Cyclic amine compounds with pesticidal activity
By developing a new cyclic amine compound with formula (I), it solves the problem that it is difficult to effectively control insects and other pests in the prior art, achieves a significant killing effect on insects, and protects plants.
Patent Information
- Application Number
- CN202080064858.8
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- Priority Date
- 2020-08-07
- Filing Date
- 2020-09-18
- Publication Date
- 2025-03-14
- Estimated Expiration
- 2040-09-18
AI Technical Summary
The prior art is difficult to effectively control insects and other pests, especially in the field of plant protection.
A novel cyclic amine compound, with formula (I), was developed for the preparation of insecticidal pesticides, used by forming salts with acids or bases.
The compound shows significant insecticidal activity, which can effectively control insects and other pests and protect plants from damage.
Smart Images

Figure CN114401963B_ABST
Abstract
Description
[0001] The present invention relates to pesticidally active, in particular insecticidal, cyclic amines, preferably azetidinyl-, pyrrolidinyl-, piperidinyl- and piperazinyl-pyridinylcarbonyl compounds, processes for their preparation, compositions comprising those compounds, and their use for controlling animal pests, including arthropods and in particular insects or representatives of the order Acarina.
[0002] WO 2015032280, CN 106316931, WO 2017195703, WO 2019039429, WO 2019082808, JP 2019077618, and JP 2019085371 describe certain azetidinyl-, pyrrolidinyl-, piperidinyl- or piperazinyl-pyridinylcarbonyl compounds for controlling pests that damage plants.
[0003] Novel pesticidal azetidinyl-, pyrrolidinyl-, piperidinyl- and piperazinyl-pyridinyl carbonyl compounds have now been found.
[0004] Therefore, the present invention relates in a first aspect to compounds having formula (I)
[0005]
[0006] in
[0007] R 1 CN, C(=S)NH 2 or C 1 -C 6 - haloalkyl;
[0008] R 2 It is H, OH, halogen, C 1 -C 6 -alkoxy or C 1 -C 6 -haloalkoxy;
[0009] R 3 It is H, OH, halogen, C 1 -C 6 -alkyl, C 1 -C 6 -haloalkyl, C 2 -C 6 -Alkenyl, C 2 -C 6 -haloalkenyl, C 2 -C 6 -Alkynyl, C 2 -C 6 -haloalkynyl, C 3 -C 6-cycloalkyl, C 3 -C 6 -halogenated cycloalkyl, C 1 -C 6 -alkoxy or C 1 -C 6 -haloalkoxy;
[0010] R 4 It is C 1 -C 6 -haloalkyl, C 2 -C 6 -Alkenyl, C 2 -C 6 -haloalkenyl, C 3 -C 6 -cycloalkyl, C 3 -C 6 -halogenated cycloalkyl, phenyl, 1 to 3 independently selected substituents R 5 substituted phenyl, heteroaryl (which is a 5- or 6-membered monocyclic or a 9- or 10-membered bicyclic), substituted with 1 to 3 independently selected substituents R 6 Substituted heteroaryl (which is a 5- or 6-membered monocyclic or a 9- or 10-membered bicyclic), phenyl-C 1 -C 3 -alkyl, or 1 to 3 independently selected substituents R 7 Substituted phenyl-C 1 -C 3- alkyl;
[0011] Z is oxygen or sulfur;
[0012] Q is a cyclic amine represented by formula IIa or a cyclic amine represented by formula IIb,
[0013]
[0014] Wherein the arrow indicates the connection to the carbonyl group;
[0015] p 1 is 0, 1, or 2 and indicates the number of methylene groups;
[0016] p 2 is 0, 1, or 2 and indicates the number of methylene groups;
[0017] q 1 is 1 or 2 and indicates the number of methylene groups;
[0018] q 2 is 1 or 2 and indicates the number of methylene groups;
[0019] X is hydrogen, hydroxy, alkoxy or halogen;
[0020] Y is cyano, C1 -C 6 -alkyl, C 1 -C 6 -alkoxy-C 1 -C 6 -alkyl, C 1 -C 6 -alkylsulfanyl-C 1 -C 6 -alkyl, C 1 -C 6 -Alkylsulfinyl-C 1 -C 6 -alkyl, C 1 -C 6 -Alkylsulfonyl-C 1 -C 6 -alkyl, C 3 -C 6 -Alkenylsulfanyl-C 1 -C 6 -alkyl, C 3 -C 6 -Alkenylsulfinyl-C 3 -C 6 -alkyl, C 3 -C 6 -Alkenylsulfonyl-C 1 -C 6 -alkyl, C 3 -C 6 -Alkynylsulfanyl-C 1 -C 6 -alkyl, C 3 -C 6 -Alkynylsulfinyl-C 1 -C 6 -alkyl, C 1 -C 6 -Alkynylsulfonyl-C 1 -C 6 -alkyl, R a R b NC(O),R c C(O)NR d , R e SO 2 NR f , R g ON=CR h , a 4- to 6-membered non-aromatic heterocyclic ring system in which one or two carbons are independently replaced by nitrogen, oxygen, sulfur or sulfonyl, a phenyl group, 1 to 3 independently selected substituents R 8 substituted phenyl, 5- or 6-membered monocyclic heteroaryl, or substituted by 1 to 3 independently selected substituents R 9 substituted 5- or 6-membered monocyclic heteroaryl;
[0021] A is cyano, C 1 -C 6 -Cyanoalkyl, C 2 -C 6 -Cyanide, C 3 -C 6 -Cyanocycloalkyl, C 1 -C 6 -haloalkyl, C 1 -C 6 -haloalkenyl, C 3 -C 6 -halogenated cycloalkyl, C 1 -C 6 -Alkoxycarbonyl, C 2 -C 6 -Alkenyloxycarbonyl, C 2 -C 6 -Alkynyloxycarbonyl, C 1 -C 6 -alkylsulfanyl-C 1 -C 6 -alkyl, C 1 -C 6 -Alkylsulfinyl-C 1 -C 6 -alkyl, C 1 -C 6 -Alkylsulfonyl-C 1 -C 6 -alkyl, R i SO 2 , R j R k NSO 2 , phenyl, 1 to 3 independently selected substituents R 10 substituted phenyl, heteroaryl (which is a 5- or 6-membered monocyclic or a 9- or 10-membered bicyclic), or substituted by 1 to 3 independently selected substituents R 11 Substituted heteroaryl (which is a 5- or 6-membered monocyclic or a 9- or 10-membered bicyclic);
[0022] R a , R b , R c , R d , R f , R g , R h , R j and R k are independently selected from hydrogen, C 1 -C 6 -alkyl, C 1 -C 6 -haloalkyl, C 2 -C6 -Alkenyl, C 2 -C 6 -haloalkenyl, C 2 -C 6 -Alkynyl, C 2 -C 6 -haloalkynyl, C 3 -C 6 -Cycloalkyl and C 3 -C 6 - halocycloalkyl;
[0023] R e and R i Independently selected from C 1 -C 6 -alkyl, C 1 -C 6 -haloalkyl, C 2 -C 6 -Alkenyl, C 2 -C 6 -haloalkenyl, C 2 -C 6 -Alkynyl, C 2 -C 6 -haloalkynyl, C 3 -C 6 -Cycloalkyl and C 3 -C 6 - halocycloalkyl;
[0024] R 5 are independently selected from halogen, cyano, C 1 -C 6 -alkyl, C 1 -C 6 -haloalkyl, C 2 -C 6 -Alkenyl, C 2 -C 6 -haloalkenyl, C 2 -C 6 -Alkynyl, C 2 -C 6 -haloalkynyl, C 3 -C 6 -Cycloalkyl, C 3 -C 6 -halogenated cycloalkyl, C 1 -C 6 -alkoxy, C 1 -C 6 -haloalkoxy, C 1 -C 6 -alkylsulfonyl, and C 1 -C 6 -haloalkylsulfanyl; and if both C1 -C 3 -haloalkoxy groups are substituted on adjacent atoms, then they can form a 5- or 6-membered ring together with the carbon atoms of the phenyl ring (e.g. -OC 1 -C 2 -haloalkylO-); and
[0025] R 6 , R 7 , R 8 , R 9 , R 10 , R 11 are independently selected from halogen, cyano, C 1 -C 6 -alkyl, C 1 -C 6 -haloalkyl, C 2 -C 6 -Alkenyl, C 2 -C 6 -haloalkenyl, C 2 -C 6 -Alkynyl, C 2 -C 6 -haloalkynyl, C 3 -C 6 -cycloalkyl, C 3 -C 6 -halogenated cycloalkyl, C 1 -C 6 -alkoxy, C 1 -C 6 -haloalkoxy, C 1 -C 6 -alkylsulfonyl, and C 1 -C 6 - haloalkylsulfanyl;
[0026] or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer and N-oxide of the compound of formula (I).
[0027] Compounds of formula (I) having at least one basic center can form acid addition salts, for example, with strong inorganic acids (such as mineral acids, for example perchloric acid, sulfuric acid, nitric acid, nitrous acid, phosphoric acid or hydrohalic acids), strong organic carboxylic acids (such as unsubstituted or halogen-substituted C 1 -C 4 Alkanecarboxylic acids, for example acetic acid, saturated or unsaturated dicarboxylic acids, for example oxalic acid, malonic acid, succinic acid, maleic acid, fumaric acid or phthalic acid, hydroxycarboxylic acids, for example ascorbic acid, lactic acid, malic acid, tartaric acid or citric acid, or benzoic acid), or organic sulfonic acids (for example unsubstituted or halogen-substituted C 1 -C4 The compounds of formula (I) having at least one acidic group can, for example, form salts with bases, for example mineral salts, such as alkali metal or alkaline earth metal salts, for example sodium, potassium or magnesium salts; or with ammonia or organic amines (such as morpholine, piperidine, pyrrolidine, mono-, di- or tri-lower alkylamines, for example ethylamine, diethylamine, triethylamine or dimethylpropylamine, or mono-, di- or tri-hydroxy lower alkylamines, for example monoethanolamine, diethanolamine or triethanolamine).
[0028] In each case, the compounds of formula (I) according to the invention are in free form, in oxidized form such as N-oxides, or in salt form (eg in the form of an agronomically usable salt).
[0029] N-oxides are oxidized forms of tertiary amines or oxidized forms of nitrogen-containing heteroaromatic compounds. They are described, for example, in the book "Heterocyclic N-oxides" by A. Albini and S. Pietra, CRC Press, Boca Raton 1991.
[0030] The compounds of formula (I) according to the invention also include hydrates which may be formed during salt formation.
[0031] As used herein, the term “C 1 -C n "-alkyl" refers to a saturated straight or branched hydrocarbon group having 1 to n carbon atoms, attached via any carbon atom, such as any of the following groups: methyl, ethyl, n-propyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, n-hexyl, n-pentyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethyl-1-methylpropyl, or 1-ethyl-2-methylpropyl.
[0032] As used herein, the term “C 2 -C n "-alkenyl" refers to a straight or branched alkenyl chain having from two to n carbon atoms and one or two double bonds, for example vinyl, prop-1-enyl, but-2-enyl.
[0033] As used herein, the term “C 2 -Cn "-alkynyl" means a straight or branched alkynyl chain having from two to n carbon atoms and one triple bond, for example ethynyl, prop-2-ynyl, but-3-ynyl,
[0034] As used herein, the term “C 3 -C n "-cycloalkyl" refers to a 3- to n-membered cycloalkyl group such as cyclopropane, cyclobutane, cyclopropane, cyclopentane and cyclohexane.
[0035] As used herein, the term “C 1 -C n "-alkoxy" refers to a straight or branched saturated alkyl group having 1 to n carbon atoms (as mentioned above), which is attached via an oxygen atom, i.e., for example, any of the following groups: methoxy, ethoxy, n-propoxy, 1-methylethoxy, n-butoxy, 1-methylpropoxy, 2-methylpropoxy or 1,1-dimethylethoxy. As used herein, the term "halogenated C 1 -C n -alkoxy" refers to C 1 -C n -alkoxy, in which one or more hydrogen atoms on the alkyl group are replaced by the same or different halogen atoms - examples include trifluoromethoxy, 2-fluoroethoxy, 3-fluoropropoxy, 3,3,3-trifluoropropoxy, 4-chlorobutoxy. Two adjacent substituents on a phenyl ring may form a 5- or 6-membered ring together with the carbons of the phenyl ring. An example is -OCF 2 O-、-OCF 2 CF 2 O-.
[0036] Halogen is typically fluorine, chlorine, bromine or iodine. This also applies correspondingly to halogen in combination with other meanings, such as haloalkyl.
[0037] As used herein, the term “C 1 -C n"-haloalkyl" refers to a straight-chain or branched saturated alkyl group (as mentioned above) having 1 to n carbon atoms, attached via any carbon atom, wherein some or all of the hydrogen atoms in these groups may be replaced by fluorine, chlorine, bromine and / or iodine, i.e., for example, any of the following: chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 2-fluoroethyl, 2-chloroethyl, 2-bromoethyl, 2-iodoethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2-chloro-2-fluoroethyl, 2-chloro-2,2-difluoroethyl, 2,2 -dichloro-2-fluoroethyl, 2,2,2-trichloroethyl, pentafluoroethyl, 2-fluoropropyl, 3-fluoropropyl, 2,2-difluoropropyl, 2,3-difluoropropyl, 2-chloropropyl, 3-chloropropyl, 2,3-dichloropropyl, 2-bromopropyl, 3-bromopropyl, 3,3,3-trifluoropropyl, 3,3,3-trichloropropyl, 2,2,3,3,3-pentafluoropropyl, heptafluoropropyl, 1-(fluoromethyl)-2-fluoroethyl, 1-(chloromethyl)-2-chloroethyl, 1-(bromomethyl)-2-bromoethyl, 4-fluorobutyl, 4-chlorobutyl, 4-bromobutyl or nonafluorobutyl. Accordingly, the term “C 1 -C 2 "Fluoroalkyl" shall mean a C 1 -C 2 Alkyl, for example any of the following: difluoromethyl, trifluoromethyl, 1-fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 1,1,2,2-tetrafluoroethyl or pentafluoroethyl. Similarly, as used herein, the term "C 2 -C n -haloalkenyl" or "C 2 -C n "-haloalkynyl" refers to a C 2 -C n -alkenyl or C 2 -C n -alkynyl moiety. Similarly, as used herein, the term "C 3 -C n "-halocycloalkyl" means a C 3 -C n -cycloalkyl.
[0038] As used herein, the term “C 1 -C n "-Cyanoalkyl" refers to a C 1 -C n-alkyl (as defined above), wherein one of the hydrogen atoms in the group is replaced by a cyano group: for example, cyanomethyl, 2-cyanoethyl, 2-cyanopropyl, 3-cyanopropyl, 1-(cyanomethyl)-2-ethyl, 1-(methyl)-2-cyanoethyl, 4-cyanobutyl, etc. Similarly, the term "C 1 -C n -cyanoalkenyl" or "C 1 -C n -cyanoalkynyl" refers to substituted C 2 -C n -alkenyl or C 1 -C n -alkynyl moiety, wherein one of the hydrogen atoms in the corresponding moiety is replaced by a cyano group.
[0039] As used herein, the term “C 1 -C n -alkylsulfanyl-C 1 -C n "-alkyl" refers to an alkyl group in which one of the carbon atoms is replaced by a sulfur atom.
[0040] As used herein, the term “C 1 -C n -Alkylsulfinyl-C 1 -C n "-alkyl" refers to an alkyl group in which one of the carbon atoms is replaced by a S(=O) group.
[0041] As used herein, the term “C 1 -C n -Alkylsulfonyl-C 1 -C n "-alkyl" refers to an alkyl group in which one of the carbon atoms is replaced by S(=O) 2 Group substitution.
[0042] As used herein, the term "4- to 6-membered non-aromatic heterocyclic ring system in which one or two carbons are replaced by nitrogen, oxygen, sulfur or sulfonyl" refers to a cyclic group in which one or two carbon atoms in the ring are independently replaced by nitrogen, oxygen, sulfur or sulfonyl, and the ring is attached to the remainder of the compound via the carbon or nitrogen atom. Examples are azetidinyl, oxetanyl, thietanyl, pyrrolidinyl, tetrahydrofuranyl, 2-oxopyrrolidinyl, 2-oxotetrahydrofuranyl, 1,1-dioxo-1,2-thiazolidinyl, 1,3-dioxolanyl, 1,3-dithiolanyl, 2-oxoxazolidinyl, piperidinyl, tetrahydropyranyl, 2-oxopiperidinyl, 1,1-dioxothiazinyl, 2-oxotetrahydropyranyl, 1,3-dioxolanyl, 1,3-dithianyl, 2-oxo-1,3-oxazinyl.
[0043] As used herein, the term "phenyl-C1 -C n -alkyl" refers to an alkyl group substituted by a phenyl ring. If the phenyl-C 1 -C n -If there is substitution on the alkyl group, the substitution is on the phenyl ring.
[0044] As used herein, the term "5- or 6-membered monocyclic heteroaryl" refers to a 5- or 6-membered aromatic ring in which 1 to 3 carbon atoms are independently replaced by nitrogen, sulfur, or oxygen. Examples are pyridyl or pyridinyl, pyridazinyl, pyrimidinyl, pyrazinyl, pyrrolyl, pyrazolyl, imidazolyl, triazolyl (e.g., 1,2,4-triazolyl), furanyl, thienyl, oxazolyl, isoxazolyl, oxadiazolyl, thiazolyl, isothiazolyl, and thiadiazolyl.
[0045] As used herein, the term "9- or 10-membered bicyclic heteroaryl" refers to a 9- or 10-membered aromatic ring consisting of two rings, with 1 to 3 carbon atoms independently replaced by nitrogen, sulfur, or oxygen (these heteroatoms may be in one ring or distributed in two rings). Examples are purinyl, quinolinyl, cinnolinyl, quinoxalinyl, indolyl, indazolyl, benzimidazolyl, benzothienyl, and benzothiazolyl.
[0046] As used herein, the term “C 1 -C n -alkoxy-C 1 -C n -alkyl" refers to a C 1 -C n - Alkoxy-substituted alkyl. Examples are methoxymethyl, methoxyethyl, ethoxymethyl and propoxymethyl.
[0047] As used herein, the term “C 1 -C n "-alkoxycarbonyl" refers to a C 1 -C n -alkoxy, through the carbonyl group, C 1 -C n -Alkoxycarbonyl is attached to the remainder of the compound. Examples are methoxycarbonyl, ethoxycarbonyl, isopropoxycarbonyl and tert-butoxycarbonyl.
[0048] As used herein, the term “C 2 -C n "-Alkenyloxycarbonyl" refers to a C-alkylene group attached to a carbonyl (C=O) group via an oxygen atom. 2 -C n -alkenyl, and wherein the attachment to the rest of the compound is through the carbon atom of the carbonyl group. Examples are vinyloxycarbonyl and allyloxycarbonyl.
[0049] As used herein, the term “C 2 -C n "-alkynyloxycarbonyl" refers to a C-alkyl group attached to a carbonyl (C=O) group via an oxygen atom. 2 -C n -alkynyl, and wherein the attachment to the rest of the compound is through the carbon atom of the carbonyl group. Examples are propargyloxycarbonyl (2-prop-2-ynyloxycarbonyl) and 2-pent-3-ynyloxycarbonyl,
[0050] As used herein, the term "control" refers to reducing the number of pests, eliminating pests, and / or preventing further pest damage, such that damage to plants or to plant-derived products is reduced.
[0051] As used herein, the term "pest" refers to insects and molluscs found in agriculture, horticulture, forestry, storage of products of plant origin (such as fruits, grains and wood); and those pests associated with damage to man-made structures. The term pest covers all stages of the life cycle of the pest.
[0052] As used herein, the term "effective amount" refers to an amount of a compound or a salt thereof that provides the desired effect upon single or multiple administrations.
[0053] The effective amount is readily determined by one skilled in the art by using known techniques and by observing the results obtained under similar circumstances. In determining the effective amount, many factors are considered, including, but not limited to: the type of plant or derived product to be applied; the pest to be controlled and its life cycle; the specific compound being applied; the type of application; and other relevant circumstances.
[0054] Embodiments according to the present invention are provided as listed below.
[0055] In an embodiment of each aspect of the present invention, R 1 yes
[0056] A.CN or C(=S)NH 2 ;or
[0057] B.CN.
[0058] In an embodiment of each aspect of the present invention, R 2 yes
[0059] A. Hydrogen, halogen, C 1 -C 6 -alkoxy or C 1 -C 6 -haloalkoxy; or
[0060] B. Hydrogen.
[0061] In an embodiment of each aspect of the present invention, R 3 yes
[0062] A. Hydrogen, OH, halogen, C 1 -C 6 -alkyl, C 1 -C 6 -haloalkyl, C 3 -C 6 -Cycloalkyl, C 3 -C 6 -halogenated cycloalkyl, C 1 -C 6 -alkoxy or C 1 -C 6 -haloalkoxy; or
[0063] B. Hydrogen, C 1 -C 6 -alkyl, or C 1 -C 6 - haloalkyl; or
[0064] C. Hydrogen, C 1 -C 3 -alkyl, or C 1 -C 3 - haloalkyl; or
[0065] D. Hydrogen, C 1 -C 2 -alkyl, or C 1 -C 2 - haloalkyl; or
[0066] E. hydrogen, methyl, ethyl, difluoromethyl, trifluoromethyl, or pentafluoroethyl; or
[0067] F. Methyl, CHF 2 , or CF 3 ;or
[0068] G.CHF 2 , or CF 3 .
[0069] In embodiments of each aspect of the invention, Z is
[0070] A. Sulfur; or
[0071] B. Oxygen.
[0072] In an embodiment of each aspect of the present invention, R 4 yes
[0073] AC 1 -C 6 -haloalkyl, C 2 -C6 -Alkenyl, C 2 -C 6 -haloalkenyl, C 3 -C 6 -cycloalkyl, C 3 -C 6 -halogenated cycloalkyl, phenyl, 1 to 3 independently selected substituents R 5 substituted phenyl, 5 or 6 membered monocyclic heteroaryl, 1 to 3 independently selected substituents R 6 substituted 5 or 6 membered monocyclic heteroaryl, substituted by 1 to 3 independently selected substituents R 6 Substituted 9- or 10-membered bicyclic, phenyl-C 1 -C 3 -alkyl, or 1 to 3 independently selected substituents R 7 Substituted phenyl-C 1 -C 3- Alkyl; or
[0074] BC 1 -C 6 -haloalkyl, C 2 -C 6 -haloalkenyl, C 3 -C 6 -cycloalkyl or C 3 -C 6 -halogenated cycloalkyl, 1 to 3 independently selected substituents R 5 substituted phenyl, 5 or 6 membered monocyclic heteroaryl, 1 to 3 independently selected substituents R 6 substituted 5 or 6 membered monocyclic heteroaryl, substituted by 1 to 3 independently selected substituents R 6 Substituted 9- or 10-membered bicyclic, phenyl-C 1 -C 3 -alkyl, or 1 to 3 independently selected substituents R 7 Substituted phenyl-C 1 -C 3- Alkyl; or
[0075] C. 1 to 3 independently selected substituents R 5 substituted phenyl, 1 to 3 independently selected substituents R 6 substituted 5 or 6 membered monocyclic heteroaryl, or substituted by 1 to 3 independently selected substituents R 6 substituted 9- or 10-membered bicyclic; or
[0076] D. 1 to 3 substituents (independently selected from halogen, cyano, C 1 -C 6 -alkyl, C 1 -C6 -haloalkyl, C 2 -C 6 -Alkenyl, C 2 -C 6 -haloalkenyl, C 2 -C 6 -Alkynyl, C 2 -C 6 -haloalkynyl, C 3 -C 6 -Cycloalkyl, C 3 -C 6 -halogenated cycloalkyl, C 1 -C 6 -alkoxy, C 1 -C 6 -haloalkoxy, C 1 -C 6 -alkylsulfonyl, and C 1 -C 6 -haloalkylsulfanyl) substituted phenyl, or one of the following: thienyl, thiazolyl, thiadiazolyl, pyridyl, pyrazolyl, 2,1,3-benzoxadiazolyl, and 1,3-benzodioxolyl - each of which is substituted by 1 to 3 substituents (independently selected from halogen, C 1 -C 3 -alkyl, C 1 -C 3 -haloalkyl, C 1 -C 3 -alkoxy, and C 1 -C 3 -haloalkoxy) substituted; or
[0077] E. 1 to 3 substituents (independently selected from halogen, cyano, C 1 -C 6 -haloalkyl, C 1 -C 6 -haloalkoxy, C 1 -C 6 -alkylsulfonyl, and C 1 -C 6 -haloalkylsulfanyl) substituted phenyl (and if the two C 1 -C 3 -haloalkoxy groups are substituted on adjacent atoms, then they can form a 5- or 6-membered ring together with the carbon atoms of the phenyl ring (e.g. -OC 1 -C 2-haloalkyl (O-)), or one of the following: thienyl, thiazolyl, thiadiazolyl, pyridyl, pyrazolyl, 2,1,3-benzoxadiazolyl, and 1,3-benzodioxolyl-each substituted with 1 to 3 substituents independently selected from fluorine, chlorine, methyl, ethyl, isopropyl, trifluoromethyl, difluoromethyl, trifluoromethoxy, and difluoromethoxy; or
[0078] F. 1 or 2 substituents (independently selected from halogen, cyano, C 1 -C 6 -alkyl, C 1 -C 6 -haloalkyl, C 1 -C 6 -haloalkoxy, C 1 -C 6 -alkylsulfonyl, and C 1 -C 6 -haloalkylsulfanyl) substituted phenyl (and if the two C 1 -C 3 -haloalkoxy groups are substituted on adjacent atoms, then they can form a 5- or 6-membered ring together with the carbon atoms of the phenyl ring (e.g. -OC 1 -C 2 -haloalkyl (O-)), or one of the following: thienyl, pyridyl, and pyrazolyl-each substituted with 1 to 3 substituents independently selected from fluoro, chloro, methyl, ethyl, isopropyl, trifluoromethyl, difluoromethyl, trifluoromethoxy, and difluoromethoxy; or
[0079] G. 1 or 2 substituents (independently selected from halogen, cyano, C 1 -C 6 -haloalkoxy and C 1 -C 6 -haloalkyl) substituted phenyl (and if the two C 1 -C 3 -haloalkoxy groups are substituted on adjacent atoms, then they can form a 5- or 6-membered ring together with the carbon atoms of the phenyl ring (e.g. -OC 1 -C 2 -haloalkyl(O-)), or one of the following: thienyl, pyridyl, and pyrazolyl-each substituted by 1 to 2 groups (independently selected from halogen, C 1 -C 6 -haloalkoxy, C 1 -C 6 -alkyl and C 1 -C 6 -haloalkyl) substituted; or
[0080] H. Halogen, cyano, C 1 -C3 -Alkylsulfonyl, C 1 -C 3 -halogenated alkylsulfanyl, C 1 -C 3 -haloalkoxy and C 1 -C 3 - haloalkyl-substituted phenyl (and if both C 1 -C 3 -haloalkoxy groups are substituted on adjacent atoms, then they can form a 5- or 6-membered ring together with the carbon atoms of the phenyl ring (e.g. -OC 1 -C 2 -haloalkyl(O-)), or one of the following: thienyl, pyridyl, and pyrazolyl-each substituted by 1 to 2 groups (independently selected from halogen, C 1 -C 3 -haloalkoxy, C 1 -C 3 -alkyl and C 1 -C 3 -haloalkyl) substituted; or
[0081] I. Substituted by one to three groups (independently selected from halogen, cyano, C 1 -C 3 -Alkylsulfonyl, C 1 -C 3 -halogenated alkylsulfanyl, C 1 -C 3 -haloalkoxy and C 1 -C 3 -haloalkyl) substituted phenyl (and if the two C 1 -C 3 -haloalkoxy groups are substituted on adjacent atoms, then they can form a 5- or 6-membered ring together with the carbon atoms of the phenyl ring (e.g. -OC 1 -C 2 -haloalkyl (O-)); or
[0082] J. Substituted by one to three groups (independently selected from halogen, cyano, C 1 -C 3 -haloalkoxy and C 1 -C 3 -haloalkyl) substituted phenyl (and if the two C 1 -C 3 -haloalkoxy groups are substituted on adjacent atoms, then they can form a 5- or 6-membered ring together with the carbon atoms of the phenyl ring (e.g. -OC 1 -C 2 -haloalkyl (O-)); or
[0083] K. One of the following: thienyl, pyridyl, and pyrazolyl - each substituted by 1 to 2 groups (independently selected from halogen, C 1 -C 3 -haloalkoxy, C 1 -C 3 -alkyl and C 1 -C 3 -haloalkyl) substituted.
[0084] In an embodiment of each aspect of the invention, Q is
[0085] A. A cyclic amine represented by formula IIa, wherein p 1 and p 2 are all 1; X is hydrogen, hydroxy, alkoxy or halogen; and Y is cyano, C 1 -C 6 -alkyl, C 1 -C 6 -alkoxy-C 1 -C 6 -alkyl, C 1 -C 6 -alkylsulfanyl-C 1 -C 6 -alkyl, C 1 -C 6 -Alkylsulfinyl-C 1 -C 6 -alkyl, C 1 -C 6 -Alkylsulfonyl-C 1 -C 6 -alkyl, R a R b NC(O),R c C(O)NR d , R e SO 2 NR f , R g ON=CR h , a 4- to 6-membered non-aromatic heterocyclic ring system in which one or two carbons are independently replaced by nitrogen, oxygen, sulfur or sulfonyl, a phenyl group, a substituted group R 8 substituted phenyl, 5- or 6-membered monocyclic heteroaryl, or substituted by 1 to 3 groups R 9 substituted 5- or 6-membered monocyclic heteroaryl;
[0086]
[0087] B. A cyclic amine represented by formula IIa, wherein p 1 and p 2 are all 1; X is hydrogen or hydroxy; and Y is cyano, C 1 -C6 -alkyl, C 1 -C 6 -alkoxy-C 1 -C 6 -alkyl, C 1 -C 6 -alkylsulfanyl-C 1 -C 6 -alkyl, C 1 -C 6 -Alkylsulfinyl-C 1 -C 6 -alkyl, C 1 -C 6 -Alkylsulfonyl-C 1 -C 6 -alkyl, R a R b NC(O),R c C(O)NR d , R e SO 2 NR f , R g ON=CR h , a 4- to 6-membered non-aromatic heterocyclic ring system in which one or two carbons are independently replaced by nitrogen, oxygen, sulfur or sulfonyl, a phenyl group, a substituted group R 8 substituted phenyl, 5- or 6-membered monocyclic heteroaryl, or substituted by 1 to 3 groups R 9 substituted 5- or 6-membered monocyclic heteroaryl; or
[0088] C. A cyclic amine represented by formula IIa, wherein p 1 and p 2 are all 1, X is hydrogen or hydroxyl; and Y is cyano, C 1 -C 6 -alkylsulfanyl-C 1 -C 6 -alkyl, C 1 -C 6 -Alkylsulfinyl-C 1 -C 6 -alkyl, C 1 -C 6 -Alkylsulfonyl-C 1 -C 6 -alkyl, R a R b NC(O),R e SO 2 NR f , R g ON=CR h, a 4- to 6-membered non-aromatic heterocyclic ring system in which one or two carbons are independently replaced by nitrogen, oxygen, sulfur or sulfonyl, a phenyl group, a substituted group R 8 substituted phenyl, 5- or 6-membered monocyclic heteroaryl, or substituted by 1 to 3 groups R 9 substituted 5- or 6-membered monocyclic heteroaryl; or
[0089] D. A cyclic amine represented by formula IIa, wherein p 1 and p 2 are all 1, X is hydrogen or hydroxyl; and Y is cyano, C 1 -C 6 -alkylsulfanyl-C 1 -C 6 -alkyl, C 1 -C 6 -Alkylsulfinyl-C 1 -C 6 -alkyl, C 1 -C 6 -Alkylsulfonyl-C 1 -C 6 -alkyl, a 4- to 6-membered non-aromatic heterocyclic ring system in which one or two carbons are independently replaced by nitrogen, oxygen, sulfur or sulfonyl, a 5- or 6-membered monocyclic heteroaryl, or a substituted group R 9 substituted 5- or 6-membered monocyclic heteroaryl; or
[0090] E. A cyclic amine represented by formula IIa, wherein p 1 and p 2 are all 1, X is hydrogen or hydroxy; and Y is a 5- or 6-membered monocyclic heteroaryl or substituted by 1 to 3 groups R 9 substituted 5- or 6-membered monocyclic heteroaryl; or
[0091] F. A cyclic amine represented by formula IIa, wherein p 1 and p 2 are all 1, X is hydrogen or hydroxy; and Y is substituted by 1 to 3 groups (independently selected from halogen, C 1 -C 6 -alkyl, and C 1 -C 6 -haloalkyl)-substituted 5- or 6-membered monocyclic heteroaryl; or
[0092] G. A cyclic amine represented by formula IIb; wherein q 1 and q 2 are all 1; and A is cyano, C 1 -C 6 -Cyanoalkyl, C 2 -C 6 -Cyanide, C 3 -C 6-Cyanocycloalkyl, C 1 -C 6 -haloalkyl, C 1 -C 6 -haloalkenyl, C 3 -C 6 -halogenated cycloalkyl, C 1 -C 6 -Alkoxycarbonyl, C 2 -C 6 -Alkenyloxycarbonyl, C 2 -C 6 -Alkynyloxycarbonyl, R i SO 2 , R j R k NSO 2 , phenyl, substituted by 1 to 3 groups R 10 substituted phenyl, heteroaryl (which is a 5- or 6-membered monocyclic or a 9- or 10-membered bicyclic), or substituted by 1 to 3 R 11 Substituted heteroaryl (which is a 5- or 6-membered monocyclic or a 9- or 10-membered bicyclic);
[0093]
[0094] H. A cyclic amine represented by formula IIb; wherein q 1 and q 2 are all 1; and A is cyano, C 1 -C 6 -Cyanoalkyl, C 1 -C 6 -haloalkyl, C 1 -C 6 -Alkoxycarbonyl, C 2 -C 6 -Alkenyloxycarbonyl, C 1 -C 6 -alkylsulfanyl-C 1 -C 6 -alkyl, C 1 -C 6 -Alkylsulfinyl-C 1 -C 6 -alkyl, C 1 -C 6 -Alkylsulfonyl-C 1 -C 6 -alkyl, phenyl, substituted by 1 to 3 groups R 10 substituted phenyl, heteroaryl (which is a 5- or 6-membered monocyclic or a 9- or 10-membered bicyclic), or substituted by 1 to 3 R 11 Substituted heteroaryl (which is a 5- or 6-membered monocyclic or a 9- or 10-membered bicyclic);
[0095] I. A cyclic amine represented by formula IIb; wherein q 1 and q 2 are all 1; and A is a 5- or 6-membered monocyclic heteroaryl group or is substituted by 1 to 3 groups R 11 substituted 5- or 6-membered monocyclic heteroaryl; or
[0096] J. A cyclic amine represented by formula IIb; wherein q 1 and q 2 are all 1; and A is substituted by 1 to 3 substituents (independently selected from halogen, C 1 -C 3 -alkyl and C 1 -C 3 -haloalkyl)-substituted 5- or 6-membered monocyclic heteroaryl.
[0097] In an embodiment of each aspect of the present invention, R a , R b , R c , R d , R f , R g , R h , R j and R k Independently selected from
[0098] A. Hydrogen, C 1 -C 3 -alkyl, C 1 -C 3 -haloalkyl, C 2 -C 4 -Alkenyl, C 2 -C 4 -haloalkenyl, C 2 -C 4 -Alkynyl, C 2 -C 4 -haloalkynyl, C 3 -C 4 -cycloalkyl and C 3 -C 4 - halocycloalkyl; or
[0099] B. Hydrogen, C 1 -C 3 -alkyl, C 1 -C 3 -haloalkyl, C 3 -C 4 -cycloalkyl and C 3 -C 4 - halocycloalkyl; or
[0100] C. Hydrogen, C 1 -C 3 -alkyl, C1 -C 3 -haloalkyl, and C 3 -C 4 - halocycloalkyl; or
[0101] D. Hydrogen, C 1 -C 3 -alkyl and C 1 -C 3 - haloalkyl; or
[0102] E. Hydrogen and C 1 -C 3 -haloalkyl.
[0103] In an embodiment of each aspect of the present invention, R e and R i Independently selected from
[0104] AC 1 -C 3 -alkyl, C 1 -C 3 -haloalkyl, C 2 -C 4 -Alkenyl, C 2 -C 4 -haloalkenyl, C 2 -C 4 -Alkynyl, C 2 -C 4 -haloalkynyl, C 3 -C 4 -Cycloalkyl and C 3 -C 4 - halocycloalkyl; or
[0105] BC 1 -C 3 -alkyl, C 1 -C 3 -haloalkyl, C 2 -C 4 -Alkenyl, C 2 -C 4 -haloalkenyl, C 2 -C 4 -Alkynyl, C 2 -C 4 -haloalkynyl, C 3 -C 4 -Cycloalkyl and C 3 -C 4 - halocycloalkyl; or
[0106] CC 1 -C 3 -alkyl and C 1 -C3 -haloalkyl.
[0107] In an embodiment of each aspect of the present invention, R 6 , R 7 , R 8 , R 9 , R 10 , R 11 Independently selected from
[0108] A. Halogen, cyano, C 1 -C 3 -alkyl, C 1 -C 3 -haloalkyl, C 2 -C 4 -Alkenyl, C 2 -C 4 -haloalkenyl, C 2 -C 4 -Alkynyl, C 2 -C 4 -haloalkynyl, C 3 -C 4 -Cycloalkyl, C 3 -C 4 -halogenated cycloalkyl, C 1 -C 3 -alkoxy, C 1 -C 3 -haloalkoxy, C 1 -C 3 -alkylsulfonyl, and C 1 -C 3 - haloalkylsulfanyl; or
[0109] B. Halogen, cyano, C 1 -C 3 -alkyl, C 1 -C 3 -haloalkyl, C 3 -C 4 -Cycloalkyl, C 3 -C 4 -halogenated cycloalkyl, C 1 -C 3 -alkoxy, C 1 -C 3 -haloalkoxy, C 1 -C 3 -alkylsulfonyl, and C 1 -C 3 - haloalkylsulfanyl; or
[0110] C. Halogen, cyano, C 1 -C 3 -alkyl, C1 -C 3 -haloalkyl, C 3 -C 4 -cycloalkyl, C 3 -C 4 -halogenated cycloalkyl, C 1 -C 3 -alkoxy, and C 1 -C 3 -haloalkoxy; or
[0111] D. Halogen, C 1 -C 3 -alkyl, C 1 -C 3 -haloalkyl, C 1 -C 3 -alkoxy, and C 1 -C 3 -haloalkoxy; or
[0112] E. Halogen, C 1 -C 3 -alkyl, C 1 -C 3 -haloalkyl, C 1 -C 3 -alkoxy, and C 1 -C 3 -haloalkoxy; or
[0113] F. Halogen, C 1 -C 3 -alkyl, and C 1 -C 3 -haloalkyl and C 1 -C 3 -haloalkoxy; or
[0114] G. Fluorine, bromine, chlorine, methyl, ethyl, isopropyl, trifluoroethyl, trifluoromethyl, difluoromethyl, trifluoromethoxy, and difluoromethoxy.
[0115] In an embodiment of each aspect of the present invention, R 5 Independently selected from
[0116] A. Halogen, cyano, C 1 -C 3 -alkyl, C 1 -C 3 -haloalkyl, C 2 -C 4 -Alkenyl, C 2 -C 4 -haloalkenyl, C 2 -C 4 -Alkynyl, C 2-C 4 -haloalkynyl, C 3 -C 4 -cycloalkyl, C 3 -C 4 -halogenated cycloalkyl, C 1 -C 3 -alkoxy, C 1 -C 3 -haloalkoxy, C 1 -C 3 -alkylsulfonyl, and C 1 -C 3 -haloalkylsulfanyl; and if both C 1 -C 3 -haloalkoxy groups are substituted on adjacent atoms, then they can form a 5- or 6-membered ring together with the carbon atoms of the phenyl ring (e.g. -OC 1 -C 2 -haloalkyl (O-); or
[0117] B. Halogen, cyano, C 1 -C 3 -alkyl, C 1 -C 3 -haloalkyl, C 3 -C 4 -cycloalkyl, C 3 -C 4 -halogenated cycloalkyl, C 1 -C 3 -alkoxy, C 1 -C 3 -haloalkoxy, C 1 -C 3 -Alkylsulfonyl, C 1 -C 3 -haloalkylsulfanyl and -OC 1 -C 2 -haloalkylO-; or
[0118] C. Halogen, cyano, C 1 -C 3 -alkyl, C 1 -C 3 -haloalkyl, C 3 -C 4 -cycloalkyl, C 3 -C 4 -halogenated cycloalkyl, C 1 -C 3 -alkoxy, C 1 -C 3 -Haloalkoxy and -OC 1 -C 2 -haloalkylO-; or
[0119] D. Halogen, C 1 -C 3 -alkyl, C 1 -C 3 -haloalkyl, C 1 -C 3 -alkoxy, C 1 -C 3 -Haloalkoxy and -OC 1 -C 2 -haloalkylO-; or
[0120] E. Halogen, C 1 -C 3 -alkyl, C 1 -C 3 -haloalkyl, C 1 -C 3 -alkoxy, C 1 -C 3 -Haloalkoxy and -OC 1 -C 2 -haloalkylO-; or
[0121] F. Halogen, C 1 -C 3 -alkyl, and C 1 -C 3 -haloalkyl, C 1 -C 3 -haloalkoxy and -OC 1 -C 2 -haloalkylO-; or
[0122] G. Fluorine, bromine, chlorine, methyl, ethyl, isopropyl, trifluoroethyl, trifluoromethyl, difluoromethyl, trifluoromethoxy, difluoromethoxy, -OCF 2 O-and-OCF 2 CF 2 O-.
[0123] The present invention thus makes available compounds of formula (I) having substituents R as defined above 1 , R 2 , R 3 , R 4 , Q and Z (in all combinations / permutations). Thus, for example, compounds of formula (I) can be obtained, wherein R 1 For the first aspect (ie, R 1 CN, C(=S)NH 2 or C 1 -C 6 -haloalkyl); R 2 is Example B (ie, R2 is hydrogen); R 3 is Example A (ie, R 3 It is hydrogen, OH, halogen, C 1 -C 6 -alkyl, C 1 -C 6 -haloalkyl, C 3 -C 6 -cycloalkyl, C 3 -C 6 -halogenated cycloalkyl, C 1 -C 6 -alkoxy or C 1 -C 6 -haloalkoxy); R 4 is Example C (ie, R 4 is composed of 1 to 3 independently selected substituents R 5 substituted phenyl, 1 to 3 independently selected substituents R 6 substituted 5 or 6 membered monocyclic heteroaryl, or substituted by 1 to 3 independently selected substituents R 6 substituted 9- or 10-membered bicyclic); Q is Example C (ie, Q is a cyclic amine represented by Formula IIa, wherein p 1 and p 2 are all 1, X is hydrogen or hydroxyl; and Y is cyano, C 1 -C 6 -alkylsulfanyl-C 1 -C 6 -alkyl, C 1 -C 6 -Alkylsulfinyl-C 1 -C 6 -alkyl, C 1 -C 6 -Alkylsulfonyl-C 1 -C 6 -alkyl, R a R b NC(O),R e SO 2 NR f , R g ON=CR h , a 4- to 6-membered non-aromatic heterocyclic ring system in which one or two carbons are independently replaced by nitrogen, oxygen, sulfur or sulfonyl, a phenyl group, 1 to 3 independently selected substituents R 8 substituted phenyl, 5- or 6-membered monocyclic heteroaryl, or substituted by 1 to 3 independently selected substituents R 9 substituted 5 or 6 membered monocyclic heteroaryl); and Z is embodiment B (ie, Z is oxygen), wherein R a is Example C (ie, R aIt is hydrogen, C 1 -C 3 -alkyl, C 1 -C 3 -haloalkyl, or C 3 -C 4 -halogenated cycloalkyl); R b is Example D (ie, R b It is hydrogen, C 1 -C 3 -alkyl or C 1 -C 3 -haloalkyl); R e is Example C (ie, R e It is C 1 -C 3 -alkyl or C 1 -C 3 -haloalkyl); R f is Example A (ie, R f It is hydrogen, C 1 -C 3 -alkyl, C 1 -C 3 -haloalkyl, C 2 -C 4 -Alkenyl, C 2 -C 4 -haloalkenyl, C 2 -C 4 -Alkynyl, C 2 -C 4 -haloalkynyl, C 3 -C 4 -Cycloalkyl and C 3 -C 4 -halogenated cycloalkyl); R g is Example A (ie, R g It is hydrogen, C 1 -C 3 -alkyl, C 1 -C 3 -haloalkyl, C 2 -C 4 -Alkenyl, C 2 -C 4 -haloalkenyl, C 2 -C 4 -Alkynyl, C 2 -C 4 -haloalkynyl, C 3 -C 4 -Cycloalkyl and C 3 -C 4 -halogenated cycloalkyl); R h is Example C (ie, R h It is hydrogen, C1 -C 3 -alkyl, C 1 -C 3 -haloalkyl, or C 3 -C 4 -halogenated cycloalkyl); R 5 is Example C (ie, R 5 are independently selected from halogen, cyano, C 1 -C 3 -alkyl, C 1 -C 3 -haloalkyl, C 3 -C 4 -Cycloalkyl, C 3 -C 4 -halogenated cycloalkyl, C 1 -C 3 -alkoxy, C 1 -C 3 -haloalkoxy and -OC 1 -C 2 -haloalkylO-; R 8 is Example E (ie, R 8 independently selected from halogen, C 1 -C 3 -alkyl, C 1 -C 3 -haloalkyl, C 1 -C 3 -alkoxy, and C 1 -C 3 -haloalkoxy); and R 9 is Example F (ie, R 9 independently selected from fluoro, bromo, chloro, methyl, ethyl, isopropyl, trifluoroethyl, trifluoromethyl, difluoromethyl, trifluoromethoxy, and difluoromethoxy).
[0124] In an embodiment of each aspect of the present invention, the compound of formula (I) has
[0125] R 1 is CN, or C(=S)NH 2 ; CN is preferred;
[0126] R 2 H, halogen, C 1 -C 6 -alkoxy or C 1 -C 6 -haloalkoxy; preferably hydrogen;
[0127] R 3 It is H, OH, halogen, C 1 -C 6 -alkyl, C1 -C 6 -haloalkyl, C 3 -C 6 -cycloalkyl, C 3 -C 6 -halogenated cycloalkyl, C 1 -C 6 -alkoxy, or C 1 -C 6 -haloalkoxy; preferably C 1 -C 3 -alkyl, C 1 -C 3 - haloalkyl;
[0128] R 4 is phenyl, 1 to 3 independently selected substituents R 5 substituted phenyl, heteroaryl (which is a 5- or 6-membered monocyclic or a 9- or 10-membered bicyclic), substituted with 1 to 3 independently selected substituents R 6 Substituted heteroaryl (which is a 5- or 6-membered monocyclic or a 9- or 10-membered bicyclic);
[0129] Z is oxygen or sulfur; preferably oxygen
[0130] Q is a cyclic amine represented by formula IIa or a cyclic amine represented by formula IIb,
[0131]
[0132] Wherein the arrow indicates the connection to the carbonyl group;
[0133] p 1 is 0 or 1 and indicates the number of methylene groups;
[0134] p 2 is 0 or 1 and indicates the number of methylene groups;
[0135] q 1 is 1 and indicates the number of methylene groups;
[0136] q 2 is 1 and indicates the number of methylene groups;
[0137] X is hydrogen or hydroxy; preferably hydrogen;
[0138] Y is C 1 -C 6 -alkoxy-C 1 -C 6 -alkyl, C 1 -C 6 -alkylsulfanyl-C 1 -C 6 -alkyl, C 1 -C 6-Alkylsulfinyl-C 1 -C 6 -alkyl, C 1 -C 6 -Alkylsulfonyl-C 1 -C 6 -alkyl, C 1 -C 6 -Alkylsulfonyl (C 1 -C 6 -alkyl)amino, C 1 -C 6 -alkoxy-N=C 1 -C 6 -alkyl, a 4- to 6-membered non-aromatic heterocyclic ring system in which one or two carbons are independently replaced by nitrogen and sulfonyl, phenyl, substituted by 1 to 3 independently selected substituents R 8 substituted phenyl, 5- or 6-membered monocyclic heteroaryl, or substituted by 1 to 3 independently selected substituents R 9 substituted 5- or 6-membered monocyclic heteroaryl;
[0139] A is for C 1 -C 3 -alkylamino-sulfonyl, di(C 1 -C 3 -alkyl)amino-sulfonyl, phenyl, 1 to 3 independently selected substituents R 10 substituted phenyl, heteroaryl (which is a 5- or 6-membered monocyclic or a 9- or 10-membered bicyclic), or substituted by 1 to 3 independently selected substituents R 11 Substituted heteroaryl (which is a 5- or 6-membered monocyclic or a 9- or 10-membered bicyclic);
[0140] R 5 are independently selected from halogen, cyano, C 1 -C 6 -haloalkyl, C 1 -C 6 -alkoxy, C 1 -C 6 -haloalkoxy, C 1 -C 6 -alkylsulfonyl, and C 1 -C 6 -haloalkylsulfanyl; and if both C 1 -C 3 -haloalkoxy groups are substituted on adjacent atoms, then they can form a 5- or 6-membered ring together with the carbon atoms of the phenyl ring (e.g. -OC 1 -C 2 -haloalkylO-); and
[0141] R 6 independently selected from halogen, C1 -C 6 -alkyl, C 1 -C 6 -haloalkyl, C 1 -C 6 -alkoxy, C 1 -C 6 -haloalkoxy, C 1 -C 6 -alkylsulfonyl, and C 1 -C 6 - haloalkylsulfanyl;
[0142] R 8 independently selected from halogen, C 1 -C 6 -alkyl, C 1 -C 6 -haloalkyl, C 1 -C 6 -alkoxy, and C 1 -C 6 -haloalkoxy;
[0143] R 9 independently selected from halogen, C 1 -C 6 -alkyl, and C 1 -C 6 - haloalkyl;
[0144] R 10 independently selected from halogen, C 1 -C 6 -alkyl, C 1 -C 6 -haloalkyl, C 1 -C 6 -alkoxy, and C 1 -C 6 -haloalkoxy; and
[0145] R 11 independently selected from halogen, C 1 -C 6 -alkyl, and C 1 -C 6 -haloalkyl.
[0146] In an embodiment of each aspect of the present invention, the compound of formula (I) has as R 1 cyano or C(=S)NH 2 As R 2 Hydrogen, as R 3 is selected from hydrogen, C 1 -C 4 -alkyl and C 1-C 3 -haloalkyl; oxygen as Z, oxygen as R 4 substituted by 1 or 2 groups (independently selected from halogen, C 1 -C 4 -alkyl, C 1 -C 4 -haloalkyl, cyano, C 1 -C 4 -halogenated alkylsulfanyl, C 1 -C 4 -Alkylsulfonyl and C 1 -C 4 -haloalkoxy) substituted phenyl, one of the following: thienyl, pyridyl, and pyrazolyl-each substituted with 1 to 2 substituents (independently selected from fluorine, chlorine, methyl, ethyl, isopropyl, trifluoromethyl, difluoromethyl, trifluoromethoxy, and difluoromethoxy); as Q a cyclic amine represented by formula IIa, wherein p 1 and p 2 are all 1, X is hydrogen or hydroxyl; and Y is cyano, C 1 -C 4 -alkylsulfanyl-C 1 -C 4 -alkyl, C 1 -C 4 -Alkylsulfinyl-C 1 -C 4 -alkyl, C 1 -C 4 -Alkylsulfonyl-C 1 -C 4 -alkyl, 1,1-dioxo-1,2-thiazolidin-2-yl, N,N-di(C 1 -C 4 -alkyl)formamide, C 1 -C 4 -alkoxy-imino-C 1 -C 4 -alkyl, C 1 -C 4 -alkylsulfonylamide, phenyl, substituted by 1 to 3 groups (independently selected from halogen, C 1 -C 3 -alkyl, and C 1 -C 3 -haloalkyl and C 1 -C 3 -haloalkoxy) substituted phenyl, or 1 to 3 substituents (independently selected from halogen, C 1 -C 3 -alkyl, and C 1 -C 3 -haloalkyl and C 1-C 3 -haloalkoxy)-substituted 5- or 6-membered monocyclic heteroaryl.
[0147] In an embodiment of each aspect of the present invention, the compound of formula (I) has as R 1 cyano or C(=S)NH 2 As R 2 Hydrogen, as R 3 is selected from hydrogen, methyl, ethyl, trifluoromethyl, difluoromethyl, and pentafluoroethyl; oxygen as Z, R 4 phenyl substituted with 1 or 2 substituents (independently selected from iodine, bromine, chlorine, fluorine, methyl, trifluoromethyl, trifluoroethyl, trifluoromethoxy, trifluoromethylsulfanyl, cyano, and methylsulfonyl), or one of the following: thienyl, pyridyl, and pyrazolyl-each substituted with 1 to 2 substituents (independently selected from fluorine, chlorine, methyl, ethyl, isopropyl, trifluoromethyl, difluoromethyl, trifluoromethoxy, and difluoromethoxy); a cyclic amine represented by formula IIa as Q, wherein p 1 and p 2 are all 1, X is hydrogen or hydroxyl; and Y is cyano, C 1 -C 2 -alkylsulfanyl-C 1 -C 2 -alkyl, C 1 -C 2 -Alkylsulfinyl-C 1 -C 2 -alkyl, C 1 -C 2 -Alkylsulfonyl-C 1 -C 2 -alkyl, 1,1-dioxo-1,2-thiazolidin-2-yl, N,N-di(C 1 -C 2 -alkyl)formamide, C 1 -C 2 -alkoxy-imino-C 1 -C 2 -alkyl, C 1 -C 2 -alkylsulfonylamide, phenyl, phenyl substituted by 1 to 3 substituents independently selected from chlorine, methyl, difluoromethyl, trifluoroethyl, trifluoromethyl, and trifluoromethoxy, or a 5- or 6-membered monocyclic heteroaryl substituted by 1 to 3 substituents independently selected from chlorine, fluorine, methyl, trifluoroethyl, trifluoromethyl, and trifluoromethoxy.
[0148] In an embodiment of each aspect of the present invention, the compound of formula (I) has as R 1 The cyano group, as R 2 Hydrogen, as R3 is selected from hydrogen, methyl, ethyl, trifluoromethyl, difluoromethyl, and pentafluoroethyl; oxygen as Z, R 4 phenyl substituted with 1 or 2 substituents (independently selected from iodine, bromine, chlorine, fluorine, methyl, trifluoroethyl, trifluoromethyl, trifluoromethoxy, trifluoromethylsulfanyl, cyano, and methylsulfonyl), or one of the following: thienyl, pyridyl, and pyrazolyl-each substituted with 1 to 2 substituents (independently selected from fluorine, chlorine, methyl, ethyl, isopropyl, trifluoromethyl, difluoromethyl, trifluoromethoxy, and difluoromethoxy); a cyclic amine represented by formula IIa as Q, wherein p 1 and p 2 are all 1, X is hydrogen or hydroxyl; and Y is cyano, C 1 -C 2 -alkylsulfanyl-C 1 -C 2 -alkyl, C 1 -C 2 -Alkylsulfinyl-C 1 -C 2 -alkyl, C 1 -C 2 -Alkylsulfonyl-C 1 -C 2 -alkyl, 1,1-dioxo-1,2-thiazolidin-2-yl, N,N-di(C 1 -C 2 -alkyl)formamide, C 1 -C 2 -alkoxy-imino-C 1 -C 2 -alkyl, C 1 -C 2 -alkylsulfonylamide, phenyl, phenyl substituted by 1 to 3 substituents (independently selected from chlorine, methyl, difluoromethyl, trifluoroethyl, trifluoromethyl, and trifluoromethoxy), or a 5- or 6-membered monocyclic heteroaryl (selected from 1,2,4-oxadiazol-3-yl, pyridin-2-yl and 1,2,4-triazol-3-yl), each of which is substituted by 1 to 3 substituents (independently selected from chlorine, fluorine, methyl, trifluoroethyl, trifluoromethyl and trifluoromethoxy).
[0149] In an embodiment of each aspect of the present invention, the compound of formula (I) has as R 1 The cyano group, as R 2 Hydrogen, as R 3 is hydrogen, methyl, difluoromethyl or trifluoromethyl; oxygen as Z, R 4phenyl substituted with 1 or 2 substituents (independently selected from iodine, bromine, chlorine, fluorine, methyl, trifluoromethyl, trifluoromethoxy, trifluoromethylsulfanyl, cyano, and methylsulfonyl), or one of the following: thienyl, pyridyl, and pyrazolyl-each substituted with 1 to 3 substituents (independently selected from fluorine, chlorine, methyl, ethyl, isopropyl, trifluoromethyl, difluoromethyl, trifluoromethoxy, and difluoromethoxy); a cyclic amine represented by formula IIa as Q, wherein p 1 and p 2 are all 1, X is hydrogen; and Y is cyano, C 1 -C 2 -alkylsulfanyl-C 1 -C 2 -alkyl, C 1 -C 2 -Alkylsulfinyl-C 1 -C 2 -alkyl, C 1 -C 2 -Alkylsulfonyl-C 1 -C 2 -alkyl, 1,1-dioxo-1,2-thiazolidin-2-yl, N,N-di(C 1 -C 2 -alkyl)formamide, C 1 -C 2 -alkoxy-imino-C 1 -C 2 -alkyl, C 1 -C 2 -alkylsulfonylamide, phenyl, phenyl substituted by 1 to 3 substituents (independently selected from chlorine, methyl, difluoromethyl, trifluoromethyl, and trifluoromethoxy), or a 5- or 6-membered monocyclic heteroaryl (selected from 1,2,4-oxadiazol-3-yl, pyridin-2-yl and 1,2,4-triazol-3-yl), each of which is substituted by 1 to 3 substituents (independently selected from chlorine, fluorine, methyl, trifluoromethyl and trifluoromethoxy).
[0150] In an embodiment of each aspect of the present invention, the compound of formula (I) has as R 1 The cyano group, as R 2 Hydrogen, as R 3 is trifluoromethyl; oxygen as Z, R 4 a phenyl group substituted with a substituent selected from chlorine, fluorine, trifluoromethyl, a cyclic amine represented by the formula IIa as Q, wherein p 1 and p 2are all 1, X is hydrogen; and Y is a 5- or 6-membered monocyclic heteroaryl (selected from 1,2,4-oxadiazol-3-yl, pyridin-2-yl and 1,2,4-triazol-3-yl), wherein each heteroaryl is substituted with 1 to 3 substituents (independently selected from chlorine, fluorine, methyl, trifluoromethyl and trifluoromethoxy).
[0151] In an embodiment of each aspect of the present invention, the compound of formula (I) has as R 1 cyano or C(=S)NH 2 As R 2 Hydrogen, as R 3 is selected from hydrogen, C 1 -C 4 -alkyl and C 1 -C 3 -haloalkyl; oxygen as Z, oxygen as R 4 substituted by 1 or 2 groups (independently selected from halogen, C 1 -C 4 -alkyl, C 1 -C 4 -haloalkyl, cyano, C 1 -C 4 -halogenated alkylsulfanyl, C 1 -C 4 -Alkylsulfonyl and C 1 -C 4 -haloalkoxy) substituted phenyl, one of the following: thienyl, pyridyl, and pyrazolyl - each with 1 to 2 substituents (independently selected from halogen, C 1 -C 4 -alkyl, C 1 -C 4 -haloalkyl, and C 1 -C 4 -haloalkoxy) substituted; as Q is a cyclic amine represented by formula IIb, wherein p 1 and p 2 All are 1, A is cyano, C 1 -C 4 -Cyanoalkyl, C 1 -C 4 -haloalkyl, C 1 -C 4 -alkylsulfanyl-C 1 -C 4 -alkyl, C 1 -C 4 -Alkylsulfinyl-C 1 -C 4 -alkyl, C 1 -C 4 -Alkylsulfonyl-C 1 -C4 -alkyl, C 1 -C 4 -Alkoxycarbonyl, C 2 -C 4 -alkenyloxycarbonyl, phenyl, substituted by 1 to 3 groups (independently selected from halogen, C 1 -C 3 -alkyl, and C 1 -C 3 -haloalkyl and C 1 -C 3 -haloalkoxy) substituted phenyl, or 1 to 3 substituents (independently selected from halogen, C 1 -C 3 -alkyl, and C 1 -C 3 -haloalkyl and C 1 -C 3 -haloalkoxy)-substituted 5- or 6-membered monocyclic heteroaryl.
[0152] In an embodiment of each aspect of the present invention, the compound of formula (I) has as R 1 cyano or C(=S)NH 2 As R 2 Hydrogen, as R 3 is selected from hydrogen, methyl, ethyl, trifluoromethyl, difluoromethyl, and pentafluoroethyl; oxygen as Z, R 4 phenyl substituted with 1 or 2 substituents (independently selected from iodine, bromine, chlorine, fluorine, methyl, trifluoromethyl, trifluoromethoxy, trifluoromethylsulfanyl, cyano, and methylsulfonyl); a cyclic amine represented by formula IIb as Q, wherein p 1 and p 2 All are 1, A is cyano, C 1 -C 4 -Cyanoalkyl, C 1 -C 4 -haloalkyl, C 1 -C 4 -alkylsulfanyl-C 1 -C 4 -alkyl, C 1 -C 4 -Alkylsulfinyl-C 1 -C 4 -alkyl, C 1 -C 4 -Alkylsulfonyl-C 1 -C 4 -alkyl, C 1 -C 4 -Alkoxycarbonyl, C 2 -C 4-alkenyloxycarbonyl, phenyl, substituted by 1 to 3 groups (independently selected from halogen, C 1 -C 3 -alkyl, and C 1 -C 3 -haloalkyl and C 1 -C 3 -haloalkoxy) substituted phenyl, or 1 to 3 substituents (independently selected from halogen, C 1 -C 3 -alkyl, and C 1 -C 3 -haloalkyl and C 1 -C 3 -haloalkoxy)-substituted 5- or 6-membered monocyclic heteroaryl.
[0153] In an embodiment of each aspect of the present invention, the compound of formula (I) has as R 1 cyano or C(=S)NH 2 As R 2 Hydrogen, as R 3 is selected from hydrogen, methyl, or trifluoromethyl; oxygen as Z, R 4 phenyl substituted with 1 or 2 substituents (independently selected from iodine, bromine, chlorine, fluorine, methyl, trifluoromethyl, trifluoromethoxy, trifluoromethylsulfanyl, cyano, and methylsulfonyl); a cyclic amine represented by formula IIb as Q, wherein p 1 and p 2 All are 1, A is cyano, C 1 -C 4 -Cyanoalkyl, C 1 -C 4 -haloalkyl, C 1 -C 4 -alkylsulfanyl-C 1 -C 4 -alkyl, C 1 -C 4 -Alkylsulfinyl-C 1 -C 4 -alkyl, C 1 -C 4 -Alkylsulfonyl-C 1 -C 4 -alkyl, C 1 -C 4 -Alkoxycarbonyl, C 2 -C 4-alkenyloxycarbonyl, phenyl, phenyl substituted by 1 to 3 substituents independently selected from chlorine, methyl, difluoromethyl, trifluoromethyl, and trifluoromethoxy, or a 5- or 6-membered monocyclic heteroaryl substituted by 1 to 3 substituents independently selected from chlorine, methyl, difluoromethyl, trifluoromethyl, and trifluoromethoxy.
[0154] In an embodiment of each aspect of the present invention, the compound of formula (I) has as R 1 cyano or C(=S)NH 2 As R 2 Hydrogen, as R 3 is selected from hydrogen, methyl, difluoromethyl or trifluoromethyl; oxygen as Z, oxygen as R 4 phenyl substituted with 1 or 2 substituents (independently selected from iodine, bromine, chlorine, fluorine, methyl, trifluoromethyl, trifluoromethoxy, trifluoromethylsulfanyl, cyano, and methylsulfonyl); a cyclic amine represented by formula IIb as Q, wherein p 1 and p 2 All are 1, A is pyridinyl substituted with 1 to 3 substituents independently selected from chloro, fluoro, methyl, difluoromethyl, trifluoromethyl, and trifluoromethoxy.
[0155] In an embodiment of each aspect of the present invention, the compound of formula (I) has as R 1 cyano or C(=S)NH 2 As R 2 Hydrogen, as R 3 is selected from hydrogen, methyl, difluoromethyl or trifluoromethyl; oxygen as Z, oxygen as R 4 phenyl substituted with 1 or 2 substituents (independently selected from iodine, bromine, chlorine, fluorine, methyl, trifluoromethyl, trifluoromethoxy, trifluoromethylsulfanyl, cyano, and methylsulfonyl); a cyclic amine represented by formula IIb as Q, wherein p 1 and p 2 All are 1, A is pyridinyl substituted with 1 to 3 substituents independently selected from chloro, fluoro, trifluoromethyl, and trifluoromethoxy.
[0156] In an embodiment of each aspect of the present invention, the compound of formula (I) has as R 1 The cyano group; as R 2 Hydrogen; as R 3 is selected from methyl, difluoromethyl or trifluoromethyl; oxygen as Z, R 4 substituted by 1 or 2 groups (independently selected from halogen, C 1 -C 3 -alkyl, C 1 -C 3 -haloalkyl, C 1 -C3 -haloalkoxy) substituted phenyl, and if the two C 1 -C 3 -haloalkoxy groups are substituted on adjacent atoms, then they can form a 5- or 6-membered ring together with the carbon atoms of the phenyl ring (e.g. -OC 1 -C 2 -haloalkyl O-); a cyclic amine represented by formula IIa as Q, wherein p 1 and p 2 are all 1, X is hydrogen; and Y is a 5- or 6-membered monocyclic heteroaryl or substituted by 1 to 3 independently selected substituents R 9 Substituted 5- or 6-membered monocyclic heteroaryl.
[0157] In an embodiment of each aspect of the present invention, the compound of formula (I) has as R 1 The cyano group; as R 2 Hydrogen; as R 3 is selected from methyl, difluoromethyl or trifluoromethyl; oxygen as Z, R 4 substituted by 1 or 2 groups (independently selected from halogen, C 1 -C 3 -alkyl, C 1 -C 3 -haloalkyl, C 1 -C 3 -alkoxy, C 1 -C 3 -Alkylsulfonyl, C 1 -C 3 -haloalkylsulfanyl, cyano, C 1 -C 3 -haloalkoxy) substituted phenyl, and if the two C 1 -C 3 -haloalkoxy groups are substituted on adjacent atoms, then they can form a 5- or 6-membered ring together with the carbon atoms of the phenyl ring (e.g. -OC 1 -C 2 -haloalkyl O-); a cyclic amine represented by formula IIa as Q, wherein p 1 and p 2 are 1, X is hydrogen; and Y is 1 to 3 independently selected substituents R 9 Substituted oxadiazolyl.
[0158] In an embodiment of each aspect of the present invention, the compound of formula (I) has as R 1 The cyano group; as R 2 Hydrogen; as R 3 is selected from methyl, difluoromethyl or trifluoromethyl; oxygen as Z, R 4substituted by 1 or 2 groups (independently selected from halogen, C 1 -C 3 -haloalkyl, C 1 -C 3 -haloalkoxy) substituted phenyl, and if the two C 1 -C 3 -haloalkoxy groups are substituted on adjacent atoms, then they can form a 5- or 6-membered ring together with the carbon atoms of the phenyl ring (e.g. -OC 1 -C 2 -haloalkyl O-); a cyclic amine represented by the formula IIa as Q, wherein p1 and p2 are both 1, X is hydrogen; and Y is 1,2,4-oxadiazol-3-yl substituted by 1 to 2 substituents (independently selected from methyl, ethyl, and isopropyl).
[0159] In an embodiment of each aspect of the present invention, the compound of formula (I) has as R 1 The cyano group; as R 2 Hydrogen; as R 3 is selected from methyl, difluoromethyl or trifluoromethyl; oxygen as Z, R 4 substituted by 1 or 2 groups (independently selected from halogen, C 1 -C 3 -haloalkyl, C 1 -C 3 -haloalkoxy) substituted phenyl, and if the two C 1 -C 3 -haloalkoxy groups are substituted on adjacent atoms, then they can form a 5- or 6-membered ring together with the carbon atoms of the phenyl ring (e.g. -OC 1 -C 2 -haloalkyl (O-); as Q, a cyclic amine represented by the formula IIb, wherein q1 and q2 are both 1 and A is a pyridyl group substituted with 1 to 3 independently selected halogen substituents.
[0160] In an embodiment of each aspect of the present invention, the compound of formula (I) has as R 1 The cyano group; as R 2 Hydrogen; as R 3 is selected from methyl, difluoromethyl or trifluoromethyl; oxygen as Z, oxygen as R 4 substituted by 1 or 2 groups (independently selected from halogen, C 1 -C 3 -haloalkyl, C 1 -C 3 -haloalkoxy) substituted phenyl, and if the two C 1 -C 3-haloalkoxy groups are substituted on adjacent atoms, then they can form a 5- or 6-membered ring together with the carbon atoms of the phenyl ring (e.g. -OC 1 -C 2 -haloalkyl (O-); as Q, a cyclic amine represented by the formula IIb, wherein q1 and q2 are both 1 and A is a pyridyl group substituted by 1 to 2 substituents independently selected from chlorine, fluorine and bromine.
[0161] In an embodiment of each aspect of the present invention, the compound of formula (I) has as R 1 The cyano group; as R 2 Hydrogen; as R 3 trifluoromethyl; oxygen as Z, as R 4 substituted by 1 or 2 groups (independently selected from halogen, C 1 -C 3 -haloalkyl, C 1 -C 3 -haloalkoxy) substituted phenyl; as Q a cyclic amine represented by the formula IIa, wherein p1 and p2 are both 1, X is hydrogen; and Y is C 1 -C 3 -alkoxymethyl, C 1 -C 3 -alkoxy N=CH-, C 1 -C 3 -alkylsulfanylmethyl, C 1 -C 3 -alkylsulfinylmethyl, C 1 -C 3 -alkylsulfonylmethyl, 1,1-dioxo-thiazolidinyl, 1-methylpyrazolyl, C 1 -C 3 -Alkylsulfonyl-C 1 -C 3 -alkylamino, methyl-1,2,4-oxadiazolyl, or methylisoxazolyl.
[0162] In an embodiment of each aspect of the present invention, the compound of formula (I) has as R 1 The cyano group; as R 2 Hydrogen; as R 3 trifluoromethyl; oxygen as Z, as R 4 substituted by 1 or 2 groups (independently selected from halogen, C 1 -C 3 -haloalkyl, C 1 -C 3 -haloalkoxy) substituted phenyl; and as Q a cyclic amine represented by formula IIa, wherein p1 and p2 are both 1, X is hydrogen; and Y is -CH 2 SCH2 CH 3 、-CH 2 S(=O)CH 2 CH 3 、-CH 2 SO 2 CH 2 CH 3 , 1,1-dioxo-1,2-thiazolidin-2-yl, 1-methylpyrazol-4-yl, methyl(methylsulfonyl)-amino (i.e., CH 3 S(O) 2 -(CH 3 )N-, 3-methyl-1,2,4-oxadiazol-5-yl, 1-methylpyrazol-3-yl or 3-methylisoxazol-5-yl.
[0163] In an embodiment of each aspect of the present invention, the compound of formula (I) has as R 1 The cyano group; as R 2 Hydrogen; as R 3 trifluoromethyl; oxygen as Z, as R 4 One of the following: 2,1,3-benzoxadiazolyl, 1,3-benzoxazolyl, thienyl, pyridyl, and pyrazolyl-each substituted by 1 to 3 groups (independently selected from halogen, C 1 -C 4 -alkyl, C 1 -C 4 -haloalkyl, and C 1 -C 4 -haloalkoxy); and a cyclic amine represented by formula IIa as Q, wherein p1 and p2 are both 1, X is hydrogen; and Y is 1,2,4-oxadiazol-3-yl substituted by 1 to 2 substituents (independently selected from methyl, ethyl, and isopropyl).
[0164] In an embodiment of each aspect of the present invention, the compound of formula (I) has as R 1 The cyano group; as R 2 Hydrogen; as R 3 trifluoromethyl; oxygen as Z, as R 4 One of the following: thienyl, pyridyl, and pyrazolyl-each substituted by 1 to 3 groups (independently selected from halogen, C 1 -C 4 -alkyl, C 1 -C 4 -haloalkyl, and C 1 -C 4-haloalkoxy) substituted; and as Q, a cyclic amine represented by the formula IIa, wherein p1 and p2 are both 1, X is hydrogen; and Y is 5-methyl-1,2,4-oxadiazol-3-yl.
[0165] In an embodiment of each aspect of the present invention, the compound of formula (I) has as R 1 cyano or C(=S)NH 2 As R 2 Hydrogen; as R 3 trifluoromethyl; oxygen or sulfur as Z, 4 having 1 to 2 substituents (independently selected from halogen and C 1 -C 4 -haloalkyl) phenyl; and as Q a cyclic amine represented by formula IIa, wherein p1 and p2 are both 1, X is hydrogen; and Y is 1,2,4-oxadiazol-3-yl substituted with 1 to 2 substituents independently selected from methyl, ethyl, and isopropyl.
[0166] In an embodiment of each aspect of the present invention, the compound of formula (I) has as R 1 cyano or C(=S)NH 2 As R 2 Hydrogen; as R 3 trifluoromethyl; oxygen as Z, as R 4 a phenyl group having 1 to 2 substituents independently selected from fluorine and trifluoromethyl; and a cyclic amine represented by the formula IIa as Q, wherein p1 and p2 are both 1, X is hydrogen; and Y is 5-methyl-1,2,4-oxadiazol-3-yl.
[0167] In an embodiment of each aspect of the present invention, the compound of formula (I) has as R 1 The cyano group; as R 2 Hydrogen; as R 3 trifluoromethyl or difluoromethyl; oxygen as Z, oxygen as R 4 phenyl, thienyl, pyridyl, and pyrazolyl-each substituted by 1 to 3 groups (independently selected from halogen, C 1 -C 4 -alkyl, C 1 -C 4 -haloalkyl, and C 1 -C 4 -haloalkoxy) and if both C 1 -C 3 -haloalkoxy groups are substituted on adjacent atoms of the phenyl ring, then they can form a 5- or 6-membered ring together with the carbon atoms of the phenyl ring (such as -OC 1 -C 2-haloalkyl O-); and as Q a cyclic amine represented by formula IIa, wherein p1 and p2 are both 1, X is hydrogen; and Y is C 1 -C 3 -alkyl-substituted 1,2,4-triazolyl.
[0168] In an embodiment of each aspect of the present invention, the compound of formula (I) has as R 1 The cyano group; as R 2 Hydrogen; as R 3 trifluoromethyl or difluoromethyl; oxygen as Z, oxygen as R 4 phenyl, thienyl, pyridyl, and pyrazolyl-each substituted by 1 to 3 groups (independently selected from halogen, C 1 -C 4 -alkyl, C 1 -C 4 -haloalkyl, and C 1 -C 4 -haloalkoxy) and if both C 1 -C 3 -haloalkoxy groups are substituted on adjacent atoms of the phenyl ring, then they can form a 5- or 6-membered ring together with the carbon atoms of the phenyl ring (such as -OC 1 -C 2 -haloalkyl O-); and as Q, a cyclic amine represented by the formula IIa, wherein p1 and p2 are both 1, X is hydrogen; and Y is 1-methyl-1,2,4-triazol-3-yl.
[0169] In an embodiment of each aspect of the present invention, the compound of formula (I) has as R 1 The cyano group; as R 2 Hydrogen; as R 3 trifluoromethyl; oxygen as Z, as R 4 substituted by 1 or 2 groups (independently selected from halogen, and C 1 -C 3 -haloalkyl) substituted phenyl; and as Q a cyclic amine represented by formula IIb, wherein q1 and q2 are both 1 and A is C 1 -C 3 -alkylamino-sulfonyl, di(C 1 -C 3 -alkyl)amino-sulfonyl, pyrazol-3-yl, or oxadiazolyl.
[0170] In an embodiment of each aspect of the present invention, the compound of formula (I) has as R 1 The cyano group; as R 2 Hydrogen; as R 3 trifluoromethyl; oxygen as Z, as R4 phenyl substituted by 1 or 2 substituents (independently selected from fluorine and trifluoromethyl); and a cyclic amine represented by formula IIb as Q, wherein q1 and q2 are both 1 and A is methylamino-sulfonyl, dimethylamino-sulfonyl, 1-methylpyrazol-3-yl, 5-methyl-1,2,4-oxadiazol-3-yl or 3-methyl-1,2,4-oxadiazol-5-yl.
[0171] In an embodiment of each aspect of the present invention, the compound of formula (I) has as R 1 The cyano group; as R 2 Hydrogen; as R 3 trifluoromethyl; oxygen as Z, substituted by 1 to 2 groups (independently selected from halogen and C 1 -C 4 -haloalkyl)-substituted phenyl; and as Q, a cyclic amine represented by the formula IIa, wherein p1 and p2 are both 1, X is a hydroxyl group; and Y is a phenyl disubstituted with 1 to 2 halogens.
[0172] In an embodiment of each aspect of the present invention, the compound of formula (I) has as R 1 The cyano group; as R 2 Hydrogen; as R 3 trifluoromethyl; oxygen as Z, phenyl substituted with 1 to 2 substituents (independently selected from fluorine and trifluoromethyl) as; and a cyclic amine represented by formula IIa as Q, wherein p1 and p2 are both 1, X is hydroxyl; and Y is phenyl substituted with chlorine.
[0173] In an embodiment of each aspect of the present invention, the compound of formula (I) has as R 1 The cyano group; as R 2 Hydrogen; as R 3 trifluoromethyl; oxygen as Z, substituted by 1 to 2 groups (independently selected from halogen and C 1 -C 4 -haloalkyl) substituted phenyl; and as Q a cyclic amine represented by formula IIa, wherein p1 and p2 are both zero, X is hydrogen; and Y is C 1 -C 3 -alkylsulfanylmethyl, C 1 -C 3 -alkylsulfonylmethyl or oxadiazolyl.
[0174] In an embodiment of each aspect of the present invention, the compound of formula (I) has as R 1 The cyano group; as R 2 Hydrogen; as R 3as trifluoromethyl; oxygen as Z, as trifluoromethyl-substituted phenyl; and as Q a cyclic amine represented by formula IIa, wherein p1 and p2 are both zero, X is hydrogen; and Y is n-propylsulfonylmethyl.
[0175] In a second aspect, the present invention makes available a composition comprising a compound of formula (I) as defined in the first aspect, one or more adjuvants and diluents, and optionally one or more other active ingredients.
[0176] In a third aspect, the present invention makes available a method for combating and controlling insects, mites, nematodes or molluscs, which method comprises applying an insecticidal, acaricidal, nematicidal or molluscicidal effective amount of a compound as defined in the first aspect or a composition as defined in the second aspect to the pest, the location of the pest, or a plant susceptible to attack by the pest.
[0177] In a fourth aspect, the present invention makes available a method for protecting plant propagation material from attack by insects, mites, nematodes or molluscs, the method comprising treating the propagation material or the site where the propagation material is planted with an effective amount of a compound of formula (I) as defined in the first aspect or a composition as defined in the second aspect.
[0178] In a fifth aspect, the present invention makes it possible to obtain a plant propagation material, such as a seed, which comprises a compound of formula (I) as defined in the first aspect or a composition as defined in the second aspect, or is treated with the compound or the composition, or has the compound or the composition adhered to it.
[0179] In another aspect, the present invention provides a method for controlling parasites in or on an animal in need thereof, the method comprising administering an effective amount of a compound of the first aspect. The present invention further provides a method for controlling parasites on the body of an animal in need thereof, the method comprising administering an effective amount of a compound of formula (I) as defined in the first aspect. The present invention further provides a method for preventing and / or treating a disease transmitted by parasites on the body, the method comprising administering an effective amount of a compound of formula (I) as defined in the first aspect to an animal in need thereof.
[0180] Compounds of formula (I) can be prepared by those skilled in the art according to known methods. More specifically, compounds of formula I and I'a and intermediates thereof can be prepared as described below in the schemes and examples. For the sake of clarity, certain stereocenters are not specified and are not intended to limit the teachings of these schemes in any way.
[0181] The process according to the invention for preparing compounds of formula (I) is carried out by methods known to those skilled in the art.
[0182] The compounds of formula (I) are novel and can be prepared by reacting an acid III (wherein R is 1-hydroxy-1-(4-(dimethylamino)methylene)-1H-1,2,3-triazolo[4,5-b]pyridinium 3-oxide hexafluorophosphate) according to Scheme 1 using a known amide coupling reagent such as 1-[bis(dimethylamino)methylene]-1H-1,2,3-triazolo[4,5-b]pyridinium 3-oxide hexafluorophosphate (HATU) and a base such as Hünig's base in a suitable solvent such as dimethylformamide (DMF) or dimethylacetamide (DMA). 1 , R 2 , R 3 , R 4 and Z are as previously defined) with amine IV-a or IV-b (wherein X, Y, A, p 1 、p 2 ,q 1 and q 2 The piperidine IV-a or piperazine IV-b is commercially available, known from the literature or can be prepared by a person skilled in the art.
[0183] Scenario 1:
[0184]
[0185] Alternatively, compounds of formula (I) can be prepared by reacting an acyl chloride V (wherein R 1 , R 2 , R 3 , R 4 and Z are as previously defined) with amine IV-a or IV-b (wherein X, Y, A, p 1 、p 2 ,q 1 and q 2 is as defined previously).
[0186] Scenario 2:
[0187]
[0188] Acid chlorides V can be prepared according to Scheme 3 from the corresponding acids III by treatment with for example oxalyl chloride or thionyl chloride in the presence of a catalytic amount of DMF in an inert solvent such as DCM or THF at temperatures between 20°C and 100°C, preferably at 25°C.
[0189] Solution 3:
[0190]
[0191] Acid III can be prepared by hydrolyzing the corresponding ester VI (wherein R 1 , R 2 , R 3 , R 4 and Z are as defined previously and R 5 =C 1 -C 6 -alkyl).
[0192] Solution 4:
[0193]
[0194] Esters VI wherein Z = oxygen can be prepared by reacting a pyridone VII (wherein R 1 , R 2 , R 3 , R 4 and R 5 is as previously defined) and an alkylating agent VIII (wherein LG 1 The reaction is carried out using a leaving group such as a halogen, for example bromine, chloride, iodine, or mesylate. It may be advantageous to add sodium iodide or a phase transfer catalyst such as tetrabutylammonium bromide or tetrabutylammonium iodide.
[0195] Solution 5:
[0196]
[0197] Alternatively, according to Scheme 6, esters VI where Z = oxygen can be prepared by reacting a pyridine IX (where R 1 , R 2 , R 3 , R 5 is as defined previously and LG 2 The ester VI wherein Z=sulfur can be prepared by reacting a pyridine IX (wherein R is a leaving group such as a halogen (e.g., fluorine, bromine, chloride, iodine) or a mesylate) with an alcohol X, and ... halogen (e.g., fluorine, bromine, chloride, iodine) or a mesylate) with an alcohol X, and Z=sulfur can be prepared by reacting a pyridine IX (wherein R is a leaving group such as fluorine, bromine, chloride, iodine) with an alcohol X, and Z=sulfur can be prepared by reacting 1 , R 2 , R 3 , R 5 is as defined previously and LG2 The thiol XI is reacted with a leaving group such as a halogen (eg fluorine, bromine, chlorine, iodine) or a mesylate.
[0198] Solution 6:
[0199]
[0200] Alternatively, according to Scheme 7, compounds of formula (I) wherein Z = oxygen can be obtained by reacting pyridone XII (wherein R 1 , R 2 , R 3 and Q is as previously defined) with an alkylating agent VIII (wherein LG 1 The reaction is carried out with a leaving group such as a halogen, for example bromine, chloride, iodine, or mesylate. It may be advantageous to add sodium iodide or a phase transfer catalyst such as tetrabutylammonium bromide or tetrabutylammonium iodide.
[0201] Solution 7:
[0202]
[0203] Alternatively, according to Scheme 8, compounds of formula (I) wherein Z = oxygen can be prepared by reacting a pyridine XIII (wherein R 1 , R 2 , R 3 and Q are as defined previously and LG 2 The ester VI wherein Z=sulfur can be prepared by reacting a pyridine XIII (wherein R is a leaving group such as a halogen (e.g., fluorine, bromine, chloride, iodine) or a mesylate) with an alcohol X, and ... halogen (e.g., fluorine, bromine, chloride, iodine) or a mesylate) with an alcohol X, and Z=sulfur can be prepared by reacting a pyridine XIII (wherein R is a leaving group such as fluorine, bromine, chloride, iodine) with an alcohol X in the presence of a base (e.g., 1 , R 2 , R 3 and Q are as defined previously and LG 2 The thiol XI is reacted with a leaving group such as a halogen (eg fluorine, bromine, chlorine, iodine) or a mesylate.
[0204] Solution 8:
[0205]
[0206] According to Scheme 9, a compound having Formula XIII (wherein R 1 , R 2, R 3 and Q are as defined previously and LG 2 is a leaving group) can be obtained by treating pyridone XII (wherein R 1 , R 2 , R 3 and Q are as defined previously).
[0207] Solution 9:
[0208]
[0209] Pyridone XII (where R 1 , R 2 , R 3 and Q are as previously defined) can be prepared by reacting an acid XIV (wherein R 1 , R 2 and R 3 is as previously defined) with amine IV-a or IV-b (wherein X, Y, A, p 1 、p 2 ,q 1 and q 2 is as defined previously).
[0210] Solution 10:
[0211]
[0212] Alternatively, a compound of Formula XII (wherein R 1 , R 2 , R 3 and Q is as defined previously) can be prepared by reacting an acyl chloride XV (wherein R 1 , R 2 and R 3 is as previously defined) is reacted with an amine IV-a or IV-b.
[0213] Solution 11:
[0214]
[0215] Acid chloride XV (where R 1 , R 2 and R 3is as defined previously) can be prepared according to Scheme 12 from the corresponding acid XIV (wherein R 1 , R 2 and R 3 is as defined previously).
[0216] Solution 12:
[0217]
[0218] Acid XIV (where R 1 , R 2 and R 3 is as defined previously) can be prepared by hydrolyzing the corresponding ester XVI (wherein R 1 , R 2 , R 3 and R 5 is as defined previously). An ester of formula XVI (wherein R 1 , R 2 , R 3 and R 5 is as previously defined) is known in the literature, for example Y. Xie et al., Pest Manag. Sci. [Pest Management Science] 2017, 73, 945-952, or can be prepared by a person skilled in the art.
[0219] Solution 13:
[0220]
[0221] Compounds of formula (I) according to the following groups 1 to 90 can be prepared according to the methods described above. The following examples are intended to illustrate the invention and show preferred compounds of formula (I) in the form of compounds of formula (Ia).
[0222]
[0223] Each of the groups 1 to 54 following Table M below includes 1752 compounds of formula (Ia) wherein R 1 , R 3 , R 5 and Z have the values given in each row of Table M, and Y and X have the values given in the associated groups 1 to 54.
[0224] Thus, compound 1.1 corresponds to a compound of formula (Ia) in which R 1 , R 3 , R 5 and Z is as defined in row 1 of Table M and wherein Y and X are as defined in Group 1; Compound 14.14 corresponds to a compound having formula (Ia) wherein R 1 , R 3 , R 5 and Z are as defined in row 14 of Table M and wherein Y and X are as defined in Group 14; and so on.
[0225] Table M:
[0226]
[0227]
[0228]
[0229]
[0230]
[0231]
[0232]
[0233]
[0234]
[0235]
[0236]
[0237]
[0238]
[0239]
[0240]
[0241]
[0242]
[0243]
[0244]
[0245]
[0246]
[0247]
[0248] Group 1: This group discloses 1752 compounds 1.1 to 1.1752 of formula (Ia) wherein Y is 5-methyl-1,2,4-oxadiazol-3-yl, X is hydrogen and R 1 , R 3 , R 5 and Z are as defined in Table M. For example, compound No. 1.1 has the following structure:
[0249]
[0250] Group 2 : This group discloses 1752 compounds 2.1 to 2.1752 of formula (Ia) wherein Y is 1-methyl-1,2,4-triazol-3-yl, X is hydrogen and R 1 , R 3 , R 5 and Z are as defined in Table M.
[0251] Group 3 : This group discloses 1752 compounds 3.1 to 3.1752 of formula (Ia) wherein Y is 3,5-dichloropyridin-2-yl, X is hydrogen and R 1 , R 3 , R 5 and Z are as defined in Table M.
[0252] Group 4 : This group discloses 1752 compounds 4.1 to 4.1752 of formula (Ia) wherein Y is 3-chloro-5-(trifluoromethyl)pyridin-2-yl, X is hydrogen and R 1 , R 3 , R 5 and Z are as defined in Table M.
[0253] Group 5 : This group discloses 1752 compounds 5.1 to 5.1752 of formula (Ia) wherein Y is phenyl, X is hydrogen and R 1 , R 3 , R 5 and Z are as defined in Table M.
[0254] Group 6: This group discloses 1752 compounds 6.1 to 6.1752 of formula (Ia) wherein Y is phenyl, X is hydroxyl and R 1 , R 3 , R 5 and Z are as defined in Table M.
[0255] Group 7 : This group discloses 1752 compounds 7.1 to 7.1752 of formula (Ia) wherein Y is 4-chloro-phenyl-1-yl, X is hydrogen and R 1 , R 3 , R 5 and Z are as defined in Table M.
[0256] Group 8 : This group discloses 1752 compounds 8.1 to 8.1752 of formula (Ia) wherein Y is 4-chloro-phenyl-1-yl, X is hydroxyl and R 1 , R 3 , R 5 and Z are as defined in Table M.
[0257] Group 9 : This group discloses 1752 compounds 9.1 to 9.1752 of formula (Ia) wherein Y is methylsulfanylmethyl, X is hydrogen and R 1 , R 3 , R 5 and Z are as defined in Table M.
[0258] Group 10 : This group discloses 1752 compounds 10.1 to 10.1752 of formula (Ia) wherein Y is methylsulfinylmethyl, X is hydrogen and R 1 , R 3 , R 5 and Z are as defined in Table M.
[0259] Group 11 : This group discloses 1752 compounds 11.1 to 11.1752 of formula (Ia) wherein Y is methylsulfonylmethyl, X is hydrogen and R 1 , R 3 , R 5 and Z are as defined in Table M.
[0260] Group 12 : This group discloses 1752 compounds 12.1 to 12.1752 of formula (Ia) wherein Y is ethylsulfanylmethyl, X is hydrogen and R 1 , R 3 , R 5 and Z are as defined in Table M.
[0261] Group 13 : This group discloses 1752 compounds 13.1 to 13.1752 having formula (Ia) wherein Y is ethylsulfinylmethyl, X is hydrogen and R 1 , R 3 , R 5 and Z are as defined in Table M.
[0262] Group 14 : This group discloses 1752 compounds 14.1 to 14.1752 having formula (Ia) wherein Y is ethylsulfonylmethyl, X is hydrogen and R 1 , R 3 , R 5 and Z are as defined in Table M.
[0263] Group 15 : This group discloses 1752 compounds 15.1 to 15.1752 having formula (Ia), wherein Y is 1,1-dioxo-1,2-thiazolidin-2-yl, X is hydrogen and R 1 , R 3 , R 5 and Z are as defined in Table M.
[0264] Group 16 : This group discloses 1752 compounds 16.1 to 16.1752 of formula (Ia) wherein Y is (E)-methoxyiminomethyl, X is hydrogen and R 1 , R 3 , R 5 and Z are as defined in Table M.
[0265] Group 17 : This group discloses 1752 compounds 17.1 to 17.1752 having formula (Ia) wherein Y is (E)-ethoxyiminomethyl, X is hydrogen and R 1 , R 3 , R 5 and Z are as defined in Table M.
[0266] Group 18 : This group discloses 1752 compounds 18.1 to 18.1752 having formula (Ia) wherein Y is dimethylcarbamoyl, X is hydrogen and R 1 , R 3 , R 5 and Z are as defined in Table M.
[0267] Group 19 : This group discloses 1752 compounds 19.1 to 19.1752 of formula (Ia) wherein Y is methanesulfonylamide, X is hydrogen and R 1 , R3 , R 5 and Z are as defined in Table M.
[0268] Group 20 : This group discloses 1752 compounds 20.1 to 20.1752 of formula (Ia) wherein Y is cyano, X is hydrogen and R 1 , R 3 , R 5 and Z are as defined in Table M.
[0269] Group 21 : This group discloses 1752 compounds 21.1 to 21.1752 of formula (Ia) wherein Y is ethoxymethyl, X is hydrogen and R 1 , R 3 , R 5 and Z are as defined in Table M.
[0270] Group 22 : This group discloses 1752 compounds 22.1 to 22.1752 of formula (Ia) wherein Y is 2-methyl-1,2,4-triazol-3-yl, X is hydrogen and R 1 , R 3 , R 5 and Z are as defined in Table M.
[0271] Group 23 : This group discloses 1752 compounds 23.1 to 23.1752 of formula (Ia) wherein Y is 1-methylpyrazol-4-yl, X is hydrogen and R 1 , R 3 , R 5 and Z are as defined in Table M.
[0272] Group 24 : This group discloses 1752 compounds 24.1 to 24.1752 of formula (Ia) wherein Y is 4-methylpyrazol-1-yl, X is hydrogen and R 1 , R 3 , R 5 and Z are as defined in Table M.
[0273] Group 25 : This group discloses 1752 compounds of formula (Ia) 25.1 to 25.1752, wherein Y is 5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl, X is hydrogen and R 1 , R 3 , R 5 and Z are as defined in Table M.
[0274] Group 26: This group discloses 1752 compounds 26.1 to 26.1752 having formula (Ia) wherein Y is methyl(methylsulfonyl)amino]piperidin-1-yl, X is hydrogen and R 1 , R 3 , R 5 and Z are as defined in Table M.
[0275] Group 27 : This group discloses 1752 compounds of formula (Ia) 27.1 to 27.1752, wherein Y is (methylsulfonyl)amino]piperidin-1-yl, X is hydrogen and R 1 , R 3 , R 5 and Z are as defined in Table M.
[0276] Group 28: This group discloses 1752 compounds 28.1 to 28.1752 of formula (Ia) wherein Y is 3-methyl-1,2,4-oxadiazol-5-yl, X is hydrogen and R1, R3, R5 and Z are as defined in Table M.
[0277] Group 29: This group discloses 1752 compounds 29.1 to 29.1752 of formula (Ia) wherein Y is 1-methylpyrazol-3-yl, X is hydrogen and R1, R3, R5 and Z are as defined in Table M.
[0278] Group 30: This group discloses 1752 compounds 30.1 to 30.1752 of formula (Ia) wherein Y is 3-methylisoxazol-5-yl, X is hydrogen and R1, R3, R5 and Z are as defined in Table M.
[0279] Group 31: This group discloses 1752 compounds 31.1 to 31.1752 of formula (Ia) wherein Y is 2-oxooxazolidin-3-yl, X is hydrogen and R1, R3, R5 and Z are as defined in Table M.
[0280] Group 32: This group discloses 1752 compounds 32.1 to 32.1752 of formula (Ia) wherein Y is 2-oxopyrrolidin-1-yl, X is hydrogen and R1, R3, R5 and Z are as defined in Table M.
[0281] Group 33: This group discloses 1752 compounds 33.1 to 33.1752 of formula (Ia) wherein Y is 1,2,3-triazol-2-yl, X is hydrogen and R1, R3, R5 and Z are as defined in Table M.
[0282] Group 34: This group discloses 1752 compounds 34.1 to 34.1752 of formula (Ia) wherein Y is 1,2,4-triazol-3-yl, X is hydrogen and R1, R3, R5 and Z are as defined in Table M.
[0283] Group 35: This group discloses 1752 compounds 35.1 to 35.1752 of formula (Ia) wherein Y is 2-oxo-5,5-dimethyl-oxazolidin-3-yl, X is hydrogen and R1, R3, R5 and Z are as defined in Table M.
[0284] Group 36: This group discloses 1752 compounds 36.1 to 36.1752 of formula (Ia) wherein Y is methylamino-carbonyl, X is hydrogen and R1, R3, R5 and Z are as defined in Table M.
[0285] Group 37: This group discloses 1752 compounds 37.1 to 37.1752 of formula (Ia) wherein Y is 2-oxopiperidin-1-yl, X is hydrogen and R1, R3, R5 and Z are as defined in Table M.
[0286] Group 38: This group discloses 1752 compounds 38.1 to 38.1752 of formula (Ia) wherein Y is acetamido, X is hydrogen and R1, R3, R5 and Z are as defined in Table M.
[0287] Group 39: This group discloses 1752 compounds 39.1 to 39.1752 of formula (Ia) wherein Y is 2-methylpropionylamino, X is hydrogen and R1, R3, R5 and Z are as defined in Table M.
[0288] Group 40: This group discloses 1752 compounds 40.1 to 40.1752 of formula (Ia) wherein Y is 1,2,3-triazol-1-yl, X is hydrogen and R1, R3, R5 and Z are as defined in Table M.
[0289] Group 41: This group discloses 1752 compounds 41.1 to 41.1752 of formula (Ia) wherein Y is 5-methylisoxazol-3-yl, X is hydrogen and R1, R3, R5 and Z are as defined in Table M.
[0290] Group 42: This group discloses 1752 compounds 42.1 to 42.1752 of formula (Ia) wherein Y is 2-oxoazetidin-1-yl, X is hydrogen and R1, R3, R5 and Z are as defined in Table M.
[0291] Group 43: This group discloses 1752 compounds 43.1 to 43.1752 of formula (Ia) wherein Y is 3-methylpyrazol-1-yl, X is hydrogen and R1, R3, R5 and Z are as defined in Table M.
[0292] Group 44: This group discloses 1752 compounds 44.1 to 44.1752 of formula (Ia) wherein Y is 1-methyl-5-oxo-4H-pyrazol-3-yl, X is hydrogen and R1, R3, R5 and Z are as defined in Table M.
[0293] Group 45: This group discloses 1752 compounds 45.1 to 45.1752 of formula (Ia) wherein Y is 3-chloro-1,2,4-triazol-1-yl, X is hydrogen and R1, R3, R5 and Z are as defined in Table M.
[0294] Group 46: This group discloses 1752 compounds 46.1 to 46.1752 of formula (Ia) wherein Y is 3-methyl-1,2,4-triazol-1-yl, X is hydrogen and R1, R3, R5 and Z are as defined in Table M.
[0295] Group 47: This group discloses 1752 compounds 47.1 to 47.1752 of formula (Ia) wherein Y is 3-methyl-5-oxo-4H-pyrazol-1-yl, X is hydrogen and R1, R3, R5 and Z are as defined in Table M.
[0296] Group 48: This group discloses 1752 compounds 48.1 to 48.1752 of formula (Ia) wherein Y is 3-methyl-2-oxo-imidazolidin-1-yl, X is hydrogen and R1, R3, R5 and Z are as defined in Table M.
[0297] Group 49: This group discloses 1752 compounds 49.1 to 49.1752 of formula (Ia) wherein Y is 5-methyl-1,1-dioxo-1,2,5-thiadiazolidin-2-yl, X is hydrogen and R1, R3, R5 and Z are as defined in Table M.
[0298] Group 50: This group discloses 1752 compounds 50.1 to 50.1752 of formula (Ia) wherein Y is 1,2-dimethylimidazol-4-yl, X is hydrogen and R1, R3, R5 and Z are as defined in Table M.
[0299] Group 51:This group discloses 1752 compounds 51.1 to 51.1752 of formula (Ia) wherein Y is 1-methylimidazol-4-yl, X is hydrogen and R1, R3, R5 and Z are as defined in Table M.
[0300] Group 52: This group discloses 1752 compounds 52.1 to 52.1752 of formula (Ia) wherein Y is 4-methyltriazol-1-yl, X is hydrogen and R1, R3, R5 and Z are as defined in Table M.
[0301] Group 53: This group discloses 1752 compounds 53.1 to 53.1752 of formula (Ia) wherein Y is 2-methyl-3-oxo-pyrazolidin-1-yl, X is hydrogen and R1, R3, R5 and Z are as defined in Table M.
[0302] Group 54: This group discloses 1752 compounds 54.1 to 54.1752 of formula (Ia) wherein Y is 1,2,4-triazol-4-yl, X is hydrogen and R1, R3, R5 and Z are as defined in Table M.
[0303] Specific examples of the compounds of the present invention are shown in the following groups 55 to 90 by formula (Ib):
[0304]
[0305] Where R 1 , R 3 , R 5 and Z are as defined above in Table M.
[0306] Each of the following groups 55 to 90 includes 1752 compounds of formula (Ib) wherein R 1 , R 3 , R 5 and Z have the values given in each row of Table M, and A has the values given in the relevant group 55 to 90. Thus, compound 55.1 corresponds to a compound of formula (Ib) in which R 1 , R 3 , R 5 and Z is as defined in row 1 of Table M and wherein A is as defined in Group 55; Compound 60.14 corresponds to a compound having formula (Ib) wherein R 1 , R 3 , R 5 and Z is as defined in row 14 of Table M and wherein A is as defined in group 60; and so on.
[0307] Group 55:This group discloses 1752 compounds 55.1 to 55.1752 of formula (Ib), wherein A is 3,5-dichloropyridin-2-yl and R 1 , R 3 , R 5 and Z are as defined in Table M. For example, compound No. 55.1 has the following structure:
[0308]
[0309] Group 56 : This group discloses 1752 compounds 56.1 to 56.1752 having formula (Ib), wherein A is 3-chloro-5-(trifluoromethyl)pyridin-2-yl and R 1 , R 3 , R 5 and Z are as defined in Table M.
[0310] Group 57 : This group discloses 1752 compounds 57.1 to 57.1752 having formula (Ib), wherein A is 3-chloro-pyridin-2-yl and R 1 , R 3 , R 5 and Z are as defined in Table M.
[0311] Group 58 : This group discloses 1752 compounds 58.1 to 58.1752 having formula (Ib), wherein A is cyano and R 1 , R 3 , R 5 and Z are as defined in Table M.
[0312] Group 59 : This group discloses 1752 compounds 59.1 to 59.1752 of formula (Ib) wherein A is cyanomethyl and R 1 , R 3 , R 5 and Z are as defined in Table M.
[0313] Group 60 : This group discloses 1752 compounds 60.1 to 60.1752 of formula (Ib) wherein A is cyanoethyl and R 1 , R 3 , R 5 and Z are as defined in Table M.
[0314] Group 61 : This group discloses 1752 compounds 61.1 to 61.1752 of formula (Ib) wherein A is 2,2,2-trifluoroethyl and R 1 , R3 , R 5 and Z are as defined in Table M.
[0315] Group 62 : This group discloses 1752 compounds 62.1 to 62.1752 of formula (Ib) wherein A is vinyloxycarbonyl and R 1 , R 3 , R 5 and Z are as defined in Table M.
[0316] Group 63 : This group discloses 1752 compounds of formula (Ib) 63.1 to 63.1752, wherein A is tert-butyloxycarbonyl and R 1 , R 3 , R 5 and Z are as defined in Table M.
[0317] Group 64 : This group discloses 1752 compounds 64.1 to 64.1752 of formula (Ib) wherein A is 4-fluoro-phenyl and R 1 , R 3 , R 5 and Z are as defined in Table M.
[0318] Group 65 : This group discloses 1752 compounds 65.1 to 65.1752 of formula (Ib) wherein A is 4-chloro-phenyl and R 1 , R 3 , R 5 and Z are as defined in Table M.
[0319] Group 66 : This group discloses 1752 compounds 66.1 to 66.1752 having formula (Ib), wherein A is 2,4-dichloro-phenyl and R 1 , R 3 , R 5 and Z are as defined in Table M.
[0320] Group 67 : This group discloses 1752 compounds 67.1 to 67.1752 having formula (Ib), wherein A is ethylsulfanylmethyl and R 1 , R 3 , R 5 and Z are as defined in Table M.
[0321] Group 68 : This group discloses 1752 compounds 68.1 to 68.1752 having formula (Ib), wherein A is ethylsulfinylmethyl and R 1 , R3 , R 5 and Z are as defined in Table M.
[0322] Group 69 : This group discloses 1752 compounds 69.1 to 69.1752 having formula (Ib), wherein A is ethylsulfonylmethyl and R 1 , R 3 , R 5 and Z are as defined in Table M.
[0323] Group 70 : This group discloses 1752 compounds 70.1 to 70.1752 having formula (Ib), wherein A is 5-methyl-1,2,4-oxadiazol-3-yl and R 1 , R 3 , R 5 and Z are as defined in Table M.
[0324] Group 71 : This group discloses 1752 compounds 71.1 to 71.1752 having formula (Ib), wherein A is 1-methylpyrazol-4-yl and R 1 , R 3 , R 5 and Z are as defined in Table M.
[0325] Group 72 : This group discloses 1752 compounds of formula (Ib) 72.1 to 72.1752, wherein A is 3-methyl-1,2,4-oxadiazol-5-yl and R 1 , R 3 , R 5 and Z are as defined in Table M.
[0326] Group 73 : This group discloses 1752 compounds of formula (Ib) 73.1 to 73.1752, wherein A is 3-chloro-5-(trifluoromethyl)pyridin-2-yl and R 1 , R 3 , R 5 and Z are as defined in Table M.
[0327] Group 74 : This group discloses 1752 compounds 74.1 to 74.1752 having formula (Ib), wherein A is methylamino-sulfonyl and R 1 , R 3 , R 5 and Z are as defined in Table M.
[0328] Group 75: This group discloses 1752 compounds of formula (Ib) 75.1 to 75.1752, wherein A is 1-methylpyrazol-3-yl and R 1 , R 3 , R 5 and Z are as defined in Table M.
[0329] Group 76 : This group discloses 1752 compounds 76.1 to 76.1752 having formula (Ib), wherein A is dimethylamino-sulfonyl and R 1 , R 3 , R 5 and Z are as defined in Table M.
[0330] Group 77 : This group discloses 1752 compounds 77.1 to 77.1752 having formula (Ib), wherein A is methylsulfonyl and R 1 , R 3 , R 5 and Z are as defined in Table M.
[0331] Group 78 : This group discloses 1752 compounds 78.1 to 78.1752 having formula (Ib), wherein A is cyano and R 1 , R 3 , R 5 and Z are as defined in Table M.
[0332] Group 79 : This group discloses 1752 compounds 79.1 to 79.1752 having formula (Ib), wherein A is cyanomethyl and R 1 , R 3 , R 5 and Z are as defined in Table M.
[0333] Group 80 : This group discloses 1752 compounds 80.1 to 80.1752 having formula (Ib), wherein A is 2-cyanoethyl and R 1 , R 3 , R 5 and Z are as defined in Table M.
[0334] Group 81 : This group discloses 1752 compounds 81.1 to 81.1752 having formula (Ib), wherein A is phenyl and R 1 , R 3 , R 5 and Z are as defined in Table M.
[0335] Group 82: This group discloses 1752 compounds 82.1 to 82.1752 having formula (Ib), wherein A is 4-F-phenyl and R 1 , R 3 , R 5 and Z are as defined in Table M.
[0336] Group 83 : This group discloses 1752 compounds 83.1 to 83.1752 having formula (Ib), wherein A is 4-Cl-phenyl and R 1 , R 3 , R 5 and Z are as defined in Table M.
[0337] Group 84 : This group discloses 1752 compounds 84.1 to 84.1752 having formula (Ib), wherein A is 1,2-dimethylimidazol-4-yl and R 1 , R 3 , R 5 and Z are as defined in Table M.
[0338] Group 85 : This group discloses 1752 compounds 85.1 to 85.1752 having formula (Ib), wherein A is 1-methylimidazol-4-yl and R 1 , R 3 , R 5 and Z are as defined in Table M.
[0339] Group 86 : This group discloses 1752 compounds 86.1 to 86.1752 having formula (Ib), wherein A is 1-cyanocyclopropyl and R 1 , R 3 , R 5 and Z are as defined in Table M.
[0340] Group 87 : This group discloses 1752 compounds 87.1 to 87.1752 having formula (Ib), wherein A is 1-cyano-1-methyl-ethyl and R 1 , R 3 , R 5 and Z are as defined in Table M.
[0341] Group 88 : This group discloses 1752 compounds 88.1 to 88.1752 having formula (Ib), wherein A is (1-cyanocyclopropyl)methyl and R 1 , R 3 , R 5 and Z are as defined in Table M.
[0342] Group 89 : This group discloses 1752 compounds 89.1 to 89.1752 having formula (Ib), wherein A is methylsulfanylmethyl and R 1 , R 3 , R 5 and Z are as defined in Table M.
[0343] Group 90 : This group discloses 1752 compounds 90.1 to 90.1752 having formula (Ib), wherein A is methylsulfonylmethyl and R 1 , R 3 , R 5 and Z are as defined in Table M.
[0344] It also makes it possible to obtain certain intermediate compounds having amines of formula III-a, III-b, Va, VI-a, VI-b, VII-a, IX-a, XII-a, XII-b, XIII-a, XIII-b, XIV-a, XV-a, some of which are novel.
[0345] Therefore, this paper makes it possible to obtain:
[0346] Compounds of formula III-a and III-b
[0347]
[0348] Where R 1 , R 3 and R 5 is defined in each row of Table M; the compound of Va
[0349]
[0350] Where R 1 , R 3 , R 5 and Z are defined in each row of Table M; compounds of VI-a and VI-b
[0351]
[0352] Where R 1 , R 3 and R 5 is defined in each row of Table M and Rx is selected from methyl, ethyl, propyl, isopropyl, butyl, isobutyl and tert-butyl (in the embodiments of Formula VI-a and VI-b, R 3 Not OH or methyl);
[0353] Compound VII-a
[0354]
[0355] Where R 1 and R 3 is defined in each row of Table M and Rx is selected from methyl, ethyl, propyl, isopropyl, butyl, isobutyl and tert-butyl;
[0356] Compound IX-a
[0357]
[0358] Where R 1 and R 3 is defined in each row of Table M, Rx is selected from methyl, ethyl, propyl, isopropyl, butyl, isobutyl and tert-butyl, and LG 2 It is chlorine;
[0359] Compound XII-a
[0360]
[0361] Where R 1 , R 3 is defined in each row of Table M, X and Y are defined in Groups 1 to 54;
[0362] Compound XII-b
[0363]
[0364] Where R 1 , R 3 is defined in each row of Table M and A is defined in groups 55 to 90;
[0365] Compound XIII-a
[0366]
[0367] Where R 1 , R 3 is defined in each row of Table M, X and Y are defined in Groups 1 to 54, and LG 2 is chlorine, bromine or fluorine;
[0368] Compound XIII-b
[0369]
[0370] Where R 1 , R 3 is defined in each row of Table M and A is defined in Tables 55 to 90, and LG 2 is chlorine, bromine or fluorine;
[0371] Compound XIV-a
[0372]
[0373] Where R 1 and R 3 is defined in each row of table M; and
[0374] Compound XV-a
[0375]
[0376] Where R 1 and R 3 It is defined in each row of table M.
[0377] The compounds of formula (I) according to the invention are active ingredients of preventive and / or therapeutic value in the field of pest control, even at low application rates, they have a very favorable biocidal spectrum and are well tolerated by warm-blooded species, fish and plants. These active ingredients according to the invention act on all or individual developmental stages of normally sensitive and also resistant animal pests (such as insects or representatives of the order Acarina). The insecticidal or acaricidal activity of the active ingredients according to the invention can manifest itself directly, i.e., the destruction of the pest occurs immediately or only after some time has passed (e.g. during molting); or manifest indirectly, for example, by reducing the egg-laying and / or hatching rate.
[0378] Examples of animal pests referred to above are:
[0379] From the order Acarina, e.g.
[0380] Acalitus spp., Aculus spp., Acaricalus spp., Aceria spp., Acarus siro, Amblyomma spp., Argas spp., Boophilus spp., Brevipalpus spp., Bryobia spp., Calipitrimerus spp., Chorioptes spp., Dermanyssusgallinae, Dermatophagoides spp., Eotetranychus spp., Eriophyes spp.), Hemitarsonemus spp., Hyalomma spp., Ixodes spp., Olygonychus spp., Ornithodoros spp., Polyphagotarsone latus, Panonychus spp., Phyllocoptruta oleivora, Phytonemus spp., Polyphagotarsonemus spp., Psoroptes spp., Rhipicephalus spp., Rhizoglyphus spp., Sarcoptes spp.), Steneotarsonemus spp., Tarsonemus spp., and Tetranychus spp.;
[0381] From the order Phthirus, e.g.
[0382] Haematopinus spp., Linognathus spp., Pediculus spp., Pemphigus spp., and Phylloxera spp.;
[0383] From the order Coleoptera, e.g.
[0384] Agriotes spp., Amphimallon majale, Anomala orientalis, Anthonomus spp., Aphodius spp., Astylus atromaculatus, Ataenius spp., Atomaria linearis, Chaetocnema tibialis, Cerotomaspp., Conoderus spp., Cosmopolites spp., Cotinis nitida, Curculio spp., Cyclocephalaspp., Dermestes spp., Diabrotica spp.), Diloboderus abderus, Epilachna spp., Eremnus spp., Heteronychus arator, Hypothenemus hampei, Lagria vilosa, Leptinotarsa decemlineata, Lissorhoptrus spp., Liogenys spp., Maecolaspis spp., Maladera castanea, Megascelis spp., Melighetes aeneus, Melolontha spp., Myochrousarmatus, Orycaephilus spp., Otiorhynchus spp., Phyllophaga spp.), Phlyctinus spp., Popillia spp., Psylliodes spp., Rhyssomatus aubtilis, Rhizopertha spp., Scarabeidae, Sitophilus spp., Sitotroga spp.), Somaticus spp., Sternechus subsignatus, Tenebrio spp., Tribolium spp., and Trogoderma spp.;
[0385] From the order Diptera, e.g.
[0386] Aedes spp., Anopheles spp., Antherigonas occata., Bactrocea oleae, Bibio hortulanus, Bradysia spp., Calliphora erythrocephala, Ceratitis spp., Chrysomyia spp., Culex spp., Cuterebra spp., Dacus spp., Delia spp., Drosophilamelanogaster, Fannia spp., Gastrophilus spp., Geomyza tripunctata, Glossina spp.), Hypoderma spp., Hyppobosca spp., Liriomyza spp., Lucilia spp., Melanagromyza spp., Musca spp., Oestrus spp., Orseolia spp., Oscinella frit, Pegomyia hyoscyami, Phorbia spp., Rhagoletis spp., Rivelia quadrifasciata, Scatella spp., Sciara spp., Stomoxys spp., Tabanus spp., Tannia spp.) and Tipula spp.;
[0387] From the order Hemiptera, e.g.
[0388] Acanthocoris scabrator, Acrosternum spp., Adelphocoris lineolatus, Aleurodes spp., Amblypelta nitida, Bathycoelia thalassina, Acanthocoris spp., Cimex spp., Clavigrallatomentosicollis, Creontiades spp., Dichelops furcatus, Edessa spp., Euchistus spp., Eurydema pulchrum, Horcia spp., Horcia spp. nobilellus), Lygus spp., Lygus spp., Tropical Scale spp., Murgantia histrionicus, Nesidiocoris tenuis, Nysius simulans, Nysius simulans, Nesidiocoris tenuis, Nysius simulans, Nysius simulans, Nysius spp. ...
[0389] Acyrthosium pisum, Adalges species, Agallina ensigera, Targuilon vein psyllid, Aleurodicus species, Aleurocanthus species, Sugarcane hole whitefly, Aleurothrixus floccosus, Aleyrodes brassicae, Amarasca biguttula, Citrus long-spiked leafhopper, Nephrodactylus species, Aphididae, Aphid species, Aspidiotus species, Solanum grove netless aphid, Bactericera cockerelli, Aleurodicus species, Brachycaudus species, Cabbage aphid, Cavariella species, Cavariella aegopodii Scop.), wax scale species, black brown round shield scale, orange brown round shield scale, leafhopper species, large white leafhopper (Cofana spectra), Cryptomyxodon species, leafhopper species, brown soft scale, corn yellow-winged leafhopper, naked whitefly species, citrus psyllid, wheat aphid, western round tail aphid species, small green leafhopper species, apple aphid, grape leafhopper species, Gascardia species, red eucalyptus psyllid (Glycaspis brimblecombei), vegetable constriction aphid (Hyadaphispseudobrassicae), large tail aphid species (Hyalopterus spp.), hyperomyzuspallidus species (Hyperomyzuspallidus), lemon fruit green leafhopper (Idioscopus clypealis), African leafhopper, Laodelphax species, water and soil hard scale, oyster shield scale species, radish aphid (Lopaphis erysimi), Lyogenys maidis, Aphids spp., Metcalfa pruinosa, Aphids spp., Aphids spp., Neotoxoptera sp., Nilaparvata spp., Nilaparvata spp.), pear green aphid, Odonaspis ruthae, sugarcane cotton aphid, bayberry whitefly, Caulis psyllid, spp. of shield scale, spp. of gall aphid, corn wax cicada, spp. of flat horned planthopper, spp. of warty aphid, spp. of root nodule aphid, spp. of Mosella, spp. of white scale, spp. of mealybug, spp. of cotton blind bug (Pseudatomoscelis seriatus), spp. of psyllid, spp. of cotton scale (Pulvinaria aethiopica), spp. of toothed shield scale, spp. of Quesada gigas, spp. of electric light leafhopper (Reciliadorsalis), spp. of constricted tube aphid, spp. of black helmet scale, spp. of banded leafhopper, spp. of dichotomous aphid, spp. of wheat aphid (Sitobion spp.), white-backed planthopper, Spissistilus festinus, Tarophagus Proserpina), aphid species, whitefly species, Tridiscus sporoboli, Trionymus spp., African psyllids, scutellaria spp., flame leafhoppers, Zyginidia scutellaris;.
[0390] From the order Hymenoptera, e.g.
[0391] Acromyrmex, Arge spp., Atta spp., Cephus spp., Diprion spp., Diprionidae, Gilpinia polytoma, Hoplocampa spp., Lasius spp., Monomorium pharaonis, Neodiprions spp., Pogonomyrmex spp., Fire ants, Solenopsis spp., and Vespa spp.
[0392] From the order Isoptera, e.g.
[0393] Coptotermes spp., Corniternes cumulans, Incisitermes spp., Macrotermes spp., Mastotermes spp., Microtermes spp., Reticulitermes spp.; Tropical fire ant (Solenopsis geminate)
[0394] From the order Lepidoptera, for example,
[0395] Species of the genus Long-winged Tortoise, Species of the genus Brown-banded Tortoise, Species of the genus Clearwing, Species of the genus Spodoptera, Cotton leafworm, Species of the genus Amylois, Bean armyworm, Species of the genus Yellow-winged Tortoise, Species of the genus Argyresthia, Species of the genus Banded Tortoise, Species of the genus Spodoptera, Cotton miner, Corn armyworm, Powderyngium striata, Peach fruit moth, Species of the genus Graminus, Species of the genus Colored Tortoise, Chrysoteuchia topiaria, Grape fruit moth, Species of the genus Leaffolder, Species of the genus Cloud-winged Tortoise, Species of the genus Sheath moth, Colias lesbia, Cosmophila flava), Sesamia spp., Greater Cabbage Borer, Apple Trichodina, Boxwood Moth, Trichodina spp., Boxwood Borer, Trichodina spp., Sudanese Bollworm, Spodoptera spp., South American Corn Seedling Borer (Elasmopalpus lignosellus), Sweet Potato Stem Borer, Mealworm spp., Epinotia spp., Estigmene acrea, Etiellazinckinella, Flower Trichodina spp., Ring Needle Trichodina, Yellow Tufted Moth spp., Feltia jaculiferia, Grapholita spp., Cloud Trichodina, Spodoptera spp., Cabbage Borer, Herpetogramma spp., White Moth, Tomato Borer, Lasmopalpus lignosellus, spiral leafminer, leafminer species, grape flower moth, Loxostege bifidalis, tussock moth species, miner species, Malacosoma spp., cabbage armyworm, tobacco hornworm, Mythimna spp., noctuid species, fall geometrid species, Orniodes indica, European corn borer, super-small tortoise species, brown tortoise species, small-eyed moth, stem borer, red bell moth, coffee leafminer, one-star armyworm, potato moth, cabbage butterfly, Pieris species, diamondback moth, white nest moth species, leaf moth species, mint gray moth (Rachiplusianu), western bean incense (Richia albicosta), white grain borer species (Scirpophaga spp.), Spodoptera species, Cynocephala species, Spodoptera species, Cotton leaf folder, Hymenoptera species, Heteroptera species, Cynocephala species, Trichoplusia species, Liriomyza species, and Lymantria species;
[0396] From the order Mallophaga, for example,
[0397] Damalina spp. and Trichodectes spp.;
[0398] From the order Orthoptera, for example,
[0399] Blatta spp., Blattella spp., Gryllotalpa spp., Leucophaea maderae, Locusta spp., Neocurtilla hexadactyla, Periplaneta spp., Scapteriscus spp., and Schistocerca spp.;
[0400] From the order Psocoptera, for example,
[0401] Liposcelis spp.;
[0402] From the order Siphonaptera, for example,
[0403] Ceratophyllus spp., Ctenocephalides spp. and Xenopsylla cheopis;
[0404] From the order of the Thysanoptera, for example,
[0405] Calliothrips phaseoli, Frankliniella spp., Heliothrips spp., Hercinothrips spp., Parthenothrips spp., Scirtothrips aurantii, Sericothrips variabilis, Taeniothrips spp., Thrips spp.;
[0406] From the order of the Thysanura, for example, Lepisma saccharina.
[0407] In another aspect, the present invention may also relate to a method for controlling damage to plants and parts thereof by plant parasitic nematodes (endoparasitic-, semiendoparasitic- and ectoparasitic nematodes), in particular the following plant parasitic nematodes, such as root knot nematodes, Meloidogyne hapla, Meloidogyne incognita, Meloidogyne javanica, Meloidogyne arenaria and other species of root knot nematodes; cyst-forming nematodes, Globodera rostochiensis and other species of Globodera; cereal cyst nematodes (Heterodera avenae), soybean cyst nematodes (Heteroderaglycines), beet cyst nematodes (Heterodera exigua) and other species of Globodera. schachtii), Heteroderatrifolii, and other Heterodera species; Seed gall nematodes, Anguina species; Stem and foliar nematodes, Aphelenchoides species; Sting nematodes, Belonolaimuslongicaudatus, and other Belonolaimus species; Pine nematodes, Bursaphelenchus xylophilus, and other Bursaphelenchus species; Ring nematodes, nematodes), Criconema species, Criconemella species, Criconemoides species, Mesocriconema species; Stemand bulb nematodes, Ditylenchus destructor, Ditylenchus dipsaci and other Ditylenchus species; Awl nematodes, Dolichodorus species;Spiral nematodes, Heliocotylenchus multicinctus and other species of the genus Helicotylenchus; Sheath and sheathoid nematodes, species of the genera Hemicycliophora and Hemicriconemoides; species of the genus Hirshmanniella; Lancenematodes, species of the genus Hoploaimus; false rootknot nematodes, species of the genus Nacobbus; Needle nematodes, Longidoruse longatus and other species of the genus Longidorus; Pin nematodes, species of the genus Pratylenchus; Lesion nematodes nematodes, Pratylenchus negletus, Pratylenchus penetrans, Pratylenchus curvitatus, Pratylenchus goodeyi, and other Pratylenchus species; Burrowing nematodes, Radopholus similis, and other Radopholus species; Reniform nematodes, Rotylenchus robustus, Rotylenchus reniformis, and other Rotylenchus species; Scutellonema species; Stubby root nematodes, Trichodorus primitivus and other species of the genus Trichodorus, species of the genus Paratrichodorus; Stunt nematodes, Tylenchorhynchus claytoni, Tylenchorhynchus dubius and other species of the genus Tylenchorhynchus;Citrus nematodes, Tylenchulus species; Dagger nematodes, Xiphinema species; and other plant parasitic nematode species, such as Subanguina spp., Hypsoperine spp., Macroposthonia spp., Melinius spp., Punctodera spp., and Quinisulcius spp.;
[0408] The compounds of the invention also have activity against molluscs. Examples include, for example, the family Pomacea; the family Arion (A. ater, A. circumscriptus, A. hortensis, A. rufus); the family Bradybaenidae (Bradybaenidae, fruticum); Cepaea (C. hortensis, C. nemoralis); Ochlodina; Deroceras (D. agrestis, D. empiricorum, D. laeve, D. reticulatum); Discus (D. rotundatus); Euomphalia; Galba (G. trunculata); Helicelia (H. itala, H. obvia); Helicigona arbustorum; Helicodiscus; Helix (H. aperta); Limax (L. cinereoniger, L. flavus, L. marginatus, L. maximus, L. tenellus); Lymnaea; Milax (M. gagates, M. marginatus, M. sowerbyi); Opeas; Pomacea (P. canaticulata); Vallonia and Zanitoides.
[0409] The active ingredients according to the invention can be used for controlling, i.e. suppressing or destroying pests of the abovementioned type, which occur in particular on plants, especially on useful and ornamental plants in agriculture, in horticulture and in forestry, or on organs of these plants, such as fruits, flowers, leaves, stems, tubers or roots, and in some cases even plant organs formed at a later point in time still remain protected against these pests.
[0410] In particular, suitable target crops are cereals, such as wheat, barley, rye, oats, rice, corn or sorghum; beets, such as sugar beets or fodder beets; fruits, such as pome, stone or soft fruit, such as apples, pears, plums, peaches, apricots, cherries or berries, such as strawberries, raspberries or blackberries; leguminous crops, such as beans, lentils, peas or soybeans; oilseed crops, such as rapeseed, mustard, poppy, olive, sunflower, coconut, castor, cocoa beans, or groundnuts; melons, such as pumpkin, cucumber, or melon; fiber plants, such as cotton, flax, hemp, or jute; citrus fruits, such as oranges, lemons, grapefruits, or tangerines; vegetables, such as spinach, lettuce, asparagus, cabbage, carrots, onions, tomatoes, potatoes, or bell peppers; lauraceae, such as avocado, cinnamon, or camphor; and also tobacco, nuts, coffee, eggplant, sugar cane, tea, pepper, grapevines, hops, plantaginaceae, and latex plants.
[0411] In particular embodiments, compounds of formula (I) control mites, rust mites and spider mites in crops, trees and plants selected from vegetables (especially tomatoes and cucurbits), citrus, pome fruits, stone fruits, nuts, cotton, tropical crops, avocados, ornamentals, beans, soybeans, strawberries and grapes.
[0412] The compositions and / or methods of the invention may also be used on any ornamental and / or vegetable crops, including flowers, shrubs, broadleaf trees and evergreen plants.
[0413] For example, the present invention can be used in any of the following ornamental plant species: Ageratum species, Alonsoa spp., Anemone species, Anisodontea capsenisis, Anthemis species, Antirrhinum species, Aster species, Begonia species (e.g., Rieger Begonia, Begonia sempervivum, Begonia tubéreux), Bougainvillea species, Brachycome spp., Brassica species (ornamental plants), Calceolaria species, Capsicum, Catharanthus roseus, Canna species, Centaurea species, Chrysanthemum species, Cineraria species (C. maritime), Coreopsis species, Crassula coccinea, Cupheaignea, Dahlia species, Delphinium species, Dicentra species, Dorotheantus species. spp.), Eustoma, Forsythia, Fuchsia, Geranium, Geranium, Geranium gnaphalium, Gerbera, Globe amaranth, Heliotropium, Hibiscus, Hydrangea, Hydrangea, Iris, Impatiens, Iresines, Kalanchoe, Lantana, March flower, Lion's ear, Lilium, Mesembryanthemum, Physalis, Monarda, Tagetes, Dianthus, Canna, Oxalis, Daisy, Geranium, Viola, Petunia, Nerium, Plecthranthus spp.), poinsettia, creeper (parthenocissus quinquefolia, Parthenocissus tricuspidata), primrose, ranunculus, azalea, rosa (rose), rudbeckia, African violet, salvia, Scaevola aemola, Schizanthus wisetonensis, sedum, Solanum, Surfinia spp., marigold, tobacco, verbena, zinnia, and other bedding plants.
[0414] For example, the present invention can be used with any of the following vegetable species: Allium species (garlic, onion, A.oschaninii, leek, shallot, scallion), fennel, celery (Apium graveolus), asparagus, beets (Beta vulgarus), Brassica species (brassica, Chinese cabbage, turnip), peppers, chickpeas, endive, chicory species (chicory, endive), watermelon, Cucumis species (cucumber, melon), Cucurbita species (zucchini, Indian pumpkin), Cyanara spp. (artichoke, cardoon), wild carrot, fennel, Hypericum species, lettuce, Lycopersicon species (tomato, cherry tomato), mint species, basil, parsley, Phaseolus species (bean, pea), peas, radish, edible rhubarb, Rosemary species, Sage species, black salsify (Scorzonera hispanica), eggplant, spinach, new valerian species (V. eriocarpa), and broad beans.
[0415] Preferred ornamental plant species include African violet, begonia, dahlia, gerbera, hydrangea, verbena, rose, kalanchoe, poinsettia, aster, cornflower, coreopsis, delphinium, monarda, phlox, rudbeckia, sedum, petunia, viola, impatiens, geranium, chrysanthemum, ranunculus, fuchsia, salvia, hydrangea, rosemary, sage, St. Johnswort, mint, sweet pepper, tomato and cucumber.
[0416] The active ingredients according to the invention are particularly suitable for controlling bean aphids, cucumber leaf beetles, tobacco budworm, peach aphid, diamondback moth and sea lily armyworm on cotton, vegetables, corn, rice and soybean crops. The active ingredients according to the invention are further particularly suitable for controlling cabbage armyworm (preferably on vegetables), codling moth (preferably on apples), green leafhopper (preferably on vegetables, vineyards), potato leaf beetle (Leptinotarsa) (preferably on potatoes) and striped stem borer (preferably on rice).
[0417] The compounds of formula (I) are particularly suitable for controlling mites, spider mites and rust mites, for example, species of the genus Acarus; Wu's genus Acarus; Thick-legged mites; Acarus species; Citrus gall mites; Citrus spiny tick; Acarus species; Steinernensis needle-spined mites; Acarus species; Pseudoamnius; Brevipalpus species; Brevipalpus rubrum; Alfalfa moss mites; Fruit moss mites; Woodworm species; Chelicerus buxi; Chelicerus species; Asger mites; Bovine itch mites; Demodex species; Demodex species; Bovine Demodex; Demodex caballi; Demodex canis; Demodex goat; Demodex equi; Demodex sheep; Demodex species; Demodex suis; Dermatosus gallinae; Dermatosus species; Eotetranychus species; Eotetranychus wei (Eotetranychus willamettei; Pear gall mite; Ribes gall mite; Halotydeus species; Grape gall mite; True spider mite species; Red-footed soil mite (Halotydeusdestructor); Semitarsine species; Scabies species; Chicken chick mite species; Yak mite species; Sarcophagida species; Neoschongastia xerothermobia; Neotrombicula autumnalis; Neotrombicula desaleri; cat ear mite; Otodectes species; coffee ear mite; holly ear mite (Oligonychusilicis); Oligonychus species; Chelicerus species; cysticercus; Otodectes species; fowl mite; ear mites; ear mites; ear mites; citrus mites; Panonychus species; apple mites; citrus leaf tick; leaf tick species; Phytoseiidae species; Pneumonyssoides caninum; Polyphagous tarsonemes; Polyphagous tarsonemes species; sheep scabies; scabies species; rabbit mites; horse mites; sheep mites; itch mites; itch mites; itch mites; wing mites; schizontidae species; root mites; cattle scabies; dog scabies; goat scabies (Sarcoptes caprae); horse scabies; sheep scabies; goat scabies (Sarcoptes rupicaprae); Sarcoptes species; Sarcoptes suis; Scabies swine; Scabies scabiei; Scabies species; Pectoral schisis species; Tarsonemus species; Tetranychus cinnabarinus; Tetranychus kanzawa; Tetranychus species; Two-spotted spider mites; Red chiggers; Chiggers species; Typhlodromus occidentalis; Tyrophagus species; Varroa jacoberii; Varroa species; Tomato gall mite (Vasates lycopersici); and Zetzellia mali.
[0418] In embodiments, compounds of formula (I) are particularly useful for controlling one or more of: citrus gall mites; tomato needle gall mites (Aculus lycopersici); Peel's needle gall mites (Aculus pelekassi); Steinni's needle gall mites; purple short-palped mites; short-palped mites spp.; fruit moss mites; hornbeam spider mites; Eriophyes spp.; pear gall mites; Eriophyes piri; Eriophyes spp.; grape gall mites; Eutetranychus africanus; Eutetranychus orientalis; sward mites; citrus mites; apple mites; grape rust mites (Phyllocoptes vitis); citrus leaf ticks; polyphagous tarsonemes; cinnabarinus spider mites; Kanzawa's spider mites; Tetranychus spp.; and two-spotted spider mites.
[0419] In another embodiment, the compounds of formula (I) are more particularly suitable for controlling one or more of the following: citrus gall mite; Pierrothiola spicata; purple short-palped mite; short-palped mite species; Eriophyes piri; grape gall mite; African true spider mite; oriental true spider mite; grassland small claw mite; apple rust mite; grape rust mite; citrus wrinkled leaf tick; side polyphagous tarsoneme; cinnabarinus spider mite; Kanzawa spider mite; Tetranychus species; and two-spotted spider mite.
[0420] The term "crops" is to be understood as also including crop plants which have been transformed by the use of recombinant DNA techniques in such a way that they are able to synthesize one or more selectively acting toxins, such as are known, for example, from toxigenic bacteria, in particular those of the genus Bacillus.
[0421] Toxins that can be expressed by such transgenic plants include, for example, insecticidal proteins, such as those from Bacillus cereus or Bacillus japonicus; or insecticidal proteins from Bacillus thuringiensis, such as delta-endotoxins, for example Cry1Ab, Cry1Ac, Cry1F, Cry1Fa2, Cry2Ab, Cry3A, Cry3Bb1, or Cry9C, or vegetative insecticidal proteins (Vips), for example Vip1, Vip2, Vip3, or Vip3A; or insecticidal proteins of bacterial colonizing nematodes, for example Photorhabdus spp. or Xenorhabdus spp., such as Photorhabdus luminescens, Xenorhabdus nematophila, or Xenorhabdus spp. nematophilus); toxins produced by animals, such as scorpion toxins, spider toxins, bee toxins and other insect-specific neurotoxins; toxins produced by fungi, such as streptomycin, plant lectins, such as pea lectin, barley lectin or snowdrop lectin; agglutinin; protease inhibitors, such as trypsin inhibitor, silk proteinase inhibitor, potato glycoprotein, cystatin, papain inhibitor; ribosome inactivating protein (RIP), such as ricin, maize-RIP, abrin, luffa seed toxin protein, saponin protein or bryophyllin; 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 channel or calcium channel blockers, juvenile hormone esterase, diuretic hormone receptor, stilbene synthase, bibenzyl synthase, chitinase and glucanase.
[0422] In the context of the present invention, delta-endotoxins (e.g., Cry1Ab, Cry1Ac, Cry1F, Cry1Fa2, Cry2Ab, Cry3A, Cry3Bb1, or Cry9C) or vegetative insecticidal proteins (Vips) (e.g., Vip1, Vip2, Vip3, or Vip3A) are understood to include, obviously, also mixed toxins, truncated toxins, and modified toxins. Mixed toxins are recombinantly produced by new combinations of 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 a naturally occurring toxin are replaced. In such amino acid replacements, it is preferred that a non-naturally occurring protease recognition sequence is inserted into the toxin, such as, for example, in the case of Cry3A055, a cathepsin-G-recognition sequence is inserted into the Cry3A toxin (see WO 03 / 018810).
[0423] Examples of such toxins or transgenic plants capable of synthesizing such toxins are disclosed in, for example, EP-A-0 374 753, WO 93 / 07278, WO 95 / 34656, EP-A-0 427 529, EP-A-451 878 and WO 03 / 052073.
[0424] Methods for preparing such transgenic plants are generally known to the person skilled in the art and are described, for example, in the publications mentioned above. CryI-type deoxyribonucleic acids and their preparation are known, for example, from WO 95 / 34656, EP-A-0 367474, EP-A-0 401 979 and WO 90 / 13651.
[0425] The toxins included in the transgenic plants render the plants tolerant to harmful insects. Such insects can be found in any insect taxonomic group, but are particularly common among beetles (Coleoptera), two-winged insects (Diptera), and moths (Lepidoptera).
[0426] 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. Examples of such plants are: (corn variety expressing Cry1Ab toxin); YieldGard (corn variety expressing Cry3Bb1 toxin); YieldGard (corn varieties expressing Cry1Ab and Cry3Bb1 toxins); (corn variety expressing Cry9C toxin); Herculex (a corn variety expressing the Cry1Fa2 toxin and the enzyme phosphinothricin N-acetyltransferase (PAT) that confers tolerance to the herbicide glufosinate-ammonium); NuCOTN (cotton variety expressing Cry1Ac toxin); Bollgard (cotton variety expressing Cry1Ac toxin); Bollgard (cotton varieties expressing Cry1Ac and Cry2Ab toxins); (cotton varieties expressing Vip3A and Cry1Ab toxins); (potato variety, expressing Cry3A toxin); GT Advantage (GA21 glyphosate tolerance trait), CB Advantage (Bt11 corn borer (CB) trait) and
[0427] Further examples of such genetically modified crops are:
[0428] 1. Bt11 corn, from Syngenta Seeds SAS, Chemin del'Hobit 27, F-31 790 St. Sauveur, France, registration number C / FR / 96 / 05 / 10. Genetically modified maize, which is resistant to attack by European corn borer (Ostrinia nubilalis and Sesamia inermis) by transgenic expression of a truncated Cry1Ab toxin. Bt11 corn also transgenic expression of the PAT enzyme to obtain tolerance to the herbicide glufosinate ammonium.
[0429] 2. Bt176 corn, from Syngenta Seeds, 27 Hobbit Road, F-31 790 Saint-Sauveur, France, registration number C / FR / 96 / 05 / 10. Genetically modified maize, which is resistant to attack by the European corn borer (Ostrinia nubilalis and Sesamia inermis) by transgenic expression of the Cry1Ab toxin. Bt176 corn also transgenic expression of the enzyme PAT to obtain tolerance to the herbicide glufosinate ammonium.
[0430] 3. MIR604 corn, from Syngenta Seeds, 27 Rue Hobbitt, F-31 790 Saint-Sauveur, France, registration number C / FR / 96 / 05 / 10. Corn made 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 corn plants is described in WO 03 / 018810.
[0431] 4. MON 863 maize, from Monsanto Europe SA, 270-272 Avenue de Tervuren, B-1150 Brussels, Belgium, registration number C / DE / 02 / 9. MON 863 expresses the Cry3Bb1 toxin and is resistant to certain coleopteran insects.
[0432] 5. IPC 531 Cotton, from Monsanto Europe NV, 270-272 Avenue Tervuren, B-1150 Brussels, Belgium, registration number C / ES / 96 / 02.
[0433] 6.1507 Maize from Pioneer Overseas Corporation, Avenue Tedesco, 7B-1160 Brussels, Belgium, registration number C / NL / 00 / 10. Genetically modified maize expressing the protein Cry1F for resistance to certain lepidopteran insects and the protein PAT for tolerance to the herbicide glufosinate ammonium.
[0434] 7. NK603×MON 810 maize, from Monsanto Europe 270-272 Avenue Tervuren, B-1150 Brussels, Belgium, registration number C / GB / 02 / M3 / 03. Made from a conventionally bred hybrid maize variety by crossing the genetically modified varieties NK603 and MON 810. NK603×MON 810 maize transgenically expresses the protein CP4 EPSPS obtained from the Agrobacterium strain CP4, rendering it tolerant to herbicides (contains glyphosate), and also Cry1Ab toxin obtained from Bacillus thuringiensis subsp. kurstakia, which confers resistance to certain lepidopteran insects, including the European corn borer.
[0435] Transgenic crops of insect-resistant plants are also described in the BATS (Zentrum für Biosicherheit und Nachhaltigkeit, Zentrum BATS, Clarastrasse 13, 4058 Basel, Switzerland) report 2003 ( http: / / bats.ch )middle.
[0436] The term "crops" is to be understood as also including crop plants that have been transformed by the use of recombinant DNA technology so that they can synthesize antipathogenic substances with selective action, such as, for example, so-called "pathogenesis-related proteins" (PRPs, see, for example, EP-A-0 392 225). Examples of such antipathogenic substances and transgenic plants capable of synthesizing such antipathogenic substances are known, for example, from EP-A-0 392 225, WO 95 / 33818 and EP-A-0 353191. Methods for producing such transgenic plants are generally known to those skilled in the art and are described, for example, in the publications mentioned above.
[0437] Crops may also be modified to increase resistance to fungal (eg, Fusarium, Anthracnose, or Phytophthora), bacterial (eg, Pseudomonas), or viral (eg, Potato Leaf Roll Virus, Tomato Spotted Wilt Virus, Cucumber Mosaic Virus) pathogens.
[0438] Crops also include those with increased resistance to nematodes, such as Heterodera glycines.
[0439] Crops with tolerance to abiotic stress include those with increased tolerance to drought, high salt, high temperature, cold, frost or light radiation, for example through expression of NF-YB or other proteins known in the art.
[0440] Antipathogenic substances that can be expressed by such transgenic plants include, for example, ion channel blockers, such as blockers of sodium channels and calcium channels, for example viral KP1, KP4 or KP6 toxins; stilbene synthases; bibenzyl synthases; chitinases; glucanases; so-called "pathogenesis-related proteins" (PRPs; see, for example, EP-A-0 392 225); antipathogenic substances produced by microorganisms, such as peptide antibiotics or heterocyclic antibiotics (see, for example, WO 95 / 33818) or proteins or polypeptide factors that are involved in plant defense against pathogens (so-called "plant disease resistance genes", as described in WO 03 / 000906).
[0441] Further areas of use of the compositions according to the invention are the protection of stored goods and storage rooms and of raw materials, such as wood, textiles, floors or buildings, and also in the hygiene sector, in particular for the protection of humans, domestic animals and productive livestock from pests of the type mentioned.
[0442] The present invention provides a compound of the first aspect for use in therapy. The present invention provides a compound of the first aspect for use in controlling parasites in or on an animal. The present invention further provides a compound of the first aspect for use in controlling parasites on the body surface of an animal. The present invention further provides a compound of the first aspect for use in preventing and / or treating a disease transmitted by parasites on the body surface.
[0443] The present invention provides the use of the compound of the first aspect for the manufacture of a drug for controlling parasites in or on an animal. The present invention further provides the use of the compound of the first aspect for the manufacture of a drug for controlling parasites on the body surface of an animal. The present invention further provides the use of the compound of the first aspect for the manufacture of a drug for preventing and / or treating diseases transmitted by parasites on the body surface.
[0444] The present invention provides the use of the compound of the first aspect in controlling parasites in or on the body of an animal. The present invention further provides the use of the compound of the first aspect in controlling parasites on the body of an animal.
[0445] When used in the context of parasites in or on animals, the term "control" means reducing the number of pests or parasites, eliminating pests or parasites and / or preventing further infestation by pests or parasites.
[0446] The terms "treat" or "treat" when used in the context of parasites in or on an animal means to inhibit, slow, halt or reverse the progression or severity of existing symptoms or disease.
[0447] The term "prevent" when used in the context of parasites in or on animals means avoiding the development of symptoms or disease in the animal.
[0448] When used in the context of parasites in or on animals, the term "animal" may refer to mammals and non-mammals, such as birds or fish. In the case of a mammal, it can be a human or a non-human mammal. Non-human mammals include, but are not limited to, livestock animals and pets. Livestock animals include, but are not limited to, cattle, camels, pigs, sheep, goats, and horses. Pets include, but are not limited to, dogs, cats, and rabbits.
[0449] "Parasits" are harmful organisms that live in or on a host animal and benefit by obtaining nutrients at the expense of the host animal. "Endoparasites" are parasites that live inside the host animal. "Exoparasites" are parasites that live on the surface of the host animal. Exoparasites include, but are not limited to, ticks, insects, and crustaceans (e.g., sea lice). The subclass Acarina (or Acarina) includes ticks and mites. Ticks include, but are not limited to, members of the genus Rhipicaphalus, such as Rhipicaphalus microplus (Boophilus microplus) and Rhipicephalus sanguineus; Amblyomrna; Dermacentor; Haemaphysalis; Hyalomma; Ixodes; Rhipicentor; Margaropus; Argas; Otobius; and Ornithodoros. Mites include, but are not limited to, members of the following genera: Dermestes, such as Dermestes gallinae; Itch, such as Sheep; Cheyletus; Dermatosus; such as Dermatosus gallinae; Ortnithonyssus; Demodex, such as Demodex canis; Sarcoptes, such as Sarcoptes hominis; and Psora. Insects include, but are not limited to, members of the following orders: Siphonaptera, Diptera, Trichoderma, Lepidoptera, Coleoptera, and Homoptera. Members of Siphonaptera include, but are not limited to, Ctenocephatides canis and Ctenocephatides canis. Members of Diptera include, but are not limited to, species of the genus Musca; Skin flies, such as horse flies and sheep flies; Biting flies; Gadflies, such as Tabunus species and Tabunus species; Black horn flies, such as Haematobium; Stomoxys; Lucilia; Midges; and mosquitoes. Members of the order Trichoderma include, but are not limited to, blood-sucking lice and chewing lice, such as the wool lice (Bovicola Ovis) and the cattle feather lice.
[0450] When used in the context of parasites in or on an animal, the term "effective amount" refers to the amount or dosage of a compound of the invention or a salt thereof, which, when administered to an animal in a single dose or multiple doses, provides the desired effect in or on the animal. The attending diagnostician (as one skilled in the art) can readily determine the effective amount by using known techniques and by observing the results obtained in similar situations. In determining the effective amount, the attending diagnostician considers many factors, including, but not limited to: the species of mammal; its size, age, and general health; the parasites to be controlled and the degree of infestation; the specific disease or condition involved; the degree of involvement or severity of the disease or condition; individual responses; the specific compound administered; the mode of administration; the bioavailability characteristics of the administered formulation; the dosage regimen selected; the use of concomitant medications; and other relevant circumstances.
[0451] The compounds of the present invention can be given to animals by any route with the desired effect, including but not limited to topical, oral, parenteral and subcutaneous. Topical administration is preferred. Formulations suitable for topical administration include, for example, solutions, emulsions and suspensions, and can be poured, dotted, sprayed, sprayed, sprayed or dipped. In an alternative, the compounds of the present invention can be given by ear tags or collars.
[0452] The salt forms of the compounds of the present invention include both pharmaceutically acceptable salts and veterinarily acceptable salts, which may be different from agrochemically acceptable salts. Pharmaceutically and veterinarily acceptable salts and common methods for preparing them are well known in the art. See, for example, Gould, PL, "Salt selection for basic drugs", International Journal of Pharmaceutics, 33: 201-217 (1986); Bastin, RJ et al. "Salt Selection and Optimization Procedures for Pharmaceutical New Chemical Entities", Organic Process Research and Development, 4: 427-435 (2000); and Berge, SM et al., "Pharmaceutical Salts", Journal of Pharmaceutical Sciences, 66: 1-19, (1977). It will be appreciated by those skilled in the art that the compounds of the present invention are easily converted into salts using techniques and conditions known to those of ordinary skill in the art, and can be separated as salts (such as hydrochlorides). In addition, it will be appreciated by those skilled in the art that the compounds of the present invention are easily converted into corresponding free alkalis, and can be separated from corresponding salts as corresponding free alkalis.
[0453] The present invention also provides methods for controlling pests (such as mosquitoes and other disease vectors; see also http: / / www.who.int / malaria / vector_control / irs / en / ). In one embodiment, the method for controlling pests comprises applying the composition of the present invention to the target pests, their loci or surfaces or substrates by brushing, rolling, spraying, coating or dipping. By way of example, IRS (indoor residual spray) application of surfaces (such as wall, ceiling or floor surfaces) is contemplated by the methods of the present invention. In another embodiment, it is contemplated that such compositions are applied to substrates such as nonwoven or fabric materials in the form of netting, coverings, bedding, curtains and tents (or can be used in the manufacture of such articles).
[0454] In one embodiment, the method for controlling such harmful organisms comprises applying the composition of the present invention of pesticidal effective amount to the target harmful organisms, their place or surface or substrate, so as to provide effective retained pesticidal activity on the surface or substrate. Such application can be carried out by brushing, rolling, spraying, coating or dipping the pesticidal composition of the present invention. By way of example, the IRS application of surfaces (such as walls, ceilings or floor surfaces) is considered by the method of the present invention, so as to provide effective retained pesticidal activity on the surface. In another embodiment, it is considered to apply such compositions for the residual control of harmful organisms on substrates, which substrates are fabric materials such as in the form of netting, coverings, bedding, curtains and tents (or can be used in the manufacture of these articles).
[0455] The substrate to be treated (including nonwovens, fabrics or nettings) can be made of natural fibers, such as cotton, raffia, jute, flax, sisal, burlap or wool, or synthetic fibers, such as polyamide, polyester, polypropylene, polyacrylonitrile, etc. Polyester is particularly suitable. Methods for textile treatment are known, for example WO 2008 / 151984, WO 2003 / 034823, US 5631072, WO 2005 / 64072, WO 2006 / 128870, EP 1724392, WO 2005113886 or WO 2007 / 090739.
[0456] A further area of use of the compositions according to the invention is in the field of tree injection / trunk treatment of all ornamental trees as well as all kinds of fruit and nut trees.
[0457] In the field of tree injection / trunk treatment, the compounds according to the invention are particularly suitable for combating wood-boring insects from the orders Lepidoptera mentioned above and from the orders Coleoptera, in particular against the wood-boring insects listed in the following Tables A and B:
[0458] Table A. Examples of exotic wood-boring insects of economic importance.
[0459]
[0460]
[0461] Table B. Examples of native wood-boring insects of economic importance.
[0462]
[0463]
[0464]
[0465] The present invention can also be used to control any insect pest that may be present in turfgrass including, for example, beetles, caterpillars, fire ants, ground pearls, millipedes, woodlice, mites, mole crickets, scale insects, mealybugs, ticks, cicadas, southern wheat bugs, and grubs. The present invention can be used to control insect pests at all stages of their life cycle, including eggs, larvae, nymphs, and adults.
[0466] In particular, the present invention can be used to control insect pests that feed on the roots of turfgrass, including grubs (such as Cyclocephala spp. (e.g., labeled beetle, C. lurida), Rhizotrogus spp. (e.g., European beetle, European root-cutting gill beetle (R. majalis)), Cotinus spp. (e.g., Green June beetle, Green June flower beetle (C. nitida)), Popillia spp. (e.g., Japanese beetle, Japanese arc beetle (P. japonica)), Phyllophaga spp. (e.g., May / June beetle), Chafer spp. (e.g., Blackturfgrass ataenius, Black velvet beetle), Maladera spp. (e.g., Asiatic garden beetle (Asiatic garden beetle)), beetle, chestnut beetle) and Tomarus species), ground pearls (Margarodes spp.), mole crickets (tawny, southern, and short-winged; mole crickets (Scapteriscus spp., Gryllotalpa africana) and leatherjackets (European crane fly, Tipula spp.).
[0467] The present invention can also be used to control insect pests of turfgrass in thatched homes, including armyworms (such as fall armyworm, Spodoptera frugiperda, and common armyworm, Pseudaletia unipuncta), cutworms, weevils (Sphenophorus spp., such as S. venatus verstitus and S. parvulus), and grass borers (such as Crambus spp. and tropical grass borer, Herpetogramma phaeopteralis).
[0468] The present invention can also be used to control insect pests in turfgrass that live above ground and feed on turfgrass leaves, including wheat stink bugs (such as the southern wheat stink bug, Blissus insularis), Bermudagrass mite (Eriophyes cynodoniensis), Grass mealybug (Antonina graminis), Propsapia bicincta, leafhoppers, cutworms (Noctuidae), and Schizaphis graminis.
[0469] The present invention may also be used to control other pests in turfgrass, such as introduced red imported fire ants (Solenopsis invicta) which create nests in the lawn.
[0470] In the hygiene sector, the compositions according to the invention are effective against epiphytic parasites such as hard ticks, soft ticks, scabies, autumn mites, flies (biting and licking), parasitic fly larvae, lice, hair lice, bird lice and fleas.
[0471] Examples of such parasites are:
[0472] From the order of the Pediculus: Haematopus spp., Linognathus spp., Pediculus spp., and Phtirus spp., Phidirus spp.
[0473] From the order Trichophagus: Felicola spp., Felicola spp., Felicola spp., Felicola spp., Werneckiella spp., Lepikentron spp., Felicola spp., Felicola spp. and Felicola spp.
[0474] From the order Diptera and the suborder Nematocerina and Brachycerina, for example, Aedes spp., Anopheles spp., Culex spp., Simulium spp., Eusimulium spp., Phlebotomus spp., Lutzomyia spp., Culicoides spp., Chrysops spp., Hybomitra spp., Atylotus spp., Tabanus spp., Haematopota spp., Philipomyia spp., Braula spp. spp.), Musca spp., Hydrotaea spp., Biting flies spp., Haematobia spp., Morellia spp., Fannia spp., Glossina spp., Calliphora spp., Lucilia spp., Chrysomyia spp., Wohlfahrtia spp., Sarcophaga spp., Oestrus spp., Hypoderma spp., Gasterophilus spp., Hippobosca spp., Lipoptena spp.) and tick species (Melophagus spp.).
[0475] From the order of the Siphonapterida, for example, Pulex spp., Ctenocephalides spp., Xenopsylla spp., Ceratophyllum spp.
[0476] From the order of the Heteropterida, for example, Cimex spp., Trypanosoma spp., Echinostoma spp., Panstrongylus spp.
[0477] From the order of the Blattarida, for example, Blatta orientalis, Periplaneta americana, Blattelagermanica and Supella spp.
[0478] The subclass Acaria (family Acarida) and the orders Meta-stigmata and Meso-stigmata, for example Argas spp., Ornithodorus spp., Otobius spp., Ixodes spp., Amblyomma spp., Boophilus spp., Dermacentor spp., Haemophysalis spp., Hyalomma spp., Rhipicephalus spp., Dermanyssus spp., Raillietia spp., Pneumonyssus spp. spp.), Sternostoma spp., and Varroa spp.
[0479] From the order Actinedida (suborder Prostigmata) and Acaridida (suborder Astigmata), for example, Acarapis spp., Cheyletiella spp., Ornithocheyletia spp., Myobia spp., Psorergates spp., Demodex spp., Trombicula spp., Listrophorus spp., Acarus spp., Tyrophagus spp., Caloglyphus spp., Hypodectes spp., Pterolichus spp. spp.), Psoroptes spp., Chorioptes spp., Otodectes spp., Sarcoptes spp., Notoedress spp., Knemidocoptes spp., Cytodites spp., and Laminosioptes spp.
[0480] The compositions according to the invention are also suitable for protecting materials in the case of, for example, wood, textiles, plastics, adhesives, glues, paints, paper and card, leather, floor coverings and construction from infestation by insects.
[0481] The compositions according to the invention can be used, for example, to combat the following pests: beetles, such as the house beetle, the longhaired beetle, the furniture beetle, the red-haired beetle, the comb-horn vein beetle, the Dendrobium pertinex, the pine twig beetle, the Priobium carpini, the brown powder beetle, the African powder beetle, the southern powder beetle, the oak powder beetle, the soft-haired powder beetle, the breast powder beetle, the scale-haired powder beetle, the wood beetle species, the wood beetle species, the coffee black beetle, the oak beetle, the brown beetle, the two-spined beetle and the bamboo beetle; and also hymenoptera, such as the blue-black bumblebee, the giant bumblebee, the Taiga bumblebee and Urocerus augur; and termites, such as the European wood termite (Kalotermes flavicollis), hemp-headed sand-building termites, Indian and Pakistani structural wood heterotermes, yellow-chested reticulate termites, Sant's reticulate termites, European reticulate termites, Darwin's Australian termites, Nevada ancient termites and house termites; and borers, such as silverfish. The compounds of formula I and I'a or their salts are particularly suitable for controlling one or more pests selected from the following families: Noctuidae, Diamondback moth, Chrysomelidae, Thripidae, Pentatomidae, Toricidae, Delphacidae, Aphididae, Noctuidae, Pyralidae, Root-knot nematode family and Heterodera family. In a preferred embodiment of each aspect, compound TX (wherein the abbreviation "TX" means "a compound selected from the compounds defined in Groups 1 to 90 and Tables P1 to P11") controls one or more pests selected from the following families: Noctuidae, Diamondback moth, Chrysomelidae, Thripidae, Pentatomidae, Toricidae, Delphacidae, Aphididae, Noctuidae, Pyralidae, Root-knot nematode family and Heterodera family.
[0482] The compounds of formula I and I'a or their salts are particularly suitable for controlling one or more pests selected from the following genera: Spodoptera species, diamondback moth species, flower thrips species, Thrips species, American stink bug species, Cydia species, brown rice hopper species, peach aphid species, Aphis species, root firefly species, aphid species, Spodoptera species and grass borer species. In a preferred embodiment of each aspect, compound TX (wherein the abbreviation "TX" means "a compound selected from the compounds defined in groups 1 to 90 and Tables P1 to P11") controls one or more pests selected from the following genera: Spodoptera species, diamondback moth species, flower thrips species, Thrips species, American stink bug species, Cydia species, brown rice hopper species, peach aphid species, Aphis species, root firefly species, aphid species, Spodoptera species and grass borer species.
[0483] The compounds of formula I and I'a or their salts are particularly useful for controlling one or more of the following: Spodoptera littoralis, Plutella xylostella, western flower thrips, Thrips tabaci, American hero stink bug, codling moth, brown rice hopper, peach aphid, soybean looper, bean aphid, cucumber leaf beetle, cereal aphid, and striped stem borer.
[0484] In a preferred embodiment of each aspect, compound TX (wherein the abbreviation "TX" means "a compound selected from the compounds defined in Groups 1 to 90 and Tables P1 to P11") controls one or more of the following: Spodoptera littoralis, Plutella xylostella, western flower thrips, Thrips tabaci, American hero stink bug, codling moth, brown rice hopper, peach aphid, soybean looper, bean aphid, cucumber leaf beetle, cereal aphid, and striped stem borer, such as Spodoptera littoralis+TX, Plutella xylostella+TX, western flower thrips+TX, Thrips tabaci+TX, American hero stink bug+TX, codling moth+TX, brown rice hopper+TX, peach aphid+TX, soybean looper+TX, bean aphid+TX, cucumber leaf beetle+TX, cereal aphid+TX, and striped stem borer+TX.
[0485] In an embodiment of each aspect, a compound from Groups 1 to 90 and Tables P1 to P11 is suitable for controlling Spodoptera littoralis, Plutella xylostella, western flower thrips, tabaci thrips, American stink bug, codling moth, brown rice hopper, peach aphid, soybean looper, bean aphid, cucumber leaf beetle, cereal aphid, and striped stem borer on cotton, vegetables, corn, corn, rice and soybean crops.
[0486] In an embodiment, a compound from Groups 1 to 90 and Tables P1 to P11 is suitable for controlling Mamestra (preferably on vegetables), Codling moth (preferably on apples), Empoasca (preferably on vegetables, vineyards), Leptinotarsa (preferably on potatoes) and Chilo suppressalis (preferably on rice).
[0487] The compounds according to the invention may have any number of benefits, including, inter alia, favorable levels of biological activity for protecting plants against insects or superior properties for use as agrochemical active ingredients (e.g., higher biological activity, favorable activity spectrum, increased safety (against non-target organisms above and below ground (such as fish, birds and bees)), improved physico-chemical properties, or increased biodegradability). In particular, it has been unexpectedly found that certain compounds of formula (I) may exhibit favorable safety relative to non-target arthropods, particularly pollinators (such as honey bees, solitary bees and bumble bees). Most particularly, relative to the Italian honey bee (Apis mellifera).
[0488] The compounds according to the invention can be used as pesticides in unmodified form, but they are usually formulated into compositions in various ways using formulation adjuvants such as carriers, solvents and surface-active substances. These formulations can be in different physical forms, for example in the form of dusting powders, gels, wettable powders, water-dispersible granules, water-dispersible tablets, effervescent compressed tablets, emulsifiable concentrates, microemulsifiable concentrates, oil-in-water emulsions, flowable oils, aqueous dispersions, oily dispersions, suspoemulsions, capsule suspensions, emulsifiable granules, soluble liquids, water-soluble concentrates (with water or water-miscible organic solvents as carriers), impregnated polymer films or in other forms known, for example, from Manual on Development and Use of FAO and WHO Specifications for Pesticides, United Nations, 1st edition, second revision (2010). Such formulations can be used directly or can be diluted before use. Dilution can be carried out with, for example, water, liquid fertilizers, micronutrients, biological organisms, oils or solvents.
[0489] These formulations can be prepared, for example, by mixing the active ingredient with a formulation adjuvant in order to obtain a composition in the form of a finely divided solid, granules, solution, dispersion or emulsion. The active ingredients can also be formulated with other adjuvants, such as finely divided solids, mineral oils, oils of plant or animal origin, modified oils of plant or animal origin, organic solvents, water, surface-active substances or combinations thereof.
[0490] These active ingredients can also be contained in very fine microcapsules. Microcapsules contain active ingredients in porous carriers. This allows the active ingredients to be released (e.g., slowly released) to the environment in controlled amounts. Microcapsules typically have a diameter of from 0.1 to 500 microns. The amount of active ingredients they contain is about 25% to 95% of the capsule weight by weight. These active ingredients can be in the form of an integral solid, in the form of fine particles in a solid or liquid dispersion, or in the form of a suitable solution. The encapsulated membrane can include, for example, natural or synthetic rubber, cellulose, styrene / butadiene copolymers, polyacrylonitrile, polyacrylate, polyester, polyamide, polyurea, polyurethane or chemically modified polymers and starch xanthate or other polymers known to those skilled in the art. Alternatively, very fine microcapsules can be formed, in which the active ingredients are contained in the form of finely dispersed particles in a solid matrix of a base material, but these microcapsules themselves are not wrapped.
[0491] Formulation adjuvants suitable for preparing the compositions according to the invention are known per se. As liquid carriers there may be used: water, toluene, xylene, petroleum ether, vegetable oils, acetone, methyl ethyl ketone, cyclohexanone, anhydrides, acetonitrile, acetophenone, amyl acetate, 2-butanone, butylene carbonate, chlorobenzene, cyclohexane, cyclohexanol, alkyl acetates, diacetone alcohol, 1,2-dichloropropane, diethanolamine, p-diethylbenzene, diethylene glycol, diethylene glycol rosinate, diethylene glycol butyl ether, diethylene glycol ethyl ether, diethylene glycol methyl ether, N,N-dimethyl Formamide, dimethyl sulfoxide, 1,4-dioxane, dipropylene glycol, dipropylene glycol methyl ether, dipropylene glycol dibenzoate, dipropylene glycol, alkyl pyrrolidone, ethyl acetate, 2-ethylhexanol, ethylene carbonate, 1,1,1-trichloroethane, 2-heptanone, α-pinene, d-limonene, ethyl lactate, ethylene glycol, ethylene glycol butyl ether, ethylene glycol methyl ether, γ-butyrolactone, glycerol, acetic acid glyceryl, diacetic acid glyceryl, triacetin, decaglycerol Hexadecane, hexanediol, isoamyl acetate, isobornyl acetate, isooctane, isophorone, cumene, isopropyl myristate, lactic acid, laurylamine, mesityl oxide, methoxypropanol, methyl isoamyl ketone, methyl isobutyl ketone, methyl laurate, methyl octanoate, methyl oleate, dichloromethane, m-xylene, n-hexane, n-octylamine, octadecanoic acid, octylamine acetate, oleic acid, oleylamine, o-xylene, phenol, polyethylene glycol, propionic acid, propyl lactate , propylene carbonate, propylene glycol, propylene glycol methyl ether, p-xylene, toluene, triethyl phosphate, triethylene glycol, xylene sulfonic acid, paraffin, mineral oil, trichloroethylene, perchloroethylene, ethyl acetate, amyl acetate, butyl acetate, propylene glycol methyl ether, diethylene glycol methyl ether, methanol, ethanol, isopropanol and higher molecular weight alcohols such as amyl alcohol, tetrahydrofuranol, hexanol, octanol, ethylene glycol, propylene glycol, glycerol, N-methyl-2-pyrrolidone, etc.
[0492] Suitable solid carriers are, for example, talc, titanium dioxide, pyrophyllite clay, silica, attapulgite clay, diatomaceous earth, limestone, calcium carbonate, bentonite, calcium montmorillonite, cottonseed hulls, wheat flour, soybean flour, pumice, wood flour, ground walnut shells, lignin and similar substances.
[0493] Many surface-active substances can be used advantageously in both solid and liquid formulations, especially in those formulations which can be diluted with a carrier before use. Surface-active substances can be anionic, cationic, nonionic or polymeric and they can act as emulsifying agents, wetting agents or suspending agents or for other purposes. Typical surface-active substances include, for example, salts of alkyl sulfates, such as diethanolammonium dodecyl sulfate; salts of alkylarylsulfonates, such as calcium dodecylbenzenesulfonate; alkylphenol / alkylene oxide addition products, such as ethoxylated nonylphenol; alcohol / alkylene oxide addition products, such as ethoxylated tridecanol; soaps, such as sodium stearate; salts of alkylnaphthalenesulfonates, such as sodium dibutylnaphthalenesulfonate; salts of dialkylsulfosuccinates, such as sodium di(2-ethylhexyl)sulfosuccinate; sorbitol esters, such as sorbitan oleate; quaternary ammoniums, such as dodecyltrimethylammonium chloride; polyethylene glycol esters of fatty acids, such as polyethylene glycol stearate; block copolymers of ethylene oxide and propylene oxide; and salts of mono- and dialkyl phosphates; and also other substances, such as are described in: McCutcheon's Detergents and Emulsifiers Annual, MC Publishing Company (MC Publishing Corp., Ridgewood New Jersey (1981).
[0494] Additional adjuvants that can be used in pesticidal formulations include crystallization inhibitors, viscosity modifiers, suspending agents, dyes, antioxidants, foaming agents, light absorbers, mixing aids, defoamers, complexing agents, substances and buffers that neutralize or change the pH, corrosion inhibitors, fragrances, wetting agents, absorption enhancers, micronutrients, plasticizers, glidants, lubricants, dispersants, thickeners, antifreeze agents, microbicides, and liquid and solid fertilizers.
[0495] The composition according to the invention may comprise an additive comprising an oil of plant or animal origin, a mineral oil, an alkyl ester of such an oil or a mixture of such an oil with an oil derivative. The amount of the oil additive in the composition according to the invention is generally from 0.01% to 10% based on the mixture to be applied. For example, the oil additive can be added to the spray tank in the desired concentration after the spray mixture has been prepared. Preferred oil additives include mineral oil or oil of plant origin, such as rapeseed oil, olive oil or sunflower oil; emulsified vegetable oils; alkyl esters of oils of plant origin, such as methyl derivatives; or oils of animal origin, such as fish oil or tallow. Preferred oil additives include C 8 -C 22 Alkyl esters of fatty acids, especially C 12 -C 18Methyl derivatives of fatty acids, such as the methyl esters of lauric acid, palmitic acid and oleic acid (methyl laurate, methyl palmitate and methyl oleate, respectively). Many oil derivatives are known from the Compendium of Herbicide Adjuvants, 10th edition, Southern Illinois University, 2010.
[0496] These compositions according to the invention generally comprise from 0.1% to 99% by weight, in particular from 0.1% to 95% by weight, of a compound according to the invention and from 1% to 99.9% by weight of a formulation auxiliary, which preferably comprises from 0 to 25% by weight of a surface-active substance. Whereas commercial products may preferably be formulated as concentrates, the end user will generally use dilute formulations.
[0497] The application rate varies within a wide range and depends on the nature of the soil, the application method, the crop plants, the harmful organisms to be controlled, the prevailing climatic conditions, and other factors governed by the application method, the application time and the target crop. In general, the compound can be applied at a rate of from 1 l / ha to 2000 l / ha, especially from 10 l / ha to 1000 l / ha.
[0498] Preferred formulations may have the following composition (wt%):
[0499] Emulsifiable concentrates :
[0500] Active ingredient: 1% to 95%, preferably 60% to 90%
[0501] Surfactant: 1% to 30%, preferably 5% to 20%
[0502] Liquid carrier: 1% to 80%, preferably 1% to 35%
[0503] Dust Agent :
[0504] Active ingredient: 0.1% to 10%, preferably 0.1% to 5%
[0505] Solid carrier: 99.9% to 90%, preferably 99.9% to 99%
[0506] Suspension concentrate:
[0507] Active ingredient: 5% to 75%, preferably 10% to 50%
[0508] Water: 94% to 24%, preferably 88% to 30%
[0509] Surfactant: 1% to 40%, preferably 2% to 30%
[0510] Wettable powder :
[0511] Active ingredient: 0.5% to 90%, preferably 1% to 80%
[0512] Surfactant: 0.5% to 20%, preferably 1% to 15%
[0513] Solid carrier: 5% to 95%, preferably 15% to 90%
[0514] Granules:
[0515] Active ingredient: 0.1% to 30%, preferably 0.1% to 15%
[0516] Solid carrier: 99.5% to 70%, preferably 97% to 85%
[0517] The following examples further illustrate (but do not limit) the present invention.
[0518] Wettable powder a) b) c) Active ingredients 25% 50% 75% Sodium lignin sulfonate 5% 5% - Sodium lauryl sulfate 3% - 5% Sodium diisobutylnaphthalene sulfonate - 6% 10% Phenol polyglycol ether (7-8 mol of ethylene oxide) - 2% - Highly dispersed silicic acid 5% 10% 10% Kaolin 62% 27% -
[0519] The combination is thoroughly mixed with the adjuvants and the mixture is thoroughly ground in a suitable grinder to obtain wettable powders which can be diluted with water to give a suspension of the desired concentration.
[0520] Powders for dry seed treatment a) b) c) Active ingredients 25% 50% 75% Light mineral oil 5% 5% 5% Highly dispersed silicic acid 5% 5% - Kaolin 65% 40% - talc - 20%
[0521] The combination is thoroughly mixed with adjuvants and the mixture is thoroughly ground in a suitable grinder to obtain a dust that can be used directly for seed treatment.
[0522] Emulsifiable concentrates Active ingredients 10% Octylphenol polyglycol ether (4-5 mol of ethylene oxide) 3% Calcium dodecylbenzenesulfonate 3% Castor oil polyglycol ether (35 mol of ethylene oxide) 4% Cyclohexanone 30% Xylene mixture 50%
[0523] Emulsions of any desired dilution which can be used in plant protection can be obtained from these concentrates by dilution with water.
[0524] Dust powder a) b) c) Active ingredients 5% 6% 4% talc 95% - - Kaolin - 94% - Mineral fillers - - 96%
[0525] Ready-to-use dusts are obtained by mixing the combination with a carrier and grinding the mixture in a suitable grinder. Such dusts can also be used for dry seed dressing of seeds.
[0526] Extruder pellets Active ingredients 15% Sodium lignin sulfonate 2% Carboxymethyl cellulose 1% Kaolin 82%
[0527] The combination is mixed and ground with the adjuvants, and the mixture is moistened with water.
[0528] The mixture is extruded and then dried in a stream of air.
[0529] Coated granules Active ingredients 8% Polyethylene glycol (molecular weight 200) 3% Kaolin 89%
[0530] This finely ground combination is applied uniformly in a mixer to the kaolin moistened with polyethylene glycol. In this way, dust-free coated granules are obtained.
[0531] Suspension concentrates
[0532] Active ingredients 40% Propylene glycol 10% Nonylphenol polyglycol ether (15 mol of ethylene oxide) 6% Sodium lignin sulfonate 10% Carboxymethyl cellulose 1% Silicone oil (in the form of a 75% emulsion in water) 1% water 32%
[0533] The finely ground combination is intimately mixed with adjuvants to give a suspension concentrate from which any desired dilution can be obtained by dilution with water. Using such dilutions, living plants together with plant propagation materials can be treated and protected against microbial infestation by spraying, pouring or immersion.
[0534] Flowable concentrate for seed treatment
[0535]
[0536]
[0537] The finely ground combination is intimately mixed with adjuvants to give a suspension concentrate from which any desired dilution can be obtained by dilution with water. Using such dilutions, living plants together with plant propagation materials can be treated and protected against microbial infestation by spraying, pouring or immersion.
[0538] Extended-release capsule suspension
[0539] 28 parts of the combination are mixed with 2 parts of an aromatic solvent and 7 parts of a toluene diisocyanate / polymethylene-polyphenyl isocyanate mixture (8:1). This mixture is emulsified in a mixture of 1.2 parts of polyvinyl alcohol, 0.05 parts of a defoamer and 51.6 parts of water until the desired particle size is reached. To this emulsion are added 2.8 parts of a 1,6-hexanediamine mixture in 5.3 parts of water. The mixture is stirred until the polymerization is complete. The obtained capsule suspension is stabilized by adding 0.25 parts of a thickener and 3 parts of a dispersant. The capsule suspension formulation contains 28% of active ingredient. The diameter of the medium capsules is 8-15 microns. The resulting formulation is applied to the seeds as an aqueous suspension in a device suitable for this purpose.
[0540] Formulation types include emulsion concentrates (EC), suspension concentrates (SC), suspoemulsions (SE), capsule suspensions (CS), water-dispersible granules (WG), emulsifiable granules (EG), emulsions, water-in-oil emulsions (EO), oil-in-water emulsions (EW), microemulsions (ME), oil dispersions (OD), oil suspensions (OF), oil-soluble liquids (OL), soluble concentrates (SL), ultra low volume suspensions (SU), ultra low volume liquids (UL), master batches (TK), dispersible concentrates (DC), wettable powders (WP), soluble granules (SG) or any technically feasible formulation in combination with agriculturally acceptable adjuvants.
[0541] Preparation Example:
[0542] LCMS method:
[0543] Method 1:
[0544] Spectra were recorded on an ACQUITY mass spectrometer (SQD or SQDII single quadrupole mass spectrometer) from Waters Corporations equipped with an electrospray source (polarity: positive or negative, capillary: 3.0 kV, cone: 30 V, extractor: 3.00 V, source temperature: 150°C, desolvation temperature: 400°C, cone gas flow: 60 L / hr, desolvation gas flow: 700 L / hr, mass range: 140 to 800 Da), and an ACQUITY UPLC from Waters Corporation (with solvent degasser, binary pump, heated column compartment, and diode array detector). Column: Waters UPLC HSST3, 1.8 μm, 30×2.1 mm, temperature: 60°C, DAD wavelength range (nm): 210 to 400, solvent gradient: A=water / methanol 9:1+0.1% formic acid, B=acetonitrile+0.1% formic acid, gradient: 0%-100% B in 2.5 min; flow rate (ml / min) 0.75.
[0545] Method 2 :
[0546] Spectra were recorded on a mass spectrometer from Waters (SQD, SQDII single quadrupole mass spectrometer) equipped with an electrospray source (polarity: positive and negative, capillary: 3.00 kV, cone range: 30 V, extractor: 2.00 V, source temperature: 150°C, desolvation temperature: 350°C, cone gas flow: 50 l / h, desolvation gas flow: 650 l / h; mass range: 100 to 900 Da) and an Acquity UPLC from Waters: binary pump, heated column compartment, diode array detector and ELSD detector. Column: Waters UPLC HSS T3, 1.8 μm, 30×2.1 mm, temperature: 60° C., DAD wavelength range (nm): 210 to 500, solvent gradient: A=water+5% MeOH+0.05% HCOOH, B=acetonitrile+0.05% HCOOH; gradient: 10%-100% B in 1.2 min; flow rate (ml / min) 0.85.
[0547] Method 3:
[0548] Spectra were recorded on a ZQ mass spectrometer (single quadrupole mass spectrometer) from Waters Corporation;
[0549] Instrument parameters: Ionization method: electrospray polarity: positive (negative) ion; capillary (kV) 3.00, cone (V) 30.00, extractor (V) 2.00, gas temperature (°C) 350, drying gas flow (mL / min) 9.8, plasma gas pressure (Neb press) 45 psig, mass range: 90 to 1000 Da.
[0550] LC: HP 1100 HPLC from Agilent: solvent degasser, quaternary pump (ZCQ) / binary pump (ZDQ), heated column compartment and diode array detector. Column: porpshell 120C18, 2.7 μm particle size, 120 angstroms, 4.6×50 mm; temperature: 30° C. DAD wavelength range (nm): 190 to 400 Solvent gradient: A=water+0.1% HCOOH. B=acetonitrile+0.08% HCOOH.
[0551]
[0552] Method 4:
[0553] Spectra were recorded on a mass spectrometer from Waters (SQD single quadrupole mass spectrometer) equipped with an electrospray source (polarity: positive or negative ion, full scan, capillary: 3.00 kV, cone range: 41 V, source temperature: 150°C, desolvation temperature: 500°C, cone gas flow: 50 L / Hr, desolvation gas flow: 1000 L / Hr; mass range: 110 to 800 Da) and an H-Class UPLC from Waters: quaternary pump, heated column compartment and diode array detector. Column: Acquity UPLC HSS T3 C18, 1.8 μm, 30×2.1 mm, temperature: 40°C, DAD wavelength range (nm): 200 to 400, solvent gradient: A = water + 5% acetonitrile + 0.1% HCOOH, B = acetonitrile + 0.05% HCOOH; Gradient: 0 min 10% B; 0.-0.2 min 10%-50% B; 0.2-0.7 min 50%-100% B; 0.7-1.3 min 100% B; 1.3-1.4 min 100%-10% B; 1.4-1.6 min 10% B; flow rate (mL / min) 0.6.
[0554] Method 5:
[0555] Spectra were recorded on a mass spectrometer from Agilent Technologies (6410 triple quadrupole mass spectrometer) equipped with an electrospray source (polarity: positive or negative ion, MS2 scan, capillary: 4.00 kV, fragmentor: 100 V, desolvation temperature: 350°C, gas flow: 11 L / min, nebulizer gas: 45 psi, mass range: 110 to 1000 Da) and a 1200 series HPLC from Agilent: quaternary pump, heated column compartment and diode array detector. Column: KINETEX EVO C18, 2.6 μm, 50×4.6 mm, temperature: 40°C, DAD wavelength range (nm): 210 to 400, solvent gradient: A=95% (water+0.1% HCOOH): 5% acetonitrile, B=acetonitrile with 0.1% HCOOH: gradient: 0 min 10% B; 0.9-1.8 min 100% B; 1.8 -2.2 min 100%-10% B; 2.2-2.5 min 10% B, flow rate (mL / min) 1.8.
[0556] The following abbreviations are used in the experimental descriptions that follow: s = singlet, d = doublet, t = triplet, q = quartet, m = multiplet, RT = retention time, min = minute. Example P1: 5-[4-(5-methyl-1,2,4-oxadiazol-3-yl)piperidin- 1-carbonyl]-6-(trifluoromethyl)-2-[[4-(trifluoromethyl)phenyl]methoxy]pyridine-3-carbonitrile (Compound P1.1):
[0557]
[0558] Step 1: Ethyl 5-cyano-6-hydroxy-2-(trifluoromethyl)pyridine-3-carboxylate
[0559]
[0560] At 4 ° C, a solution of sodium ethoxide (1.1 eq) in ethanol (20% w / w) was slowly added to a suspension of 2-cyano-acetamide (5.9 g, 70.2 mmol, 1 eq), and the mixture was stirred for 15 minutes. Then a solution of 2-(ethoxymethylene)-4,4,4-trifluoro-3-oxo-butyric acid ethyl ester (17 g, 70.1 mmol) in 34 ml of ethanol was added under ice cooling. The reaction mixture was stirred for 16 hours and allowed to reach room temperature. The reaction mixture was then poured into an ice-cold 1N hydrochloric acid solution. The resulting mixture was diluted with ice-cold water and stirred for 20 minutes. The precipitate was filtered, washed twice with ice-cold water and dried. 12.4 g of 5-cyano-6-hydroxy-2-(trifluoromethyl)pyridine-3-ethyl formate was obtained, with a purity greater than 95% as determined by quantitative NMR. CDCl 3 In 1 H-NMR[ppm]:1.29(t,3H),4.29(q,2H),8.27(s,1H).
[0561] Step 2: 5-Cyano-6-hydroxy-2-(trifluoromethyl)pyridine-3-carboxylic acid
[0562]
[0563] 5-cyano-6-hydroxy-2-(trifluoromethyl)pyridine-3-carboxylic acid ethyl ester (27.5g, 106mmol) was dissolved in ethanol (846mL) and potassium hydroxide (20.9g, 19.9mL, 317mmol, 3.0eq) dissolved in ethanol (211mL) was added. The reaction mixture was stirred at reflux for 20 hours. The reaction mixture was then diluted with ethyl acetate and 2N hydrochloric acid. The mixture was extracted three times with ethyl acetate. The combined organic layers were washed twice with water and once with brine, dried over sodium sulfate and the solvent was removed. 24.0g of 5-cyano-6-hydroxy-2-(trifluoromethyl)-pyridine-3-carboxylic acid was obtained as a yellow solid. DMSO in 1 H-NMR [ppm]: 8.69 (s, 1H), 13.85 (wide s, 2H). LC-MS (method 2): RT = 0.24 min; [M+H] + =233.
[0564] Step 3: 2-Hydroxy-5-[4-(5-methyl-1,2,4-oxadiazol-3-yl)piperidine-1-carbonyl]-6-(trifluoromethyl)pyridine-3-carbonitrile
[0565]
[0566] To a solution of 5-cyano-6-hydroxy-2-(trifluoromethyl)pyridine-3-carboxylic acid (26.0 g, 112 mmol) in DMF (840 mL) was added the hydrochloride salt of 5-methyl-3-(4-piperidinyl)-1,2,4-oxadiazole (25.1 g, 123 mmol, 1.1 eq) (synthesized as described in Nippon Soda patent application WO 2017195703). HATU (48.3 g, 123 mmol, 1.1 eq) and diisopropyl-ethylamine (88.5 mL, 515 mmol, 4.6 eq) were subsequently added. The reaction mixture was stirred at room temperature for 24 h and then poured into NaHCO 3 The mixture was extracted 3 times with ethyl acetate. The aqueous layer was acidified with 2N HCl and extracted 3 times with ethyl acetate. The combined organic layers were washed with brine, purified by Na 2 SO 4 Dry, filter and concentrate under reduced pressure. The residue is purified by combiflash. 440 mg of 2-hydroxy-5-[4-(5-methyl-1,2,4-oxadiazol-3-yl)piperidine-1-carbonyl]-6-(trifluoromethyl)pyridine-3-carbonitrile are obtained as white foam. CDCl 3 In 1 H-NMR [ppm]: 1.72-2.10 (m, 3H), 2.13-2.24 (m, 1H), 2.64 (s, 3H), 3.08-3.30 (m, 3H), 3.44-3.58 (m, 1H), 4.61 (dd, 1H), 8.91 and 8.98 (2s, 1H). LC-MS (Method 2): RT = 0.72 min; [M+H] + =382.
[0567] Step 4: 5-[4-(5-methyl-1,2,4-oxadiazol-3-yl)piperidine-1-carbonyl]-6-(trifluoromethyl)-2-[[4-(trifluoromethyl)phenyl]methoxy]pyridine-3-carbonitrile (Compound P1.1)
[0568]
[0569] To a solution of 2-hydroxy-5-[4-(5-methyl-1,2,4-oxadiazol-3-yl)piperidine-1-carbonyl]-6-(trifluoromethyl)pyridine-3-carbonitrile (4.40 g, 11.5 mmol) in acetone (58 mL) was added 4-(trifluoromethyl)-benzyl bromide (4.14 g, 2.68 mL, 17.3 mmol, 1.5 eq), followed by sodium iodide (1.73 g, 11.5 mmol, 1.0 eq) and potassium carbonate (4.88 g, 34.6 mmol, 3.0 eq). The reaction mixture was stirred at 70 ° C for 2 hours, cooled to room temperature and filtered. After removal of the solvent, the residue was purified by Combiflash. 4.97 g of 5-[4-(5-methyl-1,2,4-oxadiazol-3-yl)piperidine-1-carbonyl]-6-(trifluoromethyl)-2-[[4-(trifluoromethyl)phenyl]methoxy]pyridine-3-carbonitrile were obtained as a white solid. CDCl 3 In 1 H-NMR [ppm]: 1.7-2.05 (m, 3H), 2.12-2.24 (m, 1H), 2.59 (s, 3H), 3.02-3.26 (m, 3H), 3.40-3.51 (m, 1H), 4.51-4.68 (m, 1H), 5.62 (s, 2H), 7.62-7.71 (m, 4H), 7.94 and 7.98 (2s, 1H). LC-MS (Method 2): RT = 1.14 min; [M+H] + =540. Example P2: 6-methyl-5-[4-(5-methyl-1,2,4-oxadiazol-3-yl)piperidin [[4-(trifluoromethyl)phenyl]methoxy]pyridine-1-carbonyl]-2-[[4-(trifluoromethyl)phenyl]methoxy]pyridine-3-carbonitrile (Compound P1.43):
[0570]
[0571] Step 1: 5-cyano-2-methyl-6-[[4-(trifluoromethyl)phenyl]methoxy]pyridine-3-carboxylic acid ethyl ester:
[0572]
[0573] To a solution of 5-cyano-6-hydroxy-2-methyl-pyridine-3-carboxylic acid ethyl ester (500 mg, 2.42 mmol) in acetone (12 mL) synthesized as described in Sinochem patent application WO 2015032280, sodium iodide (383 mg, 3.42 mmol, 1.0 eq) and potassium carbonate (1.03 g, 7.27 mmol, 3.0 eq) were added, followed by addition of 4-(trifluoromethyl)-benzyl bromide (869 mg, 3.64 mmol, 1.5 eq). The reaction mixture was stirred at 70 ° C for 20 hours, cooled to room temperature and filtered. After removing the solvent, the residue was purified by silica gel column. 340 mg of 5-cyano-2-methyl-6-[[4-(trifluoromethyl)phenyl]methoxy]pyridine-3-carboxylic acid ethyl ester was obtained as a white solid. CDCl 3 In 1 H-NMR [ppm]: 1.41 (t, 3H), 2.84 (s, 3H), 4.39 (q, 2H), 5.63 (s, 2H), 7.62-7.70 (m, 4H), 8.49 (s, 1H). LC-MS (Method 2): RT = 1.24 min; [M+H] + =365.
[0574] Step 2: 5-Cyano-2-methyl-6-[[4-(trifluoromethyl)phenyl]methoxy]pyridine-3-carboxylic acid:
[0575]
[0576] 5-cyano-2-methyl-6-[[4-(trifluoromethyl)phenyl]methoxy]pyridine-3-carboxylic acid ethyl ester (340mg, 0.933mmol) was dissolved in tetrahydrofuran (2.3mL) and water (1.3mL) and lithium hydroxide monohydrate (160mg, 3.73mmol, 4eq) was added. The reaction mixture was stirred at room temperature for 2 hours. The reaction mixture was then diluted with ethyl acetate and 2N hydrochloric acid. The mixture was extracted three times with ethyl acetate. The combined organic layers were washed twice with water and once with brine, dried over sodium sulfate and the solvent was removed. 210mg of 5-cyano-2-methyl-6-[[4-(trifluoromethyl)phenyl]methoxy]-pyridine-3-carboxylic acid was obtained as a white solid. DMSO 1 H-NMR [ppm]: 2.74 (s, 3H), 5.68 (s, 2H), 7.72 (d, 2H), 7.81 (d, 2H), 8.61 (s, 1H), 13.41 (wide s, 1H). LC-MS (method 2): RT = 1.06 min; [M+H] + =337.
[0577] Step 3: 6-methyl-5-[4-(5-methyl-1,2,4-oxadiazol-3-yl)piperidine-1-carbonyl]-2-[[4-(trifluoromethyl)phenyl]methoxy]pyridine-3-carbonitrile (Compound P1.43):
[0578]
[0579] To a solution of 5-cyano-2-methyl-6-[[4-(trifluoromethyl)phenyl]methoxy]-pyridine-3-carboxylic acid (200 mg, 0.595 mmol) in DMF (6 mL) was added the hydrochloride salt of 5-methyl-3-(4-piperidinyl)-1,2,4-oxadiazole (133 mg, 0.654 mmol, 1.1 eq) (synthesized as described in Soda Co., Ltd. patent application WO 2017195703). HATU (256 mg, 0.654 mmol, 1.1 eq) and diisopropyl-ethylamine (0.37 mL, 2.14 mmol, 3.6 eq) were subsequently added. The reaction mixture was stirred at room temperature for 20 hours and then poured into NaHCO 3 The mixture was extracted 3 times with ethyl acetate. The aqueous layer was acidified with 2N HCl and extracted 3 times with ethyl acetate. The combined organic layers were washed with brine, purified by Na 2 SO 4 The mixture was dried, filtered and concentrated under reduced pressure. The residue was purified by combiflash and reverse phase combiflash. 260 mg of 6-methyl-5-[4-(5-methyl-1,2,4-oxadiazol-3-yl)piperidine-1-carbonyl]-2-[[4-(trifluoromethyl)phenyl]methoxy]-pyridine-3-carbonitrile were obtained as white foam. CDCl 3 In 1 H-NMR [ppm]: 1.70-2.08 (m, 3H), 2.12-2.22 (m, 2H), 2.52 (wide s, 3H), 2.61 (s, 3H), 3.05-3.26 (m, 3H), 3.52-3.62 (m, 1H), 4.60-4.70 (m, 1H), 5.58 (s, 2H), 7.62 (d, 1H), 7.68 (d, 1H), 7.75 (wide s, 1H). LC-MS (Method 2): RT = 1.09 min; [M+H] + =486.
[0580] Example P3: 6-(difluoromethyl)-5-[4-(5-methyl-1,2,4-oxadiazol-3-yl)piperidine-1-carbonyl]-2- [[4-(Trifluoromethyl)phenyl]methoxy]pyridine-3-carbonitrile (Compound P1.48):
[0581]
[0582] Step 1: 5-Cyano-2-(difluoromethyl)-6-hydroxy-pyridine-3-carboxylic acid
[0583]
[0584] 5-cyano-2-(difluoromethyl)-6-hydroxy-pyridine-3-carboxylic acid ethyl ester (4.0 g, 17 mmol) synthesized as described in Soda Co., Ltd. patent application WO 2017195703 was dissolved in ethanol (130 mL) and potassium hydroxide (3.3 g, 50 mmol, 2.9 eq) dissolved in ethanol (33 mL) was added. The reaction mixture was stirred at reflux for 20 hours. The reaction mixture was then diluted with ethyl acetate and 2N hydrochloric acid. The mixture was extracted three times with ethyl acetate. The combined organic layers were washed twice with water and once with brine, dried over sodium sulfate and the solvent was removed. 3.5 g of 5-cyano-2-(difluoromethyl)-6-hydroxy-pyridine-3-carboxylic acid was obtained as a white solid. DMSO 1 H-NMR [ppm]: 7.59 (t, 1H), 8.58 (s, 1H), 13.75 (wide s, 2H). LC-MS (method 2): RT = 0.23 min; [M+H] + =215.
[0585] Step 2: 6-(Difluoromethyl)-2-hydroxy-5-[4-(5-methyl-1,2,4-oxadiazol-3-yl)piperidine-1-carbonyl]pyridine-3-carbonitrile
[0586]
[0587] To a solution of 5-cyano-2-(difluoromethyl)-6-hydroxy-pyridine-3-carboxylic acid (430 mg, 2.01 mmol) in DMF (20 mL) was added the hydrochloride salt of 5-methyl-3-(4-piperidinyl)-1,2,4-oxadiazole (450 mg, 2.21 mmol, 1.1 eq) (synthesized as described in Soda Co., Ltd. patent application WO 2017195703). HATU (866 mg, 2.21 mmol, 1.1 eq) and diisopropyl-ethylamine (1.24 mL, 7.23 mmol, 3.6 eq) were subsequently added. The reaction mixture was stirred at room temperature for 20 hours and then poured into NaHCO 3 The mixture was extracted 3 times with ethyl acetate. The aqueous layer was acidified with 2N HCl and extracted 3 times with ethyl acetate. The combined organic layers were washed with brine, purified by Na 2 SO 4The mixture was dried, filtered and concentrated under reduced pressure. The residue was purified by combiflash and reverse phase combiflash. 440 mg of 6-(difluoromethyl)-2-hydroxy-5-[4-(5-methyl-1,2,4-oxadiazol-3-yl)piperidine-1-carbonyl]pyridine-3-carbonitrile were obtained as white foam. CDCl 3 In 1 H-NMR [ppm]: 1.78-1.98 (m, 2H), 2.01-2.20 (m, 2H), 2.60 (s, 3H), 3.10-3.38 (m, 3H), 3.60-3.72 (m, 1H), 4.40-4.58 (m, 1H), 6.88 (t, 1H), 7.84 and 8.12 (2s, 1H), 11.6 (wide s, 1H). LC-MS (method 2): RT = 0.63 min; [M+H] + =364.
[0588] Step 3: 6-(Difluoromethyl)-5-[4-(5-methyl-1,2,4-oxadiazol-3-yl)piperidine-1-carbonyl]-2-[[4-(trifluoromethyl)phenyl]methoxy]pyridine-3-carbonitrile (Compound P1.48):
[0589]
[0590] To a solution of 6-(difluoromethyl)-2-hydroxy-5-[4-(5-methyl-1,2,4-oxadiazol-3-yl)piperidine-1-carbonyl]pyridine-3-carbonitrile (200 mg, 0.551 mmol) in acetone (2.75 mL) was added 4-(trifluoromethyl)-benzyl bromide (197 mg, 0.826 mmol, 1.5 eq), followed by sodium iodide (87 mg, 0.551 mmol, 1.0 eq) and potassium carbonate (233 mg, 1.65 mmol, 3 eq). The reaction mixture was stirred at 70° C. for 4 hours, cooled to room temperature and filtered. After removal of the solvent, the residue was purified by silica gel chromatography. 240 mg of 6-(difluoromethyl)-5-[4-(5-methyl-1,2,4-oxadiazol-3-yl)piperidine-1-carbonyl]-2-[[4-(trifluoromethyl)phenyl]methoxy]pyridine-3-carbonitrile were obtained as a yellow gum. CDCl 3 In 1H-NMR[ppm]:1.74-2.06(m,3H),2.13-2.23(m,1H),2.59(s,3H),3.05-3.28(m,3H),3.40- 3.51(m,1H),4.51-4.68(m,1H),5.64(s,2H),6.72(t,1H),7.63-7.71(m,4H),7.92(s,1H). LC-MS (method 2): RT=1.10min; [M+H] + =522.
[0591] Example P4: 5-[4-(3,5-dichloro-2-pyridyl)piperazine-1-carbonyl]-6-(trifluoromethyl)-2-[[4-(trifluoro [methyl)phenyl]methoxy]pyridine-3-carbonitrile (Compound P2.1):
[0592]
[0593] Step 1: 5-[4-(3,5-dichloro-2-pyridinyl)piperazine-1-carbonyl]-2-hydroxy-6-(trifluoromethyl)pyridine-3-carbonitrile
[0594]
[0595] To a solution of 5-cyano-6-hydroxy-2-(trifluoromethyl)pyridine-3-carboxylic acid (4.50 g, 19.4 mmol) in DMF (194 mL) was added the hydrochloride salt of 1-(3,5-dichloro-2-pyridyl)piperazine (25.1 g, 123 mmol, 1.1 eq) (synthesized as described in Sinochem patent application WO 2015032280). HATU (8.36 g, 21.3 mmol, 1.1 eq) and diisopropyl-ethylamine (12 mL, 69.8 mmol, 3.6 eq) were subsequently added. The reaction mixture was stirred at room temperature for 4 hours and then poured into NaHCO 3 The mixture was extracted 3 times with ethyl acetate. The aqueous layer was acidified with 2N HCl and extracted 3 times with ethyl acetate. The combined organic layers were washed with brine, purified by Na 2 SO 4 The mixture was dried, filtered and concentrated under reduced pressure. The residue was purified by reverse phase combiflash. 3.90 g of 5-[4-(3,5-dichloro-2-pyridyl)piperazine-1-carbonyl]-2-hydroxy-6-(trifluoromethyl)pyridine-3-carbonitrile were obtained as a white solid. 1 H-NMR [ppm]: 3.01-3.48 (m, 6H), 3.63-3.86 (m, 2H), 8.08 (s, 1H), 8.30 (s, 1H), 8.48 (s, 1H), 13.99 (wide s, 1H). LC-MS (method 2): RT = 1.03 min; [M+H] +=446, 448, 450.
[0596] Step 2: 5-[4-(3,5-dichloro-2-pyridinyl)piperazine-1-carbonyl]-6-(trifluoromethyl)-2-[[4-(trifluoromethyl)phenyl]methoxy]pyridine-3-carbonitrile (Compound P2.1)
[0597]
[0598] To a solution of 5-[4-(3,5-dichloro-2-pyridyl)piperazine-1-carbonyl]-2-hydroxy-6-(trifluoromethyl)-pyridine-3-carbonitrile (200 mg, 0.448 mmol) in acetone (2.24 mL), 4-(trifluoromethyl)-benzyl bromide (161 mg, 0.672 mmol, 1.5 eq) was added, followed by sodium iodide (71 mg, 0.448 mmol, 1.0 eq) and potassium carbonate (190 mg, 1.34 mmol, 3.0 eq). The reaction mixture was stirred at 70 ° C for 4 hours, cooled to room temperature, and filtered. After removing the solvent, the residue was purified by a silica gel column. 240 mg of 5-[4-(3,5-dichloro-2-pyridyl)piperazine-1-carbonyl]-6-(trifluoromethyl)-2-[[4-(trifluoromethyl)phenyl]methoxy]pyridine-3-carbonitrile was obtained as a white foam. CDCl 3 In 1 H-NMR [ppm]: 3.22-3.31 (m, 2H), 3.32-3.49 (m, 4H), 3.85-4.05 (m, 2H), 5.64 (s, 2H), 7.64-7.70 (m, 5H), 7.98 (s, 1H), 8.16 (s, 1H). LC-MS (Method 2): RT = 1.31 min; [M+H] + = 604, 606, 608.
[0599] Example P5: 5-[4-(ethylsulfinylmethyl)piperidine-1-carbonyl]-6-(trifluoromethyl)-2-[[4-(trifluoromethyl)piperidine-1-carbonyl] [1-(4-(2-(4-(2-(phenyl)methoxy)pyridine-3-carbonitrile)] (compound P3.4):
[0600]
[0601] Step 1: tert-Butyl 4-(ethylsulfanylmethyl)piperidine-1-carboxylate
[0602]
[0603] To a solution of tert-butyl 4-(bromomethyl)piperidine-1-carboxylate (10.0 g, 35.9 mmol) in dry DMF (50 mL) at 0°C under argon was added sodium ethylsulfanyl (90.0%, 4.37 g, 46.7 mmol) and the resulting mixture was stirred at room temperature for 18 hours. The reaction mixture was diluted with water / brine, extracted with ether, and purified by Na2 SO 4 The residue was purified by flash chromatography (hexane:ethyl acetate 8:1) to give 9.41 g of tert-butyl 4-(ethylsulfanylmethyl)piperidine-1-carboxylate as a light yellow oil. CDCl 3 In 1 H-NMR[ppm]:1.08-1.18(m,2H),1.24(t,3H),1.44(s,9H),1.58-1.64(m,1H ),1.81(width d,2H),2.45(d,2H),2.51(q,2H),2.62-2.77(m,2H),4.10(width s,2H).
[0604] Step 2: tert-Butyl 4-(ethylsulfinylmethyl)piperidine-1-carboxylate
[0605]
[0606] tert-Butyl 4-(ethylsulfanylmethyl)piperidine-1-carboxylate (6.15 g, 23.2 mmol) was dissolved in chloroform (80 mL) and cooled to 0°C in an ice bath. 3-Chloroperbenzoic acid (77.0%, 5.36 g, 23.9 mmol) was added and the resulting mixture was stirred at room temperature for 6 hours. The reaction mixture was diluted with dichloromethane (500 mL), washed with saturated sodium carbonate and saturated sodium thiosulfate solutions, and purified by Na 2 SO 4 Dry and concentrate under reduced pressure. The residue was purified by flash chromatography (ethyl acetate:methanol 90:10) to give 6.087 g of tert-butyl 4-(ethylsulfinylmethyl)piperidine-1-carboxylate as a white solid. CDCl 3 In 1 H-NMR[ppm]:1.18-1.38(m,2H),1.35(t,3H),1.44(s,9H),1.74-1.77(m,1H),1.98- 2.02(m,1H),2.07-2.16(m,1H),2.39(dd,1H),2.66-2.83(m,5H),4.02-4.24(m,2H).
[0607] Step 3: 4-(Ethylsulfinylmethyl)piperidin-1-ium-2,2,2-trifluoroacetate
[0608]
[0609] To a solution of tert-butyl 4-(ethylsulfinylmethyl)piperidine-1-carboxylate (13.0 g, 42.5 mmol) in dichloromethane (250 mL) was added 2,2,2-trifluoroacetic acid (32.7 mL, 425 mmol) at room temperature under argon and the resulting mixture was stirred at room temperature for 72 hours. The reaction mixture was concentrated under reduced pressure to give 22 g of a brown oily residue, which was then purified by DOWEX 50WX8 to give 7.29 g of 4-(ethylsulfinylmethyl)piperidin-1-ium-2,2,2-trifluoroacetate as a light yellow semisolid (which completely solidified in the refrigerator). DMSO 1 H-NMR [ppm]: 1.19 (t, 3H), 1.40-1.52 (m, 2H), 1.85-1.92 (m, 1H), 1.95-2.01 (m, 1H), 2.04-2.16 (m, 1H), 2.60-2.68 (m, 3H), 2.77-2.83 (m, 1H), 2.86-2.98 (m, 2H), 3.24-3.32 (m, 2H), 8.34 (broad s, 1H), 6.83 (broad s, 1H).
[0610] Step 4: 5-[4-(ethylsulfinylmethyl)piperidine-1-carbonyl]-2-hydroxy-6-(trifluoromethyl)pyridine-3-carbonitrile
[0611]
[0612] To a solution of 5-cyano-6-hydroxy-2-(trifluoromethyl)pyridine-3-carboxylic acid (1.00 g, 4.3 mmol) in DMF (43 mL) was added 4-(ethylsulfinylmethyl)piperidine hydrochloride (1.00 g, 4.74 mmol, 1 eq). HATU (2.7 g, 6.89 mmol, 1.6 eq) and diisopropyl-ethylamine (2.2 mL, 12.9 mmol, 3 eq) were subsequently added. The reaction mixture was stirred at room temperature for 22 hours and then poured into NaHCO 3 The aqueous phase was extracted three times with 2-methyl-tetrahydrofuran. The combined organic layers were washed with water and brine, 2 SO 4 The mixture was dried, filtered and concentrated under reduced pressure. The residue was purified by combiflash. 370 mg of 5-[4-(ethylsulfinylmethyl)piperidine-1-carbonyl]-2-hydroxy-6-(trifluoromethyl)-pyridine-3-carbonitrile was obtained as a slightly yellow solid. 1H-NMR [ppm]: 1.00-1.45 (m, 2H), 1.19 (t, 3H), 1.56-2.16 (m, 3H), 2.55-3.50 (m, 7H), 4.36-4.50 (m, 1H), 8.41 and 8.48 (2s, 1H), 13.2 (wide s, 1H). LC-MS (method 2): RT = 0.58 min; [M+H] + =390.
[0613] Step 5: 5-[4-(ethylsulfinylmethyl)piperidine-1-carbonyl]-6-(trifluoromethyl)-2-[[4-(trifluoromethyl)phenyl]methoxy]pyridine-3-carbonitrile (Compound P3.4)
[0614]
[0615] 4-(Trifluoromethyl)-benzyl bromide (120mg, 0.078mL, 0.5mmol, 1.5eq) was added to a solution of 5-[4-(ethylsulfinylmethyl)piperidine-1-carbonyl]-2-hydroxy-6-(trifluoromethyl)pyridine-3-carbonitrile (130mg, 0.334mmol) in acetone (1.7mL), followed by sodium iodide (53mg, 0.334mmol, 1.0eq) and potassium carbonate (141mg, 1.0mmol, 3.0eq). The reaction mixture was stirred at 70°C for 4 hours, cooled to room temperature and filtered. After removing the solvent, the residue was purified by silica gel. 160mg of 5-[4-(ethylsulfinylmethyl)piperidine-1-carbonyl]-6-(trifluoromethyl)-2-[[4-(trifluoromethyl)phenyl]methoxy]pyridine-3-carbonitrile was obtained as white foam. CDCl 3 In 1 H-NMR [ppm]: 1.12-1.50 (m, 2H), 1.35 (t, 3H), 1.74-2.11 (m, 2H), 2.14-2.48 (m, 2H), 2.65-2.92 (m, 4H), 3.08-3.22 (m, 1H), 3.32-3.46 (m, 1H), 4.72-4.85 (m, 1H), 5.63 (s, 2H), 7.62-7.72 (m, 4H), 7.91 and 7.95 (2s, 1H). LC-MS (Method 2): RT = 1.05 min; [M+H] + =548.
[0616] Example P6: 2-[(2,2-dichlorocyclopropyl)methoxy]-5-[4-(5-methyl-1,2,4-oxadiazol-3-yl)
[0617] [piperidine-1-carbonyl]-6-(trifluoromethyl)pyridine-3-carbonitrile (Compound P4.1):
[0618]
[0619] To a solution of 2-hydroxy-5-[4-(5-methyl-1,2,4-oxadiazol-3-yl)piperidine-1-carbonyl]-6-(trifluoromethyl)pyridine-3-carbonitrile (340 mg, 0.892 mmol) in acetone (4.5 mL) was added 2-(bromomethyl)-1,1-dichloro-cyclopropane (273 mg, 1.34 mmol, 1.5 eq), followed by sodium iodide (141 mg, 0.892 mmol, 1.0 eq) and potassium carbonate (377 mg, 2.67 mmol, 3.0 eq). The reaction mixture was stirred at 70° C. for 48 hours, cooled to room temperature and filtered. After removal of the solvent, the residue was purified by silica gel column. 260 mg of 2-[(2,2-dichlorocyclopropyl)methoxy]-5-[4-(5-methyl-1,2,4-oxadiazol-3-yl)piperidine-1-carbonyl]-6-(trifluoromethyl)pyridine-3-carbonitrile were obtained as white foam. CDCl 3 In 1 H-NMR [ppm]: 1.52 (t, 1H) 1.70-2.05 (m, 4H), 2.13-2.30 (m, 2H), 2.61 (s, 3H), 3.02-3.28 (m, 3H), 3.41-3.56 (m, 1H), 4.52-4.78 (m, 3H), 7.93 and 7.98 (2s, 1H). LC-MS (Method 2): RT = 1.09 min; [M+H] + =504 / 506 / 508.
[0620] Example P7: 5-[4-(5-methyl-1,2,4-oxadiazol-3-yl)piperidine-1-carbonyl]-6-(trifluoromethyl)-2- [[4-(Trifluoromethyl)phenyl]methoxy]pyridine-3-carbothioamide (Compound P6.1):
[0621]
[0622] To a solution of 5-[4-(5-methyl-1,2,4-oxadiazole-3-yl)piperidine-1-carbonyl]-6-(trifluoromethyl)-2-[[4-(trifluoromethyl)phenyl]methoxy]pyridine-3-carbonitrile (0.147 g, 0.273 mmol) in DMF (2.7 mL) was added dichloromagnesium hexahydrate (72 mg, 0.354 mmol, 1.3 eq) and the mixture was stirred at room temperature for 1 hour. Sodium hydrosulfide (59 mg, 1.04 mmol, 3.80 eq) was then added and the reaction mixture was stirred at room temperature for another 1 hour. The reaction mixture was quenched with saturated aqueous ammonium chloride solution and then extracted 3 times with ethyl acetate.
[0623] The combined organic layers were purified by Na 2 SO 4Dry, filter, and concentrate under reduced pressure. The residue was purified by silica gel column to give 90 mg of 5-[4-(5-methyl-1,2,4-oxadiazol-3-yl)piperidine-1-carbonyl]-6-(trifluoromethyl)-2-[[4-(trifluoromethyl)phenyl]methoxy]pyridine-3-carbothioamide. CDCl 3 In 1 H-NMR [ppm]: 1.75-2.03 (m, 3H), 2.12-2.25 (m, 1H), 2.60 (s, 3H), 3.02-3.33 (m, 3H), 3.48-3.58 (m, 1H), 4.51-4.72 (m, 1H), 5.66 (s, 2H), 7.60-7.72 (m, 4H), 7.99 (wide s, 1H), 8.70-8.85 (m, 1H), 8.90 (s, 1H). LC-MS (Method 2): RT = 1.08 min; [M+H] + =574.
[0624] Other intermediates:
[0625] 2-Hydroxy-6-methyl-5-[4-(5-methyl-1,2,4-oxadiazol-3-yl)piperidine-1-carbonyl]pyridine-3-carbonitrile
[0626] Step 1: 5-Cyano-6-hydroxy-2-methyl-pyridine-3-carboxylic acid
[0627]
[0628] 5-cyano-6-hydroxy-2-methyl-pyridine-3-carboxylic acid ethyl ester (500mg, 2.42mmol) synthesized as described in Sinochem patent application WO 2015032280 was dissolved in ethanol (19mL) and potassium hydroxide (480mg, 7.27mmol, 3.0eq) dissolved in ethanol (4.9mL) was added. The reaction mixture was stirred at reflux for 20 hours. When the reaction was not completed, additional potassium hydroxide (480mg, 7.27mmol, 3.0eq) was added and the mixture was stirred at reflux for another 25 hours. The reaction mixture was diluted with ethyl acetate and 2N hydrochloric acid. The mixture was extracted three times with ethyl acetate. The combined organic layer was washed twice with water and once with brine, dried over sodium sulfate and the solvent was removed. 300mg of 5-cyano-6-hydroxy-2-methyl-pyridine-3-carboxylic acid as a white solid was obtained. DMSO in 1 H-NMR [ppm]: 2.61 (s, 3H), 8.41 (s, 1H), 12.93 (wide s, 1H), 13.09 (wide s, 1H). LC-MS (method 2): RT = 0.23 min; [M+H] + =179.
[0629] Step 2: 2-Hydroxy-6-methyl-5-[4-(5-methyl-1,2,4-oxadiazol-3-yl)piperidine-1-carbonyl]pyridine-3-carbonitrile
[0630]
[0631] To a solution of 5-cyano-6-hydroxy-2-methyl-pyridine-3-carboxylic acid (200 mg, 1.12 mmol) and diisopropyl-ethylamine (0.79 mL, 4.45 mmol, 4 eq) in ethyl acetate (9 mL) was added the hydrochloride salt of 5-methyl-3-(4-piperidinyl)-1,2,4-oxadiazole (252 mg, 1.23 mmol, 1.1 eq) (synthesized as described in Soda Co., Ltd. patent application WO 2017195703). Propylphosphonic anhydride (T3P, 1.29 g, 2.02 mmol, 1.8 eq) was subsequently added. The reaction mixture was stirred at room temperature for 18 hours and then diluted with ethyl acetate. The phases were separated and the organic layer was washed with brine, purified by Na 2 SO 4 The mixture was dried, filtered and concentrated under reduced pressure. The residue was suspended in methanol and filtered. 150 mg of 2-hydroxy-6-methyl-5-[4-(5-methyl-1,2,4-oxadiazol-3-yl)piperidine-1-carbonyl]pyridine-3-carbonitrile was obtained as a white foam. 1 H-NMR [ppm]: 1.50-1.70 (m, 2H), 1.80-2.10 (m, 2H), 2.22 (s, 3H), 2.66 (s, 3H), 2.90-3.30 (m, 3H), 3.52-3.70 (m, 1H), 4.23-4.49 (m, 1H), 8.09 (s, 1H), 12.76 (wide s, 1H). LC-MS (Method 2): RT = 0.57 min; [M+H] + =328.
[0632] The compounds in Tables PI, P2, P3, P4, P5, P6, P7, P8, P9, P10 and P11 were prepared as described in the Examples above or in analogous manner.
[0633] Table P1: Compounds of formula (Ic)
[0634]
[0635] The compounds in Table P1 can be prepared as described in the Examples above or in analogous manner. The following abbreviations are used in the following tables: RT = retention time, min = minutes, mp = melting point or melting range.
[0636] Table P1:
[0637]
[0638]
[0639]
[0640]
[0641]
[0642]
[0643] Table P2: Compounds of formula (Id)
[0644]
[0645] The compounds in Table P2 can be prepared as described in the Examples above or in analogous manner. The following abbreviations are used in the following tables: RT = retention time, min = minutes Table P2:
[0646]
[0647] Table P3: Compounds having formula (Ie)
[0648]
[0649] The compounds in Table P3 can be prepared as described in the Examples above or in analogous manner. The following abbreviations are used in the following tables: RT = retention time, min = minutes.
[0650] Table P3:
[0651]
[0652]
[0653]
[0654]
[0655]
[0656]
[0657]
[0658] Table P4: Compounds having formula (If)
[0659]
[0660] The compounds in Table P4 can be prepared as described in the Examples above or in analogous manner. The following abbreviations are used in the following tables: RT = retention time, min = minutes.
[0661] Table P4
[0662]
[0663]
[0664] Table P5: Compounds of formula (Ig)
[0665]
[0666] The compounds in Table P5 can be prepared as described in the Examples above or in analogous manner. The following abbreviations are used in the following tables: RT = retention time, min = minutes.
[0667] Table P5
[0668]
[0669] Table P6: Compounds of formula (Ih)
[0670]
[0671] The compounds in Table P6 can be prepared as described in the Examples above or in analogous manner. The following abbreviations are used in the following tables: RT = retention time, min = minutes.
[0672] Table P6
[0673]
[0674] Table P7: Compounds having formula (Ii)
[0675]
[0676] The compounds in Table P7 can be prepared as described in the Examples above or in analogous manner. The following abbreviations are used in the following tables: RT = retention time, min = minutes.
[0677] Table P7
[0678]
[0679]
[0680] Table P8: Compounds having formula (Ij)
[0681]
[0682] The compounds in Table P8 can be prepared as described in the Examples above or in analogous manner. The following abbreviations are used in the following tables: RT = retention time, min = minutes Table P8:
[0683]
[0684] Table P9: Compounds having formula (Ik)
[0685]
[0686] The compounds in Table P9 can be prepared as described in the Examples above or in analogous manner. The following abbreviations are used in the following tables: RT = retention time, min = minutes Table P9:
[0687]
[0688] Table P10: Compounds having formula (Im)
[0689]
[0690] The compounds in Table P10 can be prepared as described in the Examples above or in analogous manner. The following abbreviations are used in the following tables: RT = retention time, min = minutes Table P10:
[0691]
[0692] Table P11: Compounds having formula (In)
[0693]
[0694] The compounds in Table P11 can be prepared as described in the Examples above or in analogous manner. The following abbreviations are used in the following table: RT = retention time, min = minutes Table P11:
[0695]
[0696] The intermediates in Table U1 are novel and useful for the synthesis of several compounds of general structure I. They can be prepared as described in the above Examples or by analogous methods. In the following tables the following abbreviations are used: RT = retention time, min = minute.
[0697] Table U1:
[0698]
[0699]
[0700]
[0701]
[0702]
[0703] The intermediates in Table U2 are novel and useful for the synthesis of several compounds of general structure I. They can be prepared as described in the Examples above or by analogous methods. The following abbreviations are used in the following tables: s = singlet, d = doublet, t = triplet, q = quartet, m = multiplet.
[0704] Table U2:
[0705]
[0706]
[0707] By adding other insecticidal, acaricidal and / or fungicidal active ingredients, the activity of the composition according to the invention can be significantly broadened and adapted to the prevailing situation. Mixtures of compounds of formula (I) with other insecticidal, acaricidal and / or fungicidal active ingredients can also have other unexpected advantages, which can also be described as synergistic activities in a broader sense. For example, better tolerance of plants, reduced phytotoxicity, insects can be controlled at different stages of their development, or better behavior during their production (e.g., during grinding or mixing, during their storage or during their use).
[0708] Here, suitable active ingredients to be added are, for example, representatives of the following classes of active ingredients: organophosphorus compounds, nitrophenol derivatives, thioureas, juvenile hormones, formamidines, benzophenone derivatives, ureas, pyrrole derivatives, carbamates, pyrethroids, chlorinated hydrocarbons, acylureas, pyridylmethyleneamino derivatives, macrolides, neonicotinoids and Bacillus thuringiensis preparations.
[0709] Preference is given to the following mixtures of compounds of formula (I) with active substances (the abbreviation "TX" means "a compound selected from the group consisting of the compounds defined in Groups 1 to 90 and Tables P1 to P11"):
[0710] Auxiliary agent, which is selected from the group consisting of: petroleum (alias) (628) + TX,
[0711] Insect control active substances selected from the group consisting of Avermectin + TX, Acetamiprid + TX, Acetamiprid + TX, Acetamiprid + TX, Acynonapyr + TX, Biprofen + TX, Afolan + TX, Cotton Boll + TX, Allethrin + TX, α-Cypermethrin + TX, Alpha-Cypermethrin + TX, Sulfonamid + TX, Methiocarb + TX, Triazotin + TX, Sulfamethoxam + TX, Benzothion + TX, Benzpyrimoxan + TX, β-Fluoro Cypermethrin + TX, β-cypermethrin + TX, bifenazate + TX, bifenthrin + TX, binacarb + TX, bio-allethrin + TX, bio-allethrin S)-cyclopentyl isomer + TX, bio-resmethrin + TX, bistrifluan + TX, brofenoxam + TX, bromothrin + TX, bromophos-ethyl + TX, buprofezin + TX, butacarb + TX, cadusafos + TX, carbaryl + TX, butacarb + TX, and batan + TX,CAS No.: 1472050-04-6+TX, CAS No.: 1632218-00-8+TX, CAS No.: 1808115-49-2+TX, CAS No.: 2032403-97-5+TX, CAS No.: 2044701-44-0+TX, CAS No.: 2128706-05-6+TX, CAS No.: 2249718-27-0+TX, chlorantraniliprole+TX, chlordane+TX, chlorfenapyr+TX, chloranil+TX, chlorpromazine+TX, chlorpyrifos+TX, chloranil+TX, clenpyrine+TX, cloethocarb+TX, clothianidin+TX, 2-chlorophenyl N-methylcarbamate (CPMC)+TX, benzonitrile +TX, cyantraniliprole +TX, cyclic bromine amide +TX, cypermethrin +TX, cypermethrin +TX, cyclohexanil +TX, cyclohexanil +TX, cytoxanil +TX, cytoxanil +TX, cytoxanil +TX, cyhalodiamide +TX, cyhalothrin +TX, cypermethrin +TX, cypermethrin +TX, cymethrin +TX, cyromazine +TX, deltamethrin +TX, cypermethrin +TX, cypermethrin +TX, chlorpyrifos +TX, chlorfenapyr +TX, chlorfenapyr +TX, chlorfenapyr +TX, chlorfenapyr +TX, chlorfenapyr +TX, chlorfenapyr +TX, chlorfenapyr +TX, chlorfenapyr +TX, chlorfenapyr +TX, chlorfenapyr +TX, chlorfenapyr +TX, chlorfenapyr +TX, chlorfenapyr +TX, chlorfenapyr +TX, chlorfenapyr +TX, chlorfenapyr +TX, chlorfenapyr +TX, Actibacterium + TX, Dimethoate + TX, Dinotefuran + TX, Vegetable and Fruit Phosphorus + TX, Emamectin + TX, Dextran + TX, ε-momfluorothrin + TX, ε-methofluthrin + TX, Cypermethrin + TX, Ethion + TX, Ethiopromide + TX, Ethofenprox + TX, Ethozolin + TX, Ethiopromide + TX, Fenamiphos + TX, Pentothrin + TX, Fenitrothion + TX, Fenbutar + TX, Fenthiocarb + TX, Fenoxycarb + TX, Cypermethrin + TX, Fenpyraclostrobin + TX, Fenthiophos + TX, Fenthiocarb + TX, Fenoxycarb + TX, Cypermethrin + TX, Fenpyraclostrobin + TX, Fenthiophos + TX, Fenthiophos + TX, Fenvalerate + TX, Fipronil + TX, Flometoquin + TX, Flindrothiocarb + TX, Felocellar + TX, Fluazaindolizine + TX, Flufenacet + TX, Fluflufenamide + TX, Flucitrinate + TX, Flufenacet + TX, Flucythrin + TX, Fluthiamethoxam + TX, Flumethrin + TX, Flufenacet + TX, Flufenamide + TX, Flufenacet + TX, Flufenacet + TX, Flufenacet + TX, Flupyrimin + TX, Fluralaner + TX, Fluxametamide + TX, Fosthiazine + TX, γ-Flucythrin + TX, Gossyplure,TM+TX, pyramid +TX, chlorfenapyr +TX, chlorfenapyr +TX, halofenprox +TX, heptafluthrin +TX, hexathiacyclon +TX, hydrazone +TX, imidophos +TX, imidacloprid +TX, imiprodinil +TX, indoxacarb +TX, iodomethane +TX, isoprodinil +TX, Isocycloseram +TX, isothiocarb +TX, ivermectin +TX, kappa-bifenthrin +TX, kappa-tefluthrin +TX, lambda-cyhalothrin +TX, lepidomectin +TX, chlorfenapyr +TX, metaflumizone +TX, metaldehyde +TX, metamex +TX, methomyl +TX, methoxyfenopyr +TX, methoxyfenopyr +TX, Methiothrin +TX, Methiothrin +TX, Zikewei +TX, Mite +TX, Momfluorothrin +TX, Methiothrin +TX, Nitenpyram +TX, Nithiothiazide +TX, Oxydemeton +TX, Oxamyl +TX, Oxazosufyl +TX, Parathion-ethyl +TX, Permethrin +TX, Phenothrin +TX, Phosphamidon +TX, Piperonyl Butoxide +TX, Pirimicarb +TX, Pirimiphos-ethyl +TX, Polyhedrosis virus +TX, Promethrin +TX, Profenofos +TX, Profenofos +TX, Profluthrin +TX, Promethrin +TX, Profenofos +TX, Protrifen +TX, Profenofos +TX, Protrifen +TX, Profenofos +TX, Protrifen )+TX, Pyflubumide+TX, Pymetrozine+TX, Pyraclofos+TX, Pyrafluprole+TX, Pyridaben+TX, Pyridalyl+TX, Pyrifluquinazon+TX, Pyrimidine+TX, Pyrimidine+TX, Pyrafluprid+TX, Pyriflufen+TX, Pyriflufen+TX, Resmethrin+TX, Sarolaner+TX, Selamectin+TX, Flusilathrin+TX, Spinetoram+TX, Spinetoram+TX, Spirodiclofen+TX, Spiromefoxim+TX, Spiropyrim+TX, Spiropyrim+TX, Spiropyrim+TX, Spiropyrim+TX, Spiropyrim+TX, Spiropidion+TX, Spirotetramat+TX, Sulfone+TX, Tebufenozide +TX, tebufenpyrad +TX, butyl pyrimidine phosphorus (Tebupirimiphos) +TX, tefluthrin +TX, bispyribac +TX, tetrachloraniliprole (Tetrachloraniliprole) +TX, tetrachlorfon (Tetradiphon) +TX, tetramethrin +TX, tetrafluthrin +TX, acaricide +TX, flucyram +TX, θ-cypermethrin +TX, thiacloprid +TX, thiamethoxam +TX, thiocarb +TX, thiodicarb +TX, long-acting carb +TX, methyl thiophos +TX, thiophanate +TX, tioxazafen +TX, tolfenpyrad +TX, toxaphene +TX, tralomethrin +TX, transfluthrin +TX, triazolam +TX,Triazophos + TX, trichlorfon + TX, chlorpyrifos + TX, trichlorfon + TX, triflumezopyrim + TX, Tyclopyrazoflor + TX, ζ-cypermethrin + TX, seaweed extract and fermentation products derived from sugar acyl + TX, seaweed extract and fermentation products derived from sugar acyl (containing urea + TX, amino acids + TX, potassium and molybdenum, and EDTA chelated manganese) + TX, seaweed extract and fermented plant products + TX, seaweed extract and fermented plant products (containing plant hormones + TX, vitamins + TX, EDTA chelated copper + TX, zinc + TX, and iron + TX), azadirachtin + TX, Bacillus aizawai + TX, Bacillus chitinosporus AQ746 (NRRL Accession No. B-21618) + TX, Bacillus firmus + TX, Bacillus kurstak (Bacillus Kurstaki) + TX, Bacillus mycoides AQ726 (NRRL Accession No. B-21664) + TX, Bacillus pumilus (NRRL Accession No. B-30087) + TX, Bacillus pumilus AQ717 (NRRL Accession No. B-21662) + TX, Bacillus species AQ178 (ATCC Accession No. 53522) + TX, Bacillus species AQ175 (ATCC Accession No. 55608) + TX, Bacillus species AQ177 (ATCC Accession No. 55609) + TX, unspecified Bacillus subtilis + TX, Bacillus subtilis AQ153 (ATCC Accession No. 55614) +TX, Bacillus subtilis AQ30002 (NRRL Accession No. B-50421) +TX, Bacillus subtilis AQ30004 (NRRL Accession No. B-50455) +TX, Bacillus subtilis AQ713 (NRRL Accession No. B-21661) +TX, Bacillus subtilis AQ743 (NRRL Accession No. B-21665) +TX, Bacillus thuringiensis AQ52 (NRRL Accession No. B-21619) +TX, Bacillus thuringiensis BD#32 (NRRL Accession No. B-21530) +TX, Bacillus thuringiensis subsp. Kurstaki BMP 123+TX, Beauveria bassiana+TX, D-limonene+TX, Granulovirus+TX, Harpin+TX, Helicoverpa armigera nuclear polyhedrosis virus+TX, Spodoptera exigua nuclear polyhedrosis virus+TX, Tobacco budworm nuclear polyhedrosis virus+TX, Australian Helicoverpa armigera nuclear polyhedrosis virus+TX, Metarhizium species+TX, Muscodor albus 620 (NRRL registration number 30547)+TX, Muscodor roseus A3-5 (NRRL registration number 30548)+TX,Neem-based products + TX, Paecilomyces fumosorum + TX, Paecilomyces lilacinus + TX, Pasteuria szabalensis + TX, Pasteuria penetrantis + TX, Pasteuria mycoides + TX, Pasteuria thornei + TX, Pasteurella + TX, p-cymene + TX, Plutella xylostella granulosis virus + TX, Plutella xylostella nuclear polyhedrosis virus + TX, polyhedrosis virus + TX, pyrethrum + TX, QRD 420 (terpenoid blend) + TX, QRD 452 (terpenoid blend) + TX, QRD 460 (terpenoid blend) + TX, Quillaja saponaria + TX, Rhodococcus sphaeroides AQ719 (NRRL Accession No. B-21663) + TX, Spodoptera frugiperda nuclear polyhedrosis virus + TX, Streptomyces flavus (NRRL Accession No. 30232) + TX, Streptomyces species (NRRL Accession No. B-30145) + TX, terpenoid blend + TX, and Verticillium species,
[0712] an algaecide selected from the group consisting of bethoxazin [CCN] + TX, copper dioctanoate (IUPAC name) (170) + TX, copper sulfate (172) + TX, cybutryne [CCN] + TX, dichlone (1052) + TX, dichlorophen (232) + TX, endosylamine (295) + TX, fentin (347) + TX, slaked lime [CCN] + TX, nabam (566) + TX, quinoclamine (714) + TX, quinonamid (1379) + TX, simazine (730) + TX, triphenyltin acetate (IUPAC name) (347) and triphenyltin hydroxide (IUPAC name) (347) + TX,
[0713] An anthelmintic selected from the group consisting of: avermectin (1) + TX, clefosinate (1011) + TX, doramectin (alias) [CCN] + TX, emamectin (291) + TX, emamectin benzoate (291) + TX, eprinomectin (alias) [CCN] + TX, ivermectin (alias) [CCN] + TX, milbemycin oxime (alias) [CCN] + TX, moxidectin (alias) [CCN] + TX, piperazine [CCN] + TX, selamectin (alias) [CCN] + TX, spinosad (737) and thiophanate (1435) + TX,
[0714] Avicides selected from the group consisting of chloralose (127) + TX, endrin (1122) + TX, fenthion (346) + TX, pyridin-4-amine (IUPAC name) (23) and strychnine (745) + TX,
[0715] Bactericides 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, dipyrithione (1105) + TX, dodesine (1112) + TX, fenaminosulf (1144) + TX, formaldehyde (404) + TX, mercaptophenone ( alias) [CCN] + TX, kasugamycin (483) + TX, kasugamycin hydrochloride hydrate (483) + TX, nickel bis(dimethyldithiocarbamate) (IUPAC name) (1308) + TX, nitrapyrin (580) + TX, octhilinone (590) + TX, oxolinic acid (606) + TX, oxytetracycline (611) + TX, potassium hydroxyquinoline sulfate (446) + TX, probenazole (658) + TX, streptomycin (744) + TX, streptomycin sesquisulfate (744) + TX, chlorphenamine (766) + TX, and thimerosal (alias) [CCN] + TX,
[0716] A biological agent selected from the group consisting of: GV of cotton brown banded moth (alias) (12) + TX, Agrobacterium radiobacterium (alias) (13) + TX, Amblyseius spp. (alias) (19) + TX, Spodoptera exigua NPV (alias) (28) + TX, Anagrus atomus (alias) (29) + TX, Aphelinus abdominalis (alias) (33) + TX, Aphidius colemani (alias) (34) + TX, Aphidoletes aphidimyza (alias) (35) + TX, Spodoptera exigua NPV (alias) (38) + TX, Bacillus firmus (alias) (48) + TX, Bacillus sphaericus Neide)(scientific name)(49)+TX、Bacillus thuringiensis Berliner)(scientific name)(51)+TX、Bacillus thuringiensis subsp.aizawai)(scientific name)(51)+TX、Bacillus thuringiensis subsp.israelensis)(scientific name)(51)+TX、Bacillus thuringiensis subsp.japonensis)(scientific name)(51)+TX、Bacillus thuringiensis subsp.kurstaki)(scientific name)(51)+TX、Bacillus thuringiensis subsp.tenebrionis (scientific name) (51) + TX, Beauveria bassiana (alias) (53) + TX, Beauveria brongniartii (alias) (54) + TX, Chrysoperla carnea (alias) (151) + TX, Cryptolaemus montrouzieri (alias) (178) + TX, Codling moth GV (alias) (191) + TX, Dacnusa sibirica (alias) (212) + TX, Diglyphus isaea (alias) (254) + TX, Encarsia formosa (scientific name) (293) + TX, Eretmocerus eremicus) (alias) (300) + TX, Spodoptera exigua NPV (alias) (431) + TX, Heterorhabditis bacteriophora and H. megidis (alias) (433) + TX, Hippodamia convergens (alias) (442) + TX, Leptomastix dactylopii (alias) (488) + TX, Macrolophus caliginosus (alias) (491) + TX, Cabbage armyworm NPV (alias) (494) + TX, Metaphycus helvolus (alias) (522) + TX, Metarhizium anisopliae var.acridum)(scientific name)(523)+TX, Metarhizium anisopliae var.anisopliae)(scientific name)(523)+TX, Neodiprionsertifer NPV and Neodiprionsertifer rubrum NPV.lecontei)NPV(alias)(575)+TX、Phytoseiulus species(alias)(596)+TX、Paecilomyces fumosoroseus(alias)(613)+TX、Phytoseiulus persimilis(alias)(644)+TX、Spodopteraexigua multicapsid nuclear polyhedrosis virus(scientific name)(741)+TX、Steinernema bibionis(alias)(742)+TX、Steinernema carpocapsae(alias)(742)+TX、Steinernema glaseri(alias)(742)+TX、Steinernema riobrave)(alias)(742)+TX, Steinernema riobravis(alias)(742)+TX, Steinernema scapterisci(alias)(742)+TX, Steinernema spp.(alias)(742)+TX, Trichogramma species(alias)(826)+TX, Typhlodromus occidentalis(alias)(844) and Verticillium lecanii(alias)(848)+TX,.
[0717] Soil disinfectant selected from the group consisting of methyl iodide (IUPAC name) (542) and methyl bromide (537) + TX,
[0718] A chemical sterilant selected from the group consisting of apholanate [CCN] + TX, bis(aziridine) methylaminophosphine sulfide (bisazir) (alias) [CCN] + TX, busulfan (alias) [CCN] + TX, diflubenzuron (250) + TX, dimatif (alias) [CCN] + TX, hemel [CCN] + TX, hempa [CCN] + TX, metepa [CCN] + TX, methylsulfonate Methotepa [CCN] + TX, methylapholate [CCN] + TX, morzid [CCN] + TX, penfluron (alias) [CCN] + TX, tepa [CCN] + TX, thiohempa (alias) [CCN] + TX, thiotepa (alias) [CCN] + TX, trothamide (alias) [CCN] and urethaneimide (alias) [CCN] + TX,
[0719] An insect pheromone selected from the group consisting of (E)-dec-5-en-1-yl acetate and (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 X, (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-yl acetate (IUPAC name) (780) + TX, (9Z,12E)-tetradec-9,12-Dien-1-yl acetate (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-multistriatin (alias) [CCN] + TX, western pine beetle gathering pheromone (brevicomin) (alias) [CCN] + TX, codlelure (alias) [CCN] + TX, codle mone)(alias)(167)+TX、cuelure(alias)(179)+TX、disparlure(277)+TX、1-dodecyl acetate(IUPAC name)(286)+TX、1-dodecyl acetate(IUPAC name)(287)+TX、10-1-dodecyl acetate(IUPAC name)(284)+TX、dominicalure(alias)[CCN]+TX、ethyl 4-methyloctanoate(IUPAC name) C name) (317) + TX, eugenol (alias) [CCN] + TX, southern pine beetle aggregation pheromone (frontalin) (alias) [CCN] + TX, gossyplure (alias) (420) + TX, grandlure (421) + TX, grandlure I (alias) (421) + TX, grandlure II (alias) (421) + TX, grandlure III (alias) (421) + TX, grandlure IV (alias) (421) + TX, hexalure )[CCN]+TX、ipsdienol (alias)[CCN]+TX、ipsenol (alias)[CCN]+TX、japonilure (alias)(481)+TX、lineatin (alias)[CCN]+TX、litlure (alias)[CCN]+TX、looplure (alias)[CCN]+TX、medlure[CCN]+TX、megatomoic acid (alias)[CCN]+TX、methyl eugenol (alias)(540)+TX、muscalure (563)+TX、octadecene-2,13-diene-1-yl acetate (IUPAC name)(588)+TX、octadecene-3,13-Dien-1-yl acetate (IUPAC name) (589) + TX, orfralure (alias) [CCN] + TX, oryctalure (alias) (317) + TX, ostramone (alias) [CCN] + TX, siglure [CCN] + TX, sordidin (alias) (736) + TX, sulcatol (alias) [CCN] + TX, tetradecene-11-en-1-yl acetate (IUPAC name) (785) + TX, Mediterranean fruit fly attractant (839) + TX, Mediterranean fruit fly attractant A (alias) (839) + TX, Mediterranean fruit fly attractant B, 1 (Alias) (839) + TX, Mediterranean fruit fly attractant B 2 (alias) (839) + TX, Mediterranean fruit fly attractant C (alias) (839) and trunc-call (alias) [CCN] + TX,
[0720] An insect repellent selected from the group consisting of 2-(octylthio)ethanol (IUPAC name) (591) + TX, butopyronoxyl (933) + TX, butoxy(polypropylene glycol) (936) + TX, dibutyl adipate (IUPAC name) (1046) + TX, dibutyl phthalate (1047) + TX, dibutyl succinate (IUPAC name) (1048) + TX, DEET [CCN] + TX, dimethyl carbate [CCN] + TX, dimethyl phthalate [CCN] + TX, ethyl hexanediol (1137) + TX, hexylurea [CCN] + TX, methoquin-butyl (1276) + TX, methyl neodecylamide [CCN] + TX, oxamate [CCN] and picaridin [CCN] + TX,
[0721] Molluscicide selected from the group consisting of di(tributyltin) oxide (IUPAC name) (913) + TX, bromoacetamide [CCN] + TX, calcium arsenate [CCN] + TX, chloranil (999) + TX, copper acetyl arsenite [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, pentachlorophenol ( 623)+TX, sodium pentachlorophenoxide (623)+TX, tazimcarb (1412)+TX, thiodicarb (799)+TX, tributyltin oxide (913)+TX, trifenmorph (1454)+TX, trimethacarb (840)+TX, triphenyltin acetate (IUPAC name) (347) and triphenyltin hydroxide (IUPAC name) (347)+TX, pyriprole [394730-71-3]+TX,
[0722] 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) + TX, 1,2-dichloropropane and 1,3-dichloropropene (IUPAC name) + TX, 1,3-dichloropropene (233) + TX, 1,2 ...3-dichloropropene (233) + TX, 1,3-dichloropropene (233) + TX, 1,3-dichloropropene (233) + TX Abstract name) (1065) + TX, 3-(4-chlorophenyl)-5-methylrhodanine (IUPAC name) (980) + TX, 5-methyl-6-thioxo-1,3,5-thiadiazin-3-yl acetic acid (IUPAC name) (1286) + TX, 6-isopentenylaminopurine (alias) (210) + TX, avermectin (1) + TX, acetofenamide [CCN] + TX, cotton bell carb (15) + TX, aldicarb (16) + TX, aldicarb (863) + TX, AZ60541 (compound code) + TX, benclothiaz [CCN] + TX, benomyl (62) + TX, butylpyridaben (alias) + TX, carbofuran (109) + TX, carbofuran (118) + TX, carbon disulfide (945) + TX, carbofuran (119) + TX, chloropicrin (141) + TX, chlorpyrifos (145) + TX, chlorpyrifos (999) + TX, cytokinin (alias) (210) + TX , dazomethane (216) + TX, DBCP (1045) + TX, DCIP (218) + TX, diamidafos (1044) + TX, dimethoate (1051) + TX, dicliphos (alias) + TX, dimethoate (262) + TX, doramectin (alias) [CCN] + TX, emamectin (291) + TX, emamectin benzoate (291) + TX, eprinomectin (alias) [CCN] + TX, ethoprophos (312 )+TX, ethylene dibromide (316)+TX, fenamiphos (326)+TX, fenpyrad (alias)+TX, fenthiophos (1158)+TX, thiathiophene (408)+TX, butyric acid cyclophosphate (1196)+TX, furfural (alias) [CCN]+TX, GY-81 (research code) (423)+TX, cypermethrin [CCN]+TX, iodomethane (IUPAC name) (542)+TX, isamidophos (1230)+TX, chloramine Azophos (1231) + TX, ivermectin (alias) [CCN] + TX, kinetin (alias) (210) + TX, methyl aphidazole (1258) + TX, metamectin (519) + TX, metamectin potassium salt (alias) (519) + TX, metamectin sodium salt (519) + TX, methyl bromide (537) + TX, methyl isothiocyanate (543) + TX, milbemycin oxime (alias) [CCN] + TX, moxidectin (alias) [CCN] + TX, Myrotheciumverrucaria) combination (alias) (565) + TX, NC-184 (compound code) + TX, oxamyl (602) + TX, phorate (636) + TX, phosphamidon (639) + TX, phosphamidon [CCN] + TX, clomiphene (alias) + TX, selamectin (alias) [CCN] + TX, spinosad (737) + TX, terbufos (alias) + TX, terbufos (773) + TX, tetrachlorothiophene (IUPAC / Chemical Abstract name) (1422) + TX, thiafenox (alias) + TX, cypermethrin (1434) + TX, triazophos (820) + TX, triazuron (alias) + TX, dimethylol [CCN] + TX, YI-5302 (compound code) and zeatin (alias) (210) + TX, fluensulfone [318290-98-1] + TX, fluopyram + TX,
[0723] A nitrification inhibitor selected from the group consisting of potassium ethylxanthate [CCN] and nitrapyrin (580) + TX,
[0724] A plant activator selected from the group consisting of acibenzolar (6) + TX, acibenzolar-S-methyl (6) + TX, probenazole (658) and Reynoutria sachalinensis extract (alias) (720) + TX,
[0725] A rodenticide selected from the group consisting of: 2-isovaleryl indane-1,3-dione (IUPAC name) (1246) + TX, 4-(quinoxalin-2-ylamino)benzenesulfonamide (IUPAC name) (748) + TX, α-chlorohydrin [CCN] + TX, aluminum phosphide (640) + TX, antoquinol (880) + TX, arsenic trioxide (882) + TX, barium carbonate (891) + TX, bifenthrin (912) + TX, brodifacoum (89) + TX, bromodiolone (91) + TX, bromodipine (92) + TX, calcium cyanide (444) + TX, chloralose (127) + TX, chlordipine (140) + TX, cholecalciferol (alias) (850) + TX, chlordimethoate (1004) + TX, chlordimethoate (1005) + TX, naphthalene (175) + TX, cypermethrin (1009) + TX, cypermethrin (246) + TX, thiazolin (249) + TX, difacoum (273) + TX, calciferol (301) + TX, fluoxetine , fluoroacetamide (379) + TX, fluridine (1183) + TX, fluridine hydrochloride (1183) + TX, γ-HCH (430) + TX, HCH (430) + TX, hydrogen cyanide (444) + TX, iodomethane (IUPAC name) (542) + TX, lindane (430) + TX, magnesium phosphide (IUPAC name) (640) + TX, methyl bromide (537) + TX, thiamethoxam (1318) + TX, thiamethoxam (13 36) + TX, phosphine (IUPAC name) (640) + TX, phosphorus [CCN] + TX, warfarin (1341) + TX, potassium arsenite [CCN] + TX, cypermethrin (1371) + TX, scilla glycoside (1390) + TX, sodium arsenite [CCN] + TX, sodium cyanide (444) + TX, sodium fluoroacetate (735) + TX, strychnine (745) + TX, thallium sulfate [CCN] + TX, warfarin (851) and zinc phosphide (640) + TX,
[0726] 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, MGK 264 (research code) (296) + TX, piperonyl butoxide (649) + TX, pipertal (1343) + TX, propyl isomer (1358) + TX, S421 (research code) (724) + TX, sesamex (1393) + TX, sesasmolin (1394) and sulfoxide (1406) + TX,
[0727] Animal repellents, which are composed of the following substance groups: anthraquinone (32) + TX, chloralose (127) + TX, copper cyclohexane [CCN] + TX, copper oxychloride (171) + TX, diazinon (227) + TX, dicyclopentadiene (chemical name) (1069) + TX, guazatine (422) + TX, guazatine acetate (422) + TX, methiocarb (530) + TX, pyridin-4-amine (IUPAC name) (23) + TX, salam (804) + TX, trimethacarb (840) + TX, zinc cyclohexane [CCN] and ziram (856) + TX,
[0728] A virucidal agent selected from the group consisting of: imipenem (alias) [CCN] and ribavirin (alias) [CCN] + TX,
[0729] A wound protection agent selected from the group consisting of mercuric oxide (512) + TX, octhilinone (590) and thiophanate methyl (802) + TX,
[0730] Biologically active substances selected from 1,1-bis(4-chlorophenyl)-2-ethoxyethanol+TX, 2,4-dichlorophenylbenzenesulfonate+TX, 2-fluoro-N-methyl-N-1-naphthylacetamide+TX, 4-chlorophenylphenyl sulfone+TX, acetofenamide+TX, aldicarb+TX, sago+TX, fruit manphos+TX, amine dephosphite+TX, ammonium oxalate dephosphite+TX, amitraz+TX, cypermethrin+TX, arsenic trioxide+TX, azobenzene+TX, azophos+TX, benomyl+TX, benoxafos+TX, benzyl benzoate+TX, bixafen+TX, bromothiocarb ... Mite ester + TX, buprofezin + TX, butanone carbendazim + TX, butanone sulfone carbendazim + TX, butyl pyridaben + TX, calcium polysulfide + TX, octachlorocamphene + TX, chlormethoxam + TX, trithion + TX, cypermethrin + TX, cypermethrin + TX, cypermethrin + TX, cypermethrin hydrochloride + TX, cypermethrin + TX, cypermethrin + TX, cypermethrin + TX, cypermethrin + TX, ethyl cypermethrin + TX, cypermethrin (chloromebuform) + TX, cypermethrin + TX, propyl cypermethrin + TX, cypermethrin + TX, cypermethrin I + TX, cypermethrin II + TX, cypermethrin + TX, closantel + TX, coumaphos + TX, crotamiton + TX, baclofos + TX, thiocarb + TX, fruit insect phosphorus + TX, DCPM + TX, DDT + TX, dinoxophos + TX, dinoxophos-O + TX, dinoxophos-S + TX, demeton-methyl + TX, demeton-O + TX, demeton-O-methyl + TX, demeton-S + TX, demeton-S-methyl + TX, demeton-S-methyl + TX, demeton-S-methyl + TX, demeton-S-methyl + TX, demeton-S-methylsulfon + TX, bacteriostatic + TX, dichlorvos + TX, dicliphos + TX, dichlorvos + TX, dimethoate + TX, methylphos + TX, dinex + TX, dinex-diclexine + TX, dimethoate-4 + TX, dimethoate-6 +TX, anthelmintic+TX, nitropentyl+TX, nitrobenzene+TX, nitrobenzene acaricide+TX, nitrobutyl+TX, dimethoate+TX, sulfodiphenyl+TX, disulfiram+TX, DNOC+TX, dofenapyn+TX, doramectin+TX, indole+TX, eprinomectin+TX, phosphosulfate+TX, ethimphos+TX, anti-mite+TX, fenbutatin+TX, fenthiocarb+TX, fenpyrad+TX, fenpyraclostrobin+TX, fenamipyraclostrobin+TX, fentrifanil+TX, fluazifop+TX, flufenamide+TX, fluazifop+TX, FMC 1137+TX, flufenamic acid+TX, flufenamic acid hydrochloride+TX, formparanate+TX, γ-HCH+TX, fruit green+TX,Benzyl acarboxylate + TX, hexadecyl cyclopropane carboxylate + TX, isothiophos + TX, jasmonate I + TX, jasmonate II + TX, iodine + TX, lindane + TX, propanil + TX, cypermethrin + TX, dithiophos + TX, methylthiophene + TX, cypermethrin + TX, methyl bromide + TX, cypermethrin + TX, chlorpyrifos + TX, milbemycin + TX, propylamine + TX, monocrotophos + TX, maoguo + TX, moxidectin + TX, naled + TX, 4-chloro-2-(2-chloro-2-methyl-propyl)-5-[(6-iodo-3-pyridyl)methoxy]pyridazine-3-one + TX, fluazifop + TX, nikkomycin + TX, pentamethylenediamine + TX, pentamethylenediamine 1:1 zinc chloride complex +TX, omethoate +TX, isothiocarb +TX, sulfone +TX, pp'-DDT +TX, parathion +TX, permethrin +TX, fenthion +TX, phosalone +TX, thiocyanate +TX, phosphamidon +TX, polychloroterpenes +TX, polynactins +TX, chloranil +TX, cypermethrin +TX, propoxur +TX, ethidium +TX, pyrethrin +TX, pyrethrin I +TX, pyrethrin II +TX, pyrethrin +TX, pyrimethoxam +TX, pyrimithiophos +TX, quinalphos +TX, quintiofos +TX, R-1 492+TX, glyphosate+TX, rotenone+TX, octamidine+TX, clomiphene+TX, selamectin+TX, thion+TX, SSI-121+TX, sulfilam+TX, sulfluramid+TX, sulfotep+TX, sulfur+TX, flumethrin+TX, τ-fluvalinate+TX, TEPP+TX, tert-butylcarb+TX, tetrachlorothiazide+TX, thiafenox+TX, thiafenox+TX, thiafenox+TX, methyl thiocarb+TX, chlorpyrifos+TX, thiafenox+TX, thiafenox+TX, thiafenox+TX, thiafenox+TX, thiafenox+TX, thiafenox+TX, thiafenox+TX, thiafenox+TX, thiafenox+TX, thiafenox+TX, thiafenox+TX, thiafenox+TX, thiafenox+TX, thiafenox+TX, thiafenox+TX, thiafenox+TX, thiafenox+TX, thiafenox+TX, thiafenox+TX, thiafenox+TX, thiafenox+TX, thiafenox+TX, thiafenox+TX, thiafenox+TX, thiafenox+TX, thiafenox+TX, thiafenox+TX, thiafenox+TX TX, vaniliprole + TX, bethoxazin + TX, copper dioctanoate + TX, copper sulfate + TX, cybutryne + TX, dichloronaphthoquinone + TX, dichlorophen + TX, endoxan + TX, triphenyltin + TX, slaked lime + TX, mancozeb + TX, algae quinone + TX, quinone + TX, simazine + TX, triphenyltin acetate + TX, triphenyltin hydroxide + TX, yuxu phosphorus + TX, piperazine + TX, thiophanate + TX, chloralose + TX, fenthion + TX, pyridine-4-amine + TX, strychnine + TX, 1-hydroxy-1H-pyridine-2-thione + TX, 4-(quinoxaline-2-ylamino)benzenesulfonamide + TX,8-Hydroxyquinoline sulfate + TX, bronopol + TX, copper hydroxide + TX, cresol + TX, dipyrithione + TX, dodesine + TX, sodium sulfone + TX, formaldehyde + TX, mercury plus phenacetin + TX, kasugamycin + TX, kasugamycin hydrochloride hydrate + TX, nickel di(dimethyldithiocarbamate) + TX, trichloromethylpyridine + TX, octhilthione + TX, oxolinic acid + TX, oxytetracycline + TX, potassium hydroxyquinoline sulfate + TX, thiabendazole + TX, streptomycin + TX, streptomycin sesquisulfate + TX, chlorothiazide + TX, thimerosal + TX, cotton brown-banded moth GV + TX, Agrobacterium radiobacterium + TX, Amblyseius spp. + TX, celery armyworm NPV + TX, Anagrus atomus + TX, Aphelinus abdominalis + TX, cotton aphid parasitic wasp (Aphidius colemani+TX、Aphidoletes aphidimyza+TX、Spodoptera lucernea NPV+TX、Bacillus sphaericus Neide+TX、Beauveria brongniartii+TX、Chrysoperla carnea+TX、Cryptolaemusmontrouzieri+TX、Codling moth GV+TX、Dacnusa sibirica+TX、Diglyphus isaea+TX、Encarsia formosa+TX、Eretmocerus eremicus+TX、Heterorhabditis bacteriophora) and H.megidis+TX, Hippodamia convergens+TX, Leptomastix dactylopii+TX, Macrolophus caliginosus+TX, Cabbage armyworm NPV+TX, Metaphycus helvolus+TX, Metarhizium anisopliaevar.acridum+TX, Metarhizium anisopliae var.anisopliae+TX, Neodiprion sertifer NPV and N.lecontei NPV+TX,+TX, Paecilomyces fumosoroseus +TX, Phytoseiulus persimilis +TX, Steinernema bibionis +TX, Steinernema carpocapsae +TX, Steinernema glaseri +TX, Steinernema riobrave +TX, Steinernema riobravis +TX, Steinernema scapterisci +TX, Steinernema spp. +TX, Trichogramma species +TX, Typhlodromus occidentalis + TX, Verticillium lecanii + TX, apholanate + TX, bis(aziridine) methylaminophosphine sulfide + TX, busulfan + TX, dimatif + TX, hemel + TX, hemp + TX, metepa + TX, methiotepa + TX, methyl apholanate + TX, methyl thiotepa ... apholate) + TX, morzid + TX, penfluron + TX, tepa + TX, thiohempa + TX, thiohempa + TX, trothamide + TX, urethaneimide + TX, (E)-dec-5-en-1-yl acetate and (E)-dec-5-en-1-ol + TX, (E)-tridec-4-en-1-yl acetate + TX, (E)-6-methylhept-2-en-4-ol + TX, (E,Z)-tetradec-4,10-dien-1-yl acetate + TX, (Z)-dodec-7-en-1-yl acetate + TX, (Z)-hexadecene carbon-11-enal + TX, (Z)-hexadec-11-en-1-yl acetate + TX, (Z)-hexadec-13-en-11-yn-1-yl acetate + TX, (Z)-eicos-13-en-10-one + TX, (Z)-tetradec-7-en-1-al + TX, (Z)-tetradec-9-en-1-ol + TX, (Z)-tetradec-9-en-1-yl acetate + TX, (7E,9Z)-dodec-7,9-dien-1-yl acetate + TX, (9Z,11E)-tetradec-9,11-dien-1-yl acetate + TX, (9Z,12E)-tetradec-9,12-dien-1-yl acetate + TX,14-Methyloctadec-1-ene+TX, 4-methylnon-5-ol and 4-methylnon-5-one+TX, α-polystyrene+TX, western pine beetle aggregation pheromone+TX, codlelure+TX, codlemone+TX, cuelure+TX, epoxide nonadecane+TX, dodec-8-en-1-yl acetate+TX, dodec-9-en-1-yl acetate+TX, dodec-8+TX, 10-10-dien-1-yl acetate+TX, dominicalure+TX, 4-methyloctanoic acid ethyl ester+TX, eugenol+TX, southern pine beetle aggregation pheromone (f rontalin)+TX, grandlure+TX, grandlure I+TX, grandlure II+TX, grandlure III+TX, grandlure IV+TX, hexalure+TX, ipsdienol+TX, ipsenol+TX, japonilure+TX, lineatin+TX, litlure+TX, looplure+TX, medlure+TX, megatomoic acid+TX, methyl eugenol+TX, muscalure+TX, 18-decane-2,13-diene-1-yl acetate+TX, 18-decane-3,13-diene-1-yl acetate+TX, orfralure+TX, oryctalure+TX, ostramone+TX, siglure+TX, sordidin+TX, sulcatol+TX, 14-decane-11-ene-1-yl acetate+TX, trimedlure+TX, Mediterranean fruit fly attractant A+TX, Mediterranean fruit fly attractant B, 1 +TX, Mediterranean fruit fly attractant B 2+TX, Mediterranean fruit fly attractant C+TX, trunc-call+TX, 2-(octylthio)ethanol+TX, butopyronoxyl+TX, butoxy(polypropylene glycol)+TX, dibutyl adipate+TX, dibutyl phthalate+TX, dibutyl succinate+TX, DEET+TX, dimethyl carbate)+TX, dimethyl phthalate+TX, ethyl hexanediol+TX, hexamide+TX, methoquin-butyl+TX, methylneodecanamide+TX, oxamate+TX, picaridin+TX, 1-dichloro-1-nitroethane+TX, 1,1-dichloro-2,2-di(4-ethylphenyl)ethane+TX, 1,2-dichloropropane and 1,3-dichloropropylene+TX, 1-bromo-2-chloroethane+ TX, 2,2,2-trichloro-1-(3,4-dichlorophenyl)ethyl acetate + TX, 2,2-dichlorovinyl 2-ethylsulfinylethyl methyl phosphate + TX, 2-(1,3-dithiolan-2-yl)phenyl dimethylcarbamate + TX, 2-(2-butoxyethoxy)ethyl thiocyanate + TX, 2-(4,5-dimethyl-1,3-dioxolan-2-yl)phenyl methylcarbamate + TX, 2-(4-chloro-3,5-xylyloxy)ethanol + TX, 2-chlorovinyl diethyl phosphate + TX, 2-imidazolidinone + TX, 2-isovaleryl indan-1,3-di 1-Hydroxy-1-nitropropene, 1-nitropropene, 1-nitropropene, 1-nitropropene, 1-nitropropene, 1-nitropropene, 1-nitropropene, 1-nitropropene, 1-nitropropene, 1-nitropropene, 1-nitropropene, 1-nitropropene, 1-nitropropene, 1-nitropropene, 1-nitropropene, 1-nitropropene, 1-nitropropene, 1-nitropropene, 1-nitropropene, 1-nitropropene, 1-nitropropene, 1-nitropropene, 1-nitropropene, 1-nitropropene, 1-nitropropene, 1-nitropropene, 1-nitropropene, 1-nitropropene, +TX, neonicotinoids +TX, ethyl thiophanate (athidathion) +TX, methyl pyrifos +TX, Bacillus thuringiensis δ-endotoxin +TX, barium hexafluorosilicate +TX, barium polysulfide +TX, fumonisin +TX, Bayer 22 / 190 +TX, Bayer 22408 +TX, β-cyfluthrin +TX, β-cypermethrin +TX, bioethanomethrin +TX, biopermethrin +TX, bis (2-chloroethyl) ether +TX, borax +TX, bromophenazone +TX, bromo-DDT +TX, hexachlorvinphos +TX, cypermethrin +TX,Butathiofos + TX, butyl phosphine + TX, calcium arsenate + TX, calcium cyanide + TX, carbon disulfide + TX, carbon tetrachloride + TX, badan hydrochloride + TX, cevadine + TX, bornyl + TX, chlordane + TX, chlordecone + TX, chloroform + TX, chloropicrin + TX, chlornitrile oxime + TX, chlorprazophos + TX, cis-resmethrin + TX, cismethrin + TX, clocythrin (alias) + TX, copper acetoarsenite + TX, copper arsenate + TX, copper oleate + TX, coumithoate + TX, cryolite + TX, CS 708+TX, benzonitrile+TX, cypermethrin+TX, cypermethrin+TX, cypermethrin+TX, d-carbofuran+TX, DAEP+TX, dazomethane+TX, decarbofuran+TX, diamidafos+TX, isochlorophos+TX, diamidafos+TX, dicresyl+TX, cypermethrin+TX, dieldrin+TX, diethyl 5-methylpyrazol-3-yl phosphate+TX, dior+TX, tetrafluoromethoxythrin+TX, dimethoate+TX, pyrethrin+TX, methylchlorfenapyr+TX, dichlorvos+TX, propanol+TX, pentotropol+TX, dinoseb+TX, fenpyroxene+TX, vegetable phosphorus+TX, thiopyrafos+TX, DSP+TX, ecdysterone+TX, EI 1642+TX, EMPC+TX, EPBP+TX, etaphos+TX, ethiobencarb+TX, ethyl formate+TX, ethylene dibromide+TX, ethylene dichloride+TX, ethylene oxide+TX, EXD+TX, ethiobencarb+TX, ethiobencarb+TX, fenitrothion+TX, fenoxacrim+TX, cypermethrin+TX, fenthion+TX, ethylfenthion+TX, flucofuron+TX, butylfenthion+TX, phosphonium phosphate+TX, butylcyclothion+TX, furathiocarb+TX, pyrethroid+TX, biguanide salt+TX, biguanide acetate+TX, tetramethoate Sodium thiocarbonate + TX, halfenprox + TX, HCH + TX, HEOD + TX, heptachlor + TX, cypermethrin + TX, HHDN + TX, hydrogen cyanide + TX, quinoline + TX, IPSP + TX, chlorfenapyr + TX, carbochlorin + TX, isodrin + TX, isoflavone + TX, transplanting spirit + TX, rice blast spirit + TX, oxathiophos + TX, juvenile hormone I + TX, juvenile hormone II + TX, juvenile hormone III + TX, chlorpentyl + TX, methoprene + TX, lead arsenate + TX, bromophenylphos + TX, acetamiprid + TX, thiathion + TX, m-isopropyl methyl carbamate + TX,Magnesium phosphide + TX, phosphorus azide + TX, methyl aphidite + TX, aphidite + TX, mercurous chloride + TX, methyl sulfoxide + TX, metamethylenetetramine + TX, metamethylenetetramine potassium salt + TX, metamethylenetetramine sodium salt + TX, methylsulfonyl fluoride + TX, butylene phosphonate + TX, methoprolol + TX, methyl ether thiocyanate + TX, methoxychlor + TX, methyl isothiocyanate + TX, methyl chloroform + TX, dichloromethane + TX, oxadiazine + TX, anticide + TX, naphthion + TX, naphthalene + TX, NC-170 + TX, nicotine + TX, nicotine sulfate + TX, nithiazine + TX, pronicotine + TX, O-5-dichloro-4-iodophenyl O-ethylethyl phosphonothioate + TX, O,O-diethyl O-4-methyl-2-oxo-2H-benzopyran-7-yl phosphonothioate + TX, O,O-diethyl O-6-methyl-2-propylpyrimidin-4-yl phosphonothioate + TX, O,O,O',O'-tetrapropyl dithiodipyrophosphate + TX, oleic acid + TX, p-dichlorobenzene + TX, methyl parathion + TX, pentachlorophenol + TX, pentachlorophenyl laurate + TX, PH 60-38+TX, fenthion+TX, parathion+TX, phosphine+TX, methyl phoxim+TX, methamidophos+TX, polychlorinated dicyclopentadiene isomers+TX, potassium arsenite+TX, potassium thiocyanate+TX, precocious element I+TX, precocious element II+TX, precocious element III+TX, amimidophos+TX, profluthrin+TX, fenthion+TX, pyraclostrobin+TX, anti-pyrethroids+TX, quassia extract (quassia) + TX, quinalphos-methyl + TX, oxathion + TX, iodophos + TX, resmethrin + TX, rotenone + TX, thiamethoxam + TX, ryanodine + TX, sabadilla + TX, octamethrin + TX, clostridium + TX, SI-0009 + TX, thiamethoxam + TX, sodium arsenite + TX, sodium cyanide + TX, sodium fluoride + TX, sodium hexafluorosilicate + TX , sodium pentachlorophenol + TX, sodium selenate + TX, sodium thiocyanate + TX, sulcofuron + TX, sulcofuron-sodium + TX, sulfuryl fluoride + TX, thiopromide + TX, tar + TX, thiamethoxam + TX, TDE + TX, butylpyrimidinphos + TX, dimethophos + TX, cyclopentyl thiocarb + TX, tetrachloroethane + TX, thiochlorvos + TX, thiophanate-sodium + TX, Cyclohexanil + TX, cypermethrin + TX, cypermethrin + TX, cypermethrin sodium + TX, tetrabromothrin + TX, permethrin + TX, trichlormetaphos-3 + TX, cypermethrin + TX, chlorpyrifos + TX, tolprocarb + TX, chlorpyrifos + TX, chlorpyrifos + TX, chlorpyrifos + TX, chlorpyrifos + TX, chlorpyrifos + TX, veratridine + TX, XMC + TX,Zetamethrin + TX, zinc phosphide + TX, tolfenphos + TX, chlorfluanidine + TX, tetrafluanidine + TX, bis(tributyltin) oxide + TX, bromoacetamide + TX, iron phosphate + TX, niclosamide-ethanolamine + TX, tributyltin oxide + TX, pyrifos + TX, snail killer + TX, 1,2-dibromo-3-chloropropane + TX, 1,3-dichloropropylene + TX, 3,4-dichlorotetrahydrothiophene 1,1-dioxide + TX, 3-(4-chlorophenyl)-5-methylrhodanine + TX, 5-methyl-6 -1,3,5-thio-thiodiazin-3-yl acetic acid + TX, 6-isopentenylaminopurine + TX, benclothiaz + TX, cytokinin + TX, DCIP + TX, furfural + TX, isamidophos + TX, kinetin + TX, verrucosporium mycorrhizal composition + TX, tetrachlorothiophene + TX, xylenol + TX, zeatin + TX, potassium ethylxanthate + TX, acibenzolar + TX, acibenzolar-S-methyl + TX, Reynoutria sachalinensis) extract + TX, α-chlorohydrin + TX, Antu + TX, barium carbonate + TX, bismuth urea + TX, brodifacoum + TX, brodifacoum + TX, brodifacoum + TX, chlordifacoum + TX, cholecalciferol + TX, chlorfenapyr + TX, clofodine + TX, clofodine + TX, clofodine + TX, clofodine + TX, clofodine + TX, clofodine + TX, clofodine + TX, calciferol + TX, fludioxaline + TX, fluoroacetamide + TX, fludioxaline +TX, flumethrin hydrochloride +TX, warfarin +TX, fosfos +TX, phosphorus +TX, warfarin +TX, warfarin +TX, scillarin +TX, scutellaria glycoside +TX, sodium fluoroacetate +TX, thallium sulfate +TX, warfarin +TX, 2-(-2-butoxyethoxy)ethyl piperate +TX, 5-(1,3-benzodioxol-5-yl)-3-hexylcyclohex-2-enone +TX, farnesol with nerolidol +TX, synergistic acetylene ether +TX, MGK 264+TX, piperonyl butoxide+TX, piperonyl aldehyde+TX, piperonyl ester (propyl isomer)+TX, S421+TX, piperonyl powder+TX, sesasmolin+TX, sulfoxide+TX, anthraquinone+TX, copper cyclohexaneate+TX, copper oxychloride+TX, dicyclopentadiene+TX, serene+TX, zinc cyclohexaneate+TX, zinc thiram+TX, imanin+TX, ribavirin+TX, mercuric oxide+TX, thiophanate-methyl+TX, azaconazole+TX, bifenthrin+TX, fuconazole+TX, cyproconazole+TX, fenpropimorph+TX, diniconazole+TX, epoxiconazole+TX, fenbuconazole+TX, fluquinconazole+TX, fluquinconazole+TX, flusilazole+TX, flutriafol+TX, furopyram+TX, hexaconazole+TX, imazalil+TX, imipenem+TX, cyproconazole+TX, metconazole+TX, myclobutanil+TX,Paclobutrazol + TX, pyriclobutrazol + TX, penconazole + TX, prothioconazole + TX, pyrifenox + TX, prochloraz + TX, propiconazole + TX, pyraclostrobin + TX, simeconazole + TX, tebuconazole + TX, fluconazole + TX, triadimefon + TX, triadimenol + TX, triflumizole + TX, trichlorfon + TX, pyrimidine + TX, chlorfenapyr + TX, flufenapyr + TX, bupirimate + TX, dimethirimol + TX, ethirimol + TX, dodecacyclic morpholine + TX, fenpropidine + TX, butylbenzene Morpholine + TX, spiroxafil + TX, tridemorph + TX, cyprodinil + TX, pyraclostrobin + TX, pyrimethanil + TX; fenpiclonil + TX, fludioxonil + TX, benalaxyl + TX, furalaxyl + TX, metalaxyl + TX, R-metalaxyl + TX; furamide + TX; oxadixyl + TX, carbendazim + TX, debacarb + TX, thiabendazole + TX, chlozolinate + TX, dichlozoline + TX, myclozoline + TX, Procymidone + TX, vinclozoline + TX, boscalid + TX, carboxin + TX, furamide + TX, flutolanil + TX, oxacarb + TX, penthiopyrad + TX, thiofuran + TX, dodine + TX, biguanide + TX, azoxystrobin + TX, enestroburin + TX, enestroburin + TX, flutoxanil + TX, fluoxastrobin + TX, enestroburin + TX, oxacarb + TX, oxacarb + TX, pyraclostrobin + TX, pyraclostrobin + TX, pyraclostrobin + TX, pyraclostrobin + TX, pyraclostrobin + TX, Ester + TX, pyraclostrobin + TX, pyraclostrobin + TX, pyraclostrobin + TX, ferbam + TX, mancozeb + TX, maneb + TX, methanamide + TX, mancozeb + TX, mancozeb + TX, captol + TX, captan + TX, pyraclostrobin + TX, foltan + TX, tolylfluanid + TX, Bordeaux mixture + TX, copper oxide + TX, mancozeb + TX, quinoline copper + TX, phthalocyanine + TX, kefansan + TX, isoblastic acid + TX, chlorpyrifos + TX, methyl tolclofos + TX, captol + TX, benzathine + TX, blasticidin-S + TX, chloroneb + TX, thiophanate-methyl + TX,Cymoxanil + TX, diclocymet + TX, diclomezine + TX, dicloran + TX, diethofencarb + TX, oxadiazine + TX, flumorph + TX, dithianon + TX, ethaboxam + TX, etridiazole + TX, oxadiazine + TX, fenamidone + TX, fenoxanil + TX, ferimzone + TX, fluazinam + TX , fluopicolide + TX, flusulfamide + TX, fluopicolide + TX, fenacet + TX, fosetyl-aluminium + TX, hymexazol + TX, propineb + TX, cyazofamid + TX, methasulfocarb + TX, mefenacet + TX, pencycuron + TX, phthalide + TX, polyoxins + TX, propamocarb + TX, pyraclostrobin + TX, iodoquinolin + TX, oxadiazol ... roquinazid) + TX, pyroquilon + TX, pyraclostrobin + TX, quinoxyfen + TX, pentachloronitrobenzene + TX, thiazolamide + TX, triazoxide + TX, tricyclazole + TX, triazine + TX, validamycin + TX, valeramide + TX, zoxamide + TX, mandipropamid + TX, isopyrazam + TX, sedaxane + TX, benzovintriazole + TX, trifluoroacetic acid + TX, 3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid (3' ,4',5'-trifluoro-diphenyl-2-yl)-amide+TX, isoflurane+TX, isothiocyanamide+TX, dipymetitrone+TX, 6-ethyl-5,7-dioxo-pyrrolo[4,5][1,4]dithiino[1,2-c]isothiazole-3-carbonitrile+TX, 2-(difluoromethyl)-N-[3-ethyl-1,1-dimethyl-indan-4-yl]pyridine-3-carboxamide+TX, 4-(2,6-difluorophenyl)-6-methyl-5-phenyl-pyridazine-3-carbonitrile+TX, (R)-3-(difluoromethyl)-1-methyl-N-[1,1,3-trimethylindan-4-yl]pyrazole-4-carboxamide+TX,4-(2-bromo-4-fluoro-phenyl)-N-(2-chloro-6-fluoro-phenyl)-2,5-dimethyl-pyrazol-3-amine+TX, 4-(2-bromo-4-fluorophenyl)-N-(2-chloro-6-fluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine+TX, fluindapyr+TX, jiaxiangjunzhi+TX, lvbenmixianan+TX, dichlobentiazox+TX, mandestrobin+TX, 3-(4,4-difluoro-3,4-dihydro-3,3-dimethylisoquinolin-1-yl)quinol 1-[(1-methyltetrazolyl-5-yl)phenyl-methylene]amino]oxymethyl]-2-pyridinyl]carbamic acid tert-butyl ester + TX, pyraziflumid + TX, inpyrfluxam + TX, trolprocarb + TX, chlorfluanidazole + TX, ipfentrifluconazole + TX, 2-(difluoromethyl)-N-[(3R)-3-ethyl-1,1-dimethyl-indan-4-yl]pyridine-3-carboxamide + TX, N'-(2,5-dimethyl-4-phenoxy-phenyl)-N-ethyl-N-methyl-formamidine + TX, N'-[4-(4,5-dichlorothiazol-2-yl)oxy-2,5-dimethyl-phenyl]-N-ethyl-N-methyl-formamidine + TX, [2-[3-[2-[1-[2-[3,5-bis(difluoromethyl)pyrazol-1-yl]acetyl]-4-piperidinyl]thiazol-4-yl]-4,5-dihydroisoxazol-5-yl]-3-chloro-phenyl] methanesulfonate + TX, N-[6-[[(Z)-[(1-methyltetrazol-5-yl)-phenyl-methylene]amino]oxymethyl]-2-pyridinyl]carbamic acid but-3-ynyl ester + TX, N-[[5-[4-(2, 4-dimethylphenyl)triazol-2-yl]-2-methyl-phenyl]methyl]carbamic acid methyl ester + TX, 3-chloro-6-methyl-5-phenyl-4-(2,4,6-trifluorophenyl)pyridazine + TX, pyridachlometyl + TX, 3-(difluoromethyl)-1-methyl-N-[1,1,3-trimethylindan-4-yl]pyrazole-4-carboxamide + TX, 1-[2-[[1-(4-chlorophenyl)pyrazol-3-yl]oxymethyl]-3-methyl-phenyl]-4-methyl-tetrazol-5-one + TX, 1-methyl-4-[3-methyl-2-[[2-methyl-4-(3,4,5-trimethylpyrazol-1-yl)phenoxy]methyl]phenyl]tetrazol-5-one + TX,aminopyrifen+TX, azopyrafen+TX, indazolesulfazopyrafen+TX, fluopicolide+TX, (Z,2E)-5-[1-(4-chlorophenyl)pyrazol-3-yl]oxy-2-methoxyimino-N,3-dimethyl-pent-3-enamine+TX, florylpicoxamid+TX, fenpicoxamid+TX, tebufloquin+TX, ipflufenoquin+TX, quinofumelin+TX, isoproterenol+TX, N-[2-[2,4-dichloro-phenoxy]phenyl]-3-(difluoro- 1-methyl-pyrazole-4-carboxamide + TX, N-[2-[2-chloro-4-(trifluoromethyl)phenoxy]phenyl]-3-(difluoromethyl)-1-methyl-pyrazole-4-carboxamide + TX, benzathiostrobin + TX, cyanostrobin + TX, 5-amino-1,3,4-thiadiazole-2-thiol zinc salt (2:1) + TX, fluopyram + TX, fluthiazolinone + TX, fluopyram + TX, pyrapropoyne + TX, picarbutrazox + TX, 2-(difluoromethyl)-N-(3-ethyl-1,1-dimethyl-indan-4-yl)pyridine-3-carboxamide + TX, 2-(difluoromethyl)-N-((3R)- 1,1,3-trimethylindan-4-yl)pyridine-3-carboxamide + TX, 4-[[6-[2-(2,4-difluorophenyl)-1,1-difluoro-2-hydroxy-3-(1,2,4-triazol-1-yl)propyl]-3-pyridinyl]oxy]benzonitrile + TX, metyltetraprole + TX, 2-(difluoromethyl)-N-((3R)-1,1,3-trimethylindan-4-yl)pyridine-3-carboxamide + TX, α-(1,1-dimethylethyl)-α-[4'-(trifluoromethoxy)[1,1'-diphenyl]-4-yl]-5-pyrimidinemethanol + TX, fluoxapiprolin + TX, enoxastrobin (enoxastrobin) + TX, 4-[[6-[2-(2,4-difluorophenyl)-1,1-difluoro-2-hydroxy-3-(1,2,4-triazol-1-yl)propyl]-3-pyridyl]oxy]benzonitrile + TX, 4-[[6-[2-(2,4-difluorophenyl)-1,1-difluoro-2-hydroxy-3-(5-sulfanyl-1,2,4-triazol-1-yl)propyl]-3-pyridyl]oxy]benzonitrile + TX, 4-[[6-[2-(2,4-difluorophenyl)-1,1-difluoro-2-hydroxy-3-(5-thioxo-4H-1,2,4-triazol-1-yl)propyl]-3-pyridyl]oxy]benzonitrile + TX, trinexapac-ethyl + TX, syringoxystrobin + TX,Zhongshengmycin + TX, thiophanate-copper + TX, thiazole zinc + TX, amitolin (amectotractin) + TX, isoprodinil + TX, (N-methoxy-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]cyclopropanecarboxamide + TX, N,2-dimethoxy-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]propionamide + TX, N-ethyl-2- Methyl-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]propanamide+TX, 1-methoxy-3-methyl-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea+TX, 1,3-dimethoxy-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea+TX, 3-ethyl-1-methoxy-1-[[4 -[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea+TX, N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]propionamide+TX, 4,4-dimethyl-2-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]isoxazolidin-3-one+TX, 5,5-dimethyl-2-[[4-[5-(trifluoromethyl)-1,2,4 -oxadiazol-3-yl]phenyl]methyl]isoxazolidin-3-one+TX, 1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]pyrazole-4-carboxylic acid ethyl ester+TX, and N,N-dimethyl-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]-1,2,4-triazol-3-amine+TX), wherein the compounds other than TX in the mixture can be prepared from WO 2017 / 055473, WO 2017 / 055469,WO2017 / 093348 and WO 2017 / 118689, 2-[6-(4-chlorophenoxy)-2-(trifluoromethyl)-3-pyridyl]-1-(1,2,4-triazol-1-yl)propan-2-ol+TX (the compound can be prepared by the method described in WO 2017 / 029179), 2-[6-(4-bromophenoxy)-2-(trifluoromethyl)-3-pyridyl]-1-(1,2,4-triazol-1-yl)propan-2-ol+TX (the compound can be prepared by the method described in WO 2017 / 029179), 3-[2-(1-chlorocyclopropyl)-3-(2-fluorophenyl)-2-hydroxy-propyl]imidazole-4-carbonitrile+TX (the compound can be prepared by the method described in WO 2016 / 156290), 3-[2-(1-chlorocyclopropyl)-3-(3-chloro-2-fluoro-phenyl)-2-hydroxy-propyl]imidazole-4-carbonitrile + TX (the compound can be prepared by the method described in WO 2016 / 156290), 2-amino-6-methyl-pyridine-3-carboxylic acid (4-phenoxyphenyl) methyl ester + TX (the compound can be prepared by the method described in WO 2014 / 006945), 2,6-dimethyl-1H,5H-[1,4]dithiino[2,3-c:5,6-c']bipyrrole-1,3,5,7(2H,6H)-tetraketone + TX (the compound can be prepared by the method described in WO 2011 / 138281), N-methyl-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzenecarboxamide+TX, N-methyl-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide+TX,
[0731] (Z,2E)-5-[1-(2,4-dichlorophenyl)pyrazol-3-yl]oxy-2-methoxyimino-N,3-dimethyl-pent-3-enamine + TX (the compound can be prepared by the method described in WO 2018 / 153707), N'-(2-chloro-5-methyl-4-phenoxy-phenyl)-N-ethyl-N-methyl-formamidine + TX, N'-[2-chloro-4-(2-fluorophenoxy)-5-methyl-phenyl]-N-ethyl-N-methyl-formamidine + TX (the compound can be prepared by the method described in WO 2016 / 202742), and 2-(difluoromethyl)-N-[(3S)-3-ethyl-1,1-dimethyl-indan-4-yl]pyridine-3-carboxamide + TX (the compound can be prepared by the method described in WO2014 / 095675),
[0732] Microbial agents, including: Acinetobacter lwoffii + TX, Acremonium + TX + TX, Cephalosporium acremonium + TX + TX, Acremonium diospyri + TX, Acremonium obclavatum + TX, AdoxGV +TX, Agrobacterium radioactive strain K84 +TX, Alternaria+TX, Alternaria cassiae+TX, Alternaria destruens +TX, Psoralea corylifolia +TX, Aspergillus flavus AF36 +TX, Aspergillus flavus NRRL 21882 +TX, Aspergillus species +TX, Adenophora spp. +TX, Azospirillum +TX, ( +TX、TAZO )+TX, nitrogen-fixing bacteria+TX, Azotobacter chroocuccum +TX, nitrogen-fixing bacteria cysts (BionaturalBlooming )+TX, Bacillus amyloliquefaciens+TX, Bacillus cereus+TX, Bacillus chitinosporus strain CM-1+TX, Bacillus chitinosporus strain AQ746+TX, Bacillus licheniformis strain HB-2 (Biostart TM )+TX, Bacillus licheniformis strain 3086 ( +TX、Green )+TX, Bacillus circulans+TX, Bacillus firmus( +TX, +TX, )+TX, Bacillus firmus strain I-1582+TX, Bacillus macerans+TX, Bacillus marismortui+TX, Bacillus megaterium+TX, Bacillus mycoides strain AQ726+TX, Bacillus lactis )+TX, Bacillus pumilus species+TX, Bacillus pumilus strain GB34 (Yield )+TX, Bacillus pumilus strain AQ717+TX, Bacillus pumilus strain QST 2808( +TX, Ballad )+TX, Bacillus spahericus +TX, Bacillus species +TX, Bacillus strain AQ175 +TX, Bacillus strain AQ177 +TX, Bacillus strain AQ178 +TX, Bacillus subtilis strain QST713 ( +TX, +TX, )+TX, Bacillus subtilis strain QST 714 +TX, Bacillus subtilis strain AQ153+TX, Bacillus subtilis strain AQ743+TX, Bacillus subtilis strain QST3002+TX, Bacillus subtilis strain QST3004+TX, Bacillus subtilis variant strain FZB24 ( +TX, )+TX, Bacillus thuringiensis Cry 2Ae+TX, Bacillus thuringiensis Cry1Ab+TX, Bacillus thuringiensis aizawai GC 91 +TX, Bacillus thuringiensis israelensis ( +TX, +TX, )+TX, Bacillus thuringiensis kurstaki ( +TX, +TX, +TX, +TX, Scutella +TX, Turilav +TX, +TX、Dipel +TX, +TX, )+TX, Bacillus thuringiensis Kurstak BMP 123 +TX, Bacillus thuringiensis Kurstak HD-1 (Bioprotec-CAF / )+TX, Bacillus thuringiensis strain BD#32+TX, Bacillus thuringiensis strain AQ52+TX, Bacillus thuringiensis var.aizawai ( +TX, )+TX, bacteria spp. +TX, +TX, )+TX, Clavipactermichiganensis phage +TX, +TX, Beauveria bassiana ( +TX, Brocaril )+TX, Beauveria bassiana GHA (Mycotrol +TX, Mycotrol +TX, )+TX, Beauveria brongniartii ( +TX, Schweizer +TX, )+TX, Beauveria spp.+TX, Botrytis cineria+TX, Bradyrhizobium japonicum +TX, Brevibacillusbrevis +TX, Bacillus thuringiensis tenebrionis +TX, BtBooster+TX, Burkholderia cepacia ( +TX, +TX、Blue )+TX, Burkholderiagladii+TX, Burkholderia gladioli+TX, Burkholderia spp.+TX, Canadian thistle fungus (CBH Canadian )+TX, Candida butyri+TX, Candida famata+TX, Candida fructus+TX, Candida glabrata+TX, Candida guilliermondii+TX, Candida melibiosica+TX, Candida oleophila strain O+TX, Candida parapsilosis+TX, Candida pelliculosa+TX, Candida pulcherrima+TX, Candida reukaufii+TX, Candida saitoana( +TX, )+TX, Candida sake+TX, Candida spp.+TX, Candida tenius+TX, Cedecea dravisae+TX, Cellulomonas flavigena+TX, Chaetomium cochliodes +TX, Chaetomium globosum +TX, Chromobacterium subtsugae strain PRAA4-1T +TX, Cladosporium cladosporioides+TX, Cladosporium oxysporum+TX, Cladosporium chlorocephalum+TX, Cladosporium spp.+TX, Cladosporium tenuissimum+TX, Clonostachys rosea +TX, Colletotrichum acutatum +TX, Coniothyrium minitans (Cotans )+TX, Coniothyrium spp.+TX, Cryptococcus albidus +TX, Cryptococcus humicola +TX, Cryptococcus infirmo-miniatus +TX, Cryptococcus laurentii +TX, Cryptophlebia leucotreta granulovirus +TX, Cupriavidus campinensis+TX, Cydia pomonella granulovirus +TX, Cydia pomatia granulosis virus ( +TX, Madex +TX, Madex Max / )+TX、Cylindrobasidium laeve +TX, Cylindrocladium+TX, Debaryomyceshansenii+TX, Drechslera hawaiinensis+TX, Enterobacter cloacae+TX, Enterobacteriaceae+TX, Entomophtora virulenta +TX, Epicoccum nigrum +TX, Epicoccum purpurascens +TX, Epicoccum species +TX, Filobasidium floriforme +TX, Fusarium acuminate +TX, Fusarium thunbergii +TX, Fusarium oxysporum / Biofox )+TX, Fusarium sp.+TX, Fusarium spp.+TX, Galactomyces geotrichum+TX, Gliocladium catenulatum ( +TX, )+TX, Gliocladium roseum+TX, Gliocladium species +TX, Gliocladium virens +TX, Granulovirus +TX, Halobacillus halophilus +TX, Halobacillus litoralis +TX, Halobacillus trueperi +TX, Halomonas species +TX, Halomonas subglaciescola +TX, Halovibrio variabilis +TX, Hansenula vitis +TX, Helicoverpa armigera nuclear polyhedrosis virus +TX, Spodoptera exigua nuclear polyhedrosis virus +TX, isoflavone-formononetin +TX, Kloeckner's yeast +TX, Kloeckner's yeast species +TX, Lagenidium giganteum +TX, Lecanicillium longisporum +TX, Lecanicillium muscarium +TX, Lymantria dispar nuclear polyhedrosis virus +TX, Halococcus halophilus +TX, Meira geulakonigii +TX, Metarhizium anisopliae +TX, Metarhizium anisopliae )+TX, Metschnikowia fruticola +TX, Metschnikowia pulcherrima+TX, Microdochium dimerum +TX, Micromonospora coerulea +TX, Microsphaeropsis ochracea +TX, Muscodor albus 620 +TX, Muscodor roseus strain A3-5+TX, Mycorrhizae spp. ( +TX、Root )+TX, Myrotheca verrucosa strain AARC-0255 +TX、BROS +TX, Ophiostoma piliferum strain D97 +TX, Paecilomyces farinosus +TX, Paecilomyces fumosorum +TX, )+TX, Paecilomyces lilacinus (Biostat )+TX, Paecilomyces lilacinus strain 251 (MeloCon )+TX, Paenibacillus polymyxa+TX, BlightBan )+TX, Pantoea species+TX, Pasteurella species +TX, Pasteuria nishizawae +TX, Penicillium chrysogenum +TX, Penicillium billai ( +TX, )+TX, Penicillium breviscomplexum+TX, Penicillium affine+TX, Penicillium purpurogenum+TX, Penicillium species+TX, Pure green Kentella+TX, Phlebiopsis gigantean +TX, phosphate-solubilizing bacteria +TX, Phytophthora cryptogenomica +TX, Phytophthora palmi +TX, Pichia anomala +TX, Pichia guilermondii +TX, Pichia membranaceus +TX, Pichia nail +TX, Pichia stipitis +TX, Pseudomonas aeruginosa +TX, Pseudomonas aureofasciens (Spot-Less )+TX, Pseudomonas cepacia+TX, Pseudomonas chlororaphis +TX, Pseudomonas corrugate +TX, Pseudomonas fluorescens strain A506 (BlightBan )+TX, Pseudomonas putida+TX, Pseudomonas reactans+TX, Pseudomonas species+TX, Pseudomonas syringae +TX, Pseudomonas aureus+TX, Pseudomonas fluorescens +TX, Pseudozyma flocculosa strain PF-A22 UL (Sporodex )+TX、Puccinia canaliculata+TX、Puccinia thlaspeos(Wood )+TX, Pythium oligandrum+TX, Pythium oligandrum +TX, )+TX, Pythium entangled +TX, Rhanella aquatilis +TX, Rhanella spp. +TX, Rhizobia ( +TX, )+TX, Rhizoctonia+TX, Rhodococcus globerulus strain AQ719+TX, Rhodosporidiumdiobovatum+TX, Rhodosporidium toruloides+TX, Rhodotorula spp.+TX, Rhodotorula glutinis+TX, Rhodotorula graminis+TX, Rhodotorula mucilagnosa+TX, Rhodotorula rubra+TX, Saccharomyces cerevisiae+TX, Salinococcus roseus+TX, Sclerotinia minor+TX, Sclerotinia minor +TX, Scytalidium spp.+TX, Scytalidium uredinicola+TX, Spodoptera exigua nuclear polyhedrosisvirus( +TX, )+TX, Serratia marcescens+TX, Serratia plymuthica+TX, Serratia spp.+TX, Sordaria fimicola+TX, Spodoptera littoralisnucleopolyhedrovirus +TX, Sporobolomyces roseus +TX, Stenotrophomonas maltophilia +TX, Streptomyces ahygroscopicus +TX, Streptomyces albaduncus +TX, Streptomyces exfoliates +TX, Streptomyces galbus +TX, Streptomyces griseoplanus +TX, Streptomyces griseoviridis +TX, Streptomyces lydicus +TX, Streptomyces lydicus WYEC-108 +TX, Streptomyces violaceus +TX, Tilletiopsis minor +TX, Tilletiopsis spp. +TX, Trichoderma asperellum (T34 )+TX, Trichoderma gamsii +TX, Trichoderma atroviride +TX, Trichoderma hamatum TH 382+TX, Trichoderma harzianum rifai +TX, Trichoderma harzianum T-22( +TX, PlantShield +TX, +TX, )+TX, Trichoderma harzianum T-39 +TX, Trichoderma mainhamatum +TX, Trichoderma koningii +TX, Trichoderma spp. LC 52 +TX, Trichoderma lignorum +TX, Trichoderma longibrachiatum +TX, Trichoderma polysporum (Binab )+TX, Trichoderma taxi+TX, Trichoderma virens+TX, Trichoderma virens (formerly known as Gliocladium virens GL-21) +TX, Trichoderma viride +TX, Trichoderma viride strain ICC 080 +TX, Trichosporon pullulans +TX, Trichosporon spp. +TX, Trichothecium spp. +TX, Trichothecium roseum +TX, Typhula phacorrhiza strain 94670 +TX, Typhula phacorrhiza strain 94671 +TX, Ulocladium atrum +TX, Ulocladium oudemansii +TX, Ustilago maydis +TX, various bacteria and supplemental micronutrients (Natural )+TX, various fungi (Millennium )+TX, Verticillium chlamydosporium+TX, Verticillium lecanii ( +TX, )+TX、Vip3Aa20 +TX, Virgibaclillus marismortui +TX, Xanthomonas campestris pv.Poae +TX, Xenorhabdus burnetii +TX, Xenorhabdus nematophila;
[0733] Plant extracts, including: pine oil +TX, Plasma Neem +TX, +TX, +TX, +TX, Plant IGR( +TX, )+TX, canola oil (Lilly Miller )+TX, Chenopodium ambrosioides near ambrosioides +TX, chrysanthemum extract +TX, neem oil extract +TX, Labiatae essential oil +TX, clove-rosemary-peppermint and thyme oil extract (Garden insect )+TX, betaine +TX, garlic +TX, lemongrass oil +TX, neem oil +TX, catnip (Nepeta cataria) (catnip oil) +TX, Nepeta catarina +TX, nicotine +TX, oregano oil +TX, Pedaliaceae oil +TX, Pyrethrum+TX, Soapbark Tree (Quillaja saponaria) +TX, Reynoutria sachalinensis ( +TX, )+TX, rotenone (Eco )+TX, Rutaceae plant extract +TX, soybean oil (Ortho )+TX, tea tree oil (Timorex )+TX, thyme oil+TX, MMF+TX, +TX, Rosemary-Sesame-Peppermint-Thyme and Cinnamon Extract Blend (EF )+TX, clove-rosemary and peppermint extract blend (EF )+TX, Clove-Peppermint-Garlic Oil and Mint Blend (Soil )+TX, kaolin +TX, storage glucan of brown algae
[0734] Pheromones, including: 3M Sprayable Blackheaded Fireworm )+TX, Codling moth pheromone (Paramount dispenser-(CM) / Isomate )+TX, Grape leaf roller pheromone (3MMEC-GBM Sprayable )+TX, leaf roller pheromone (3MMECLR Sprayable )+TX, Muscamone (Snip7Fly +TX、Starbar Premium Fly )+TX, 3M oriental fruit mothsprayable )+TX, Peachtree Borer pheromone +TX, Tomato Pinworm pheromone (3M Sprayable )+TX, Entostat powder (Exosex )+TX、(E+TX,Z+TX,Z)-3+TX,8+TX,11-tetradecatriene acetate+TX、(Z+TX,Z+TX,E)-7+TX,11+TX,13-hexadecadienal+TX、(E+TX,Z)-7+TX,9-dodecadien-1-yl acetate+TX、2-methyl-1-butanol+TX、calcium acetate+TX、 +TX, +TX, +TX, Lavandulyl senecioate;
[0735] Macrobial agents, including: Aphidius ervi + TX, Aphidius ervi +TX, Acerophagus papaya+TX, Coccinella bispotata +TX, Coccinella bispotata +TX, Coccinella bispotata +TX, Ageniaspis citricola+TX, Polyembryonic wasp+TX, Amblyseius andersoni( +TX, )+TX, Amblyseius californicus ( +TX, )+TX, Cucumber mite ( +TX, Bugline )+TX, Pseudoseiidae +TX, Bugline +TX, )+TX, Amblyseius ostreatus +TX, Amitus hesperidum+TX, Anagrus atomus+TX, Anagyrus fusciventris+TX, Anagyrus kamali+TX, Anagyrus loecki+TX, Anagyrus pseudococci +TX, Anicetus benefices +TX, Anisopteromalus calandrae +TX, Anthocoris nemoralis +TX, Short-spurred Aphid Wasp ( +TX, )+TX, Aphelinus asychis+TX, Aphidius colemani +TX, Alphididae +TX, Aphidida cirrhosa +TX, Aphidida serrata +TX, Aphid midge +TX, Aphid midge +TX, Lingnan yellow aphid wasp +TX, Indian yellow aphid wasp +TX, Aprostocetus hagenowii +TX, Atheta coriaria +TX, Bombus species +TX, European bumblebee (Natupol )+TX, European Bumblebee ( +TX, )+TX, Cephalonomiastephanoderis+TX, Chilocorus nigritus+TX, Chrysoperlacarnea +TX, Common lacewing +TX, Chrysoperlarufilabris+TX, Cirrospilus ingenuus+TX, Cirrospilusquadristriatus+TX, Citrostichus phyllocnistoides+TX, Closterocerus chamaeleon+TX, Closterocerus species+TX, Coccidoxenoides perminutus +TX, Coccophagus cowperi+TX, Coccophagus lycimnia+TX, Coccophagus luteola+TX, Coccophagus rapae+TX, Coccophagus monticola+TX +TX, )+TX、Japanese square-headed beetle+TX、Siberian jawed braconid wasp+TX、Siberian jawed braconid wasp +TX, Pea leafminer +TX, small black ladybug (Delphastuscatalinae) +TX, Delphastus pusillus+TX, Diachasmimorpha krausii+TX, Long-tailed fly miner+TX, Diaparsis jucunda+TX, Diaphorencyrtusaligarhensis+TX, Pea leafminer+TX, Pea leafminer +TX, )+TX, Siberian Braconidia ( +TX, )+TX, species of the genus Encarsia+TX, Aphididae spp.+TX, Encarsia spp. +TX, +TX, )+TX, Eretmocerus eremicus +TX, Encarsia guadeloupae +TX, Encarsia haitiensis +TX, Syrphididae +TX, Eretmoceris siphonini+TX, Eretmocerus californicus+TX, Eretmocerus eremicus( +TX, Eretline )+TX, Eretmocerus eremicus +TX, Henri's aphid wasp+TX, Monsoni's aphid wasp ( +TX, Eretline )+TX, Eretmocerus siphonini+TX, Exochomus quadripustulatus+TX, Feltiella acarisuga +TX, Acarina +TX, Alishan fly miner +TX, Fopiusceratitivorus +TX, Wirless )+TX, thrips slender +TX, Galendromus occidentalis +TX, Goniozus legneri +TX, Echinops spheniscus +TX, Harmonia axyridis +TX, Heterorhabditis species (Lawn )+TX, Heterorhabditis elegans (NemaShield +TX, +TX, +TX, +TX, +TX, +TX, +TX, )+TX, Heterorhabditis megidis (Nemasys +TX, BioNem +TX、Exhibitline +TX, )+TX, Hippodamia convergens+TX, Hypoaspis aculeifer ( +TX, )+TX、Hypoaspis miles +TX, )+TX, black branch gall wasp+TX, Lecanoideus floccissimus+TX, Lemophagus errabundus+TX, three-color beautiful jumping wasp (Leptomastideaabnormis)+TX, orange powder scale parasitic wasp (Leptomastix dactylopii) +TX, Leptomastix epona+TX, Lindorus lophanthae+TX, Lipolexis oregmae+TX, Lucilia serrata +TX, Aphididae caliginosus+TX, Macrolophus caliginosus( +TX、Macroline +TX, )+TX、Mesoseiulus longipes+TX、Metaphycus flavus+TX、Metaphycus lounsburyi+TX、Ceratitis hornworm +TX, Microterys flavus +TX, Muscidifuraxraptorellus and Spalangia cameroni +TX, Neodryinus typhlocybae+TX, Neodryinus californicus+TX, Neodryinus typhlocybae +TX, Neoseiulus fallacis +TX, Nesideocoris tenuis ( +TX, )+TX, bronze black fly +TX, Orius insidiosus( +TX, Oriline )+TX, Orius laevigatus ( +TX, Oriline )+TX、Oriusmajusculus(Oriline )+TX, small black flower stink bug +TX, Pauesia juniperorum+TX, Pediobius foveolatus+TX, Phasmarhabditis hermaphrodita +TX, Phymastichus coffea+TX, Phytoseiulus macropilus+TX, Phytoseiulus chilensis +TX、Phytoline )+TX, Cynomorium scaly +TX, Pseudacteon curvatus+TX, Pseudacteon obtusus+TX, Pseudacteon tricuspis+TX, Pseudaphycus maculipennis+TX, Pseudleptomastix mexicana+TX, Psyllaephagus pilosus+TX, Psyttalia concolor (complex)+TX, Quadrastichus spp.+TX, Rhyzobius lophanthae+TX, Australian ladybird+TX, Rumina decollate+TX, Semielacherpetiolatus+TX, Aphid +TX, Nematac +TX, +TX, BioNem +TX, +TX, +TX, )+TX, Steinernema carinata ( +TX, Nemasys +TX, BioNem +TX, +TX, +TX, +TX、Exhibitline +TX, +TX, )+TX, Steinernema kraussei (Nemasys +TX, BioNem +TX、Exhibitline )+TX, Steinernema riobrave ( +TX, )+TX, Steinernema scapterisci (Nematac )+TX, Steinernematid species+TX, Steinernematid species (Guardian )+TX, Deep-point mite-eating ladybird +TX, bright-bellied glaze wasp +TX, Tetrastichus setifer +TX, Thripobius semiluteus +TX, Chinese long-tailed wasp (Torymus sinensis) +TX, Tricholine )+TX, Trichogrammatidae +TX, Trichogramma splenicum +TX, Trichogramma microplus +TX, Trichogramma ostriniae +TX, Trichogramma platneri +TX, Trichogramma sphenobarbus +TX, Xanthopimplastemmator; and
[0736] Other biological agents, including: abscisic acid + TX, +TX, Chondrostereum purpureum (Chontrol )+TX, Discosporium +TX, copper octanoate +TX, Delta trap +TX, Erwinia amylovora (Harpin) ( +TX、Ni-HIBIT Gold )+TX, ferric phosphate +TX, Funnel trap )+TX, +TX, Grower's +TX, Homo-brassonolide +TX, iron phosphate (Lilly Miller Worry Free Ferramol Slug & Snail )+TX、MCP hail trap )+TX、parasitic insect Microctonus hyperodae+TX、Mycoleptodiscus terrestris +TX, +TX, +TX, +TX, Pheromone Net (Thripline )+TX, potassium bicarbonate +TX, potassium salt of fatty acids +TX, potassium silicate solution +TX, potassium iodide + potassium thiocyanate +TX, +TX, spider venom +TX, locust microsporidia (Semaspore Organic Grasshopper )+TX, Trapline +TX, Rebell )+TX and the captured object (Takitrapline )+TX; an auxiliary agent selected from the group consisting of: petroleum (alias) (628)+TX;
[0737] Insect control active substances selected from the group consisting of Avermectin + TX, Acetoquinone + TX, Acetamiprid + TX, Acetamiprid + TX, Acetamiprid + TX, Acynonapyr + TX, Biprofen + TX, Afolan + TX, Cotton Boll + TX, Allethrin + TX, α-Cypermethrin + TX, Alpha-Cypermethrin + TX, Sulfonamide + TX, Methiocarb + TX, Triazotin + TX, Cypermethrin + TX, Benzothion + TX, Benzpyrimoxan + TX, β-Cypermethrin + TX, β-Cypermethrin + TX, Bifenazate + TX, Bifenthrin + TX, Binamitox + TX, Bio-allethrin + TX, Bio-allethrin S)-cyclopentyl isomer + TX, Bio-resmethrin Ester + TX, bistrifluanuron + TX, bromofenac + TX, bromothiophene + TX, bromophos-ethyl + TX, buprofezin + TX, butanone + TX, cadusofos + TX, carbaryl + TX, butansulfuron + TX, batan + TX, CAS No.: 1472050-04-6 + TX, CAS No.: 1632218-00-8 + TX, CAS No.: 1808115-49-2 + TX, CAS No.: 2032403-97-5 + TX, CAS No.: 2044701-44-0 + TX, CAS No.: 2128706-05-6 + TX, CAS No.: 2249718-27-0 + TX, chloranil Benzamide + TX, Chlordane + TX, Chlorfenapyr + TX, Chlorprophmethrin + TX, Chlorfenapyr + TX, Clenpyrine + TX, Cloethocarb + TX, Clothianidin + TX, 2-Chlorophenyl N-methylcarbamate (CPMC) + TX, Cyanophos + TX, Cyantraniliprole + TX, Cyclofenapyr + TX, Cyclobutrifluram + TX, Pyrethroids + TX, Cyclofenapyr + TX, Cyclopyrafen + TX, Cyfluthrin + TX, Cyhalodiamide + TX, Cyhalothrin + TX, Cypermethrin Ester + TX, cypermethrin + TX, Cyproflanilide + TX, Cyprodione + TX, Deltamethrin + TX, Fenpyrazone + TX, Chlormethrin + TX, Dibrom + TX, Dicloromezotiaz + TX, Fluomezofen + TX, Diflubenzuron + TX, Dipropyridaz + TX, Diclofenac + TX, Dinotefuran + TX, Vegetable and Fruit Phosphorus + TX, Emamectin + TX, Dextran + TX, ε-momfluorothrin + TX, ε-Methiofluthrin + TX, Cypermethrin + TX, Ethion + TX, Ethiopromide + TX, Ethofenprox + TX, Ethiopromide + TX, Fenpyrazone + TX,Quinazaquin + TX, Penfluthrin + TX, Fenitrothion + TX, Fenbutar + TX, Fenthiocarb + TX, Fenoxycarb + TX, Cypermethrin + TX, Fenpyroxymate + TX, Fensulfuron + TX, Fenthion + TX, Yesalin + TX, Cypermethrin + TX, Fipronil + TX, Flometoquin + TX, Flyoxaline + TX, Felocellar + TX, Flucitrinate + TX, Fluazaindolizine + TX, Fentilamide + TX, Flumid + TX, Flucitrinate + TX X, flufenacet + TX, flucythrin + TX, fluthiamethoxam + TX, flumethrin + TX, flubendiamide + TX, flufenox + TX, fluhexafon + TX, fluchlorfenapyr + TX, flupyram + TX, Flupentiofenox + TX, flupyrazone + TX, Flupyrimin + TX, fluralaner + TX, fluvalinate + TX, Fluxametamide + TX, thiathion + TX, γ-cyhalothrin + TX, Gossyplure, TM+TX, pyramid +TX, chlorfenapyr +TX, chlorfenapyr +TX, halofenprox +TX, heptafluthrin +TX, hexathiacyclon +TX, hydrazone +TX, imidophos +TX, imidacloprid +TX, imiprodinil +TX, indoxacarb +TX, iodomethane +TX, isoprodinil +TX, Isocycloseram +TX, isothiocarb +TX, ivermectin +TX, kappa-bifenthrin +TX, kappa-tefluthrin +TX, lambda-cyhalothrin +TX, lepidomectin +TX, chlorfenapyr +TX, metaflumizone +TX, metaldehyde +TX, metamex +TX, methomyl +TX, methoxyfenopyr +TX, methoxyfenopyr +TX, Methiothrin +TX, Methiothrin +TX, Zikewei +TX, Mite +TX, Momfluorothrin +TX, Methiothrin +TX, Nicofluprole +TX, Nitenpyram +TX, Nithiothiazide +TX, Oxydemeton +TX, Oxamyl +TX, Oxazosulfyl +TX, Parathion-ethyl +TX, Permethrin +TX, Phenothrin +TX, Phosphamidon +TX, Piperonyl Butoxide +TX, Pirimicarb +TX, Pirimiphos-ethyl +TX, Polyhedrosis virus +TX, Promethrin +TX, Probromophos +TX, Probromophos +TX, Profluthrin +TX, Promethrin +TX, Promethrin +TX, Profenthion +TX, Promethrin +TX, Profenthion +TX, Profenthion +TX, Profenthrin Protrifenbute + TX, Pyflubumide + TX, Pymetrozine + TX, Pyrafluprole + TX, Pyridaben + TX, Pyridalyl + TX, Pyrifluquinazon + TX, Pyrimidine + TX, Pyrimidine + TX, Pyrafluprid + TX, Fyflufen + TX, Resmothrin + TX, Sarolaner + TX, Selamectin + TX, Fluosimethrin + TX, Spinetoram + TX, Spinosad + TX, Spirodiclofen + TX, Spiromefoxine + TX, Spiropyrim + TX, Spiropidion + TX, Spiromefen + TX, Spiropyrim + TX, Ethyl ester + TX, sulfone cypermethrin + TX, cypermethrin + TX, cypermethrin + TX, cypermethrin + TX, cypermethrin + TX, cypermethrin + TX, cypermethrin + TX, cypermethrin + TX, flucyranoids + TX, θ-cypermethrin + TX, thiacloprid + TX, thiamethoxam + TX, cypermethrin + TX, thiocarb + TX, long-acting carb + TX, methyl thiocarb + TX, cypermethrin + TX, tioxazafen + TX, tolfenpyrad + TX, toxaphene + TX, tralomethrin + TX,Transfluthrin + TX, Acyril + TX, Triazophos + TX, Trichlorfon + TX, Chlorpyrifos + TX, Triflumezopyrim + TX, Tyclopyrazoflor + TX, ζ-Cypermethrin + TX, Seaweed extract and fermentation products derived from sugar acyl + TX, Seaweed extract and fermentation products derived from sugar acyl (containing urea + TX, amino acids + TX, potassium and molybdenum, and EDTA chelated manganese) + TX, Seaweed extract and fermented plant products + TX, Seaweed extract and fermented plant products (containing plant hormones + TX, vitamins + TX, EDTA chelated copper + TX, zinc + TX, and iron + TX), Azadirachtin + TX, Bacillus aizawai + TX, Bacillus chitiniferum chitinosporus) AQ746 (NRRL Accession No. B-21618) + TX, Bacillus firmus + TX, Bacillus kurstaki + TX, Bacillus mycoides AQ726 (NRRL Accession No. B-21664) + TX, Bacillus pumilus (NRRL Accession No. B-30087) + TX, Bacillus pumilus AQ717 (NRRL Accession No. B-21662) + TX, Bacillus species AQ178 (ATCC Accession No. 53522) + TX, Bacillus species AQ175 (ATCC Accession No. 55608) + TX, Bacillus species AQ177 (ATCC Accession No. 55609) + TX, unspecified Bacillus subtilis + TX, Bacillus subtilis AQ153 (ATCC registration number 55614) + TX, Bacillus subtilis AQ30002 (NRRL registration number B-50421) + TX, Bacillus subtilis AQ30004 (NRRL registration number B-50455) + TX, Bacillus subtilis AQ713 (NRRL registration number B-21661) + TX, Bacillus subtilis AQ743 (NRRL registration number B-21665) + TX, Bacillus thuringiensis AQ52 (NRRL registration number B-21619) + TX, Bacillus thuringiensis BD#32 (NRRL registration number B-21530) + TX, Bacillus thuringiensis subspec. kurstaki BMP 123+TX, Beauveria bassiana+TX, D-limonene+TX, Granulovirus+TX, Harpin+TX, Helicoverpa armigera nuclear polyhedrosis virus+TX, Spodoptera exigua nuclear polyhedrosis virus+TX, Tobacco budworm nuclear polyhedrosis virus+TX, Australian Helicoverpa armigera nuclear polyhedrosis virus+TX, Metarhizium species+TX, Muscodor albus 620 (NRRL registration number 30547)+TX,Muscodor roseus A3-5 (NRRL Accession No. 30548) + TX, neem-based products + TX, Paecilomyces fumosorum + TX, Paecilomyces lilacinus + TX, Pasteuria pseudoszavara + TX, Pasteuria penetranta + TX, Pasteuria mycorrhiza + TX, Pasteuria thornei + TX, Pasteuria + TX, p-cymene + TX, Plutella xylostella granulosis virus + TX, Plutella xylostella nuclear polyhedrosis virus + TX, polyhedrosis virus + TX, pyrethrum + TX, QRD 420 (terpenoid blend) + TX, QRD 452 (terpenoid blend) + TX, QRD 460 (terpenoid blend) + TX, Quillaja saponaria + TX, Rhodococcus sphaeroides AQ719 (NRRL Accession No. B-21663) + TX, Spodoptera frugiperda nuclear polyhedrosis virus + TX, Streptomyces flavus (NRRL Accession No. 30232) + TX, Streptomyces species (NRRL Accession No. B-30145) + TX, terpenoid blend + TX, and Verticillium species;
[0738] an algaecide selected from the group consisting of bethoxazin [CCN] + TX, copper dioctanoate (IUPAC name) (170) + TX, copper sulfate (172) + TX, cybutryne [CCN] + TX, dichlone (1052) + TX, dichlorophen (232) + TX, endosylamine (295) + TX, fentin (347) + TX, slaked lime [CCN] + TX, nabam (566) + TX, quinoclamine (714) + TX, quinonamid (1379) + TX, simazine (730) + TX, triphenyltin acetate (IUPAC name) (347) and triphenyltin hydroxide (IUPAC name) (347) + TX;
[0739] Anthelmintics selected from the group consisting of: avermectin (1) + TX, clefosinate (1011) + TX, cybutaflutol + TX, doramectin (alias) [CCN] + TX, emamectin (291) + TX, emamectin benzoate (291) + TX, eprinomectin (alias) [CCN] + TX, ivermectin (alias) [CCN] + TX, milbemycin oxime (alias) [CCN] + TX, moxidectin (alias) [CCN] + TX, piperazine [CCN] + TX, selamectin (alias) [CCN] + TX, spinosad (737) and thiophanate (1435) + TX;
[0740] Avicides selected from the group consisting of chloralose (127) + TX, endrin (1122) + TX, fenthion (346) + TX, pyridin-4-amine (IUPAC name) (23) and strychnine (745) + TX;
[0741] Bactericides 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, dipyrithione (1105) + TX, dodesine (1112) + TX, fenaminosulf (1144) + TX, formaldehyde (404) + TX, mercaptophenone ( alias) [CCN] + TX, kasugamycin (483) + TX, kasugamycin hydrochloride hydrate (483) + TX, nickel bis(dimethyldithiocarbamate) (IUPAC name) (1308) + TX, nitrapyrin (580) + TX, octhilinone (590) + TX, oxolinic acid (606) + TX, oxytetracycline (611) + TX, potassium hydroxyquinoline sulfate (446) + TX, probenazole (658) + TX, streptomycin (744) + TX, streptomycin sesquisulfate (744) + TX, chlorphenamine (766) + TX, and thimerosal (alias) [CCN] + TX;
[0742] A biological agent selected from the group consisting of: GV of cotton brown banded moth (alias) (12) + TX, Agrobacterium radiobacterium (alias) (13) + TX, Amblyseius spp. (alias) (19) + TX, Spodoptera exigua NPV (alias) (28) + TX, Anagrus atomus (alias) (29) + TX, Aphelinus abdominalis (alias) (33) + TX, Aphidius colemani (alias) (34) + TX, Aphidoletes aphidimyza (alias) (35) + TX, Spodoptera exigua NPV (alias) (38) + TX, Bacillus firmus (alias) (48) + TX, Bacillus sphaericus Neide)(scientific name)(49)+TX、Bacillus thuringiensis Berliner)(scientific name)(51)+TX、Bacillus thuringiensis subsp.aizawai)(scientific name)(51)+TX、Bacillus thuringiensis subsp.israelensis)(scientific name)(51)+TX、Bacillus thuringiensis subsp.japonensis)(scientific name)(51)+TX、Bacillus thuringiensis subsp.kurstaki)(scientific name)(51)+TX、Bacillus thuringiensis subsp.tenebrionis (scientific name) (51) + TX, Beauveria bassiana (alias) (53) + TX, Beauveria brongniartii (alias) (54) + TX, Chrysoperla carnea (alias) (151) + TX, Cryptolaemus montrouzieri (alias) (178) + TX, Codling moth GV (alias) (191) + TX, Dacnusa sibirica (alias) (212) + TX, Diglyphus isaea (alias) (254) + TX, Encarsia formosa (scientific name) (293) + TX, Eretmocerus eremicus) (alias) (300) + TX, Spodoptera exigua NPV (alias) (431) + TX, Heterorhabditis bacteriophora and H. megidis (alias) (433) + TX, Hippodamia convergens (alias) (442) + TX, Leptomastix dactylopii (alias) (488) + TX, Macrolophus caliginosus (alias) (491) + TX, Cabbage armyworm NPV (alias) (494) + TX, Metaphycus helvolus (alias) (522) + TX, Metarhizium anisopliae var.acridum)(scientific name)(523)+TX, Metarhizium anisopliae var.anisopliae)(scientific name)(523)+TX, Neodiprionsertifer NPV and Neodiprionsertifer rubrum NPV.lecontei)NPV(alias)(575)+TX、Phytoseiulus species(alias)(596)+TX、Paecilomyces fumosoroseus(alias)(613)+TX、Phytoseiulus persimilis(alias)(644)+TX、Spodopteraexigua multicapsid nuclear polyhedrosis virus(scientific name)(741)+TX、Steinernema bibionis(alias)(742)+TX、Steinernema carpocapsae(alias)(742)+TX、Steinernema glaseri(alias)(742)+TX、Steinernema riobrave)(alias)(742)+TX, Steinernema riobravis(alias)(742)+TX, Steinernema scapterisci(alias)(742)+TX, Steinernema spp.(alias)(742)+TX, Trichogramma spp.(alias)(826)+TX, Typhlodromus occidentalis(alias)(844) and Verticillium lecanii(alias)(848)+TX;.
[0743] A soil disinfectant selected from the group consisting of methyl iodide (IUPAC name) (542) and methyl bromide (537) + TX;
[0744] A chemical sterilant selected from the group consisting of apholanate [CCN] + TX, bis(aziridine) methylaminophosphine sulfide (bisazir) (alias) [CCN] + TX, busulfan (alias) [CCN] + TX, diflubenzuron (250) + TX, dimatif (alias) [CCN] + TX, hemel [CCN] + TX, hempa [CCN] + TX, metepa [CCN] + TX, methylsulfonate Methotepa [CCN] + TX, methylapholate [CCN] + TX, morzid [CCN] + TX, penfluron (alias) [CCN] + TX, tepa [CCN] + TX, thiohempa (alias) [CCN] + TX, thiotepa (alias) [CCN] + TX, trothamide (alias) [CCN] and urethaneimide (alias) [CCN] + TX;
[0745] An insect pheromone selected from the group consisting of (E)-dec-5-en-1-yl acetate and (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 X, (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-yl acetate (IUPAC name) (780) + TX, (9Z,12E)-tetradec-9,12-Dien-1-yl acetate (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-multistriatin (alias) [CCN] + TX, western pine beetle gathering pheromone (brevicomin) (alias) [CCN] + TX, codlelure (alias) [CCN] + TX, codle mone)(alias)(167)+TX、cuelure(alias)(179)+TX、disparlure(277)+TX、1-dodecyl acetate(IUPAC name)(286)+TX、1-dodecyl acetate(IUPAC name)(287)+TX、10-1-dodecyl acetate(IUPAC name)(284)+TX、dominicalure(alias)[CCN]+TX、ethyl 4-methyloctanoate(IUPAC name) C name) (317) + TX, eugenol (alias) [CCN] + TX, southern pine beetle aggregation pheromone (frontalin) (alias) [CCN] + TX, gossyplure (alias) (420) + TX, grandlure (421) + TX, grandlure I (alias) (421) + TX, grandlure II (alias) (421) + TX, grandlure III (alias) (421) + TX, grandlure IV (alias) (421) + TX, hexalure )[CCN]+TX、ipsdienol (alias)[CCN]+TX、ipsenol (alias)[CCN]+TX、japonilure (alias)(481)+TX、lineatin (alias)[CCN]+TX、litlure (alias)[CCN]+TX、looplure (alias)[CCN]+TX、medlure[CCN]+TX、megatomoic acid (alias)[CCN]+TX、methyl eugenol (alias)(540)+TX、muscalure (563)+TX、octadecene-2,13-diene-1-yl acetate (IUPAC name)(588)+TX、octadecene-3,13-Dien-1-yl acetate (IUPAC name) (589) + TX, orfralure (alias) [CCN] + TX, oryctalure (alias) (317) + TX, ostramone (alias) [CCN] + TX, siglure [CCN] + TX, sordidin (alias) (736) + TX, sulcatol (alias) [CCN] + TX, tetradecene-11-en-1-yl acetate (IUPAC name) (785) + TX, Mediterranean fruit fly attractant (839) + TX, Mediterranean fruit fly attractant A (alias) (839) + TX, Mediterranean fruit fly attractant B, 1 (Alias) (839) + TX, Mediterranean fruit fly attractant B 2 (alias) (839) + TX, Mediterranean fruit fly attractant C (alias) (839) and trunc-call (alias) [CCN] + TX;
[0746] An insect repellent selected from the group consisting of 2-(octylthio)ethanol (IUPAC name) (591) + TX, butopyronoxyl (933) + TX, butoxy(polypropylene glycol) (936) + TX, dibutyl adipate (IUPAC name) (1046) + TX, dibutyl phthalate (1047) + TX, dibutyl succinate (IUPAC name) (1048) + TX, DEET [CCN] + TX, dimethyl carbate [CCN] + TX, dimethyl phthalate [CCN] + TX, ethyl hexanediol (1137) + TX, hexylurea [CCN] + TX, methoquin-butyl (1276) + TX, methyl neodecylamide [CCN] + TX, oxamate [CCN] and picaridin [CCN] + TX;
[0747] Molluscicide selected from the group consisting of di(tributyltin) oxide (IUPAC name) (913) + TX, bromoacetamide [CCN] + TX, calcium arsenate [CCN] + TX, chloranil (999) + TX, copper acetyl arsenite [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, pentachlorophenol ( 623)+TX, sodium pentachlorophenoxide (623)+TX, tazimcarb (1412)+TX, thiodicarb (799)+TX, tributyltin oxide (913)+TX, trifenmorph (1454)+TX, trimethacarb (840)+TX, triphenyltin acetate (IUPAC name) (347) and triphenyltin hydroxide (IUPAC name) (347)+TX, pyriprole [394730-71-3]+TX;
[0748] 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) + TX, 1,2-dichloropropane and 1,3-dichloropropene (IUPAC name) + TX, 1,3-dichloropropene (233) + TX, 1,2 ...3-dichloropropene (233) + TX, 1,3-dichloropropene (233) + TX, 1,3-dichloropropene (233) + TX Abstract name) (1065) + TX, 3-(4-chlorophenyl)-5-methylrhodanine (IUPAC name) (980) + TX, 5-methyl-6-thioxo-1,3,5-thiadiazin-3-yl acetic acid (IUPAC name) (1286) + TX, 6-isopentenylaminopurine (alias) (210) + TX, avermectin (1) + TX, acetofenamide [CCN] + TX, cotton bell carb (15) + TX, aldicarb (16) + TX, aldicarb (863) + TX, AZ60541 (compound code) + TX, benclothiaz [CCN] + TX, benomyl (62) + TX, butylpyridaben (alias) + TX, carbofuran (109) + TX, carbofuran (118) + TX, carbon disulfide (945) + TX, carbofuran (119) + TX, chloropicrin (141) + TX, chlorpyrifos (145) + TX, chlorpyrifos (999) + TX, cyclohexane + TX, cytokinin (alias) (2 10) + TX, dazomethane (216) + TX, DBCP (1045) + TX, DCIP (218) + TX, diamidafos (1044) + TX, dimethoate (1051) + TX, dicliphos (alias) + TX, dimethoate (262) + TX, doramectin (alias) [CCN] + TX, emamectin (291) + TX, emamectin benzoate (291) + TX, eprinomectin (alias) [CCN] + TX, ethoprophos (312) + TX, ethylene dibromide (316) + TX, fenamiphos (326) + TX, fenpyrad (alias) + TX, fenthiophos (1158) + TX, thiathiophos (408) + TX, butyric acid cyclohexane (1196) + TX, furfural (alias) [CCN] + TX, GY-81 (research code) (423) + TX, thiophos [CCN] + TX, iodomethane (IUPAC name) (542) + TX, isamidophos (1230) + TX , chlorfenapyr (1231) + TX, ivermectin (alias) [CCN] + TX, kinetin (alias) (210) + TX, methyl aphid (1258) + TX, metamectin (519) + TX, metamectin potassium salt (alias) (519) + TX, metamectin sodium salt (519) + TX, methyl bromide (537) + TX, methyl isothiocyanate (543) + TX, milbemycin oxime (alias) [CCN] + TX, moxidectin (alias) [CCN] + TX, Myrotheciumverrucaria) combination (alias) (565) + TX, NC-184 (compound code) + TX, oxamyl (602) + TX, phorate (636) + TX, phosphamidon (639) + TX, phosphamidon [CCN] + TX, clomiphene (alias) + TX, selamectin (alias) [CCN] + TX, spinosad (737) + TX, terbufos (alias) + TX, terbufos (773) + TX, tetrachlorothiophene (IUPAC / Chemical Abstract name) (1422) + TX, thiafenox (alias) + TX, cypermethrin (1434) + TX, triazophos (820) + TX, triazuron (alias) + TX, dimethylol [CCN] + TX, YI-5302 (compound code) and zeatin (alias) (210) + TX, fluensulfone [318290-98-1] + TX, fluopyram + TX;
[0749] A nitrification inhibitor selected from the group consisting of potassium ethylxanthate [CCN] and nitrapyrin (580) + TX;
[0750] A plant activator selected from the group consisting of acibenzolar (6) + TX, acibenzolar-S-methyl (6) + TX, probenazole (658) and Reynoutria sachalinensis extract (alias) (720) + TX;
[0751] A rodenticide selected from the group consisting of: 2-isovaleryl indane-1,3-dione (IUPAC name) (1246) + TX, 4-(quinoxalin-2-ylamino)benzenesulfonamide (IUPAC name) (748) + TX, α-chlorohydrin [CCN] + TX, aluminum phosphide (640) + TX, antoquinol (880) + TX, arsenic trioxide (882) + TX, barium carbonate (891) + TX, bifenthrin (912) + TX, brodifacoum (89) + TX, bromodiolone ( Including α-bromadiolone) + TX, bromodiol (92) + TX, calcium cyanide (444) + TX, chloralose (127) + TX, chloranone (140) + TX, cholecalciferol (alias) (850) + TX, chlordimethoate (1004) + TX, cypermethrin (1005) + TX, cypermethrin (175) + TX, cypermethrin (1009) + TX, cypermethrin (246) + TX, thiazolin (249) + TX, cypermethrin (273) + TX, calciferol (301) + TX, Fludioxaline (357) + TX, fluoroacetamide (379) + TX, fludioxaline (1183) + TX, fludioxaline hydrochloride (1183) + TX, γ-HCH (430) + TX, HCH (430) + TX, hydrogen cyanide (444) + TX, iodomethane (IUPAC name) (542) + TX, lindane (430) + TX, magnesium phosphide (IUPAC name) (640) + TX, methyl bromide (537) + TX, fosfomycin (1318) + TX, fosfomycin (1 336) + TX, phosphine (IUPAC name) (640) + TX, phosphorus [CCN] + TX, warfarin (1341) + TX, potassium arsenite [CCN] + TX, warfarin (1371) + TX, scilla glycoside (1390) + TX, sodium arsenite [CCN] + TX, sodium cyanide (444) + TX, sodium fluoroacetate (735) + TX, strychnine (745) + TX, thallium sulfate [CCN] + TX, warfarin (851) and zinc phosphide (640) + TX;
[0752] Synergists 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, MGK 264 (research code) (296) + TX, piperonyl butoxide (649) + TX, pipertal (1343) + TX, propyl isomer (1358) + TX, S421 (research code) (724) + TX, sesamex (1393) + TX, sesasmolin (1394) and sulfoxide (1406) + TX;
[0753] Animal repellents, which are composed of the following substance groups: anthraquinone (32) + TX, chloralose (127) + TX, copper cyclohexane [CCN] + TX, copper oxychloride (171) + TX, diazinon (227) + TX, dicyclopentadiene (chemical name) (1069) + TX, guazatine (422) + TX, guazatine acetate (422) + TX, methiocarb (530) + TX, pyridin-4-amine (IUPAC name) (23) + TX, salam (804) + TX, trimethacarb (840) + TX, zinc cyclohexane [CCN] and ziram (856) + TX;
[0754] A virucidal agent selected from the group consisting of: imipenem (alias) [CCN] and ribavirin (alias) [CCN] + TX;
[0755] A wound protection agent selected from the group consisting of mercuric oxide (512) + TX, octhilinone (590) and thiophanate-methyl (802) + TX;
[0756] Biologically active substances selected from 1,1-bis(4-chlorophenyl)-2-ethoxyethanol+TX, 2,4-dichlorophenylbenzenesulfonate+TX, 2-fluoro-N-methyl-N-1-naphthylacetamide+TX, 4-chlorophenylphenyl sulfone+TX, acetofenamide+TX, aldicarb+TX, sago+TX, fruit manphos+TX, amine dephosphite+TX, ammonium oxalate dephosphite+TX, amitraz+TX, cypermethrin+TX, arsenic trioxide+TX, azobenzene+TX, azophos+TX, benomyl+TX, benoxafos+TX, benzyl benzoate+TX, bixafen+TX, bromothiocarb ... Mite ester + TX, buprofezin + TX, butanone carbendazim + TX, butanone sulfone carbendazim + TX, butyl pyridaben + TX, calcium polysulfide + TX, octachlorocamphene + TX, chlormethoxam + TX, trithion + TX, cypermethrin + TX, cypermethrin + TX, cypermethrin + TX, cypermethrin hydrochloride + TX, cypermethrin + TX, cypermethrin + TX, cypermethrin + TX, cypermethrin + TX, ethyl cypermethrin + TX, cypermethrin (chloromebuform) + TX, cypermethrin + TX, propyl cypermethrin + TX, cypermethrin + TX, cypermethrin I + TX, cypermethrin II + TX, cypermethrin + TX, closantel + TX, coumaphos + TX, crotamiton + TX, baclofos + TX, thiocarb + TX, fruit insect phosphorus + TX, DCPM + TX, DDT + TX, dinoxophos + TX, dinoxophos-O + TX, dinoxophos-S + TX, demeton-methyl + TX, demeton-O + TX, demeton-O-methyl + TX, demeton-S + TX, demeton-S-methyl + TX, demeton-S-methyl + TX, demeton-S-methyl + TX, demeton-S-methyl + TX, demeton-S-methylsulfon + TX, bacteriostatic + TX, dichlorvos + TX, dicliphos + TX, dichlorvos + TX, dimethoate + TX, methylphos + TX, dinex + TX, dinex-diclexine + TX, dimethoate-4 + TX, dimethoate-6 +TX, anthelmintic+TX, nitropentyl+TX, nitrobenzene+TX, nitrobenzene acaricide+TX, nitrobutyl+TX, dimethoate+TX, sulfodiphenyl+TX, disulfiram+TX, DNOC+TX, dofenapyn+TX, doramectin+TX, indole+TX, eprinomectin+TX, phosphosulfate+TX, ethimphos+TX, anti-mite+TX, fenbutatin+TX, fenthiocarb+TX, fenpyrad+TX, fenpyraclostrobin+TX, fenamipyraclostrobin+TX, fentrifanil+TX, fluazifop+TX, flufenamide+TX, fluazifop+TX, FMC 1137+TX, flufenamic acid+TX, flufenamic acid hydrochloride+TX, formparanate+TX, γ-HCH+TX, fruit green+TX,Benzyl acarboxylate + TX, hexadecyl cyclopropane carboxylate + TX, isothiophos + TX, jasmonate I + TX, jasmonate II + TX, iodine + TX, lindane + TX, propanil + TX, cypermethrin + TX, dithiophos + TX, methylthiophene + TX, cypermethrin + TX, methyl bromide + TX, cypermethrin + TX, chlorpyrifos + TX, milbemycin + TX, propylamine + TX, monocrotophos + TX, maoguo + TX, moxidectin + TX, naled + TX, 4-chloro-2-(2-chloro-2-methyl-propyl)-5-[(6-iodo-3-pyridyl)methoxy]pyridazine-3-one + TX, fluazifop + TX, nikkomycin + TX, pentamethylenediamine + TX, pentamethylenediamine 1:1 zinc chloride complex +TX, omethoate +TX, isothiocarb +TX, sulfone +TX, pp'-DDT +TX, parathion +TX, permethrin +TX, fenthion +TX, phosalone +TX, thiocyanate +TX, phosphamidon +TX, polychloroterpenes +TX, polynactins +TX, chloranil +TX, cypermethrin +TX, propoxur +TX, ethidium +TX, pyrethrin +TX, pyrethrin I +TX, pyrethrin II +TX, pyrethrin +TX, pyrimethoxam +TX, pyrimithiophos +TX, quinalphos +TX, quintiofos +TX, R-1 492+TX, glyphosate+TX, rotenone+TX, octamidine+TX, clomiphene+TX, selamectin+TX, thion+TX, SSI-121+TX, sulfilam+TX, sulfluramid+TX, sulfotep+TX, sulfur+TX, flumethrin+TX, τ-fluvalinate+TX, TEPP+TX, tert-butylcarb+TX, tetrachlorothiazide+TX, thiafenox+TX, thiafenox+TX, thiafenox+TX, methyl thiocarb+TX, chlorpyrifos+TX, thiafenox+TX, thiafenox+TX, thiafenox+TX, thiafenox+TX, thiafenox+TX, thiafenox+TX, thiafenox+TX, thiafenox+TX, thiafenox+TX, thiafenox+TX, thiafenox+TX, thiafenox+TX, thiafenox+TX, thiafenox+TX, thiafenox+TX, thiafenox+TX, thiafenox+TX, thiafenox+TX, thiafenox+TX, thiafenox+TX, thiafenox+TX, thiafenox+TX, thiafenox+TX, thiafenox+TX, thiafenox+TX, thiafenox+TX, thiafenox+TX, thiafenox+TX TX, vaniliprole + TX, bethoxazin + TX, copper dioctanoate + TX, copper sulfate + TX, cybutryne + TX, dichloronaphthoquinone + TX, dichlorophen + TX, endoxan + TX, triphenyltin + TX, slaked lime + TX, mancozeb + TX, algae quinone + TX, quinone + TX, simazine + TX, triphenyltin acetate + TX, triphenyltin hydroxide + TX, yuxu phosphorus + TX, piperazine + TX, thiophanate + TX, chloralose + TX, fenthion + TX, pyridine-4-amine + TX, strychnine + TX, 1-hydroxy-1H-pyridine-2-thione + TX, 4-(quinoxaline-2-ylamino)benzenesulfonamide + TX,8-Hydroxyquinoline sulfate + TX, bronopol + TX, copper hydroxide + TX, cresol + TX, dipyrithione + TX, dodesine + TX, sodium sulfone + TX, formaldehyde + TX, mercury plus phenacetin + TX, kasugamycin + TX, kasugamycin hydrochloride hydrate + TX, nickel di(dimethyldithiocarbamate) + TX, trichloromethylpyridine + TX, octhilthione + TX, oxolinic acid + TX, oxytetracycline + TX, potassium hydroxyquinoline sulfate + TX, thiabendazole + TX, streptomycin + TX, streptomycin sesquisulfate + TX, chlorothiazide + TX, thimerosal + TX, cotton brown-banded moth GV + TX, Agrobacterium radiobacterium + TX, Amblyseius spp. + TX, celery armyworm NPV + TX, Anagrus atomus + TX, Aphelinus abdominalis + TX, cotton aphid parasitic wasp (Aphidius colemani+TX、Aphidoletes aphidimyza+TX、Spodoptera lucernea NPV+TX、Bacillus sphaericus Neide+TX、Beauveria brongniartii+TX、Chrysoperla carnea+TX、Cryptolaemusmontrouzieri+TX、Codling moth GV+TX、Dacnusa sibirica+TX、Diglyphus isaea+TX、Encarsia formosa+TX、Eretmocerus eremicus+TX、Heterorhabditis bacteriophora) and H.megidis+TX, Hippodamia convergens+TX, Leptomastix dactylopii+TX, Macrolophus caliginosus+TX, Cabbage armyworm NPV+TX, Metaphycus helvolus+TX, Metarhizium anisopliaevar.acridum+TX, Metarhizium anisopliae var.anisopliae+TX, Neodiprion sertifer NPV and N.lecontei NPV+TX,+TX, Paecilomyces fumosoroseus +TX, Phytoseiulus persimilis +TX, Steinernema bibionis +TX, Steinernema carpocapsae +TX, Steinernema glaseri +TX, Steinernema riobrave +TX, Steinernema riobravis +TX, Steinernema scapterisci +TX, Steinernema spp. +TX, Trichogramma species +TX, Typhlodromus occidentalis + TX, Verticillium lecanii + TX, apholanate + TX, bis(aziridine) methylaminophosphine sulfide + TX, busulfan + TX, dimatif + TX, hemel + TX, hemp + TX, metepa + TX, methiotepa + TX, methyl apholanate + TX, methyl thiotepa ... apholate) + TX, morzid + TX, penfluron + TX, tepa + TX, thiohempa + TX, thiohempa + TX, trothamide + TX, urethaneimide + TX, (E)-dec-5-en-1-yl acetate and (E)-dec-5-en-1-ol + TX, (E)-tridec-4-en-1-yl acetate + TX, (E)-6-methylhept-2-en-4-ol + TX, (E,Z)-tetradec-4,10-dien-1-yl acetate + TX, (Z)-dodec-7-en-1-yl acetate + TX, (Z)-hexadecene carbon-11-enal + TX, (Z)-hexadec-11-en-1-yl acetate + TX, (Z)-hexadec-13-en-11-yn-1-yl acetate + TX, (Z)-eicos-13-en-10-one + TX, (Z)-tetradec-7-en-1-al + TX, (Z)-tetradec-9-en-1-ol + TX, (Z)-tetradec-9-en-1-yl acetate + TX, (7E,9Z)-dodec-7,9-dien-1-yl acetate + TX, (9Z,11E)-tetradec-9,11-dien-1-yl acetate + TX, (9Z,12E)-tetradec-9,12-dien-1-yl acetate + TX,14-Methyloctadec-1-ene+TX, 4-methylnon-5-ol and 4-methylnon-5-one+TX, α-polystyrene+TX, western pine beetle aggregation pheromone+TX, codlelure+TX, codlemone+TX, cuelure+TX, epoxide nonadecane+TX, dodec-8-en-1-yl acetate+TX, dodec-9-en-1-yl acetate+TX, dodec-8+TX, 10-10-dien-1-yl acetate+TX, dominicalure+TX, 4-methyloctanoic acid ethyl ester+TX, eugenol+TX, southern pine beetle aggregation pheromone (f rontalin)+TX, grandlure+TX, grandlure I+TX, grandlure II+TX, grandlure III+TX, grandlure IV+TX, hexalure+TX, ipsdienol+TX, ipsenol+TX, japonilure+TX, lineatin+TX, litlure+TX, looplure+TX, medlure+TX, megatomoic acid+TX, methyl eugenol+TX, muscalure+TX, 18-decane-2,13-diene-1-yl acetate+TX, 18-decane-3,13-diene-1-yl acetate+TX, orfralure+TX, oryctalure+TX, ostramone+TX, siglure+TX, sordidin+TX, sulcatol+TX, 14-decane-11-ene-1-yl acetate+TX, trimedlure+TX, Mediterranean fruit fly attractant A+TX, Mediterranean fruit fly attractant B, 1 +TX, Mediterranean fruit fly attractant B 2+TX, Mediterranean fruit fly attractant C+TX, trunc-call+TX, 2-(octylthio)ethanol+TX, butopyronoxyl+TX, butoxy(polypropylene glycol)+TX, dibutyl adipate+TX, dibutyl phthalate+TX, dibutyl succinate+TX, DEET+TX, dimethyl carbate)+TX, dimethyl phthalate+TX, ethyl hexanediol+TX, hexamide+TX, methoquin-butyl+TX, methylneodecanamide+TX, oxamate+TX, picaridin+TX, 1-dichloro-1-nitroethane+TX, 1,1-dichloro-2,2-di(4-ethylphenyl)ethane+TX, 1,2-dichloropropane and 1,3-dichloropropylene+TX, 1-bromo-2-chloroethane+ TX, 2,2,2-trichloro-1-(3,4-dichlorophenyl)ethyl acetate + TX, 2,2-dichlorovinyl 2-ethylsulfinylethyl methyl phosphate + TX, 2-(1,3-dithiolan-2-yl)phenyl dimethylcarbamate + TX, 2-(2-butoxyethoxy)ethyl thiocyanate + TX, 2-(4,5-dimethyl-1,3-dioxolan-2-yl)phenyl methylcarbamate + TX, 2-(4-chloro-3,5-xylyloxy)ethanol + TX, 2-chlorovinyl diethyl phosphate + TX, 2-imidazolidinone + TX, 2-isovaleryl indan-1,3-di 1-Hydroxy-1-nitropropene, 1-nitropropene, 1-nitropropene, 1-nitropropene, 1-nitropropene, 1-nitropropene, 1-nitropropene, 1-nitropropene, 1-nitropropene, 1-nitropropene, 1-nitropropene, 1-nitropropene, 1-nitropropene, 1-nitropropene, 1-nitropropene, 1-nitropropene, 1-nitropropene, 1-nitropropene, 1-nitropropene, 1-nitropropene, 1-nitropropene, 1-nitropropene, 1-nitropropene, 1-nitropropene, 1-nitropropene, 1-nitropropene, 1-nitropropene, 1-nitropropene, +TX, neonicotinoids +TX, ethyl thiophanate (athidathion) +TX, methyl pyrifos +TX, Bacillus thuringiensis δ-endotoxin +TX, barium hexafluorosilicate +TX, barium polysulfide +TX, fumonisin +TX, Bayer 22 / 190 +TX, Bayer 22408 +TX, β-cyfluthrin +TX, β-cypermethrin +TX, bioethanomethrin +TX, biopermethrin +TX, bis (2-chloroethyl) ether +TX, borax +TX, bromophenazone +TX, bromo-DDT +TX, hexachlorvinphos +TX, cypermethrin +TX,Butathiofos + TX, butyl phosphine + TX, calcium arsenate + TX, calcium cyanide + TX, carbon disulfide + TX, carbon tetrachloride + TX, badan hydrochloride + TX, cevadine + TX, bornyl + TX, chlordane + TX, chlordecone + TX, chloroform + TX, chloropicrin + TX, chlornitrile oxime + TX, chlorprazophos + TX, cis-resmethrin + TX, cismethrin + TX, clocythrin (alias) + TX, copper acetoarsenite + TX, copper arsenate + TX, copper oleate + TX, coumithoate + TX, cryolite + TX, CS 708+TX, benzonitrile+TX, cypermethrin+TX, cypermethrin+TX, cypermethrin+TX, d-carbofuran+TX, DAEP+TX, dazomethane+TX, decarbofuran+TX, diamidafos+TX, isochlorophos+TX, diamidafos+TX, dicresyl+TX, cypermethrin+TX, dieldrin+TX, diethyl 5-methylpyrazol-3-yl phosphate+TX, dior+TX, tetrafluoromethoxythrin+TX, dimethoate+TX, pyrethrin+TX, methylchlorfenapyr+TX, dichlorvos+TX, propanol+TX, pentotropol+TX, dinoseb+TX, fenpyroxene+TX, vegetable phosphorus+TX, thiopyrafos+TX, DSP+TX, ecdysterone+TX, EI 1642+TX, EMPC+TX, EPBP+TX, etaphos+TX, ethiobencarb+TX, ethyl formate+TX, ethylene dibromide+TX, ethylene dichloride+TX, ethylene oxide+TX, EXD+TX, ethiobencarb+TX, ethiobencarb+TX, fenitrothion+TX, fenoxacrim+TX, cypermethrin+TX, fenthion+TX, ethylfenthion+TX, flucofuron+TX, butylfenthion+TX, phosphonium phosphate+TX, butylcyclothion+TX, furathiocarb+TX, pyrethroid+TX, biguanide salt+TX, biguanide acetate+TX, tetramethoate Sodium thiocarbonate + TX, halfenprox + TX, HCH + TX, HEOD + TX, heptachlor + TX, cypermethrin + TX, HHDN + TX, hydrogen cyanide + TX, quinoline + TX, IPSP + TX, chlorfenapyr + TX, carbochlorin + TX, isodrin + TX, isoflavone + TX, transplanting spirit + TX, rice blast spirit + TX, oxathiophos + TX, juvenile hormone I + TX, juvenile hormone II + TX, juvenile hormone III + TX, chlorpentyl + TX, methoprene + TX, lead arsenate + TX, bromophenylphos + TX, acetamiprid + TX, thiathion + TX, m-isopropyl methyl carbamate + TX,Magnesium phosphide + TX, phosphorus azide + TX, methyl aphidite + TX, aphidite + TX, mercurous chloride + TX, methyl sulfoxide + TX, metamethylenetetramine + TX, metamethylenetetramine potassium salt + TX, metamethylenetetramine sodium salt + TX, methylsulfonyl fluoride + TX, butylene phosphonate + TX, methoprolol + TX, methyl ether thiocyanate + TX, methoxychlor + TX, methyl isothiocyanate + TX, methyl chloroform + TX, dichloromethane + TX, oxadiazine + TX, anticide + TX, naphthion + TX, naphthalene + TX, NC-170 + TX, nicotine + TX, nicotine sulfate + TX, nithiazine + TX, pronicotine + TX, O-5-dichloro-4-iodophenyl O-ethylethyl phosphonothioate + TX, O,O-diethyl O-4-methyl-2-oxo-2H-benzopyran-7-yl phosphonothioate + TX, O,O-diethyl O-6-methyl-2-propylpyrimidin-4-yl phosphonothioate + TX, O,O,O',O'-tetrapropyl dithiodipyrophosphate + TX, oleic acid + TX, p-dichlorobenzene + TX, methyl parathion + TX, pentachlorophenol + TX, pentachlorophenyl laurate + TX, PH 60-38+TX, fenthion+TX, parathion+TX, phosphine+TX, methyl phoxim+TX, methamidophos+TX, polychlorinated dicyclopentadiene isomers+TX, potassium arsenite+TX, potassium thiocyanate+TX, precocious element I+TX, precocious element II+TX, precocious element III+TX, amimidophos+TX, profluthrin+TX, fenthion+TX, pyraclostrobin+TX, anti-pyrethroids+TX, quassia extract (quassia) + TX, quinalphos-methyl + TX, oxathion + TX, iodophos + TX, resmethrin + TX, rotenone + TX, thiamethoxam + TX, ryanodine + TX, sabadilla + TX, octamethrin + TX, clostridium + TX, SI-0009 + TX, thiamethoxam + TX, sodium arsenite + TX, sodium cyanide + TX, sodium fluoride + TX, sodium hexafluorosilicate + TX , sodium pentachlorophenol + TX, sodium selenate + TX, sodium thiocyanate + TX, sulcofuron + TX, sulcofuron-sodium + TX, sulfuryl fluoride + TX, thiopromide + TX, tar + TX, thiamethoxam + TX, TDE + TX, butylpyrimidinphos + TX, dimethophos + TX, cyclopentyl thiocarb + TX, tetrachloroethane + TX, thiochlorvos + TX, thiophanate-sodium + TX, Cyclohexanil + TX, cypermethrin + TX, cypermethrin + TX, cypermethrin sodium + TX, tetrabromothrin + TX, permethrin + TX, trichlormetaphos-3 + TX, cypermethrin + TX, chlorpyrifos + TX, tolprocarb + TX, chlorpyrifos + TX, chlorpyrifos + TX, chlorpyrifos + TX, chlorpyrifos + TX, chlorpyrifos + TX, veratridine + TX, XMC + TX,Zetamethrin+TX, zinc phosphide+TX, tolfenphos+TX, chlorfluanidine+TX, tetrafluanidine+TX, bis(tributyltin)oxide+TX, bromoacetamide+TX, iron phosphate+TX, niclosamide-ethanolamine+TX, tributyltin oxide+TX, pyrifos+TX, snail killer+TX, 1,2-dibromo-3-chloropropane+TX, 1,3-dichloropropylene+TX, 3,4-dichlorotetrahydrothiophene 1,1-dioxide+TX, 3-(4-chlorophenyl)-5-methylrhodanine+TX, 5-methyl-6-thioxo-1,3,5-thiadiazine- 3-acetic acid + TX, 6-isopentenylaminopurine + TX, 2-fluoro-N-(3-methoxyphenyl)-9H-purine-6-amine + TX, benclothiaz + TX, cytokinin + TX, DCIP + TX, furfural + TX, isamidophos + TX, kinetin + TX, verrucosporium mycorrhizal composition + TX, tetrachlorothiophene + TX, xylenol + TX, zeatin + TX, potassium ethylxanthate + TX, acibenzolar + TX, acibenzolar-S-methyl + TX, Reynoutria sachalinensis) extract + TX, α-chlorohydrin + TX, Antu + TX, barium carbonate + TX, bismuth urea + TX, brodifacoum + TX, brodifacoum (including α-brodifacoum) + TX, brodifacoum + TX, chlordifacoum + TX, cholecalciferol + TX, chlorfenapyr + TX, clofodine + TX, clofodine + TX, clofodine + TX, clofodine + TX, clofodine + TX, clofodine + TX, clofodine + TX, calciferol + TX, fludioxaline + TX, fluoroacetamide + T X, flumethrin + TX, flumethrin hydrochloride + TX, warfarin + TX, fosfos + TX, phosphorus + TX, warfarin + TX, warfarin + TX, scillarin + TX, sodium fluoroacetate + TX, thallium sulfate + TX, warfarin + TX, 2-(2-butoxyethoxy)ethyl piperate + TX, 5-(1,3-benzodioxol-5-yl)-3-hexylcyclohex-2-enone + TX, farnesol with nerolidol + TX, synergistic acetylene ether + TX, MGK 264+TX, piperidine+TX, piperidine aldehyde+TX, piperidine ester (propyl isomer)+TX, S421+TX, piperidine powder+TX, sesasmolin+TX, sulfoxide+TX, anthraquinone+TX, copper cyclohexaneate+TX, copper oxychloride+TX, dicyclopentadiene+TX, salen+TX, zinc cyclohexaneate+TX, zinc thiram+TX, imanin+TX, ribavirin+TX, mercuric oxide+TX, thiophanate-methyl+TX, azaconazole+TX, bifenthrin+TX, oxadiazole+TX, cyproconazole+TX, difenoconazole+TX, diniconazole+TX, epoxiconazole+TX, fenbuconazole+TX, fluquinconazole+TX, flusilazole+TX, flutriafol+TX, furopyram+TX,Hexaconazole + TX, imazalil + TX, imipenem + TX, cyproconazole + TX, metconazole + TX, myclobutrazol + TX, paclobutrazol + TX, pyrifenox + TX, prochloraz + TX, propiconazole + TX, pyraclostrobin + TX, simeconazole + TX, tebuconazole + TX, fluconazole + TX, triadimefon + TX, triadimenol + TX, triflumizole + TX, trichlorfon + TX, pyrimidine + TX, chlorfenapyr + TX, flufenapyr + TX, bupirimate + TX, dimethirimol + TX, bupirimate ( ethirimol + TX, dodecacyclic morpholine + TX, fenpropidin + TX, fenpropimorph + TX, spiroxafil + TX, tridecafil + TX, cyprodinil + TX, pyraclostrobin + TX, pyrimethanil + TX; fenpiclonil + TX, fludioxonil + TX, benalaxyl + TX, furalaxyl + TX, metalaxyl + TX, R-metalaxyl + TX; furamide + TX; oxadixyl + TX, carbendazim + TX, debacarb + TX, thiabendazole + TX, chlozolina te)+TX, dichlozoline+TX, myclozoline+TX, procymidone+TX, vinclozoline+TX, boscalid+TX, carboxin+TX, furamide+TX, flutolanil+TX, oxacarb+TX, penthiopyrad+TX, thiofuran+TX, docodine+TX, biguanide+TX, azoxystrobin+TX, etherbacteramide+TX, enestroburin+TX, enestroburin+TX X, fluopicolide + TX, fluoxastrobin + TX, kresoxim-methyl + TX, fenoxystrobin + TX, oxathiocarb + TX, oxathiocarb + TX, picoxystrobin + TX, pyraclostrobin + TX, pyraclostrobin + TX, ferbam + TX, mancozeb + TX, maneb + TX, maneb + TX, mesabine + TX, methyl propineb + TX, maneb + TX, captamipan + TX, captan + TX, pyraclostrobin + TX, thiabendazole + TX, Bordeaux mixture + TX, copper oxide + TX, mancozeb + TX, quinoline copper + TX, phthalocyanine + TX, kefansan + TX, isothiocyanate + TX, chlorpyrifos + TX, methyl tolclofos + TX, captamipan + TX, benzothiocyanate + TX,Blasticidin + TX, chloroneb + TX, thiophanate-methyl + TX, cyfluanid + TX, cymoxanil + TX, cybutaflutamide + TX, diclocymet + TX, diclomezine + TX, dicloran + TX, diethofencarb + TX, oxadiazine + TX, flumorph + TX, dithianon + TX, ethaboxam + TX, etridiazole + TX, famoxadone + TX, fenamidone + TX , fenoxanil + TX, ferimzone + TX, fluazinam + TX, fluopicolide + TX, flusulfamide + TX, flupyraclostrobin + TX, fenacet + TX, fosetyl-aluminium + TX, hymexazol + TX, propineb + TX, cyazofamid + TX, methasulfocarb + TX, mefenamic acid + TX, pencycuron + TX, phthalide + TX, polyoxin ( polyoxins)+TX, propamocarb+TX, pyraclostrobin+TX, proquinazid+TX, pyroquilon+TX, pyriofenone+TX, quinoxyfen+TX, pentachloronitrobenzene+TX, thiazolamide+TX, triazoxide+TX, tricyclazole+TX, triazine+TX, validamycin+TX, valeramide+TX, zoxamide+TX, mandipropamid+TX, flubeneteram+TX, isoflurane+TX, opyrazam)+TX, sedaxane+TX, benzovinflumizone+TX, fluopyrazol hydroxylamide+TX, 3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid (3',4',5'-trifluoro-biphenyl-2-yl)-amide+TX, isoflurane+TX, isoflucypram+TX, isothiopyram+TX, dimethylnitramine+TX, 6-ethyl-5,7-dioxo-pyrrolo[4,5][1,4]dithiino[1,2-c]isothiazole-3-carbonitrile+TX, 2-(difluoromethyl)-N-[3-ethyl-1,1-dimethyl-indan-4-yl]pyridine-3-carboxamide+TX,4-(2,...
Claims
1. A compound having formula (I) in R 1 is CN or C(=S)NH2; R 2 It is H; R 3 is H, C1-C6-alkyl or C1-C6-haloalkyl; R 4 is C1-C6-haloalkyl, C2-C6-haloalkenyl, C3-C6-cycloalkyl, C3-C6-halocycloalkyl, phenyl, 1 to 3 independently selected substituents R 5 substituted phenyl, heteroaryl, 1 to 3 independently selected substituents R 6 substituted heteroaryl, phenyl-C1-C3-alkyl, or 1 to 3 independently selected substituents R 7 Substituted phenyl-C1-C 3- Alkyl, wherein the heteroaryl is a 5- or 6-membered monocyclic or a 9-membered bicyclic, each having 1 to 3 carbon atoms independently replaced by nitrogen, sulfur, or oxygen; Z is oxygen or sulfur; Q is a cyclic amine represented by formula IIa or a cyclic amine represented by formula IIb, Wherein the arrow indicates the connection to the carbonyl group; p 1 is 0 or 1 and indicates the number of methylene groups; p 2 is 0 or 1 and indicates the number of methylene groups; q 1 is 1 and indicates the number of methylene groups; q 2 is 1 and indicates the number of methylene groups; X is hydrogen, hydroxy or alkoxy; Y is cyano, C1-C6-alkoxy-C1-C6-alkyl, C1-C6-alkylsulfanyl-C1-C6-alkyl, C1-C6-alkylsulfinyl-C1-C6-alkyl, C1-C6-alkylsulfonyl-C1-C6-alkyl, R a R b NC(O),R c C(O)NR d , R e SO2NR f , R g ON=CR h , a 4- to 6-membered non-aromatic heterocyclic ring system in which one or two carbons are independently replaced by nitrogen, oxygen, sulfur or sulfonyl, a phenyl group, substituted by 1 to 3 independently selected substituents R 8 Substituted phenyl, 5 or 6 membered monocyclic heteroaryl, each of which has 1 to 3 carbon atoms independently replaced by nitrogen, sulfur, or oxygen, or by 1 to 3 independently selected substituents R 9 substituted 5- or 6-membered monocyclic heteroaryl groups, each of which has 1 to 3 carbon atoms independently replaced by nitrogen, sulfur, or oxygen; A is cyano, C1-C6-cyanoalkyl, R i SO2、R j R k NSO2, phenyl, 1 to 3 independently selected substituents R 10 substituted phenyl, or 1 to 3 independently selected substituents R 11 Substituted heteroaryl, wherein the heteroaryl is a 5- or 6-membered monocyclic or a 9- or 10-membered bicyclic, each having 1 to 3 carbon atoms independently replaced by nitrogen, sulfur, or oxygen; R a , R b , R c , R d , R f , R g , R h , R j and R k independently selected from hydrogen and C1-C6-alkyl; R e and R i are independently C1-C6-alkyl; R 5 is independently selected from halogen, cyano, C1-C6-alkyl, C1-C6-haloalkyl, C1-C6-alkoxy, C1-C6-haloalkoxy, C1-C6-alkylsulfonyl, and C1-C6-haloalkylsulfanyl; and if two C1-C3-haloalkoxy groups are substituted on adjacent atoms, they may form a 5- or 6-membered ring together with the carbons of the phenyl ring; and R 6 , R 7 , R 8 , R 9 , R 10 , R 11 independently selected from halogen, C1-C6-alkyl and C1-C6-haloalkyl; or an agrochemically acceptable salt, stereoisomer or tautomer of the compound of formula (I).
2. The compound according to claim 1, wherein R 1 It is CN.
3. The compound according to claim 1 or claim 2, wherein R 2 It's H.
4. The compound according to claim 1 or claim 2, wherein R 3 is hydrogen, C1-C6-alkyl or C1-C6-haloalkyl.
5. The compound according to claim 1, wherein R 4 is C1-C6-haloalkyl, C2-C6-haloalkenyl, C3-C6-cycloalkyl, C3-C6-halocycloalkyl, phenyl, substituted by 1 to 3 groups R 5 Substituted phenyl, 5- or 6-membered monocyclic heteroaryl, substituted by 1 to 3 groups R 6 substituted 5- or 6-membered monocyclic heteroaryl, phenyl-C1-C3-alkyl, or substituted by 1 to 3 groups R 7 Substituted phenyl-C1-C 3- Alkyl, where R 5 , R 6 and R 7 As defined in claim 1.
6. The compound according to claim 1, wherein Z is oxygen.
7. The compound according to claim 1, wherein Q is a cyclic amine represented by the formula IIa, wherein p 1 and p 2 are all 1; X is hydrogen; and Y is cyano, C1-C6-alkoxy-C1-C6-alkyl, C1-C6-alkylsulfanyl-C1-C6-alkyl, C1-C6-alkylsulfinyl-C1-C6-alkyl, C1-C6-alkylsulfonyl-C1-C6-alkyl, R a R b NC(O),R c C(O)NR d , R e SO2NR f , R g ON=CR h , a 4- to 6-membered non-aromatic heterocyclic ring system in which one or two carbons are independently replaced by nitrogen, oxygen, sulfur or sulfonyl, a phenyl group, a substituted group R 8 substituted phenyl, 5- or 6-membered monocyclic heteroaryl, or substituted by 1 to 3 groups R 9 substituted 5- or 6-membered monocyclic heteroaryl, wherein R a , R b , R c , R d , R e , R f , R g , R h , R 8 and R 9 As defined in claim 1.
8. The compound according to claim 1, wherein Q is a cyclic amine represented by the formula IIb, wherein q 1 and q 2 are all 1; and A is cyano, C1-C6-cyanoalkyl, C1-C6-haloalkyl, R i SO2、R j R k NSO2, phenyl, substituted by 1 to 3 groups R 10 substituted phenyl, 5- or 6-membered monocyclic heteroaryl, or substituted by 1 to 3 groups R 11 substituted 5- or 6-membered monocyclic heteroaryl, wherein R i , R j , R k , R 10 and R 11 As defined in claim 1.
9. A composition comprising a compound as defined in any one of claims 1 to 8, one or more adjuvants and diluents, and optionally one or more other active ingredients.
10. A method for combating and controlling insects, mites, nematodes or molluscs, which comprises applying an insecticidal, acaricidal, nematicidal or molluscicidal effective amount of a compound as defined in any one of claims 1 to 8 or a composition as defined in claim 9 to the pest, the location of the pest, or a plant susceptible to attack by the pest.
11. A compound of III-a or III-b Where R 1 , R 3 and R 5 is defined in claim 1; A compound of Va Among them, Z, R 1 , R 3 and R 5 as defined in claim 1; or A compound of VI-a or VI-b Where R 1 , R 3 , and R 5 is defined in claim 1, and Rx is selected from methyl, ethyl, propyl, isopropyl, butyl, isobutyl and tert-butyl.
Citation Information
Patent Citations
DNA sequences encoding polypeptides having beta-1,3-glucanase activity
EP0353191A2
Novel bacillus thuringiensis isolate denoted b.t. ps81gg, active against lepidopteran pests, and a gene encoding a lepidopteran-active toxin
EP0367474A1
Insecticidal toxines, genes coding therefor, antibodies binding them, transgenic plant cells and plants expressing these toxines
EP0374753A2
Disease-resistant transgenic plants
EP0392225A2
Novel bacillus thuringiensis isolates active against lepidopteran pests, and genes encoding novel lepidopteran-active toxins
EP0401979A2