol (907) + TX), bromethrin (fenfluridix), fenbutafenazamide [1207727 ] + 04-5-bromucofenamate) + TX (918, bromucofos (921), bromucofos (921-TX) + TX), bromucofos (921-TX), bromphen (907) + (bromphen, bromphen-5) + (bromphen) (TX) + TX) + (920) +, bromphenthoate (921, bromphenthoate) + (920) + (TX) + (921), bromphenthoate (921-5) + (TX) +, Buprofezin (99) + TX, butoxycarb (103) + TX, butoxycarb (104) + TX, butypyridazin (butypyridazon) (alias) + TX, lime sulphur (calceium polysufide) (IUPAC name) (111) + TX, fenamiphene (capheochlor) (941) + TX, clomethomyl (carbonolate) (943) + TX, carbaryl (115) + TX), carbofuran (118) + TX, carbophos (947) + TX, CGA 50'439 (research code) (125) + TX, chlormefenapyr (chinomethionat) (126) + TX, chlorphenide (959) + TX), chlorfenamidine (964) + TX, chlorfenadine hydrochloride (964) + TX, bromfenapyr (130) +, chlorpheniramate (968) + (971), chlorphenide (971) + chlorphenide (975), chlorphenoxide (975) + TX) + chlorphenide (975), chlorphenide (975) + TX, chlorphenide (975) + (975), chlorphenide) + TX) + chlorphenide (971, chlorphenide (975), chlorphenide (975), chlorphenide) + TX) + (971), chlorphenide (975) and chlorphenide, Chlorfluazuron (chloromethylthioron) (978) + TX, propylate acaricide (chloropyralate) (983) + TX, chlorpyrifos (145) + TX, chlorpyrifos-methyl (146) + TX, chlorfenapyr (chlorothiophos) (994) + TX, cyfluthrin (cinerin) I (696) + TX, cyfluthrin II (696) + TX, cyfluthrin (cinerins) (696) + TX, clofentezine (158) + TX, closantel [ CCN ] + TX, coumaphos [ 174) + TX, crotamiton [ CCN ] + TX, crotoxyphos (crotoxyphos) (1010) + TX, thiabendazole (1013) +, flufenofos (cyantrate) (1020) + TX TX, cyflufenamate (CAS number: 400882-07-7) + TX, cyhalothrin (196) + tin (199), cyhalothrin (1037) + (DCPM) + (201), cyhalothrin) + TX, cyhalothrin (201, cyhalothrin) + TX, cyhalothrin (1037, cyhalothrin, tianlepos-S (1037) + TX, systemic phosphorus (demeton) (1038) + TX, systemic phosphorus-methyl (224) + TX, systemic phosphorus-O (1038) + TX, systemic phosphorus-O-methyl (224) + TX, systemic phosphorus-S (1038) + TX, systemic phosphorus-S-methyl (224) + TX, sulfur phosphorus (demeton-S-methyl) fon (1039) + TX, chlordiazuron (226) + TX, chlorfenapyr (dialifos) (1042) + TX, diazinon (227) + TX, dichlofluanid (230) + TX, dichlorvos (236) +, dicliphos) (alias) + TX, propamocarb (242) + TX, chlorotaphos (TX) + TX), diclofenphos (1071) +, meclofen (1081) +, diclofen (1081) + TX) (653, diclofen) + TX, diclofen (1089) + TX, diclofen (1089, diclofen) + TX, diclofen) + (1089, diclofen) +, Dicetomidine (dinobuton) (269) + TX, dinocap (dinocap) (270) + TX, dinocap-4 [ CCN ] + TX, dinocap-6 [ CCN ] + TX, clomiphene (1090) + TX, nitropentyl (dinopenton) (1092) + TX, dinocap (dinosulfon) (1097) + TX, dibutyl nitrate (dinoterbon) (1098) + TX, phoxim (1102) + TX, sulfodiphenyl (IUPAC name) (1103) + TX, disulfoton [ CCN ] + TX, disulfoton (278) + acaricide, DNOC (282) + TX, phenoxypropargite (dofenapyn) (1113) + TX, doramectin (another name) [ CCN ] + TX ], thiodan (294) + TX, indithiotepa (ethion) (1121) +, ethidium (ethion) (11312) + TX), ethion fenthion (297), thion) + (ethion (309) + thion) + (ethion) +) (113) +, ethion (ethion) +) (1132) + TX, ethion (ethion) +) (1134, ethion (ethion, anti-acarid (fenzaflor) (1147) + TX, fenazaquin (328) + TX, fenbutatin oxide (330) + TX, fenoxycarb (fenothiocarb) (337) + TX, fenpropathrin (342) + TX, fenpyrd + TX, fenpyroximate (fenpyroximate) (345) + TX, fenpyroximate (fenson) (1157) + TX), nitrofen (fenthifenil) (1161) + TX, fenvalerate (349) + TX, fipronil (354) + TX, fluacrypyrim (fluvalinate) (360) + TX, fluazuron (1166) + TX), fluthia (flubentazine) (1167) + TX), flufenuron (366) + TX, flufenvalerate (fluthrinate) (367), fluthrin (fluthrin) (1179) + TX), flufenpropathrin (1167) + TX) (1185, flufenpropathrin (118tx) + TX) (1174, fluthrin (1185) + TX), fluthrin (118tx), fenpropathrin (1175), fluthrin (118tx), and TX, Varroamidine hydrochloride (405) + TX, parathion (formothion) (1192) + TX, carboxim (formcaranate) (1193) + TX, γ -HCH (430) + TX, glyodin (1205) + TX, benzofenafen (halfenprox) (424) + TX, heptenyl ether (hepenophos) (432) + TX, hexadecylcyclopropanecarboxylate (IUPAC/chemical abstracts name) (1216) + TX, hexythiazox (441) + TX, iodomethane (IUPAC name) (542) + TX, isocarbophos (isocarbophos) (alias) +, isopropyl O- (methoxyaminothiophosphoryl) salicylate (IUPAC name) (473) + TX, ivermectin (alias) [ TX n ] + TX, jasmin (473) +), jasminum (696) I (696) +), jasminum (696) + (ethoxyfenthion) (430) +, iodophor (TX) +, mefenofos (430) +, mefenofos (TX n) + (430) +, thiofenofos (430) + (TX), mefenofos) + (430) +, mefenofos (TX n) +, mefenofos (430) +, mefenofos (mefenofos), mefeno, Propisocyan (malonoben) (1254) + TX, triazophos (mecarbam) (502) + TX, dithiafos (mephosphan) (1261) + TX, methidafen (another name) [ CCN ] + TX, chlorfenvinphos (methacrifos) (1266) + TX, methamidophos (527) + TX, methidathion (529) + TX, methiocarb (530) +, methomyl (531) + TX, bromomethane (537) + TX, metolcarb) (550) + TX, metocloprop (556) + TX, carbofuran (mexacarbate) (1290) +, fenaminomectin (557) + mil, milbemycin (bemycine) (another name TX) [ CCN ] + TX ], flupride (pamixx) (1293) +, monocrotophos (561) +, methomyloxphos (1300, bromhexidine) + (NC) + TX), methomyl (1307) + (TX), formoxyl (NC) + TX), methomyl (TX), methomylox (TX) + (TX), bromhexedron (TX) + (TX), bromhexidide (1300, bromhexidil (NC-TX), penx) (1300 n) + (NC-TX), penoxsultrin (512) + (1307) + (NC-TX), bromphen (512) + (NC-TX), bromphen (1303) + (TX), compound (1309) + (NC-, Nicomycin (alias) [ CCN ] + TX, pentacyanocarb (nitrilacarb) (1313) + TX, pentacyanocarb (nitrilacarb)1:1 zinc chloride complex (1313) + TX, NNI-0101 (compound code) + TX, NNI-0250 (compound code) + TX, omethoate (omethoate) (594) + TX, oxamyl (602) + TX), sulfolobus (oxydeprofos) (1324) + TX, sulfolobus (oxydisulfoton) (1325) + TX, pp' -DDT (219) + TX, parathion (615) + TX, permethrin (626) + TX, petroleum oil alias (628) + TX, fenthion (1330) + TX, oryzanol TX, phorate (636) + TX, phorate (636), phorate (133) +, phoxim (1348) +, phoxim (1349) + (phoxim, phoxim (642) + (642), phoxim (TX), phorate (642) + (TX), phorate (636), TX, phorate (636), phorate (1349) + (642) + (ne, miticides (polynacatins) (alias) (653) + TX, prochloraz (1350) + TX, profenofos (662) + TX, lufenuron (promacyl) (1354) + TX, propargite (671) + TX, pyriproxyfen (propetamphos) (673) + TX, propoxur (678) + TX, ethidathion (prothathion) (1360) + TX, thiophosphate (prothhione) (1362) + TX, pyrethrin I (696) + TX, pyrethrin II (696) + TX, pyrethrin (pyrethins) (696) + TX, pyridaben (699) + TX, pyridaben (pyridaben) (701) + TX), pyriproxyfen (pyridaben) (706) + TX), pyrithion (1370) + TX, quinalphos (711, quinalphos) (1382) + (1382) (1382) + TX (1382), phytol (1382) + TX + codes (1382, and (1382) (study code of Califos) (706) + TX, and (1382) Captan (sebufos) (alternative name) + TX, selamectin (selamectin) (alternative name) [ CCN ] + TX, SI-0009 (compound code) + TX, sulbactam (thiophmide) (1402) + TX, spirodiclofen (738) + TX, spiromesifen (739) + TX, SSI-121 (research code) (1404) + TX), sulfenolan (alternative name) [ CCN ] + TX, sulfluramid (750) + TX, thiotep (sulfotep) (753) + TX, sulfur (754) + TX, SZI-121 (research code) (757) + TX, tau-fluvalinate (398) + TX, tebufenpyrad (1423) + TX, TEPP (1417) + TX, tertbutyrin (batem) (alternative name) + 777, thiotephos (653, tetradifenofos) (786) + (tetradifenodicid (tetradifenox) + TX) (653, tetradifenodicid) + TX, tetradifenox (5) + TX) Bendiocarb (thiocarboxime) (1431) + TX, bendiocarb (thiofanox) (800) + TX, thiometeon (thiometon) (801) + TX, dicofox (1436) + TX, sulbactin (thioningensis) (alias) [ CCN ] + TX, fenamiphos (triaminophos) (1441) + TX, triallate (triaathene) (1443) + TX, triazophos (820) + TX, triazophos (triazuron) (alias) + TX, trichlorfon (824) + TX, triclopyr (trifenox) (1455) + TX, triactin (trinactin) (653) + TX, pirimibeno (847) + TX), metaflumetonitrile (vanilliole) [ CCN ] and YI-5302 (compound code) +,

an algaecide selected from the group consisting of: benoxazin [ CCN ] + TX, copper dioctoate (IUPAC name) (170) + TX, copper sulfate (172) + TX, cybutryne [ CCN ] + TX, dichloronaphthoquinone (dichlone) (1052) + TX, dichlorophenol (232) + TX, endothal (295) + TX, triphenyltin (fentin) (347) + TX, slaked lime [ CCN ] + TX, sodium metiram (nabam) (566) + TX, quinoxalinone (quinoxamine) (714) + TX, quinonediamine (quinonamide) (1379) + TX, sima (730) + TX, triphenyltin acetate (IUPAC name) (347), and triphenyltin hydroxide (IUPAC name) (347) + TX,

an anthelmintic agent selected from the group consisting of: abamectin (1) + TX, yohimoto (1011) + TX, doramectin (alias) [ CCN ] + TX, emamectin (291) + TX, emamectin benzoate (291) + TX, eprinomectin (alias) [ CCN ] + TX, ivermectin (alias) [ CCN ] + TX, milbemycin (alias) [ CCN ] + TX, moxidectin (alias) [ CCN ] + TX, piperazine [ CCN ] + TX, selamectin (alias) [ CCN ] + TX, spinosad (737), and tobramin (thiophanate) (1435) + TX,

an avicide selected from the group consisting of: aldochlorose (127) + TX, endrin (1122) + TX, fenthion (346) + TX, pyridin-4-amine (IUPAC name) (23) and strychnine (745) + TX,

a bactericide selected from the group consisting of: 1-hydroxy-1H-pyridine-2-thione (IUPAC name) (1222) + TX, 4- (quinoxalin-2-ylamino) benzenesulfonamide (IUPAC name) (748) + TX, 8-hydroxyquinoline sulfate (446) + TX, bronopol (97) + TX, copper dioctanoate (IUPAC name) (170) + TX, copper hydroxide (IUPAC name) (169) + TX, cresol [ CCN ] + TX, dichlorophen (232) + TX, bispyrithion (1105) + TX, docosane (1112) + TX, sodium diuronate (fenaminosf) (1144) + TX, formaldehyde (404) + TX, mercapafen (alias) [ CCN ] + 580, kasugamycin (483) + TX, kasugamycin hydrochloride hydrate (483) + TX), bis (dimethyldithiocarbamate) nickel (pac name) (1308) + TX, trichloropicoline (nicarin) (py) + TX, Octhiolone (octhiazolinone) (590) + TX, oxolinic acid (606) + TX, oxytetracycline (611) + TX, potassium hydroxyquinoline sulfate (446) + TX, probenazole (658) + TX, streptomycin (744) + TX, streptomycin sesquisulfate (744) + TX, phyllo-cumylphthalein (766) + TX, and thimerosal (alias) [ CCN ] + TX),

a biological agent selected from the group consisting of: spodoptera fusca granulosis virus (Adoxophyes orana GV) (12) + TX, Agrobacterium radiobacter (alternative) (13) + TX, Amblyseius spp.) (alternative) (19) + TX, Spodoptera littoralis nucleopolyhedrosis virus (Anagrelide falcifera NPV) (alternative) (28) + TX, and primula pteronymus alatus branus wasp (Anagres a A) waspBacillus (alias) (29) + TX, Aphis brevis (Aphelenchus abdominis) (alias) (33) + TX, Aphis gossypii parasitic wasp (Aphis collina) (alias) (34) + TX, Aphis aphidicola (Aphis aphidicola), Aphis aphidicola (alias) (35) + TX, Spodoptera globosa nuclear polyhedrosis virus (Autographa californica NPV) (alias) (38) + TX, Bacillus firmus (alias) (48) + TX, Bacillus sphaericus (Bacillus subtilis) Neide (scientific name) (49) + TX, Bacillus thuringiensis (Bacillus thuringiensis) spore (scientific name) (51) + TX, Bacillus thuringiensis subspecies (Bacillus thuringiensis sp) (51. sp.) (Bacillus subtilis sp.) (scientific name) + TX), Bacillus thuringiensis subspecies (Bacillus thuringiensis sp. (51. sp.) (Bacillus subtilis) Bacillus thuringiensis subsp.tenebrionis (academic name) (51) + TX, Beauveria bassiana (Beauveria bassiana) (alias) (53) + TX, Beauveria broccoli (Beauveria bassiana) (alias) (54) + TX, Chrysopa chrysosporium (alias) (151) + TX, Cryptolaemus montoruieri (Cryptolaemus monothiozieri) (178) + TX, Cydia pomonella granulosis virus (Cydia pomonella GV) (alias) (191) + TX), Citrobacter canicola (Dacnosa sibirica) (alias) (212) + TX), Pisum sativum TX (TX), Pectinatus spp (Diglyphus glauca) (alias) (254) +, Microphyria carotovora) (alias) (293), Pseudobulbus callorhyemaria serohilus) (300, Heterobolus heterosporum) (Heterobolus heterosporum, Heterobolus cryptophycus (Heterophycus carotovora) and Heterophycus pluripus pluvialis (300) Coccinella variegate (hippophae convergens) (alternative name) (442) + TX, citrus pink scale insect parasitic wasp (Leptomastix dactylopii) (alternative name) (488) + TX, lygus (macrophyllus caliginosus) (alternative name) (491) + TX, cabbage looper nucleopolyhedrovirus (Mamestra brassicica NPV) (494) + TX, latifolius latus (Metaphicus helophorus) (alternative name) (522) + TX, Metarhizium anisopliae locust variant (Metarhizium anisopliae var. acridum) (academic name) (523) + TX, Metarhizium anisopliae var. auratus)liae) (academic name) (523) + TX, newcastle disease nucleopolyhedrovirus (Neodiprion serofer NPV) and newcastle disease nucleopolyhedrovirus (n.leconteri NPV) (alias) (575) + TX, Orius sp.) (alias) (596) + TX, Paecilomyces fumosoroseus (pseudopex fumosus) (alias) (613) + TX, physciospiroid (Phytoseiulus persimilis) (alias) (644) + TX, Spodoptera exigua (Spodoptera exigua) polynuclear capsid nucleopolyhedrovirus (alias) (741) + TX), wireworm (Steinernema biponis) (alias) (742) + TX), Steinernema (steiner sponicae) (alias) (742) + 742), steiner (steiner TX) (alias) (742) + TX), steineria (steiner (742), steineria (steineria persicaria) (alias) (742) + TX) (742, steineria (steineria) + TX) (742) + TX, steineria (alias) (742) + TX), steineria (another mark) (742) + (steineria) + (steineria) + TX) (742), steineria (steineria) + (steiner (742), steiner (steineria) + (TX) (742), Mole cricket filaria schneideri (Steinernema scapterisci) (alternative name) (742) + TX, filaria schneideri (alternative name) (742) + TX, Trichogramma species (trichogram spp.) (alternative name) (826) + TX, western blind mites (typhlomous occidentalis) (alternative name) (844) and Verticillium lecanii (Verticillium lecanii) (848) + TX), bacillus amyloliquefaciens variant (bacillus subtilis var. amyloliquefaciens) strain FZB24 (available from Novozymes corporation of semem 5400, VA, 24153, u.s.a., trade name) and available under the trade name salozyme, inc

Well known as such) + TX,

a soil disinfectant selected from the group consisting of: iodomethane (IUPAC name) (542) and bromomethane (537) + TX,

a chemical sterilant selected from the group consisting of: triazophos (apolate) [ CCN ] + TX, bis (aziridine) methylaminophosphine sulfide (bisazir) (also known as [ CCN ] + TX), busulfan (also known as [ CCN ] + TX), diflubenzuron (250) + TX, dimethoff (dimatif) (also known as [ CCN ] + TX), hexamethylmelamine (hemel) [ CCN ] + TX, hexametaphosphate [ CCN ] + TX ], methidathion (methpa) [ CCN ] + TX ], methidathion (mepta) [ CCN ] + TX ], methidathion (methiotepa) [ CCN ] + TX ], methidathion (methlyphosphole) [ CCN ] + TX ], methidathion (morph) [ CCN ] + TX ], methidathion (also known as [ CCN ] + TX ], thiuram [ CCN ] + TX ], thion (tepa) [ CCN ] + TX ], thiuram (also known as [ CCN ] + TX ], thiuram (s ] + TX),

an insect pheromone selected from the group consisting of: (E) -dec-5-en-1-yl acetate with (E) -dec-5-en-1-ol (IUPAC name) (222) + TX, (E) -tridec-4-en-1-yl acetate (IUPAC name) (829) + TX, (E) -6-methylhept-2-en-4-ol (IUPAC name) (541) + TX, (E, Z) -tetradec-4, 10-dien-1-yl acetate (IUPAC name) (779) + TX, (Z) -dodec-7-en-1-yl acetate (IUPAC name) (285) + TX, (Z) -hexadec-11-enal (IUPAC name) (436) + TX, (Z) -hexadec-11-en-1-yl acetate (IUPAC name) (437) TX, (Z) -hexadec-13-en-11-yn-1-yl acetate (IUPAC name) (438) + TX, (Z) -eicos-13-en-10-one (IUPAC name) (448) + TX, (Z) -tetradec-7-en-1-al (IUPAC name) (782) + TX, (Z) -tetradec-9-en-1-ol (IUPAC name) (783) + TX, (Z) -tetradec-9-en-1-yl acetate (IUPAC name) (784) + TX, (7E,9Z) -dodec-7, 9-dien-1-yl acetate (IUPAC name) (283) + TX, (9Z,11E) -tetradec-9, 11-dien-1-ylacetate (IUPAC name) (780) + TX, (9Z,12E) -tetradeca-9, 12-dien-1-ylacetate (IUPAC name) (781) + TX, 14-methyloctadec-1-ene (IUPAC name) (545) + TX, 4-methylnonan-5-ol and 4-methylnonan-5-one (IUPAC name) (544) + TX, alpha-polylysine (alias) [ CCN ] + TX, bark beetle assembly pheromone (brevicomin) (alias [ CCN ] + TX), dodecadienol (codelue) (alias [ CCN ] + TX), available Mongolian (codeilee) (alias) (167) +, cue-TX) (alias) (TX) + TX), epoxy nonadecane (paralute) (277) +, dodeca-8-ene-1-ylacetate (IUPAC name) + TX) +, Dodec-9-en-1-yl acetate (IUPAC name) (287) + TX, dodec-8 + TX, 10-dien-1-yl acetate (IUPAC name) (284) + TX, dominicaurer (alias) [ CCN ] + TX, ethyl 4-methyloctanoate (IUPAC name) (317) + TX, eugenol (alias) [ CCN ] + TX, south pine bark beetle pheromone (frontalin) (alias) [ CCN ] + TX, largetecin (gossiplure) (alias) (420) + TX, trap alkene mixture (grandilure) (421) + TX), trap alkene mixture I (alias) (421) + TX), trap alkene mixture II (alias) (421) + TX, trap alkene mixture III (alias) (421) + TX), trap alkene mixture IV (421) + TX, hexane inducer (hexafluor) [ CCN ] + tre (alias) (ccidiol) + (ccidiol) (TX) + TX), Mini enol (ipsenol) (alias) [ CCN ] + TX, scarab sex attractant (japonilure) (alias) (481) + TX, trimethyldioxytricyclononane (lineatin) (alias) [ CCN ] + TX, litlure (alias) [ CCN ] + TX, meadowsweet attractant (looplure) (alias) [ CCN ] + TX), killer ester (medlure) [ CCN ] + TX, megatomoic acid (alias) [ CCN ] + TX, chequer (lure) (mestranol) (alias) (540) +, lure (musure) (563) + TX, octadeca-2, 13-dien-1-ylacetate (IUPAC name) (588) + TX, octadeca TX-3, 13-dien-1-ylacetate (IUPAC name) (589) + fr) (alias) (orgen) (alias) (coconut ] + TX) + noc (noc) + (coc (noc) (ghost) (alias) (coconut ] + TX) +, Trap loop (siglure) [ CCN ] + TX, sordidin (alias) (736) + TX, phagostimulol (sulctitol) (alias) [ CCN ] + TX, tetradec-11-en-1-yl acetate (IUPAC name) (785) + TX, Bactrocera minax attractant (839) + TX, Bactrocera minax attractant A (alias) (839) + TX, Bactrocera minax attractant B1 (alias) (839) + TX, Bactrocera minax attractant B2 (alias) (839) + TX, Bactrocera minax attractant C (alias) (839) and trunc-call (alias) [ CCN ] + TX,

an insect repellent selected from the group consisting of: 2- (octylthio) ethanol (IUPAC name) (591) + TX, diethyltolunoxyl (933) + TX, butoxy (polypropylene glycol) (936) + TX, dibutyl adipate (IUPAC name) (1046) + TX, dibutyl phthalate (1047) + TX, dibutyl succinate (IUPAC name) (1048) + TX, diethyltoluamide [ CCN ] + TX, dichlofluanid [ CCN ] + TX, dimethyl phthalate [ CCN ] + TX, ethylhexanediol (1137) + TX, hexylurea [ CCN ] + TX, mequinate (methoquin-butyl) (1276) + TX, methylneodecanoamide [ CCN ] + TX, oxamate [ CCN ] and pyroxadine [ CCN ] + TX),

an insecticide selected from the group consisting of: 1-dichloro-1-nitroethane (IUPAC/chemical abstracts name) (1058) + TX, 1-dichloro-2, 2-bis (4-ethylphenyl) ethane (IUPAC name) (1056) + TX, 1, 2-dichloropropane (IUPAC/chemical abstracts name) (1062) + TX, 1, 2-dichloropropane (IUPAC name) (1063) + TX) with 1, 3-dichloropropene, 1-bromo-2-chloroethane (IUPAC/chemical abstracts name) (916) + TX, 2, 2-trichloro-1- (3, 4-dichlorophenyl) ethyl acetate (IUPAC name) (1451) + TX, 2, 2-dichlorovinyl 2-ethylsulfinylethyl methyl phosphate (IUPAC name) (1066) + TX, dimethylcarbamic acid 2- (1, 3-dithiolan-2-yl) phenyl ester (IUPAC/chemical abstracts name) (1109) + TX, 2- (2-butoxyethoxy) ethyl thiocyanate (IUPAC/chemical abstracts name) (935) + TX, 2- (4, 5-dimethyl-1, 3-dioxolan-2-yl) phenyl methylcarbamate (IUPAC/chemical abstracts name) (1084) + TX, 2- (4-chloro-3, 5-xylyloxy) ethanol (IUPAC name) (986) + TX, 2-chloroethenyl diethyl phosphate (IUPAC name) (984) + TX, 2-imidazolinone (IUPAC name) (1225) +, 2-isovaleryl indan-1, 3-dione (IUPAC name) (1246) + TX, 2-methyl (prop-2-ynyl) aminophenyl methylcarbamate (IUPAC name) (1284) + TX, 2-thiocyanoethyl laurate (IUPAC name) (1433) + TX, 3-bromo-1-chloroprop-1-ene (IUPAC name) (917) + TX, 3-methyl-1-phenylpyrazol-5-yl dimethylcarbamate (IUPAC name) (1283) + TX), 4-methyl (prop-2-ynyl) amino-3, 5-dimethylphenyl methylcarbamate (IUPAC name) (1285) + TX, 5-dimethyl-3-oxocyclohex-1-enyl methylcarbamate (IUPAC name) (1085) + TX, abamectin (1) + TX, acephate (2) + TX, Acetamiprid (4) + TX, housefly phosphorus (alias) [ CCN ] + TX, acetofenapyr [ CCN ] + TX, flupropathrin (9) + TX, acrylonitrile (IUPAC name) (861) + TX, bollworm (15) + TX, aldicarb (16) + TX, aldicarb (863) + TX, chloromononaphthalene (864) + TX, allethrin (17) + TX, aloamicin (alias) [ CCN ] + TX, fenoxycarb (866) + TX, alpha-cypermethrin (202) + TX, alpha-ecdysone (alias) [ CCN ] + TX, aluminum phosphide (640) + TX, thiothiofos (870) + TX, thioamide (872) + TX, fenoxycarb (873) +) + TX, aminotransferase (TX) +, amifosthiazate (875), amifosthiazide) + oxalate (875), methidathionine (24), nicotine (877) + (382) + I) + TX, methidathion (883) + TX), and captopril (887) + I) +, AZ 60541 (compound code) + TX, azadirachtin (alternative name) (41) + TX, azadirachtin (42) + TX, valethion-ethyl (44) + TX, valethion-methyl (45) + TX, azophos (889) + TX, bacillus thuringiensis endotoxins (alternative name) (52) + TX, barium hexafluorosilicate (alternative name) [ CCN ] + TX, barium polysulfide (IUPAC/chemical abstracts name) (892) + TX, fumigathrin [ CCN ] + TX, Bayer 22/190 (research code) (893) + TX, Bayer 22408 (research code) (894) + TX, bendiocarb (58) + TX, benfuracarb (60) + TX, thiocyanomethione (66) + TX, beta-cyfluthrin (194) + TX, beta-cypermethrin (203) + TX, bifenthrin (76) + TX, bioallethrin (78), bioallethrin S) + S (79) + cyclopentenyl (79) + TX) Beethofenprox (bioethanemethrin) [ CCN ] + TX, biothrin (908) + TX, pyrethrin (80) + TX, di (2-chloroethyl) ether (IUPAC name) (909) + TX, diflubenzuron (83) + TX, borax (86) + TX, bromethrin (alias) + TX, bromophenylphosphine (914) + TX, bromodienol (918) + TX, bromo-DDT (alias) [ CCN ] + TX, bromothiophosphate (920) + TX, bromothiophosphate-ethyl (921) + TX), methiocarb (924) + TX, buprofezin (99) + TX, fipronil (926) + TX), demethoxypyrifos (buthionine) (927) + TX, carboxim (103) + TX, butylphosphine (932) + TX, thionocetone (104) +, buthoxycarb (alias) +, thiobensulide (109) + calcium Polysulfate (PAC) + (111) + TX), calcium polysulfate (TX) + (111, TX) + (TX) +, Chlorfenapyr (941) + TX, cloxacarb (943) + TX, carbaryl (115) + TX, carbofuran (118) + TX, carbon disulfide (IUPAC/chemical abstracts name) (945) + TX, carbon tetrachloride (IUPAC name) (946) + TX, thiophosphoryl (947) + TX, thiobutachlor (119) + TX, cartap (123) + TX, cartap hydrochloride (123) +, simvastatin (alias) (725) + TX, borneol pellet (960) + TX, chlordane (128) + TX, kaempferia (963) + TX, chlorfenadine (964) + TX, chlorfenadine hydrochloride (964) + TX, phosphorus oxychloride (129) + TX, chlorfenapyr (130) + TX, chlorfenvinphos (131) + TX, chlorfluazuron (132) +, phosphorus (136), chloroform [ N ] + TX ], nitromethane (990) + (990) + TX) + pyridine (990), and chlorfenapyr (990) + TX, Chlorpyrifos (145) + TX, chlorpyrifos-methyl (146) + TX, tebufenphos (994) + TX, cyclamate (150) + TX, cinerin I (696) + TX, cinerin II (696) + TX, cinerin (696) + TX, cis-resmethrin) (alias) + TX, cis-resmethrin (cismethrin) (80) +), cyfluthrin (alias) + TX, oxamyl (999) + TX, closantel (alias) [ CCN ] + TX, clothianidin (165) + TX, copper acetoarsenite [ CCN ] + TX, copper arsenate [ CCN ] + TX ], copper oleate [ CCN ] + TX, coumaphos (174) + TX, TX) + 1006, crotamiton (TM) [ CCN ] + TX ], crotamiton (alias 1010, ethoprophos (alias) (CS) + TX, kromorph (alias) (TX) + TX, TX + 708, chlomorph (177) + (CS) + (alias) + TX), Cyanophos (1019) + TX, cyanophos (184) + TX, buthifos (1020) + TX, cyhalothrin [ CCN ] + TX, cycloprothrin (188) + TX, cyfluthrin (193) + TX, cyhalothrin (196) + TX, cypermethrin (201) + TX, cyphenothrin (206) + TX, cyromazine (209) + TX, fenthion (another name) [ CCN ] + TX, d-limonene (another name) [ CCN ] + TX, d-tetramethrin (another name) (788) + TX, DAEP (1031) +, dazomethyl (216) + TX, DDT (219) + TX, monomethyl carbofuran (1034) + TX, deltamethrin (223) + TX), tylophos (1037) +, tylophos-O (7) + TX), thiolophos (1037) + (1038) + TX), demeton (1038) + TX, systemic phophos (1038) + (1038) + TX), Systemic phosphorus-O-methyl (224) + TX, systemic phosphorus-S (1038) + TX, systemic phosphorus-S-methyl (224) + TX, systemic phosphorus-S-methyl sulfone (1039) + TX, diafenthiuron (226) + TX, chlormethiphos (1042) + TX, diamidophos (1044) + TX, diazinon (227) + TX, isochlorophos (1050) + TX, ethoprophos (1051) +, dichlorvos (236) + TX, dicliphos (alias) + TX), diclesyl (alias) + TX, diclesyl) (alias) [ CCN ] + TX, pethos (243) + TX, dicyclanil (244) + TX, dieldrin (TX) + TX, diethyl 5-methylpyrazol-3-yl phosphate (pac name) + TX, pyrethrum (250, dipropylenetheine (alias) + (lospermethrin) + (ccl TX), and dipropylenetetramethrin (alias) + (ccl) + + TX), diethyl5-methylpyrazol-3-yl phosphate (pac) (pac name) + TX), pyrethrum (250, dipropylenemethyl ether) (alias) + (ccl + TX, and mefhrin) + (alias) +, Fluorofos (1081) + TX, dimercarb (1085) + TX, dimethoate (262) + TX, bifenthrin (1083) + TX, methomyl (265) + TX, dichlorvone (1086) + TX, fenaminophen (1089) + TX, fenaminophen (dinex-dicexene) (1089) + TX, propyrol (1093) + TX, penthiophenol (1094) + 164 dinocap (1095) + TX, dinotefuran (271) + TX, bendiofen (1099) + TX, bensulosin (1100) + TX, dioxacarb (1101) + TX, dioxathiophos (1102) + TX, disulfoton (278) + TX, dithianthiodiethofen (1118) + (dithifos) (1108) + TX, EI (282) + TX, Doramectin (DSP) + TX, and the other names of dimehypo (291) + TX) (291, ecdysone (1118) + TX), and the other names of the same No. TX) (1108, E + TX, E + TX, and E + E-D (TM) (E + E, EMPC (1120) + TX, empenthrin (292) + TX, endosulfan (294) + TX, ifolin (1121) + TX, endrin (1122) + TX, EPBP (1123) + TX, EPN (297) + TX, bayan ether (1124) + TX, eprinomectin (alias) [ CCN ] + TX, esfenvalerate (302) + TX, oxford prothioconazole (alias) [ CCN ] + TX, ethiofencarb (308) + TX, ethiofenphos (309) + TX, ethiprole (310) + TX, thiothiofos (1134) + TX, fenamiphos (312) + TX, ethyl formate (IU name) [ CCN ] + TX, ethyl-DDD (alias) (1056) + TX, dibromoethane (316) + TX, dichloroethane (chemical name) (1136) + TX, ethylene oxide [ CCN ] + 319) + pyrithiothrin (1142) + D (1143) + TX, ethoprophos (1142) + TX), ethoprophos (1143) + TX, and 1142, Fenamiphos (326) + TX, amitrazole (1147) + TX, pyraclofos (1148) + TX, fenoxycarb (1149) + TX, pentafluoropyrethrin (1150) + TX, fenitrothion (335) + TX, fenobucarb (336) + TX), oxapyrimethanil (1153) + TX, fenoxycarb (340) + TX, cypermethrin (1155) + TX, fenpropathrin (342) + TX, fenpyrad (alias) + TX, fosfenphos (1158) + TX, fenthion (346) + TX, ethyl fenthion [ CCN ] + TX, fenvalerate (349) + TX, fipronil (354) + TX, flonicamid (358) +), flubendiamide (CAS) registration number TX + TX 272451-65-7) + TX, flucyclofuroron (1168) + fenfluroxypyr), cyflufen (366) + TX), flufenoxuron (1169) + TX, flubenflumeturon (1169) + TX) +, Trifusarin (1171) + TX, flumethrin (372) + TX, fluvalinate (1184) + TX, FMC 1137 (research code) (1185) + TX, bendiofos (1191) + TX, vaboxamidine (405) + TX, vaboxamidine hydrochloride (405) + TX, thiophosphor (1192) + TX, acamprosate (formosanate) (1193) + TX, fenthion (1194) + TX, fosapremilast (1195) + TX, thizofos (408) + TX, thiothifenphos (1196) + TX, furametpyr (412) + 1070), pyrethrum (1200) + TX, gamma-cyhalothrin (197) + TX), HCH (430) + TX, biguanide salt (422) + TX, biguanide acetate (422) + TX 1211, GY-81 (research code) (423) + TX, fenazafenpropyrifos (197) + hydrazide (425) + TX), femtozoatum (425) + TX, and bufenozide (425) + TX, Heptenophos (432) + TX, phosmet [ CCN ] + TX, hexaflumuron (439) + TX, HHDN (864) + TX, hydramethylnon (443) + TX, hydrocyanic acid (444) + TX, methoprene (445) + TX, hymexacarb (1223) + TX, imidacloprid (458) + TX, prallethrin (460) + TX, indoxacarb (465) +, iodomethane (IUPAC name) (542) + TX, IPSP (1229) + TX, cloxathion (1231) + TX, carbochlorazol (1232) +, isocarbophos (alias) (TX), isoethazine (1235) + TX, isoxaphos (1236) + TX, propamocarb (1237) + TX), isoprocarb (472) + TX, O- (methoxyaminothiophosphoryl) isopropyl salicylate (IUPAC name) (474) +, isoprothiolane (1244) + TX), isoprothiolane (480) + (1237) + TX), isoprocarb (TX) + TX, isoprocarb (480) + (480) + TX), Heliotropin I (696) + TX, heliotropin II (696) + TX, iodophos (1248) + TX, juvenile hormone I (alias) [ CCN ] + TX, juvenile hormone II (alias) [ CCN ] + TX, juvenile hormone III (alias) [ CCN ] + TX, dioxolane (1249) + TX, methoprene (484) + TX, lambda-cyhalothrin (198) +), lead arsenate [ CCN ] + TX, lepimectin (CCN) + TX, parabromophos (1250) + TX, lindane (430) + TX, propidium (lirimfos) (1251) + TX, lufenuron (490) + TX, fosthiazate (1253) + TX, metaisopropylphenyl methylcarbamate TX (PAC name) (1014) + TX, magnesium phosphide (IUPAC name) (640), malathion (05) +, fenaminosulfenamide (4) + (triazophos) (502) + TX, triazophos (502 TX) + TX) (502, Triazophos (TX) (502 TX) + TX) (1014) + TX) (MCT) (502, triazophos) (1255), Myzufos (1260) + TX, benfop (1261) + TX, mercurous chloride (513) + TX, disulfotoxin (1263) + TX, metaflumizone (CCN) + TX, metam (519) + TX), metam potassium (alian) (519) + TX, metam sodium (519) + TX, chlorfenvinphos (1266) + TX, methamidophos (527) + TX), methanesulfonyl fluoride (IUPAC/chemical abstracts name) (1268) + TX, methidathion (529) + TX, methiocarb (530) + TX, ethoprophos (1273) +, methomyl (531) + TX, methomyl (532) + TX, mefenoxate (1276) + TX) +, methomyl TX (533) + TX) +, methoxyfenozide 534, methoxychlor (535) + TX), methomyl (537, methyl bromide) + N (CCN) + TX, dichloromethane (543) + TX, methicone (543) + TX + methyl chloride (533) + TX), methicone (543, methyl chloride (CCN) + TX), Metofluthrin [ CCN ] + TX, metolcarb (550) + TX, oxacloprid (1288) + TX, metocloprid (556) + TX, mecarb (1290) + TX, cimetidine (557) + TX, milbemycin (alias) [ CCN ] + TX, profenofos (1293) + TX, mirex (1294) + TX), monocrotophos (561) + TX, methoprene (1300) + TX, moxidectin (alias) [ CCN ] + TX, naphthalphosphon (alias) [ CCN ] + TX, naled sodium bromide (567) + TX, naphthalene (IUPAC/chemical abstracts name) (1303) + TX), NC-170 (research code) (1306) + TX, NC-184 (compound code) + TX, nicotine (578) + TX, nicotine sulfate (578) + TX, trifluralin (578), prodiamine (1309) + TX), nitenpyram (579) + (131571), thiocyanamide (1311) + zinc chloride (1311) +, NNI-0101 (compound code) + TX, NNI-0250 (compound code) + TX, nornicotine (classical name) (1319) + TX, noviflumuron (585) + TX, noviflumuron (586) + TX, O-5-dichloro-4-iodophenyl O-ethylthiophosphonate (IUPAC name) (1057) + TX, O, O-diethyl O-4-methyl-2-oxo-2H-chromen-7-yl thiophosphonate (IUPAC name) (1074) + TX, O, O-diethyl O-6-methyl-2-propylpyrimidin-4-yl thiophosphonate (IUPAC name) (1075) + TX, O, O, O ', O' -tetrapropyldithio (IUPAC name) (pyrophosphate 4) + TX), Oleic acid (IUPAC name) (593) + TX, omethoate (594) + TX, oxamyl (602) + TX, oxydisulfide-methyl (609) + TX, phosphorous isochione (1324) + TX, phorate (1325) + TX), pp' -DDT (219) + TX, p-dichlorobenzene [ CCN ] + TX, parathion (615) + TX, parathion-methyl (616) + TX, chlorfluazuron (alias) [ CCN ] + TX, pentachlorophenol (623) + TX, pentachlorophenyl laurate (lupac name) (623) + TX), permethrin (626) + TX, petroleum oil (alias) (628) + TX, PH 60-38 (research code) (1328) + TX, fenthion (1330) + TX, phenothrin (630) + TX), oryza (TX) + TX, phorate (133636) + TX, thiothiothion (637, thiothifenthion (638) + (637) + (638) + TX), thiothifenthion (631) + (TX) + TX), Parathion (1339) + TX, phosphamidos (639) + TX, phosphine (IUPAC name) (640) + TX, phoxim (642) + TX, phoxim-methyl (1340) + TX, primidophos (pirimephos) (1344) + TX, pirimicarb (651) + TX, ethylpyrimidinophos (1345) + TX), pirimiphos (652) + TX, polychloroprene isomers (IUPAC name) (1346) + TX, turpentine chloride (polycholoterpenes) (traditional name) (1347) + TX, potassium arsenite [ CCN ] + TX, potassium thiocyanate [ CCN ] + TX, propynthrin (655) + TX, propathrin I (alias) [ CCN ] + TX, propathrin II (alias) [ cctx ] + TX, propathrin III (CCN ] + TX), acephate (pridophosphates) (1349) + [ CCN ] + TX, propathrin [ c) + (1354) + (1355) + fenproxyfen (1355), bromphen (1354) + TX), methicillin(s) + TX), methicillin (1347) + TX), methomyl (methicillin) + (methicillin) +, Bensulprofos (1356) + TX, amirocarb (673) + TX, propoxur (678) + TX, ethiprole (1360) + TX, prothioconazole (686) + TX, phenthofos (1362) + TX, propylbifenthrin (protifenbute) [ CCN ] + TX, pymetrozine (688) + TX, pyrazothion (689) + TX, fenamiphos (693) + TX, resmethrin (pyrethrin) (1367) + TX, pyrethrin I (696) + TX, pyrethrin II (696) + TX, pyrethrins (696) +) + TX, pyridaben (699) + TX, pyridaben (700) + TX, pyridaphenthion (701) + TX), pyriproxyfen (706) + TX, pyrithion (1370) + TX, pyriproxyfen (708), propylether (696) + TX, qua extract (CCqua) (1380) + quinalphos (1381) + TX), quinalphos (1381) + TX, quinalphos (1386) + TX, quinalphos TX) + (1382, quinalphos (p-S) + TX), quinalphos (1381, quinalphos (p-S) + TX) + (TX), pyrazofos (1381), r-1492 (research code) (1382) + TX, rafoxanide (alias) [ CCN ] + TX, resmethrin (719) + TX, rotenone (722) + TX, RU 15525 (research code) (723) + TX, RU 25475 (research code) (1386) + TX, ryania (alias) (1387) + TX, linadine (traditional name) (1387) + TX, sabotara (alias) (725) + TX, octamethylphosphote (1389) + TX, thiotepa (alias) + TX, selamectin (alias) [ CCN ] + 040, SI-0009 (compound code) + TX, SI-0205 (compound code) + TX, SI-4 (compound code) + TX, SI-0405 (compound TX code) + TX, silafluofen) + SN, SN 72129 (research code) (1397, arsenite [ CCN ] + 444, sodium arsenite) + TX, and TX + TX, Sodium fluoride (IUPAC/chemical abstracts name) (1399) + TX, sodium hexafluorosilicate (1400) + TX, sodium pentachlorophenate (623) + TX, sodium selenate (IUPAC name) (1401) + TX, sodium thiocyanate [ CCN ] + TX, sulthion (1402) + TX, spinosad (737) + TX, spiromesifen (739) + TX, spirotetramat (CCN) + TX), salflouron (sulcuron) (746) + TX, sodium sulkoflouron (sulcuron-sodium) (746) + TX), sulfluron (750) + TX, diclofenofos (753) + TX, sulfuryl fluoride (756) + TX, thioprofenofos (1408) + TX, tar (758) (another name) + TX, tau-fluvalinate (TX) + TX, thiofenbucarb (1412) +, TDE (1414), tebufenozide (762) + TX) + teflufen (758) + TX), tefluthrin (769) + TX), Tefluthrin (TX) + TX, teflufen (769), Tefluthrin (TX) +, Thiotepa (770) + TX, TEPP (1417) + TX, cyclopentene allethrin (1418) + TX, tertbutyrin (terbam) (alternative name) + TX, terbufos (773) + TX, tetrachloroethane [ CCN ] + TX, chlorfenvinphos (777) + TX, tetramethrin (787) + TX, theta cypermethrin (204) + TX, thiacloprid (791) + TX, sefanoko (thiafenox) (alternative name) + TX, thiamethoxam (792) + TX, benzothiophen (thiocfos) (1428) + TX, carbofuran (1431) + TX, thiocyclam (798) +, thiocyclam (798) + TX), thiodicarb (799) + TX), carboxim (800) + TX, fosetyl (801) +, fenamiphos (1434), thiocyclam (803) + (803) + TX), thiocyclam (803) + TX, thiocyclam (803) + TX) (alternative name of Succinamide (803) +) + TX, thiodicarb (803) + TX, thiocyclam (803) + TX), Tetrabromthrin (812) + TX, transfluthrin (813) + TX, trans-permethrin (1440) + TX, fenclofos (1441) + TX, triazamate (818) + TX, triazophos (820) + TX, azolecarb (alias) + TX), trichlorfon (824) + TX, trimetaphosphate-3 (trichlorormethops-3) (alias) [ CCN ] + TX, clomiphos (1452) + TX, propoxyphos (1455) + TX, triflumuron (835) + TX, methiocarb (840) +, methoprene thioester (1459) + TX, pirimiphos (847) + TX, metaflumiclone (vanillyl) [ CCN ] + TX, tridyx (725) + TX) +, veratrole (725), veratrine (725), zepine (725) +, zevalicarb (853) + (Ynethrin) + TX), valmethrin (205) + tetramethrin (Yttx), symmetribuzin) + TX, Yttx (205-TX) + TX), valmethrin (I) + TX, cypermethrin (205, zeta-TX) + TX (I), cypermethrin (thiram (I) + TX, triazamate (thiram, Zinc phosphide (640) + TX, oxazaphos (zolaprofos) (1469) and ZXI 8901 (research code) (858) + TX, cyantraniliprole [736994-63-19] + TX, chlorantraniliprole [500008-45-7] + TX, cyenopyrafen (cyenopyrafen) [560121-52-0] + TX, cyflumetofen [400882-07-7] + TX, fluquinazin (pyrifluquinazon) [337458-27-2] + TX, spinetoram [187166-40-1+187166-15-0] + TX, spirotetramat [203313-25-1] + TX, sulfoxaflor [946578-00-3] + TX ], fipronil (sulfoflor) [704886-18-0] + TX ], tefluthrin [ 915288-8613-24-200 ] + 847, tefluthrin (8488-849-0 ] + TX), Trifluorobenzene pyrimidine (triflumzopyrim) (disclosed in WO 2012/092115) + TX,

a molluscicide selected from the group consisting of: di (tributyltin) oxide (IUPAC name) (913) + TX, bromoacetamide [ CCN ] + TX, calcium arsenate [ CCN ] + TX, oxamyl (cloethocarb) (999) + TX, copper acetoarsenite [ CCN ] + TX, copper sulfate (172) + TX, triphenyltin (347) + TX, iron phosphate (IUPAC name) (352) + TX, metaldehyde (518) + TX, methiocarb (530) + TX, niclosamide (576) + TX, niclosamide-ethanolamine (576) + TX, sodium pentachlorophenate (623) + TX, sodium pentachlorophenoxide (623) + TX, thiacloprid (tauromcarb) (1412) + TX), thiodicarb (799) +, tributyltin oxide (913) + TX, snail killer (trifenmorph) (1454) + TX, methiocarb (840), triphenyltin acetate (PAC-394730) + (PAC-71),

a nematicide selected from the group consisting of: AKD-3088 (compound code) + TX, 1, 2-dibromo-3-chloropropane (IUPAC/chemical abstracts name) (1045) + TX, 1, 2-dichloropropane (IUPAC/chemical abstracts name) (1062) + TX, 1, 2-dichloropropane and 1, 3-dichloropropene (IUPAC name) (1063) + TX, 1, 3-dichloropropene (233) + TX, 3, 4-dichlorotetrahydrothiophene 1, 1-dioxide (IUPAC/chemical abstracts name) (1065) + TX, 3- (4-chlorophenyl) -5-methylrhodanine (IUPAC name) (980) + TX, 5-methyl-6-thio-1, 3, 5-thiadiazin-3-ylacetic acid (IUPAC name) (1286) + TX, 6-isopentenylaminopurine (alias) (210) + TX), Abamectin (1) + TX, acetofenapyr [ CCN ] + TX, boll-weevil (15) + TX, aldicarb (aldicarb) (16) + TX, aldicarb (863) + TX, AZ 60541 (compound code) + TX, chlorthaliz [ CCN ] + TX, benomyl (62) + TX, butyridazole (alias) + TX, colistin (109) + TX, carbofuran) (118) + TX, carbon disulfide (945) + TX, carbosulfan (119) +, chloropicrin (141) + TX, chlorpyrifos (145) + TX, oxamyl (999) + TX, cytokinin (alias) (210) + TX, dazomethion (216) + TX, DBCP (1045) +, DCIP (218) +, clematidine (1044) + (130) +, disulfotoxin (alias) + (1051) +, disulfotoxin) + (TX) + TX), desmethosulfastin (1051) +, diclofop (1051) +, butine (218) +, diclofop (113) + TX), diclofop (1051) +, diclofop(s) + (1051, diclofop) +, emamectin (291) + TX, emamectin benzoate (291) + TX, eprinomectin (alias) [ CCN ] + TX, ethoprophos (312) + TX, dibromoethane (316) + TX, fenamiphos (326) + TX, fenpyrad (alias) + TX), fosfamid (1158) + TX, fosthiazate (408) + TX, sulfothiotepa (1196) + TX), furfural (alias) [ CCN ] + TX, GY-81 (research code) (423) + TX, sufosfamid [ CCN ] + TX, iodomethane (IUPAC name) (542) +, isoamidophos (isamidofos) (1230) +, cloxathiotepa (1231) + TX, ivermectin (alias) [ CCN ] + TX, kinetin (alias) (210) + TX), methamphosphine (1258) +, methamphetamine (519) + (519) + TX), methamine (519) + sodium salt (519) + (519) + TX), methamine (519) + (537) + TX), methamine (519, methamine) + TX) Methyl isothiocyanate (543) + TX, milbeoxime (alias) [ CCN ] + TX, moxidectin (alias) [ CCN ] + TX, myrosina verrucosa (alias) (565) + TX, NC-184 (compound code) + TX, oxamyl (602) + TX, phorate (636) + TX), phosphamide (639) + TX, foscarnet [ CCN ] + TX, captan (alias) + TX), selamectin (alias) [ CCN ] + TX, spinosad (737) + TX, tertbutylcarb (alias) + TX, terbufos (773) + TX), tetrachlorothiophene (pac/chemicosane name) (1422) + TX, thianox (alias) + TX, ethoprophos (1434) +, triazophos (fefe) +, triazophos (triazazuzu) (773) +), triazophos (pac/chemigum) (alias) (1422) +, xylenol code (alias) + TX), and zea (compound code) + TX) (210 i) + TX, zea, Fluensulfone [318290-98-1] + TX,

a nitrification inhibitor selected from the group consisting of: potassium ethylxanthate [ CCN ] and chloropyridine (nitrapyrin) (580) + TX,

a plant activator selected from the group consisting of: acylanilide (6) + TX, acibenzolar-S-methyl (6) + TX, probenazole (658) and Polygonum cuspidatum (Reynoutria sachalinensis) extract (also known as) (720) + TX,

a rodenticide selected from the group consisting of: 2-isovalerylindan-1, 3-dione (IUPAC name) (1246) + TX, 4- (quinoxalin-2-ylamino) benzenesulfonamide (IUPAC name) (748) + TX, α -chlorohydrin [ CCN ] + TX, aluminum phosphide (640) + TX, barbital (880) + TX, arsenic trioxide (882) + TX, barium carbonate (891) + TX, bismuthyl urea (912) + TX, brodifuron (89) + TX, brodifuron (91) + TX, brodifaconine (92) + TX, calcium cyanide (444) + TX, aldonitzamide (127) + TX, muridone (140) + TX, vitamin D3 (alias) (850) + TX, clomurazol (1004) + TX, rodenticide (1005) + TX, rodenticide naphthalene (175) + TX, rodenticine (1009) + TX, dexrazine (246) + TX, diclodiclodiclodiclodiclodiclodiclodiclodiclodiclodiclodiclodiclodiclodiclodiclodiclodiclodiclodiclodiclodiclodiclodiclodiclodiclodiclodiclodiclodiclodic, Vitamin D2(301) + TX, flocoumafen (357) + TX, fluoroacetamide (379) + TX, murphodine (1183) + TX, murphodine hydrochloride (1183) + TX, gamma-HCH (430) + TX, hydrocyanic acid (444) + TX, iodomethane (IUPAC name) (542) + TX, lindane (430) + TX, magnesium phosphide (IUPAC name) (640) + TX, methyl bromide (537) + TX, diclofop (1318) + TX, murphophos (1336) + TX, hydrogen phosphide (IUPAC name) (640) + TX, phosphorus [ CCN ] + TX, muridone (1341) + TX, potassium arsenite [ CCN ] + TX, murumyl (1371) + TX, heteroside (1390) + TX, sodium arsenite [ CCN ] + TX ], sodium cyanide (444) +, fosetyl [ CCN ] + TX ], sodium acetate (640) + TX) + zinc phosphide (640) + TX),

a synergist selected from the group consisting of: 2- (2-butoxyethoxy) ethyl piperate (IUPAC name) (934) + TX, 5- (1, 3-benzodioxol-5-yl) -3-hexylcyclohex-2-enone (IUPAC name) (903) + TX, farnesol with nerolidol (alias) (324) + TX, MB-599 (research code) (498) + TX, MGK264 (research code) (296) + TX, piperonyl butoxide) (649) + TX, piperonal (1343) + TX, propyl isomer (propyl isr) (1358) + TX, S (research code) (724) + TX, piperonyl (semex) (1393) + TX, sesamolin (sesamolin) (421) and sulfoxide (1406) + TX,

an animal repellent selected from the group consisting of: anthraquinone (32) + TX, aldocloro chloride (127) + TX, copper naphthenate [ CCN ] + TX, copper oxychloride (171) + TX, diazinon (227) + TX, dicyclopentadiene (chemical name) (1069) + TX, guazatine (422) + TX), guazatine (422) + TX, methiocarb (530) + TX), pyridin-4-amine (IUPAC name) (23) + TX, seram (804) + TX, trimethacarb (840) + TX, zinc naphthenate [ CCN ] and ziram (856) TX,

a virucidal agent selected from the group consisting of: immanine (alternative name) [ CCN ] and ribavirin (alternative name) [ CCN ] + TX,

a wound protectant selected from the group consisting of: mercuric oxide (512) + TX, octhiazone (590) and thiophanate-methyl (802) + TX,

and a biologically active compound selected from the group consisting of: ametoctradin [865318-97-4]+ TX, indazolesulfamide [348635-87-0]+ TX, azaconazole [60207-31-0]+ TX, benzovindifiuzole [1072957-71-1 ]]+ TX, Biphenyltriazolol [70585-36-3]+ TX, Bixafen [581809-46-3]+ TX, bromuconazole [116255-48-2]+ TX, coumoxystrobin [850881-70-8]+ TX, cyproconazole [94361-06-5]+ TX, difenoconazole [ 119446-68-3%]+ TX, diniconazole [83657-24-3]+ TX, enestroburin [238410-11-2]+ TX, epoxiconazole [106325-08-0]+ TX, fenbuconazole [114369-43-6]+ TX, fenpyrazamine [473798-59-3]+ TX, fluquinconazole [136426-54-5]+ TX, flusilazole [85509-19-9]+ TX, flutriafol [76674-21-0]+ TX, fluxapyroxad [907204-31-3]+ TX, Fluopyram [658066-35-4 ]]+ TX, alkene oxime amine [366815-39-6]+ TX, Isopropitamine [875915-78-9]+ TX, hexaconazole [79983-71-4 ]]+ TX, imazalil [35554-44-0]+ TX, imipramazole [86598-92-7]+ TX, ipconazole [125225-28-7]+TX、ipfentrifluconazole[1417782-08-1]+ TX isotianil[224049-04-1]+ TX, mandibun [173662-97-0](may be prepared according to the procedure described in WO 2010/093059) + TX, Chlorofloxacin [1417782-03-6]+ TX, metconazole [125116-23-6]+ TX, myclobutanil [88671-89-0]+ TX, paclobutrazol [76738-62-0]+ TX, fenoxaprop [101903-30-4]+ TX, penflufen [494793-67-8]+ TX, penconazole [66246-88-6]+ TX, prothioconazole [178928-70-6]+ TX, pyrifenox [88283-41-4 ]]+ TX, prochloraz [67747-09-5]+ TX, propiconazole 60207-90-1]+ TX, simeconazole [149508-90-7]+ TX, tebuconazole [107534-96-3]+ TX, tetraconazole [112281-77-3]+ TX, triazolone [43121-43-3]+ TX, triadimenol [55219-65-3]+ TX, triflumizole [99387-89-0]+ TX, triticonazole [131983-72-7]+ TX, pyrimidineol [12771-68-5]+ TX, chlorobenzopyrimidinol [60168-88-9]+ TX, fluoropyrimidinol [63284-71-9]+ TX, bupirimate [41483-43-6]+ TX, dimethirimol [5221-53-4 ]]+ TX, ethirimol [23947-60-6]+ TX, dodecacyclomorpholine [1593-77-7]+ TX, fenpropidin [67306-00-7 ]]+ TX, butylbenzene morpholine [67564-91-4 ]]+ TX, spiroxamine [118134-30-8]+ TX, tridemorph [81412-43-3]+ TX, cyprodinil [121552-61-2]+ TX, mepanipyrim [110235-47-7]+ TX, pyrimethanil [53112-28-0]+ TX, fenpiclonil [74738-17-3]+ TX, fludioxonil [131341-86-1 ]]+ TX, Fluindapyr [1383809-87-7 ]]+ TX, benalaxyl (benalaxyl) [71626-11-4]+ TX, furalaxyl (furalaxyl) [57646-30-7]+ TX, metalaxyl [57837-19-1]+ TX, R-metalaxyl [70630-17-0]+ TX, furoamide [58810-48-3]+ TX, Oxadixyl (Oxadixyl) [77732-09-3]+ TX, benomyl [17804-35-2]+ TX, carbendazim [10605-21-7]+ TX, Probencarb (debacarb) [62732-91-6]+ TX, fuberidazole [3878-19-1]+ TX, thiabendazole [148-79-8]+ TX, ethidium (chlolinate) [84332-86-5]+ TX, sclerotium (dichlozoline) [24201-58-9]+ TX, Iprodione (Iprodione) [36734-19-7]+ TX, myclozoline [54864-61-8]+ TX, procymidone [32809-16-8]+ TX, vinclozoline [50471-44-8]+ TX, boscalid [188425-85-6 ]]+ TX, carboxin [5234-68-4 ]]+ TX, methylfuroamide [24691-80-3]+ TX, flutolanil [66332-96-5 ]]+ TX, Fluorothiazole nitrile (Flutolanil) [958647-10-4 ]]+ TX, mefenacet [55814-41-0]+ TX, Oxycoxin[5259-88-1]+ TX, penthiopyrad [183675-82-3]+ TX, thifluzamide [130000-40-7]+ TX, biguanide octyl salt [108173-90-6]+ TX, Dosidine [2439-10-3][112-65-2](free base) + TX, iminoctadine [13516-27-3]+ TX, azoxystrobin [131860-33-8]+ TX, dimoxystrobin [149961-52-4]+ TX, enestroburin { Glasgow british crop protection committee international conference (proc.bcpc, int.congr., Glasgow.)2003, 1, 93} + TX, fluoxastrobin [361377-29-9 [ ]]+ TX, kresoxim-methyl [143390-89-0]+ TX, metominostrobin [133408-50-1]+ TX, trifloxystrobin [141517-21-7]+ TX, orysastrobin [248593-16-0]+ TX, picoxystrobin [117428-22-5]+ TX, pyraclostrobin [175013-18-0]+ TX, pyraoxystrobin [862588-11-2]+ TX, ferbam [14484-64-1 ]]+ TX, mancozeb [8018-01-7]+ TX, maneb [12427-38-2]+ TX, metiram [9006-42-2 ]]+ TX, propineb (propineb) [12071-83-9]+ TX, Sailun [137-26-8]+ TX, zineb [12122-67-7]+ TX, ziram [137-30-4 ]]+ TX, captafol [2425-06-1]+ TX, captan [133-06-2 ]]+ TX, antibacterial [1085-98-9 ]]+ TX, Oxyfluoride [41205-21-4 ]]+ TX, folpet [ 133-07-3%]+ TX, tolylfluanid [731-27-1]+ TX, Bordeaux mixture [8011-63-0]+ TX, copper hydroxide (copperhydroxide) [20427-59-2]+ TX, copper chloride (copperoxochlorid) [1332-40-7]+ TX, copper sulfate (copperemulfat) [7758-98-7]+ TX, copper oxide (copperoxid) [1317-39-1]+ TX, mancopper [53988-93-5 ]]+ TX, oxine-copper [10380-28-6]+ TX, dinocap [131-72-6 ]]+ TX, phthaloyl-isoproyl [10552-74-6]+ TX, kewensan [ 17109-49-8)]+ TX, iprobenphos [26087-47-8]+ TX, isoprothiolane [50512-35-1]+ TX, Phosphaphos (phosdiphen) [36519-00-3]+ TX, pyrazophos [13457-18-6 ]]+ TX, tolclofos-methyl [57018-04-9]+ TX, Acibenzolar-S-methyl [135158-54-2]+ TX, trichlorfon [101-05-3]+ TX, benthiavalicarb [413615-35-7]+ TX, blasticidin-S [2079-00-7]+ TX, chinomethionat (2439-01-2)]+ TX, chloroneb [2675-77-6]+ TX, chlorothalonil [1897-45-6]+ TX, cyflufenamid [180409-60-3]+ TX, cymoxanil [57966-95-7]+ TX, dichloronaphthoquinone [117-80-6 ]]+ TX, diclorocyanid (diclocymet)[139920-32-4]+ TX, pyridaben (diclomezine) [62865-36-5]+ TX, chloronitroamine (dicloran) [99-30-9 ]]+ TX, diethofencarb [87130-20-9]+ TX, dimethomorph [110488-70-5]+ TX, SYP-LI90 (flumorph) [211867-47-9 ]]+ TX, dithianon [3347-22-6]+ TX, ethaboxam (ethaboxam) [162650-77-3]+ TX, terrazole [2593-15-9 ]]+ TX, famoxadone [131807-57-3]+ TX, fenamidone (fenamidone) [161326-34-7]+ TX, Fenoxanil [115852-48-7]+ TX, triphenyltin (fentin) [668-34-8]+ TX, pyriminozone (ferimzone) [89269-64-7]+ TX, fluazinam [79622-59-6]+ TX, Fluopyram [239110-15-7]+ TX, flusulfamide [106917-52-6]+ TX, fenhexamid [126833-17-8]+ TX, fosetyl-aluminum [39148-24-8 ]]+ TX, hymexazol (hymexazol) [10004-44-1]+ TX, propineb [140923-17-7]+ TX, IKF-916 (Cyazofamid) [120116-88-3 ]]+ TX, kasugamycin [6980-18-3]+ TX, metosulcarb [66952-49-6]+ TX, metrafenone [220899-03-6]+ TX, pencycuron [66063-05-6]+ TX, phthalide [27355-22-2]+ TX, piperazole [500207-04-5]+ TX, polyoxins [11113-80-7]+ TX, probenazole [27605-76-1]+ TX, propamocarb [25606-41-1]+ TX, iodoquinazolinone [189278-12-4 ]]+ TX, pydiflumetofen [1228284-64-7]+ TX, pyraclostrobin [915410-70-7 ]]+ TX, pyroquilon [57369-32-1]+ TX, pyridinolone [688046-61-9]+ TX, pyribencarb [799247-52-2]+ TX, pyriconazole [847749-37-5]+ TX, quinoxyfen [124495-18-7]+ TX, pentachloronitrobenzene [82-68-8 ]]+ TX, sulfur [7704-34-9 ]]+TX、Timorex Gold^TM(plant extract containing tea Tree oil from Stockton Group) + TX, isobutoxyquinoline [376645-78-2]+ TX, tiadinil [223580-51-6]+ TX, imidazoxide [72459-58-6]+ TX, trifluoromethoxylcarb [911499-62-2]+ TX, nitrapyrin-strobin [902760-40-1 ]]+ TX, tricyclazole [41814-78-2]+ TX, azinam [26644-46-2]+ TX, validamycin [37248-47-8]+ TX, valifenalate [283159-90-0 ]]+ TX, zoxamide (RH7281) [156052-68-5]+ TX, mandipropamid [374726-62-2]+ TX, isopyrazam [881685-58-1 ]]+ TX, cyanoalkeneBacterial ester + TX, sedaxane [874967-67-6 ]]+ TX, trinexapac-ethyl (95266-40-3)]+ TX, 3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid (9-dichloromethylene-1, 2,3, 4-tetrahydro-1, 4-methano-naphthalen-5-yl) -amide (disclosed in WO 2007/048556) + TX, 3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid (3 ', 4', 5 ' -trifluoro-biphenyl-2-yl) -amide (disclosed in WO 2006/087343) + TX, [ (3S,4R,4aR,6S,6aS,12R,12 bS) -3- [ (cyclopropylcarbonyl) oxy]-1,3,4,4a,5,6,6a,12,12a,12 b-decahydro-6, 12-dihydroxy-4, 6a,12 b-trimethyl-11-oxo-9- (3-pyridinyl) -2H,11H naphtho [2,1-b]Pyrano [3,4-e ] s]Pyran-4-yl]Methyl-cyclopropanecarboxylic acid ester [915972-17-7]+ TX and 1,3, 5-trimethyl-N- (2-methyl-1-oxopropyl) -N- [3- (2-methylpropyl) -4- [2,2, 2-trifluoro-1-methoxy-1- (trifluoromethyl) ethyl]Phenyl radical]-1H-pyrazole-4-carboxamide [926914-55-8]+TX，

Or a biologically active compound selected from the group consisting of: n- [ (5-chloro-2-isopropyl-phenyl) methyl ] -N-cyclopropyl-3- (difluoromethyl) -5-fluoro-1-methyl-pyrazole-4-carboxamide (which may be prepared according to the procedure described in WO 2010/130767) + TX, 2, 6-dimethyl-1H, 5H- [1,4] dithio [2,3-c:5,6-c' ] bipyrrole-1, 3,5,7(2H,6H) -tetraone (which may be prepared according to the procedure described in WO 2011/138281) + TX, 6-ethyl-5, 7-dioxo-pyrrolo [4,5] [1,4] dithio [1,2-c ] isothiazole-3-carbonitrile + TX, 4- (2-bromo-4-fluoro-phenyl) -N- (2-chloro-6-fluoro-phenyl) -2, 5-dimethyl-pyrazol-3-amine (which can be prepared according to the procedure described in WO 2012/031061) + TX, 3- (difluoromethyl) -N- (7-fluoro-1, 1, 3-trimethyl-indan-4-yl) -1-methyl-pyrazole-4-carboxamide (which can be prepared according to the procedure described in WO 2012/084812) + TX, CAS 850881-30-0+ TX, 3- (3, 4-dichloro-1, 2-thiazol-5-ylmethoxy) -1, 2-benzothiazole 1, 1-dioxide (which may be prepared according to the procedure described in WO 2007/129454) + TX, 2- [2- [ (2, 5-dimethylphenoxy) methyl ] phenyl ] -2-methoxy-N-methyl-acetamide + TX, 3- (4, 4-difluoro-3, 4-dihydro-3, 3-dimethylisoquinolin-1-yl) quinolone (which may be prepared according to the procedure described in WO 2005/070917) + TX, 2- [ 2-fluoro-6- [ (8-fluoro-2-methyl-3-quinolyl) oxy ] phenyl ] propan-2-ol (which may be prepared according to the procedure described in WO 2011/081174) + TX, beta-glucosidase, and beta-glucosidase, 2- [2- [ (7, 8-difluoro-2-methyl-3-quinolinyl) oxy ] -6-fluoro-phenyl ] propan-2-ol (which can be prepared according to the procedure described in WO 2011/081174) + TX, thiapiprazole + TX [1003318-67-9], tert-butyl N- [6- [ [ [ (1-methyltetrazol-5-yl) -phenyl-methylene ] amino ] oxymethyl ] -2-pyridinyl ] carbamate + TX, N- [2- (3, 4-difluorophenyl) phenyl ] -3- (trifluoromethyl) pyrazine-2-carboxamide (which can be prepared according to the procedure described in WO 2007/072999) + TX, 3- (difluoromethyl) -1-methyl-N- [ (3R) -1,1, 3-trimethylindan-4-yl ] pyrazole-4-carboxamide (which may be prepared according to the procedure described in WO 2014/013842) + TX, 2,2, 2-trifluoroethyl N- [ 2-methyl-1- [ [ (4-methylbenzoyl) amino ] methyl ] propyl ] carbamate + TX, (2RS) -2- [4- (4-chlorophenoxy) - α, α, α -trifluoro-o-tolyl ] -1- (1H-1,2, 4-triazol-1-yl) propan-2-ol + TX, (2RS) -2- [4- (4-chlorophenoxy) - α, α, α -trifluoro-o-tolyl ] -3-methyl-1- (1H-1,2, 4-triazol-1-yl) butan-2-ol + TX, 2- (difluoromethyl) -N- [ (3R) -3-ethyl-1, 1-dimethyl-indan-4-yl ] pyridine-3-carboxamide + TX, 2- (difluoromethyl) -N- [ 3-ethyl-1, 1-dimethyl-indan-4-yl ] pyridine-3-carboxamide + TX, N '- (2, 5-dimethyl-4-phenoxy-phenyl) -N-ethyl-N-methyl-formamidine + TX, N' - [4- (4, 5-dichlorothiazol-2-yl) oxy-2, 5-dimethyl-phenyl ] -N-ethyl-N-methyl-formamidine (which may be prepared according to the procedure described in WO 2007/031513) + TX, [2- [3- [2- [1- [2- [3, 5-bis (difluoromethyl) pyrazol-1-yl ] acetyl ] -4-piperidinyl ] thiazol-4-yl ] -4, 5-dihydroisoxazol-5-yl ] -3-chloro-phenyl ] methanesulfonate (which may be prepared according to the procedure described in WO 2012/025557) + TX, N- [6- [ [ (Z) - [ (1-methyltetrazol-5-yl) -phenyl-methylene ] amino ] oxymethyl ] -2-pyridinyl ] carbamic acid but-3-ynyl ester (which may be prepared according to the procedure described in WO 2012/025557) Prepared according to the procedure described in WO 2010/000841) + TX, 2- [ [3- (2-chlorophenyl) -2- (2, 4-difluorophenyl) oxiran-2-yl ] methyl ] -4H-1,2, 4-triazole-3-thione (which may be prepared according to the procedure described in WO 2010/146031) + TX, N- [ [5- [4- (2, 4-dimethylphenyl) triazol-2-yl ] -2-methyl-phenyl ] methyl ] carbamate + TX, 3-chloro-6-methyl-5-phenyl-4- (2,4, 6-trifluorophenyl) pyridazine (which may be prepared according to the procedure described in WO 2005/121104) + TX, thion, 2- [ 2-chloro-4- (4-chlorophenoxy) phenyl ] -1- (1,2, 4-triazol-1-yl) propan-2-ol (which may be prepared according to the procedure described in WO 2013/024082) + TX, 3-chloro-4- (2, 6-difluorophenyl) -6-methyl-5-phenyl-pyridazine (which may be prepared according to the procedure described in WO 2012/020774) + TX, 4- (2, 6-difluorophenyl) -6-methyl-5-phenyl-pyridazine-3-carbonitrile (which may be prepared according to the procedure described in WO 2012/020774) + TX, (R) -3- (difluoromethyl) -1-methyl-N- [1,1, 3-trimethylindan-4-yl ] pyrazole-4-carboxamide (which may be prepared according to the procedure described in WO 2011/162397) + TX, 3- (difluoromethyl) -N- (7-fluoro-1, 1, 3-trimethyl-indan-4-yl) -1-methyl-pyrazole-4-carboxamide (which may be prepared according to the procedure described in WO 2012/084812) + TX, 1- [2- [ [1- (4-chlorophenyl) pyrazol-3-yl ] oxymethyl ] -3-methyl-phenyl ] -4-methyl-tetrazol-5-one (which may be prepared according to the procedure described in WO 2013/162072) + TX, and, 1-methyl-4- [ 3-methyl-2- [ [ 2-methyl-4- (3,4, 5-trimethylpyrazol-1-yl) phenoxy ] methyl ] phenyl ] tetrazol-5-one (which may be prepared according to the procedure described in WO 2014/051165) + TX, (Z,2E) -5- [1- (4-chlorophenyl) pyrazol-3-yl ] oxy-2-methoxyimino-N, 3-dimethyl-pent-3-enamine + TX, 2-amino-6-methyl-pyridine-3-carboxylic acid (4-phenoxyphenyl) methyl ester + TX, N- (5-chloro-2-isopropylbenzyl) -N-cyclopropyl-3- (difluoromethyl) -5- Fluoro-1-methylpyrazole-4-carboxamide [1255734-28-1] (may be prepared according to the procedure described in WO 2010/130767) + TX, 3- (difluoromethyl) -N- [ (R) -2, 3-dihydro-1, 1, 3-trimethyl-1H-inden-4-yl ] -1-methylpyrazole-4-carboxamide [1352994-67-2] + TX, N '- (2, 5-dimethyl-4-phenoxy-phenyl) -N-ethyl-N-methyl-formamidine + TX, N' - [4- (4, 5-dichloro-thiazol-2-yloxy) -2, 5-dimethyl-phenyl ] -N-ethyl-N-methyl- (iv) formamidine + TX, N '- (2, 5-dimethyl-4-phenoxy-phenyl) -N-ethyl-N-methyl-formamidine + TX, N' - [4- (4, 5-dichloro-thiazol-2-yloxy) -2, 5-dimethyl-phenyl ] -N-ethyl-N-methyl-formamidine + TX,

(fenpicoxamid[517875-34-2](as described in WO 2003/035617)) + TX, (1S) -2, 2-bis (4-fluorophenyl) -1-methylethyl N- { [3- (acetoxy) -4-methoxy-2-pyridinyl]Carbonyl } -L-alanine ester 1961312-55-9](as described in WO 2016/122802) + TX, 2- (difluoromethyl) -N- (1,1, 3-trimethylindan-4-yl) pyridine-3-carboxamide + TX, 2- (difluoromethyl) -N- (3-ethyl-1, 1-dimethyl-indan-4-yl) pyridine-3-carboxamide + TX, 2- (difluoromethyl) -N- (1, 1-dimethyl-3-propyl-indan-4-yl) pyridine-3-carboxamide + TX, 2- (difluoromethyl) -N- (3-isobutyl-1, 1-dimethyl-indan-4-yl) pyridine-3-carboxamide + TX, 2- (difluoromethyl) -N- [ (3R) -1,1, 3-trimethylindan-4-yl]Pyridine-3-carboxamide + TX, 2- (difluoromethyl) -N- [ (3R) -3-ethyl-1, 1-dimethyl-indan-4-yl]Pyridine-3-carboxamide + TX, and 2- (difluoromethyl) -N- [ (3R) -1, 1-dimethyl-3-propyl-indan-4-yl]Pyridine-3-carboxamide + TX, wherein each of these carboxamide compounds may be prepared according to the procedures described in WO 2014/095675 and/or WO 2016/139189.

References in parentheses after the active ingredient, e.g. [3878-19-1 ]]Refers to the chemical Abstract registry number. The mixed compatibility described above is known. Included among The active ingredients are The Pesticide Manual]"[ The Pesticide Manual-A World Complex [ Pesticide Manual-Global overview ]](ii) a 13 th edition; editing: c.d.s.tomlin; the British Crop Protection Coomcil]]Wherein they are described therein with the entry numbers given in parentheses above for the particular compound; for example, the compound "abamectin" is described by entry number (1). In "[ CCN]"in the case of addition to a particular compound, the compound is included in the Compendium of Common Names of pesticides]"which may be on the internet [ a.wood;Compendium of Pesticide Common Names，

1995-2004]obtaining the above; for example, the compound "acetoprole" is described in the Internet address http:// www.alanwood.net/pesticides/acetoprole.

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

The active ingredient mixture of a compound of formula (I) selected from one of the compounds shown in table 1.1 to 1.11, table 2.1 to 2.10, or compounds 1.1 to 1.6 according to the invention listed in table T1 (below) is preferably in a mixing ratio of from 100:1 to 1:6000, especially from 50:1 to 1:50, more especially in a ratio of from 20:1 to 1:20, even more especially from 10:1 to 1:10, very especially from 5:1 and 1:5, especially preferably from 2:1 to 1:2, and a ratio of from 4:1 to 2:1 is likewise preferred, especially in a ratio of 1:1, 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 5: 5, or 5:1, or 4:2, or 4:3, or 3, Or a ratio of 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 of controlling pests, said method comprising applying a composition comprising a mixture as described above to the pests or their environment, except for methods for treating the human or animal body by surgery or therapy and diagnostic methods carried out on the human or animal body.

Mixtures comprising a compound as shown in tables 1.1 to 1.11, tables 2.1 to 2.10 or a compound 1.1 to 1.6 according to the invention as listed in table T1 (below), and one or more active ingredients as described above may be applied, for example, in the form of a single "ready-to-use-with-water", in a combined spray mixture (said mixture consisting of separate formulations of the individual active ingredient components) (such as a "tank mix") and, when applied in a sequential manner (i.e. one after another over a reasonably short period of time, such as several hours or days), in combination using the individual active ingredients. The order of administration of the compounds as shown in tables 1.1 to 1.11, tables 2.1 to 2.10 or compounds 1.1 to 1.6 according to the invention as listed in table T1 (below) and one or more active ingredients as described above is not critical to the practice of the invention.

The compositions according to the invention may also comprise other solid or liquid auxiliaries, 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, adhesives and/or tackifiers, fertilizers or other active ingredients for achieving a specific 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, screening 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 the one or more auxiliaries and/or by grinding the active ingredient together with the one or more auxiliaries. The methods for preparing the compositions and the use of the compounds (I) for preparing the compositions are also subjects of the present invention.

Another aspect of the present invention relates to the use of a fungicide or an insecticidal mixture comprising at least one compound of formula (I) or at least one preferred individual compound as defined above, or of a composition comprising at least one compound of formula (I) or at least one preferred individual compound as defined above (in admixture with other fungicides or insecticides as described above), or of a compound of formula (I) or at least one preferred individual compound as defined above, for controlling or preventing infestation of plants, for example useful plants (such as crop plants), their propagation material (e.g. seeds), harvested crops (e.g. harvested food crops), or non-living material by insects or phytopathogenic microorganisms, preferably fungal organisms.

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

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

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 containing at least one of the compounds. The frequency of application and rate of application will depend on the risk of infestation by the respective pathogen or insect. However, the compounds of formula (I) may also penetrate the plants through the roots via the soil (systemic action) by soaking the locus of the plants 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 granules may be applied to irrigated paddy fields. The compounds of formula (I) can 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, for example compositions comprising a compound of formula (I) and, if desired, solid or liquid adjuvants or monomers for encapsulating a compound of formula (I), can be prepared in known manner, typically by intimately mixing and/or grinding the compound with extenders, for example solvents, solid carriers and optionally surface-active compounds (surfactants).

Advantageous application rates are generally from 5g to 2kg of active ingredient (a.i.)/hectare (ha), preferably from 10g to 1kg a.i./ha, most preferably from 20g to 600g a.i./ha. When used as a seed soaking agent, suitable dosages are 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 from 0.001 to 50g of compound of the formula (I) per kg of seed, preferably from 0.01 to 10g per kg of seed, is generally sufficient.

Suitably, the composition of the compound of formula (I) according to the invention is applied prophylactically (meaning before disease development) or curatively (meaning after disease development).

The compositions OF the present invention may be used in any conventional form, for example, in a two-pack, powder for dry seed treatment (DS), emulsion for seed treatment (ES), flowable concentrate for seed treatment (FS), solution for seed treatment (LS), water dispersible powder for seed treatment (WS), capsule suspension for seed treatment (CF), gel for seed treatment (GF), Emulsion Concentrate (EC), Suspension Concentrate (SC), Suspoemulsion (SE), Capsule Suspension (CS), water dispersible granule (WG), Emulsifiable Granule (EG), water-in-oil Emulsion (EO), oil-in-water Emulsion (EW), Microemulsion (ME), dispersible oil suspension (OD), oil suspension (OF), oil soluble liquid concentrate (OL), soluble concentrate (SL), ultra-low volume Suspension (SU), ultra-low volume liquid concentrate (UL), The parent 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 ingredients with suitable formulation inerts (diluents, solvents, fillers and optionally other formulation ingredients such as surfactants, biocides, antifreeze agents, stickers, thickeners and compounds which provide an adjuvant effect). Conventional sustained-release formulations intended to sustain the drug effect for a long period of time 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 (e.g., wetting and dispersing agents) and other compounds that provide an adjuvant effect, such as condensation products of formaldehyde with naphthalene sulfonate, alkyl aryl sulfonate, lignosulfonate, fatty alkyl sulfate and ethoxylated alkyl phenol and ethoxylated fatty alcohol.

The seed-dressing formulations are applied to the seed in a manner known per se using the combinations and diluents according to the invention in the form of suitable seed-dressing formulations, for example in the form of aqueous suspensions or dry powders having good adhesion to the seed. Such seed dressing formulations are known in the art. Seed dressing formulations may contain the individual active ingredients or the combination 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), optionally together with other active agents, in particular microbicides 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. Concentrated forms of the compositions typically contain between about 2% and 80%, preferably between about 5% and 70% by weight of active agent. The application forms of the formulations can, for example, contain from 0.01 to 20%, preferably from 0.01 to 5%, by weight of active agent. Whereas commercial products will preferably be formulated as concentrates, the end user will typically use dilute formulations.

However, it is preferred to formulate commercial products as concentrates, and the end user will typically use dilute formulations.

Table 1.1:this table discloses 29 specific compounds of formula (T-1):

wherein A is:

R¹and R²Is hydrogen, R³Is methoxy and Z is as defined in table 1 below.

Tables 1.2 to 1.11, which follow table 1.1, each make available 29 individual compounds of the formula (T-1), of which A, R¹、R²And R³Are as specifically defined in tables 1.2 to 1.11, which refer to table 1 (wherein Z is specifically defined).

TABLE 1

TABLE 1.2: this table discloses 29 specific compounds of formula (T-1), wherein a is:

R¹and R²Is hydrogen, R³Is methoxy and Z is as defined in table 1 above.

TABLE 1.3: this table discloses 29 specific compounds of formula (T-1), wherein a is:

R¹and R²Is hydrogen, R³Is methoxy and Z is as defined in table 1 above.

TABLE 1.4: this table discloses 29 specific compounds of formula (T-1), wherein a is:

R¹and R²Is hydrogen, R³Is methoxy and Z is as defined in table 1 above.

TABLE 1.5: this table discloses 29 specific compounds of formula (T-1), wherein a is:

and R is¹And R²Is hydrogen, R³Is methoxy and Z is as defined in table 1 above.

TABLE 1.6: this table discloses 29 specific compounds of formula (T-1), wherein a is:

and R is¹Is hydrogen, R²Is methyl, and R³Is methoxy and Z is as defined in table 1 above.

TABLE 1.7: this table discloses 29 specific compounds of formula (T-1), wherein a is:

and R is¹Is hydrogen, R²Is methyl, and R³Is methoxy and Z is as defined in table 1 above.

TABLE 1.8: this table discloses 29 specific compounds of formula (T-1), wherein a is:

R¹and R²Is hydrogen, R³Is 2, 2-difluoroethoxy and Z is as defined in table 1 above.

TABLE 1.9: this table discloses 29 specific compounds of formula (T-1), wherein a is:

R¹and R²Is hydrogen, R³Is 2, 2-difluoroethoxy and Z is as defined in table 1 above.

TABLE 1.10: this table discloses 29 specific compounds of formula (T-1), wherein a is:

R¹and R²Is hydrogen, R³Is ethoxy and Z is as defined in table 1 above.

TABLE 1.11: this table discloses 29 specific compounds of formula (T-1), wherein a is:

R¹and R²Is hydrogen, R³Is ethoxy and Z is as defined in table 1 above.

TABLE 2.1: this table discloses 28 specific compounds having the formula (T-2):

wherein A is:

R¹and R²Is hydrogen, and Z^aIs defined as in table 2 below.

Tables 2.2 to 2.7 (which follow table 2.1) each make available 28 individual compounds of the formula (T-2), of which A, R¹、R²And R³Are as defined in tables 2.2 to 2.10, referring to Table 2 (wherein Z is^aIs specifically defined).

TABLE 2

TABLE 2.2: this table discloses 28 specific compounds of formula (T-2), wherein a is:

R¹and R²Is hydrogen, and Z^aIs as defined in table 2 above.

TABLE 2.3: this table discloses 28 specific compounds of formula (T-2), wherein a is:

R¹and R²Is hydrogen, and Z^aIs as defined in table 2 above.

TABLE 2.4: this table discloses 28 specific compounds of formula (T-2), wherein a is:

R¹and R²Is hydrogen, and Z^aIs as defined in table 2 above.

TABLE 2.5: this table discloses 28 specific compounds of formula (T-2), wherein a is:

and R is¹And R²Is hydrogen, and Z^aIs as defined in table 2 above.

TABLE 2.6: this table discloses 28 specific compounds of formula (T-2), wherein a is:

and R is¹Is hydrogen, R²Is methyl, and Z^aIs as defined in table 2 above.

TABLE 2.7: this table discloses 28 specific compounds of formula (T-2), wherein a is:

and R is¹Is hydrogen, R²Is methyl, and Z^aIs as defined in table 2 above.

TABLE 2.8: this table discloses 28 specific compounds of formula (T-2), wherein a is:

R¹and R²Is hydrogen, and Z^aIs as defined in table 2 above.

TABLE 2.9: this table discloses 29 specific compounds of formula (T-2), wherein a is:

R¹and R²Is hydrogen, and Z^aIs as defined in table 2 above.

TABLE 2.10: this table discloses 28 specific compounds of formula (T-2), wherein a is:

R¹and R²Is hydrogen, and Z^aIs as defined in table 2 above.

Examples of the invention

The following examples serve to illustrate the invention.

The compounds of the invention may be distinguished from known compounds by greater efficacy at low rates of administration, as evidenced by one of ordinary skill in the art using the experimental procedures outlined in the examples, using lower rates of administration (if necessary), e.g., 50ppm, 12.5ppm, 6ppm, 3ppm, 1.5ppm, 0.8ppm, or 0.2 ppm.

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

Throughout this specification, temperatures are given in degrees Celsius (. degree. C.) and "mp" means melting point. LC/MS means liquid chromatography mass spectrometry, and the description of apparatus and method a is as follows:

the description of the LC/MS apparatus and method A is:

SQ detector 2 from Waters corporation

An ionization method comprises the following steps: electrospray ionization

Polarity: positive and negative ions

Capillary (kV)3.0, taper hole (V)30.00, extractor (V)2.00, source temperature (deg.C) 150, desolvation temperature (deg.C) 350, taper hole gas flow (L/Hr)0, desolvation gas flow (L/Hr)650

The mass range is as follows: 100 to 900Da

DAD wavelength range (nm): 210 to 500

The method comprises the following steps: waters acquisition UPLC, using the following HPLC gradient conditions:

(solvent A: water/methanol 20:1+ 0.05% formic acid, and solvent B: acetonitrile + 0.05% formic acid)

Column type: waters acquisition UPLC HSS T3; column length: 30 mm; inner diameter of column: 2.1 mm; granularity: 1.8 microns; temperature: at 60 ℃.

Where necessary, enantiomerically pure final compounds can be obtained, where appropriate, from racemic materials via standard physical separation techniques (such as reverse phase chiral chromatography) or by stereoselective synthetic techniques (for example by using chiral starting materials).

Formulation examples

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

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

Emulsifiable concentrateConcentrate

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

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

Extruder granules

The active ingredient is mixed with these adjuvants and milled, and the mixture is moistened with water. The mixture was extruded and then dried in an air stream.

Coated particles

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

Polyethylene glycol (molecular weight 200) 3%

89 percent of kaolin

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

Suspension concentrates

The finely ground active ingredient is intimately mixed with the auxiliaries to give a suspension concentrate from which suspensions of any desired dilution can be obtained by dilution with water. With such dilutions, living plants as well as plant propagation material can be treated and protected against microbial infestation by spraying, pouring or dipping.

Flowable concentrate for seed treatment

The finely ground active ingredient is intimately mixed with the auxiliaries to give a suspension concentrate from which suspensions of any desired dilution can be obtained by dilution with water. With such dilutions, living plants as well as plant propagation material can be treated and protected against microbial infestation by spraying, pouring or dipping.

Sustained release 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 tolylene diisocyanate/polymethylene-polyphenylisocyanate 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 2.8 parts of a mixture of 1, 6-hexanediamines in 5.3 parts of water. The mixture was stirred until the polymerization reaction was complete.

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

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

List of abbreviations

AIBN ═ azobisisobutyronitrile

broad singlet

DMF ═ dimethylformamide

DMA ═ dimethyl acetamide

DIPEA ═ N, N-di-isopropylethylamine

EtOAc ═ ethyl acetate

HCl ═ hydrochloric acid

mp is melting point

Degree centigrade

MeOH ═ methanol

NaOH (sodium hydroxide)

NBS ═ N-bromosuccinimide

min is minutes

rt-room temperature

h is hour

TFAA ═ trifluoroacetic anhydride

THF ═ tetrahydrofuran

R_tRetention time (in minutes)

LC/MS liquid chromatography-mass spectrometry (the description of the apparatus and method for LC/MS analysis is given above)

Preparation examples

The compounds of formula (I) can be prepared accordingly using the synthetic techniques described above and below.

Example 1: this example illustrates N-methoxy-N- [1- [5- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl]-2-thienyl]Ethyl radical]Alternative preparation of cyclopropane thiocarboxamides (Compound 1.2 of Table T1)

Step 1: preparation of N-methoxycyclopropanecarboxamide

To a solution of O-methylhydroxylamine (0.80g, 21.8mmol) and potassium carbonate (0.52mL, 2.88mmol) in ethyl acetate (7.7mL) cooled by an ice bath was added cyclopropanecarbonyl chloride (2.0g, 18.2mmol) dropwise over 30 minutes. The ice bath was removed and after stirring the contents for 2 hours, EtOH (5mL) was introduced and the contents stirred for an additional 30 minutes. The solid was filtered and then dried under vacuum to provide 2.14g of the title compound as a white solid.

¹H NMR(400MHz,DMSO-d₆)ppm:11.13(s,1H),3.57(s,3H),1.34(m,1H),0.87(m,1H),0.68(m,3H)。

Step 2: n- [1- (5-cyano-2-thienyl) ethyl]Preparation of (E) -N-methoxy-cyclopropanecarboxamide

To a solution of N-methoxycyclopropanecarboxamide (0.18g, 1.02mmol) in acetonitrile (2mL) was introduced lithium hydroxide (0.04g, 1.85mmol) followed by 5- (1-bromoethyl) thiophene-2-carbonitrile (0.2g, 5.50 mmol). The reaction was heated at 60 ℃ for 16 hours, then cooled to 25 ℃ and quenched with water. The contents were extracted with ethyl acetate and the total combined organic layers were dried over sodium sulfate, filtered and concentrated under reduced pressure. The resulting crude product was purified by flash chromatography on silica gel (cyclohexane/EtOAc eluent gradient 1:0 to 7:3) to give 0.20g of the title compound as a white solid. mp: 109 ℃ -112 DEG C

¹H NMR(400MHz,CDCl₃)ppm:7.49(d,1H),7.02(d,1H),5.85(s,1H),3.75(s,3H),2.05(m,1H),1.70(m,2H),1.05(m,2H),0.89(m,2H)。

And step 3: n- [1- [5- [ N' -Hydroxycarboxamido)]-2-thienyl]Ethyl radical]Process for preparing (E) -N-methoxy-cyclopropanecarboxamide Preparation of

To a solution of N- [1- (5-cyano-2-thienyl) ethyl ] -N-methoxy-cyclopropanecarboxamide (0.20g, 0.80mmol) and EtOH (2.5mL) was introduced hydroxylamine hydrochloride (0.11g, 1.60mmol) and triethylamine (0.22mL, 1.60 mmol). The reaction was then heated at 80 ℃ for 2 hours, cooled to 25 ℃ and concentrated under reduced pressure and dried under vacuum to afford 0.24g of the title compound as a white solid.

¹H NMR(400MHz,DMSO-d₆)ppm:9.60(brs,1H),7.30(d,1H),6.95(d,1H),5.87(s,2H),5.70(s,1H),3.65(s,3H),2.10(m,1H),1.55(d,3H),0.82(m,4H)。

And 4, step 4: N-methoxy-N- [1- [5- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl]-2-thienyl]Second step Base of]Preparation of cyclopropanecarboxamides

To the cooled N- [1- [5- [ N' -hydroxyformamidino group by ice bath]-2-thienyl]Ethyl radical]To a crude solution of-N-methoxy-cyclopropanecarboxamide (0.80mmol) in tetrahydrofuran (2.4mL) was added trifluoroacetic anhydride (0.17mL, 1.20 mmol). The reaction mixture was stirred at 25 ℃ overnight and then with saturated NaHCO₃Dilute, extract with dichloromethane, dry over sodium sulfate, filter, and concentrate under reduced pressure. The resulting crude residue was purified by flash chromatography on silica gel (cyclohexane/EtOAc eluent gradient 99:1 to 7:3) to provide 0.24g of the title compound as an amorphous white solid. LC/MS (method a) retention time was 1.13 minutes and mass to charge ratio (mass charge) was not detected.

¹H NMR(400MHz,CDCl₃)ppm:7.76(d,1H),7.09(d,1H),5.95(s,1H),3.75(s,3H),2.10(m,1H),1.70(m,3H),1.05(m,2H),0.85(m,2H)。

¹⁹F NMR(400MHz,CDCl₃)ppm:-65.36(s)。

And 5: N-methoxy-N- [1- [5- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl]-2-thienyl]Second step Base of]CyclopropanPreparation of alkanethiocarboxamides

To a solution of N-methoxy-N- [1- [5- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ] -2-thienyl ] ethyl ] cyclopropanecarboxamide (0.090g, 0.27mmol) in toluene (1mL) was introduced phosphorus pentasulfide (0.07g, 0.31mmol) and the reaction was heated at reflux. After 4 hours, the contents were brought to 25 ℃, then poured into a mixture of water and ethyl acetate. The layers were separated, the organic layer was dried over sodium sulfate, concentrated under reduced pressure, and the resulting crude residue was purified by flash chromatography on silica gel (cyclohexane/EtOAc eluent gradient 1:0 to 6:4) to provide 0.04g of the title compound as a yellow gum. LC/MS (method a) retention time 1.22 min, 378(M + H).

¹H NMR(400MHz,CDCl₃)ppm:7.76(d,1H),7.25(d,1H),3.75(s,3H),2.55(m,1H),1.80(m,3H),1.70(m,1H),1.55(m,1H),1.35(m,1H),1.05(m,2H)。

¹⁹F NMR(400MHz,CDCl₃)ppm:-65.36(s)。

Example 2: this example illustrates 1- [ [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ] amino]Phenyl radical]Methyl radical]Preparation of piperidine-2-thione (Compound 1.5 of Table T1)

Step 1: 4- [ (2-oxo-1-piperidinyl) methyl group]Preparation of benzonitrile

A solution of 4- (bromomethyl) benzonitrile (2.0g, 10.2mmol), piperidin-2-one (1.04g, 10.5mmol) and potassium carbonate (1.41g, 10.2mmol) in acetonitrile (20mL) was heated at 85 ℃ for 20 hours. After cooling to 25 ℃, the solvent was removed under reduced pressure, and the obtained residue was dissolved in ethyl acetate and washed with water. The organic layer was then dried over sodium sulfate and concentrated under reduced pressure. The crude yellow residue obtained was purified by flash chromatography on silica gel (cyclohexane: EtOAc eluent gradient 9:1 to 0:1) to give 0.28g of the title compound as a yellow oil. LC/MS (method a) retention time 0.71 min, 215(M + H).

¹H NMR(400MHz,CDCl₃)ppm:7.62(d,2H),7.36(d,2H),4.64(s,2H),3.22(m,2H),2.49(t,2H),1.82(m,4H)。

Step 2: n-hydroxy-4- [ (2-oxo-1-piperidinyl) methyl]Preparation of benzamidine

To a heterogeneous solution of hydroxylamine hydrochloride (0.27g, 3.9mmol) and ethanol (33mL) was added triethylamine (0.55mL, 3.92mmol) at 25 ℃. The resulting suspension was stirred for 30 minutes, then 4- [ (2-oxo-1-piperidinyl) methyl ] benzonitrile (0.28g, 1.31mmol) was introduced and the reaction mixture was heated at a temperature of 50 ℃ for 18 hours. Volatiles were removed under reduced pressure and the crude reaction mixture was used in the next step without additional purification or characterization. LC/MS (method a) retention time 0.24 min, 248(M + H).

And step 3: 4- [ [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ] methyl ester]Phenyl radical]Methyl radical]Preparation of morpholin-3-ones

To a solution of crude N-hydroxy-4- [ (2-oxo-1-piperidinyl) methyl ] benzamidine (320mg, 1.29mmol) in tetrahydrofuran (2mL) was added trifluoroacetic anhydride (0.27mL, 1.94mmol) dropwise at 25 ℃. After stirring overnight, the solvent was removed under reduced pressure to give an orange oil, which was dissolved in a minimum amount of dichloromethane and then washed with saturated aqueous sodium bicarbonate. The organic phase was dried over sodium sulfate, filtered, and the volatiles were removed under reduced pressure. The crude residue was purified by silica gel combiflash chromatography (cyclohexane: EtOAc eluent gradient 99:1 to 9:1) to provide 265mg of the title compound as a colorless oil which solidified upon storage at 4 ℃. mp is 31-34 ℃. LC/MS (method a) retention time 0.99 min, 326(M + H).

¹H NMR(400MHz,CDCl₃)ppm:8.07(d,2H),7.41(d,2H),4.68(s,2H),3.24(m,2H),2.50(m,2H),1.83(m,4H)。

¹⁹F NMR(400MHz,CDCl₃)ppm:-65.34(s)。

And 4, step 4: 1- [ [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ] methyl ester]Phenyl radical]Methyl radical]Preparation of piperidine-2-thione Prepare for

To a suspension of 4- [ [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ] phenyl ] methyl ] morpholin-3-one (0.10g, 0.31mmol) in toluene (1mL) was introduced phosphorus pentasulfide (0.075g, 0.34mmol) and the reaction was heated at reflux. After 2 hours, the contents were brought to 25 ℃, then poured into a mixture of water and ethyl acetate. The layers were separated, the organic layer was dried over sodium sulfate, concentrated under reduced pressure, and the resulting crude residue was purified by flash chromatography on silica gel (cyclohexane/EtOAc eluent gradient 1:0 to 1:1) to provide 0.09g of the title compound as a yellow solid. mp 92-95 ℃. LC/MS (method a) retention time 1.11 min, 342(M + H).

¹H NMR(400MHz,CDCl₃)ppm:8.10(d,2H),7.50(d,2H),5.42(s,2H),3.42(m,2H),3.15(m,2H),1.91(m,2H),1.80(m,2H)。

¹⁹F NMR(400MHz,CDCl₃)ppm:-65.34(s)。

Example 3: this example illustrates 5, 5-dimethyl-2- [ [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ] methyl]Phenyl radical]Methyl radical]Preparation of isoxazolidine-3-thione (Compound 1.6 of Table T1)

Step 1: 4- [ (5, 5-dimethyl-3-oxo-isoxazolidin-2-yl) methyl]Preparation of benzonitrile

To a solution of 5, 5-dimethylisoxazolidin-3-one (1.00g, 8.7mmol) in dimethylacetamide (5mL) was added sodium carbonate (0.84g, 7.8mmol), water (5mL) and 4- (bromomethyl) benzonitrile (1.8g, 9.1 mmol). The contents were then heated at 85 ℃ for 3.5 hours. After cooling to 25 ℃, the reaction mixture was poured into water and extracted with ethyl acetate. The organic layer was then dried over sodium sulfate and concentrated under reduced pressure to give 1.75g of the title compound. LC/MS (method a) retention time 0.80 min, 231(M + H).

¹H NMR(400MHz,CDCl₃)ppm:7.64(d,2H),7.42(d,2H),4.73(s,2H),2.64(m,2H),1.26(s,6H)。

Step 2: 4- [ (5, 5-dimethyl-3-oxo-isoxazolidin-2-yl) methyl]Preparation of (E) -N-hydroxy-benzamidine

To a heterogeneous solution of hydroxylamine hydrochloride (0.36g, 5.21mmol) and ethanol (5mL) was added triethylamine (0.53mL, 5.21mmol) at 25 ℃. The resulting suspension was stirred for 30 minutes, then 4- [ (5, 5-dimethyl-3-oxo-isoxazolidin-2-yl) methyl ] benzonitrile (1.00g, 4.34mmol) was introduced and the reaction mixture was heated at 50 ℃ for 6 hours. Volatiles were removed under reduced pressure and the crude reaction mixture was used in the next step without additional purification or characterization. LC/MS (method a) retention time 0.27 min, 264(M + H).

And step 3:5, 5-dimethyl-2- [ [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ] methyl ester]Phenyl radical]Methyl radical]Iso-oxa Preparation of oxazolidin-3-ones

To crude 4- [ (5, 5-dimethyl-3-oxo-isoxazolidin-2-yl) methyl at 25 ℃]To a stirred solution of (E) -N-hydroxy-benzamidine (1.0g, 3.61mmol) in ethyl acetate (20mL) was added pyridine (0.44mL, 5.41 mmol). After 10 minutes, CF was added by gentle bubbling₃COCl (0.530g, 3.97mmol) gas. After 2 hours, the mixture was diluted with ethyl acetate, washed with water, dried over sodium sulfate, filtered, and the volatiles were removed under reduced pressure. The crude residue was purified by silica gel combiflash chromatography (cyclohexane: EtOAc eluent gradient 99:1 to 9:1) to afford 1.27g of the title compound as a colorless oil which solidified upon storage. mp.: 51-54 ℃. LC/MS (method a) retention time 1.04 min, 342(M + H).

¹H NMR(400MHz,CDCl₃)ppm:8.14(d,2H),7.55(d,2H),5.23(s,2H),2.82(s,2H),1.44(s,6H)。

And 4, step 4:5, 5-dimethyl-2- [ [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ] methyl ester]Phenyl radical]Methyl radical]Iso-oxa Preparation of oxazolidine-3-thiones

To a suspension of 5, 5-dimethyl-2- [ [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ] phenyl ] methyl ] isoxazolidin-3-one (0.10g, 0.29mmol) in toluene (1mL) was introduced phosphorus pentasulfide (0.072g, 0.32mmol) and the reaction was heated at reflux. After 2 hours, the contents were brought to 25 ℃, then poured into a mixture of water and ethyl acetate. The layers were separated, the organic layer was dried over sodium sulfate, concentrated under reduced pressure, and the resulting crude residue was purified by flash chromatography on silica gel (cyclohexane/EtOAc eluent gradient 1:0 to 1:1) to provide 0.09g of the title compound as a yellow gum. LC/MS (method a) retention time 1.16 min, 358(M + H).

¹H NMR(400MHz,CDCl₃)ppm:8.12(d,2H),7.55(d,2H),5.25(s,2H),3.20(s,3H),1.30(s,6H)。

¹⁹F NMR(400MHz,CDCl₃)ppm:-65.33(s)。

Where necessary, enantiomerically pure final compounds can be obtained, where appropriate, from racemic materials via standard physical separation techniques (such as reverse phase chiral chromatography) or by stereoselective synthetic techniques (for example by using chiral starting materials).

_tTable T1: melting point (mp) data and/or retention time (R) of a compound according to formula (I):

biological examples

Leaf disks or leaf segments of different plant species were cut from plants grown in the greenhouse. The cut leaf disks or leaf segments were placed on water agar in a multiwell plate (24-well format). Leaf discs were sprayed with the test solution either before (prophylactic) or after (therapeutic) inoculation. The compounds to be tested were prepared as DMSO solutions (maximum 10mg/mL) and diluted to the appropriate concentration with 0.025% Tween20 just prior to spraying. The inoculated leaf discs or leaf segments are incubated under defined conditions (temperature, relative humidity, light, etc.) according to the corresponding test system. Depending on the disease system, a single assessment of disease levels was made 3 to 14 days after inoculation. The percent disease control relative to the untreated test leaf discs or leaf segments is then calculated.

General example of liquid culture assay in well plates:

mycelial fragments or conidia suspensions of the fungus (freshly prepared from liquid cultures of the fungus or from low temperature storage) were mixed directly into the nutrient broth. A DMSO solution of test compound (max 10mg/mL) was diluted 50-fold with 0.025% Tween20 and 10 μ Ι _ of this solution was pipetted into a microtiter plate (96-well format). The nutrient broth containing the fungal spore/mycelium fragment was then added to give the final concentration of test compound. The test plates are incubated in the dark at 24 ℃ and 96% relative humidity. Depending on the disease system, inhibition of fungal growth was determined photometrically after 2 to 7 days and the percentage antifungal activity was calculated relative to the untreated test article.

Example 1: fungicidal activity against Puccinia recondita f.sp.tritici Sex/wheat/leaf disc prevention method (brown rust)

Wheat leaf segment cultivar Kanzler was placed on agar in multi-well plates (24-well format) and sprayed with formulated test compound diluted in water. Leaf discs were inoculated with a spore suspension of the fungus 1 day after application. Inoculated leaf sections were incubated at 19 ℃ and 75% relative humidity (rh) in a climatic chamber under a 12 hour light/12 hour dark light regimen, and compound activity was assessed as the percent disease control when appropriate levels of disease damage occurred in untreated test leaf sections (7 to 9 days post application) compared to untreated.

In this test, the following compounds gave at least 80% disease control at 200ppm in the applied formulation when compared to untreated control leaf discs showing extensive disease development under the same conditions.

Compounds (from table T1)1.1, 1.2, 1.4, 1.5, and 1.6.

Example 2: fungicidal activity/wheat/leaf disc treatment against puccinia recondita (brown rust)

Wheat leaf segment cultivar Kanzler was placed on agar in multiwell plates (24-well format). The leaf segments are then inoculated with a spore suspension of the fungus. The plates were stored in the dark at 19 ℃ and 75% relative humidity. 1 day after inoculation, formulated test compound diluted in water was applied. The leaf sections were incubated at 19 ℃ and 75% relative humidity in a climatic chamber under a 12 hour light/12 hour dark light regimen, and compound activity was assessed as the percentage of disease control when appropriate levels of disease damage occurred in untreated test leaf sections (6 to 8 days after application) compared to untreated.

In this test, the following compounds gave at least 80% disease control at 200ppm in the applied formulation when compared to untreated control leaf discs showing extensive disease development under the same conditions.

Compounds (from table T1)1.1, 1.2, 1.4, 1.5, and 1.6.

Example 3: fungicidal activity/soybean/leaf disc prophylaxis against phakopsora pachyrhizi (asian soybean rust)

The soybean leaf discs were placed on water agar in a multi-well plate (24-well format) and sprayed with formulated test compound diluted in water. One day after application, leaf discs were inoculated by spraying the spore suspension on the lower leaf surface. After an incubation period of 24-36 hours in the dark in a climatic chamber at 20 ℃ and 75% rh, the leaf disks are kept at 20 ℃ with 12h light/day and 75% rh. The activity of the compounds was evaluated as the percent disease control when appropriate levels of disease damage occurred in untreated test leaf discs (12 to 14 days after application) compared to untreated.

In this test, the following compounds gave at least 80% disease control at 200ppm in the applied formulation when compared to untreated control leaf discs showing extensive disease development under the same conditions.

Compounds (from table T1)1.1, 1.2, 1.4, 1.5, and 1.6.

Example 4: against Microthecium cucurbitacearum (glomeriella lagenarium) (Colletotrichum cucurbitacearum) lagenarium)) liquid culture for fungicidal activity/cucumber/preventive method (anthracnose)

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

In this test, the following compounds in the applied formulation gave at least 80% disease control at 20ppm when compared to an untreated control showing extensive disease development under the same conditions.

Compounds (from table T1)1.1, 1.2, 1.4, 1.5, and 1.6.

Claims (13)

1. A compound having the formula (I):

wherein

A is A-1, A-2, A-3, or A-4;

and A-1, A-2, A-3, or A-4 is optionally substituted with one or two independently selected halogen groups;

R¹and R²Independently selected from hydrogen, methyl and cyano; or

R¹And R²Together with the carbon atom to which they are bonded form a cyclopropyl ring;

R³is hydroxy, C_1-4Alkoxy or C_1-3A haloalkoxy group;

z is R⁴Wherein R is⁴Is C_3-6Cycloalkyl or heterocyclyl, wherein the heterocyclyl moiety is a 4-to 6-membered non-aromatic ring, said ring comprising 1 or 2 rings independently selected from N, NR⁵Heteroatoms or groups of O and S; wherein said cycloalkyl or heterocyclyl is optionally substituted by 1 or 2 substituents selected from R⁶May be the same or different;

R⁶is cyano, halogen, hydroxy, amino, methyl, ethyl, propyl, cyclopropyl, prop-2-enyl, prop-2-ynyl, difluoromethyl, trifluoromethyl, methoxy, ethoxy, difluoromethoxy, prop-2-enyloxy, prop-2-ynyloxy, N-methylamino, N-dimethylamino, methylcarbonyl, methoxycarbonyl, formylamino, N-methylaminocarbonyl, N-dimethylaminocarbonylOr methoxycarbonylamino; and wherein Z may optionally contain 1 atom selected from C (O) or S (O)₂A group of (a); and is

R⁵Represents hydrogen, methyl, methoxy, formyl or acyl;

or

R³And Z together with the-N-C (═ S) -group to which they are bonded form a 4-to 7-membered non-aromatic heterocyclyl ring, wherein said heterocyclyl optionally comprises 1 or 2 substituents independently selected from N, O, S, C (O) and S (O)₂Provided that said heterocyclyl ring does not contain 2 adjacent atoms selected from O and S, and said heterocyclyl is optionally substituted with 1 or 2 substituents, which may be the same or different, selected from: cyano, halogen, hydroxy, amino, C_1-4Alkyl radical, C_1-4Haloalkyl and C_1-4An alkoxy group; or the group R³And Z is a heterocyclic radical formed by C_3-6Cycloalkyl substituted to form a spiro ring;

or a salt or N-oxide thereof.

2. The compound of claim 1, wherein a is a-1 optionally substituted with 1 or 2 fluoro groups, or a is unsubstituted a-4.

3. A compound according to claim 1 or claim 2, wherein R¹And R²Independently selected from hydrogen and methyl.

4. A compound according to any one of claims 1 to 3, wherein R³Is C_1-4An alkoxy group.

5. A compound according to any one of claims 1 to 4, wherein R³Is methoxy.

6. A compound according to any one of claims 1 to 5, wherein R⁴Is C_3-4Cycloalkyl, optionally substituted with 1 or 2 substituents, which may be the same or different, selected from: cyano, halogenHydroxyl, amino, methyl, ethyl and propyl.

7. A compound according to any one of claims 1 to 6, wherein R⁴Is cyclopropyl optionally substituted by 1R⁶Wherein R is⁶Selected from cyano, halogen, hydroxy, amino, methyl, ethyl, n-propyl and isopropyl.

8. A compound according to any one of claims 1 to 3, wherein R³And Z together with the-N-C (═ S) -group to which they are bonded form a group selected from:

wherein X₁And X₂is-CH₂-or-O-and each group is optionally substituted with 1 or 2 substituents which may be the same or different selected from: cyano, halogen, hydroxy, amino, C_1-4Alkyl radical, C_1-4Haloalkyl and C_1-4An alkoxy group.

9. The compound of claim 8, wherein R³And Z together with the-N-C (═ S) -group to which they are bonded form a group selected from:

wherein X₁And X₂is-CH₂-or-O-and each group is optionally substituted with 1 or 2 substituents which may be the same or different selected from: cyano, halogen, hydroxy, amino, methyl, ethyl, C_1-2Fluoroalkyl, methoxy and ethoxy.

10. An agrochemical composition comprising a fungicidally effective amount of a compound according to any one of claims 1 to 9.

11. The composition of claim 10, further comprising at least one additional active ingredient and/or an agrochemically acceptable diluent or carrier.

12. 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 9, or a composition comprising such a compound as active ingredient, is applied to the plants, parts thereof or the locus thereof.

13. Use of a compound according to any one of claims 1 to 9 as a fungicide.