Pesticidally active bicyclic compounds
By using a pesticidal active compound with a 7-membered bicyclic structure, the problem of difficulty in controlling damage to plants by insects and arthropods in the prior art is solved, thereby achieving effective protection of plants and improved control of pests.
Patent Information
- Application Number
- CN202480012393.X
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Priority Date
- 2023-02-13
- Filing Date
- 2024-02-06
- Publication Date
- 2025-09-23
AI Technical Summary
It is difficult to effectively control the damage to plants caused by pests such as arthropods and insects with existing technologies, especially to fight and protect plant propagation materials.
Pesticide-active compounds having a 7-membered bicyclic structure, including compounds of Formula I and Formula II, are used to reduce damage and protect plant propagation materials by applying an effective amount of the compound to the pest, its locus, or susceptible plants.
Provides improved control of animal pests, reduces damage to plants, protects plant propagation material, and achieves effective pest control.
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Figure CN120693061A_ABST
Abstract
Description
[0001] The present invention relates to a method for controlling animal pests, including arthropods and in particular insects or representatives of the orders Hemiptera, Lepidoptera or Acarina, by using certain compounds having a 7-membered bicyclic ring with pesticidal activity, in particular insecticidal activity. Furthermore, the present invention relates to certain compounds having a 7-membered bicyclic ring with pesticidal activity, in particular insecticidal activity, processes for their preparation, compositions containing these compounds, and their use for controlling animal pests, including arthropods and in particular insects or representatives of the orders Lepidoptera, Hemiptera or Acarina.
[0002] WO 2022 / 192224 describes certain bicyclic compounds for controlling invertebrate pests.
[0003] It has now been found that certain pesticidally active compounds having a seven-membered bicyclic ring can be used for controlling animal pests, including arthropods and in particular insects or representatives of the orders Hemiptera or Lepidoptera or Acarina.
[0004] Therefore, the present invention relates in a first aspect to a method for combating and / or controlling animal pests to achieve the following:
[0005] (i) reducing damage to plants, which method comprises applying an effective amount of a compound of formula I or formula II to the pest, to the locus of the pest, or to a plant susceptible to attack by the pest; or
[0006] (ii) protecting plant propagation material, which method comprises treating the propagation material or the site where the propagation material is planted with an effective amount of a compound of formula I or formula II;
[0007] Among them, the compound of formula I and formula II is
[0008]
[0009] in
[0010] X, independently of Formula I or II, is O, S, SO, SO2, SO(NH), or CH2;
[0011] R 1 、R 2 、R 3 and R 4, independent of formula I or II, are each independently selected from hydrogen, halogen, cyano, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy, C1-C4-haloalkoxy, C1-C4-alkylthio, C1-C4-haloalkylthio, C1-C4-alkylsulfinyl, C1-C4-haloalkylsulfinyl, C1-C4-alkylsulfonyl, and C1-C4-haloalkylsulfonyl;
[0012] R 5 、R 6 and R 7 , independent of formula I or II, are each independently selected from hydrogen, halogen, cyano, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy, C1-C4-haloalkoxy, C1-C4-alkylthio, C1-C4-haloalkylthio, C1-C4-alkylsulfinyl, C1-C4-haloalkylsulfinyl, C1-C4-alkylsulfonyl, and C1-C4-haloalkylsulfonyl;
[0013] Y is hydrogen, C1-C6-alkyl, C3-C6-alkenyl, C3-C6-alkynyl, C3-C6-cycloalkyl-C1-C2-alkyl, aryl-C1-C2-alkyl, or C1-C4-alkoxy-C1-C2-alkyl;
[0014] J is hydrogen, C1-C6-alkyl, C3-C6-alkenyl, C3-C6-alkynyl, or substituted by C3-C6-cycloalkyl, aryl, C5-C 10 -heteroaryl, or C4-C 10 -heterocyclyl-substituted C1-C2-alkyl, the C1-C6-alkyl, C3-C6-alkenyl, C3-C6-alkynyl may be independently substituted by 1 to 3 groups independently selected from R a The C3-C6-cycloalkyl group may be substituted by 1 to 3 substituents independently selected from R c Substituents are substituted, and the aryl, C5-C 10 -heteroaryl, and C4-C 10 - The heterocyclic group may be independently selected from 1 to 4 b or
[0015] J is aryl, C5-C 10 -heteroaryl, or C4-C 10 -heterocyclic group, the aryl, C5-C 10 -heteroaryl, and C4-C 10 - The heterocyclic group may be independently selected from 1 to 4 b or
[0016] J is C1-C6-alkyl-C(O), C3-C6-cycloalkyl-C(O), aryl-C(O), C5-C 10 -heteroaryl-C(O), or C4-C 10 -heterocyclyl-C(O), the alkyl group may be 1 to 3 independently selected from R a The cycloalkyl group may be substituted by 1 to 3 substituents independently selected from R c Substituents are substituted, and the aryl, C5-C 10 -heteroaryl, and C4-C 10 - The heterocyclic group may be independently selected from 1 to 4 d or
[0017] J is C1-C6-alkyl-S(O)2, C3-C6-cycloalkyl-S(O)2, aryl-S(O)2, C5-C 10 -heteroaryl-S(O)2, or C4-C 10 -heterocyclyl-S(O)2, the alkyl group may be 1 to 3 independently selected from R a The cycloalkyl group may be substituted by 1 to 3 substituents independently selected from R c Substituents are substituted, and the aryl, C5-C 10 -heteroaryl, and C4-C 10 - The heterocyclic group may be independently selected from 1 to 4 e or
[0018] J is C1-C6-alkoxy, C3-C6-cycloalkyl-C1-C2-alkoxy, aryl-C1-C2-alkoxy, C5-C 10 -heteroaryl-C1-C2-alkoxy, or C4-C 10 -heterocyclyl-C1-C2-alkoxy, the alkoxy group may be 1 to 3 independently selected from R a The cycloalkyl group may be substituted by 1 to 3 substituents independently selected from R c Substituents are substituted, and the aryl, C5-C 10 -heteroaryl, and C4-C 10 - The heterocyclic group may be independently selected from 1 to 4 f Substituents substituted;
[0019] T is hydrogen, C1-C6-alkyl, C3-C6-alkenyl, C3-C6-alkynyl, C3-C6-cycloalkyl-C1-C2-alkyl, aryl-C1-C2-alkyl, or C5-C 10 -heteroaryl-C1-C2-alkyl, the alkyl, C3-C6-alkenyl, C3-C6-alkynyl may be replaced independently of one another by 1 to 3 groups independently selected from Ra The cycloalkyl group may be substituted by 1 to 3 substituents independently selected from R c Substituents are substituted, and the aryl, and C5-C 10 -heteroaryl may be substituted independently of each other by 1 to 4 independently selected g Substituents substituted;
[0020] R a , independently of formula I or II, and independently of the substituent to which it is attached, is selected from halogen, cyano, and C1-C3-alkoxy;
[0021] R b 、R d 、R e 、R f , and R g , independently of formula I or II and independently of the substituent to which it is attached, is selected from halogen, cyano, C1-C3-alkyl, C1-C3-alkoxy, NH2C(O), (C1-C3-alkyl)N(H)C(O), NH2C(O)-C1-C3-alkoxy, (C1-C3-alkyl)SO2, benzyl, phenyl, phenoxy, C5-C6-heteroaryl and C4-C 10 - heterocyclyl (the phenyl, phenoxy, heteroaryl and heterocyclyl may be substituted independently of each other by 1 to 4 substituents independently selected from halogen, cyano, and C1-C3-alkyl);
[0022] R c , independently of formula I or II, is selected from halogen, cyano, C1-C3-alkyl, and C1-C3-alkoxy;
[0023] or an agronomically acceptable salt, stereoisomer, tautomer and / or N-oxide of a compound of Formula I or Formula II.
[0024] It has now been further discovered that certain novel compounds having a 7-membered bicyclic ring provide improved control of these animal pests. Thus, a second aspect of the present invention relates to a compound of formula II or formula II-I,
[0025]
[0026] in
[0027] In Formula I, X is O, S, SO, SO2, or SO(NH);
[0028] In Formula II, X is O, S, SO, SO2, SO(NH) or CH2;
[0029] R 1 、R 2 、R3 and R 4 , independent of formula I or II, are each independently selected from hydrogen, halogen, cyano, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy, C1-C4-haloalkoxy, C1-C4-alkylthio, C1-C4-haloalkylthio, C1-C4-alkylsulfinyl, C1-C4-haloalkylsulfinyl, C1-C4-alkylsulfonyl, and C1-C4-haloalkylsulfonyl;
[0030] R 5 、R 6 and R 7 , independent of formula I or II, are each independently selected from hydrogen, halogen, cyano, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy, C1-C4-haloalkoxy, C1-C4-alkylthio, C1-C4-haloalkylthio, C1-C4-alkylsulfinyl, C1-C4-haloalkylsulfinyl, C1-C4-alkylsulfonyl, and C1-C4-haloalkylsulfonyl;
[0031] Y is hydrogen, C1-C6-alkyl, C3-C6-alkenyl, C3-C6-alkynyl, C3-C6-cycloalkyl-C1-C2-alkyl, aryl-C1-C2-alkyl, or C1-C4-alkoxy-C1-C2-alkyl;
[0032] J is C1-C6-alkyl, C3-C6-alkenyl, C3-C6-alkynyl, or is replaced by C3-C6-cycloalkyl, aryl, C5-C 10 -heteroaryl, or C4-C 10 -heterocyclyl-substituted C1-C2-alkyl, the C1-C6-alkyl, C3-C6-alkenyl, C3-C6-alkynyl may be independently substituted by 1 to 3 groups independently selected from R a The C3-C6-cycloalkyl group may be substituted by 1 to 3 substituents independently selected from R c Substituents are substituted, and the aryl, C5-C 10 -heteroaryl, and C4-C 10 - The heterocyclic group may be independently selected from 1 to 4 b or
[0033] J is aryl, C5-C 10 -heteroaryl, or C4-C 10 -heterocyclic group, the aryl, C5-C 10 -heteroaryl, and C4-C 10 - The heterocyclic group may be independently selected from 1 to 4 b or
[0034] J is C1-C6-alkyl-C(O), C3-C6-cycloalkyl-C(O), aryl-C(O), C5-C 10 -heteroaryl-C(O), or C4-C 10 -heterocyclyl-C(O), the alkyl group may be 1 to 3 independently selected from R a The cycloalkyl group may be substituted by 1 to 3 substituents independently selected from R c Substituents are substituted, and the aryl, C5-C 10 -heteroaryl, and C4-C 10 - The heterocyclic group may be independently selected from 1 to 4 d or
[0035] J is C1-C6-alkyl-S(O)2, C3-C6-cycloalkyl-S(O)2, aryl-S(O)2, C5-C 10 -heteroaryl-S(O)2, or C4-C 10 -heterocyclyl-S(O)2, the alkyl group may be 1 to 3 independently selected from R a The cycloalkyl group may be substituted by 1 to 3 substituents independently selected from R c Substituents are substituted, and the aryl, C5-C 10 -heteroaryl, and C4-C 10 - The heterocyclic group may be independently selected from 1 to 4 e or
[0036] J is C1-C6-alkoxy, C3-C6-cycloalkyl-C1-C2-alkoxy, aryl-C1-C2-alkoxy, C5-C 10 -heteroaryl-C1-C2-alkoxy, or C4-C 10 -heterocyclyl-C1-C2-alkoxy, the alkoxy group may be 1 to 3 independently selected from R a The cycloalkyl group may be substituted by 1 to 3 substituents independently selected from R c Substituents are substituted, and the aryl, C5-C 10 -heteroaryl, and C4-C 10 - The heterocyclic group may be independently selected from 1 to 4 f Substituents substituted;
[0037] T is hydrogen, C1-C6-alkyl, C3-C4-alkenyl, C3-C4-alkynyl, C3-C6-cycloalkyl-C1-C2-alkyl, aryl-C1-C2-alkyl, or C5-C 10-heteroaryl-C1-C2-alkyl, the alkyl, C3-C4-alkenyl, and C3-C4-alkynyl groups may be replaced independently of one another by 1 to 3 groups independently selected from R a The cycloalkyl group may be substituted by 1 to 3 substituents independently selected from R c Substituents are substituted, and the aryl and C5-C 10 -heteroaryl may be substituted independently of each other by 1 to 4 independently selected g Substituents substituted;
[0038] R a , independently of formula I or II, and independently of the substituent to which it is attached, is selected from halogen, cyano, and C1-C3-alkoxy;
[0039] R b 、R d 、R e 、R f , and R g , independently of formula I or II and independently of the substituent to which it is attached, is selected from halogen, cyano, C1-C3-alkyl, C1-C3-alkoxy, NH2C(O), (C1-C3-alkyl)N(H)C(O), NH2C(O)-C1-C3-alkoxy, (C1-C4-alkyl)SO2, benzyl, phenyl, phenoxy, C5-C6-heteroaryl and C4-C 10 - heterocyclyl (the phenyl, phenoxy, heteroaryl and heterocyclyl may be substituted independently of each other by 1 to 4 substituents independently selected from halogen, cyano, and C1-C3-alkyl);
[0040] R c , independently of Formula I or II, is selected from halogen, cyano, C1-C3-alkyl, and C1-C3-alkoxy; provided that when X in Formula II is CH2, T is not hydrogen, C1-C4-alkyl, 2-fluoroethyl, 2-methyl-4-pyrimidinyl)methyl, 2-(methylsulfonyl)phenyl]methyl, 2,6-di(tert-butyl)-4-methylphenyl, 1,4-dihydro-6-methyl-4-oxo-3-pyridazinyl)methyl, 1,3-dihydro-1,3-dioxo-2H-isoindol-2-yl, or tetrahydro-4,4-dimethyl-2-oxo-3-furanyl; or when X in Formula II is O, T is not hydrogen or C1-C2-alkyl; or an agronomically acceptable salt, stereoisomer, tautomer and / or N-oxide of a compound of Formula II or Formula II-I.
[0041] Compounds of formula I and formula II (respectively, II and II-I) with at least one basic center can form, for example, acid addition salts 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, for example, halogen-substituted C1-C4-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 such as unsubstituted or, for example, halogen-substituted C1-C4-alkanesulfonic acids or arylsulfonic acids, for example methanesulfonic acid or p-toluenesulfonic acid. The compounds of formula I and II 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 salts, potassium salts 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 trihydroxy-lower alkylamines, for example monoethanolamine, diethanolamine or triethanolamine).
[0042] N-oxides are oxidized forms of tertiary amines or oxidized forms of nitrogen-containing heteroaryl compounds. They are described, for example, in the book "Heterocyclic N-oxides" by A. Albini and S. Pietra, CRC Press, Boca Raton, 1991.
[0043] In each case, the compounds of formula I or II according to the invention are in free form, in oxidized form (such as N-oxides) or in salt form (for example agronomically usable salts).
[0044] The compounds of formula I or II according to the invention also include hydrates which may be formed during salt formation.
[0045] As used herein, the term "C1-C n "-alkyl" refers to a saturated alkyl group, for example any of the groups methyl and ethyl.
[0046] As used herein, the term "C2-C n "Alkenyl" refers to a straight or branched alkenyl chain having two to n carbon atoms and one or two double bonds, for example vinyl, prop-1-enyl, but-2-enyl.
[0047] As used herein, the term "C2-C n "Alkynyl" refers to a straight or branched alkynyl chain having two to n carbon atoms and one triple bond, for example ethynyl, prop-2-ynyl, but-3-ynyl.
[0048] As used herein, the term "C3-C n "-cycloalkyl" refers to a 3-membered to n-membered cycloalkyl group such as cyclopropane and cyclobutane.
[0049] As used herein, the term "C1-C n "-alkoxy" refers to a linear or branched saturated alkyl group having 1 to n carbon atoms (as mentioned above), which is attached via an oxygen atom, ie, for example, any of the groups methoxy and ethoxy. The term "halogenated C1-C2-alkyl" as used herein n -alkoxy" refers to such C1-C n - alkoxy groups in which one or more hydrogen atoms of the alkyl group are replaced by one or more identical or different halogen atoms - examples include trifluoromethoxy, difluoromethoxy, fluoromethoxy or 2-fluoroethoxy.
[0050] Halogen is typically fluorine, chlorine, bromine or iodine. This also applies correspondingly to halogen in combination with other meanings, such as haloalkyl.
[0051] As used herein, the term "C1-C n "-haloalkyl" refers to straight-chain saturated alkyl groups (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 groups: chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 2-fluoroethyl, 2-chloroethyl, 2-bromoethyl, 2-iodoethyl, 2,2-difluoroethyl, 2,2,2- The term "C1-C2 fluoroalkyl" shall mean a C1-C2 alkyl group having 1, 2, 3, 4, or 5 fluorine atoms, such as difluoromethyl, trifluoromethyl, 1-fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 1,1,2,2-tetrafluoroethyl, or pentafluoroethyl.
[0052] As used herein, the term "C1-C n -alkoxy-C1-C n -alkyl" refers to a C1-C n - alkoxy-substituted alkyl groups. Examples are methoxymethyl, methoxyethyl and ethoxymethyl.
[0053] The term "C1-C n-alkyl-C(O)" refers to a substituent having an alkyl group bonded to a C(=O) moiety which is linked to the remainder of the compound via its carbon atom. Examples include CH3C(O) and isopropylC(O). The terms "aryl-C(O)", "C5-C n -heteroaryl-C(O)", and "C4-C n -heterocyclyl-C(O)" refers to an aryl group, a C5-C n -heteroaryl and C4-C n - heterocyclyl, the moiety being linked to the remainder of the compound via its carbon atom in each case.
[0054] The term "C1-C n -alkyl-S(O)2" refers to a substituent having an alkyl group bonded to a S(=O)2 moiety which is linked to the remainder of the compound via its sulfur atom. The terms "aryl-S(O)2", "C5-C n -heteroaryl-S(O)2", and "C4-C n -heterocyclyl-S(O)2" refers to an aryl group, a C5-C n -heteroaryl and C4-C n - heterocyclyl, this moiety is linked to the remainder of the compound in each case via its sulfur atom.
[0055] The term "C3-C n -cycloalkyl-C1-C m -alkoxy" refers to a substituent having a cycloalkyl group having 3 to n carbon atoms bonded to a carbon atom of an alkoxy moiety having 1 to m carbon atoms, which moiety is linked to the rest of the compound via its oxygen atom. m -alkoxy", "C5-C n -heteroaryl-C1-C m -alkoxy", and "C4-C n -heterocyclyl-C1-C m -alkoxy" refers to an aryl group, a C5-C n -heteroaryl and C4-C n -heterocyclyl, the moiety being linked to the rest of the compound via its oxygen atom.
[0056] As used herein, the term "C1-C n -alkylsulfanyl" or "C1-C n -alkylthio" refers to a C1-C n -alkyl moiety. Similarly, as used herein, the term "C1-Cn -haloalkylthio" or "C1-C n -haloalkylsulfanyl" refers to a C1-C n -haloalkyl moiety.
[0057] As used herein, the term "C1-C n -alkylsulfinyl" refers to a C1-C ... n Similarly, as used herein, the term "C1-C n -haloalkylsulfinyl" or "C1-C n -haloalkylsulfinyl" refers to a C1-C2-alkylsulfinyl group attached via the sulfur atom of an S(=O) group. n -haloalkyl moiety.
[0058] As used herein, the term "C1-C n -alkylsulfonyl" refers to a C1-C2 group attached via the sulfur atom of a S(=O)2 group. n -alkyl moiety. Similarly, as used herein, the term "C1-C n -haloalkylsulfonyl" or "C1-C n -haloalkylsulfonyl" refers to a C1-C2 group attached via the sulfur atom of a S(=O)2 group. n -haloalkyl moiety.
[0059] As used herein, the term "aryl" refers to a fully unsaturated carbocyclic monocyclic, bicyclic or tricyclic ring. Examples of such substituents include phenyl, naphthyl, anthracenyl, indenyl or phenanthrenyl. The term "C q -C n "-aryl" refers to a q- to n-membered carbocyclic monocyclic or bicyclic ring. Examples are phenyl (or Ja) and naphthyl.
[0060] The term "C4-C n -heterocyclyl" refers to a 4- to n-membered heterocyclic ring. Examples are Ka to Kbd in Scheme 3.
[0061] As used herein, the term "C5-C n "-heteroaryl" refers to a fully unsaturated 5- to n-membered heterocyclic ring. In the case where the heteroaryl group is bicyclic, at least one of the rings is fully unsaturated. Examples are illustrated in Schemes 1 and 2. In the case where the heteroaryl ring is substituted, the substituents may be on carbon atoms in the ring backbone and / or heteroatoms such as N in the ring backbone.
[0062] As used herein with respect to Formula I or Formula II, the term "7-membered bicyclic ring" refers to a bicyclic ring composed of 7 ring atoms in its backbone, which is composed of a saturated 6-membered heterocyclic ring and a saturated 3-membered carbocyclic ring, as shown in the figure below, wherein D can be CH2, S, SO, SO2, SO(NH), or O.
[0063]
[0064] As used herein, the term "carbocycle" refers to an atomic ring in which the ring backbone is formed solely of carbon. The ring may be a monocyclic or fused bicyclic ring. One or more carbocyclic ring members may be present in the ring as a C(=O), C(=S), C(NH), or C(NOR) moiety (wherein R is hydrogen, C1-C3-alkyl, C5-C6-aryl-CH2, or C5-C6-heteroaryl-CH2). The ring may be saturated or partially unsaturated.
[0065] As used herein, the term "heterocycle" refers to a carbocyclic ring in which at least one ring member forming the ring backbone is not carbon, for example, selected from nitrogen, oxygen, and sulfur. The ring can be a monocyclic or fused bicyclic ring. Typically, the heterocyclic ring contains no more than 4 nitrogens, no more than 2 oxygens, and no more than 2 sulfurs. One or more carbon ring members can exist in the ring as C(=O), C(=S), C(NH), or C(NOR) moieties (wherein R is hydrogen, C1-C3-alkyl, C5-C6-aryl-CH2, or C5-C6-heteroaryl-CH2). One or more S ring members can exist in the ring as S(=O), S(=O)2, or S(=ONH) moieties. The ring can be saturated or partially unsaturated. Examples are illustrated in Scheme 3. When the heterocycle is substituted, the substituents can be on carbon atoms in the ring backbone and / or heteroatoms in the ring backbone, such as N.
[0066] 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.
[0067] As used herein, the term "pest" refers to insects and molluscs present in agriculture, horticulture, forestry, storage of products of plant origin (such as fruit, grain and wood); and those pests associated with damage to man-made structures. The term pest covers all stages of the pest life cycle.
[0068] Examples of "5- or 6-membered heteroaromatics" refer to 5- or 6-membered aromatic rings in which 1 to 3 carbon atoms are independently replaced by nitrogen, sulfur, or oxygen. Examples are pyridyl (pyridyl or pyridinyl), pyridazinyl, pyrimidinyl, pyrazinyl, pyrrolyl, pyrazolyl, imidazolyl, triazolyl (e.g., 1,2,4-triazolyl), furyl, thienyl, oxazolyl, isoxazolyl, oxadiazolyl, thiazolyl, isothiazolyl, and thiadiazolyl.
[0069] Examples of "9-membered or 10-membered heteroaromatic" refer to 9-membered or 10-membered aromatic rings consisting of two rings in which 1 to 4 carbon atoms are 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, benzothiophenyl, benzoxazolyl, benzothiazolyl, imidazo[1,2-a]pyridinyl, and imidazo[4,5-b]pyridinyl.
[0070] As used herein, the chemical abbreviations SO2, S(O)2, and S(=O)2 refer to a sulfonyl moiety. As used herein, the chemical abbreviations C(O) and C(=O)2 refer to a carbonyl moiety. As used herein, the chemical abbreviations CO2, C(O)O, and C(=O)O refer to an oxycarbonyl moiety. "CHO" means formyl.
[0071] As used herein, "animal pests" refers to pests that damage plants or animals, cause harm to plants or animals, or affect the growth and / or health of plants or animals. Examples of such pests may be from the phyla Nematoda, Arthropoda, and Mollusca.
[0072] 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.
[0073] As used herein, the term "pesticide" refers to a substance or composition used to control or destroy animal pests that are harmful to plants or crops, especially cultivated plants or crops, or to animals.
[0074] Staggered lines as used herein, for example, in J1 to J57, indicate the point of connection / attachment to the rest of the compound.
[0075] An effective amount is readily determined by one skilled in the art by using known techniques and by observing results obtained under similar circumstances. In determining an 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.
[0076] The molecular depictions drawn herein follow standard conventions for depicting stereochemistry. To indicate stereoconfiguration, bonds extending out of the drawing plane toward the viewer are represented by solid wedges, with the wide end of the wedge attached to an atom extending out of the drawing plane toward the viewer. Bonds extending below the drawing plane and away from the viewer are represented by dashed wedges, with the wide end of the wedge attached to an atom further away from the viewer.
[0077] Due to the presence of chiral carbon atoms in Formula I and II, the compounds of the present invention may exist as stereoisomers. Therefore, the present invention includes individual stereoisomers of compounds having Formula I or II as well as mixtures of stereoisomers of compounds having Formula I or II.
[0078] Compounds of formula I and II (and correspondingly formula II and II-I) can exist as mixtures of stereoisomers or as individual stereoisomers. For example, four possible stereoisomers of formula I are depicted below as formulas Ia, Ib, Ic, and Id, referring to the three cyclopropane chiral centers identified by asterisks (*); and four possible stereoisomers of formula II are depicted as formulas IIa, IIb, IIc, and IId (in each case, X is CH2, S, SO, SO2, or SO(NH)). The skilled person will appreciate that other chiral centers are also possible, such as at R 1 Place.
[0079] Selection of stereoisomers having formula I
[0080]
[0081] wherein X is CH2, S, SO, SO2, or SO(NH); and R 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 , Y and J are as defined herein.
[0082] Selection of stereoisomers having formula II
[0083]
[0084] wherein X is CH2, S, SO, SO2, or SO(NH); and R 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 , and T are as defined herein.
[0085] The present invention includes diastereomeric mixtures containing equal amounts of a single diastereoisomer. Additionally, the present invention includes mixtures enriched in one of the enantiomers compared to the racemic mixture. The present invention also includes substantially pure enantiomers.
[0086] In the case of compounds of Formula I and Formula II (where X=O), two possible stereoisomers of Formula I are depicted below as Formulas Iaa and Icc, depicting the relative orientation of the carbons identified with an asterisk (*); and two possible stereoisomers of Formula II are depicted as Formulas IIaa and IIcc. The skilled person will appreciate that other chiral centers are possible, such as at R 1 Place.
[0087] Selection of stereoisomers having formula I
[0088]
[0089] where R 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 , Y and J are as defined herein.
[0090] Selection of stereoisomers having formula II
[0091]
[0092] where R 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 , Y and J are as defined herein.
[0093] Compounds of Formula I or II may contain additional chiral centers. For example, substituents and other molecular components such as J (in the case of Formula I) or T (in the case of Formula II) may themselves contain chiral centers. The present invention includes racemic mixtures as well as enriched and substantially pure stereoconfigurations at these additional chiral centers.
[0094] Due to the restricted rotation around the amide bond (e.g., C(=O)-N) in Formula I or II, the compounds of the present invention may exist as one or more conformers. The present invention includes mixtures of conformers. In addition, the present invention includes compounds that are enriched in one conformer relative to other conformers.
[0095] The present invention includes all stereoisomers, conformers and mixtures thereof in all proportions, as well as isotopic forms, such as deuterated compounds.
[0096] Compounds of formula I or II, their stereoisomers, tautomers, N-oxides, and salts typically exist in more than one form, and therefore compounds of formula I or II include all crystalline and non-crystalline forms of the compounds represented by formula I or II, respectively. Non-crystalline forms include solid embodiments, such as waxes and gums, and liquid embodiments, such as solutions and melts. Crystalline forms include embodiments that essentially represent a single crystal type and embodiments that represent a mixture of polymorphs (i.e., different crystal types). The term "polymorph" refers to a specific crystalline form of a compound that can crystallize in different crystalline forms, which have different molecular arrangements and / or conformations in the crystal lattice. Although polymorphs can have the same chemical composition, they can also differ in composition due to the presence or absence of co-crystallized water or other molecules, which can be weakly or strongly bound to the crystal lattice. Polymorphs can differ in chemical, physical, and biological properties such as crystal shape, density, hardness, color, chemical stability, melting point, hygroscopicity, suspendability, dissolution rate, and bioavailability. It will be understood by those skilled in the art that the polymorphs of the compounds represented by Formula I or II can exhibit beneficial effects (e.g., suitable for preparing useful formulations, improved biological properties) relative to another polymorph or mixture of polymorphs of the same compound of Formula I or II, respectively. The preparation and separation of specific polymorphs of the compounds of Formula I or II can be achieved by methods known to those skilled in the art, including, for example, crystallization using a selected solvent and temperature. The compounds of the present invention can exist as one or more crystalline polymorphs. The present invention includes both individual polymorphs and mixtures of polymorphs, including mixtures that are enriched in one polymorph relative to other polymorphs. For a comprehensive discussion of polymorphism, see R. Hilfiker, ed., Polymorphism in the Pharmaceutical Industry, Wiley-VCH, Weinheim, 2006. It will be understood by those skilled in the art that the comments about Formula I in this paragraph are equally applicable to compounds having Formula II.
[0097] Examples according to the present invention are provided as listed below.
[0098] In an embodiment of each aspect of the invention, the invention relates to compounds having formula I.
[0099] In an embodiment of each aspect of the invention, the compound of formula I (when X is CH2, S, SO, SO2, or SO(NH)) is
[0100] A. a mixture of a compound having formula Ia and a compound having formula Ib, wherein the ratio of Ia to Ib is at least 75:25 (50 weight percent enantiomeric excess of Ia); or
[0101] B. a mixture of a compound having Formula Ia and a compound having Formula Ib, wherein the ratio of Ia to Ib is at least 90:10 (80 weight percent enantiomeric excess of Ia); or
[0102] C. a mixture of a compound having Formula Ia and a compound having Formula Ib, wherein the ratio of Ia to Ib is at least 95:5 (90 weight percent enantiomeric excess of Ia); or
[0103] D. a mixture of a compound having Formula Ia and a compound having Formula Ib, wherein the ratio of Ia to Ib is at least 98:2 (96 weight percent enantiomeric excess of Ia); or
[0104] E. a mixture of a compound having formula Ia and a compound having formula Ib, wherein the ratio of Ia to Ib is at least 99:1 (98 percent enantiomeric excess of Ia); or
[0105] F. Compounds of Formula Ia.
[0106] In an embodiment of each aspect of the invention, the compound of formula I (when X is O) is
[0107] G. a mixture of a compound having formula Iaa and a compound having Icc, wherein the ratio of Iaa to Icc is at least 75:25 (50 weight percent enantiomeric excess of Iaa); or
[0108] H. a mixture of a compound having formula Iaa and a compound having Icc, wherein the ratio of Iaa to Icc is at least 90:10 (80 weight percent enantiomeric excess of Iaa); or
[0109] I. A mixture of a compound having formula Iaa and a compound having Icc, wherein the ratio of Iaa to Icc is at least 95:5 (90 weight percent enantiomeric excess of Iaa); or
[0110] J. a mixture of a compound having formula Iaa and a compound having Icc, wherein the ratio of Iaa to Icc is at least 98:2 (96 weight percent enantiomeric excess of Iaa); or
[0111] K. a mixture of a compound having formula Iaa and a compound having Icc, wherein the ratio of Iaa to Icc is at least 99:1 (98 percent enantiomeric excess of Iaa); or
[0112] L. Compounds having formula Iaa.
[0113] In the embodiments of each aspect of the present invention (except the second aspect), X in Formula I is as follows
[0114] AX is O, S, SO, SO2, CH2, or SO(NH); or
[0115] BX is O, S, SO, SO2, or SO(NH); or
[0116] CX is O, S, SO, or SO2; or
[0117] DX is O.
[0118] In an embodiment of the second aspect, X in Formula I is as follows
[0119] AX is O, S, SO, SO2, or SO(NH); or
[0120] BX is O.
[0121] In an embodiment of each aspect of the invention, the invention relates to a compound having formula II.
[0122] In an embodiment of each aspect of the present invention, X in Formula II is as follows
[0123] AX is O, S, SO, SO2, CH2, or SO(NH); or
[0124] BX is O, S, SO, SO2, or SO(NH); or
[0125] CX is O, S, SO, or SO2; or
[0126] DX is O.
[0127] In an embodiment of each aspect of the invention, the compound of formula II (when X is CH2, S, SO, SO2, or SO(NH)) is
[0128] A. A mixture of a compound having Formula IIa and a compound having Formula IIb, wherein the ratio of IIa to IIb is at least 75:25 (50 weight percent enantiomeric excess of IIa); or
[0129] B. a mixture of a compound having formula IIa and a compound having formula IIb, wherein the ratio of IIa to IIb is at least 90:10 (80 weight percent enantiomeric excess of IIa); or
[0130] C. a mixture of a compound having Formula IIa and a compound having IIb, wherein the ratio of IIa to IIb is at least 95:5 (90 weight percent enantiomeric excess of IIa); or
[0131] D. a mixture of a compound having Formula IIa and a compound having IIb, wherein the ratio of IIa to IIb is at least 98:2 (96 weight percent enantiomeric excess of IIa); or
[0132] E. A mixture of a compound having Formula IIa and a compound having IIb, wherein the ratio of IIa to IIb is at least 99:1 (98 percent enantiomeric excess of IIa); or
[0133] F. Compounds of Formula IIa.
[0134] In an embodiment of each aspect of the present invention, the compound of formula II (when X is CH2) comprises
[0135] A. a mixture of a compound having formula IIaa and a compound having IIcc, wherein the ratio of IIaa to IIcc is at least 75:25 (50 weight percent enantiomeric excess of IIaa); or
[0136] B. a mixture of a compound having formula IIaa and a compound having IIcc, wherein the ratio of IIaa to IIcc is at least 90:10 (80 weight percent enantiomeric excess of IIaa); or
[0137] C. a mixture of a compound having formula IIaa and a compound having IIcc, wherein the ratio of IIaa to IIcc is at least 95:5 (90 weight percent enantiomeric excess of IIaa); or
[0138] D. a mixture of a compound having formula IIaa and a compound having IIcc, wherein the ratio of IIaa to IIcc is at least 98:2 (96 weight percent enantiomeric excess of IIaa); or
[0139] E. a mixture of a compound having formula IIaa and a compound having IIcc, wherein the ratio of IIaa to IIcc is at least 99:1 (98 percent enantiomeric excess of IIaa); or
[0140] F. Compounds of Formula IIaa.
[0141] In an embodiment of each aspect of the invention, R 1 、R 2 、R 3 and R 4 yes
[0142] A. hydrogen, halogen, cyano, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy, or C1-C4-haloalkoxy; or
[0143] B. hydrogen, halogen, cyano, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy, or C1-C4-haloalkoxy; or
[0144] C. hydrogen, halogen, cyano, C1-C4-alkyl, or C1-C4-haloalkyl; or
[0145] D. hydrogen, chlorine, fluorine, bromine, iodine, cyano, methyl, ethyl, isopropyl, trifluoromethyl or difluoromethyl; or
[0146] E. hydrogen, chlorine, fluorine, methyl, trifluoromethyl or difluoromethyl; or
[0147] F. Hydrogen.
[0148] In an embodiment of each aspect of the invention, R 5 、R 6 , and R 7 yes
[0149] A. hydrogen, halogen, cyano, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy, or C1-C4-haloalkoxy; or
[0150] B. hydrogen, halogen, cyano, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy, or C1-C4-haloalkoxy; or
[0151] C. hydrogen, halogen, cyano, C1-C4-alkyl, or C1-C4-haloalkyl;
[0152] D. hydrogen, chlorine, fluorine, bromine, iodine, cyano, methyl, ethyl, isopropyl, trifluoromethyl or difluoromethyl; or
[0153] E. hydrogen, chlorine, fluorine, methyl, trifluoromethyl or difluoromethyl; or
[0154] F. Hydrogen.
[0155] In an embodiment of each aspect of the invention, Y is
[0156] A. hydrogen, C1-C4-alkyl, C3-C4-alkenyl, C3-C4-alkynyl, C3-C6-cycloalkyl-CH2, aryl-CH2, or C1-C4-alkoxy-CH2; or
[0157] B. hydrogen, methyl, ethyl, isopropyl, allyl, propargyl, cyclopropylmethyl, benzyl, methoxymethyl, or ethoxymethyl; or
[0158] C. hydrogen, methyl, ethyl, cyclopropylmethyl, benzyl, or methoxymethyl; or
[0159] D. Hydrogen.
[0160] In an embodiment of each aspect of the invention, J is
[0161] A. Hydrogen, C1-C4-alkyl, C3-C6-alkenyl, C3-C6-alkynyl, C3-C4-cycloalkyl-CH2CH2, C3-C4-cycloalkyl-CH2, aryl-CH2CH2, aryl-CH2, C5-C 10 -heteroaryl-CH2CH2, C5-C 10 -heteroaryl-CH2, C4-C 10 -heterocyclyl-CH2, or C4-C 10 -heterocyclyl-CH2CH2, the C1-C4-alkyl, C3-C4-alkenyl, and C3-C4-alkynyl groups may be replaced independently of one another by 1 to 3 groups independently selected from R a The cycloalkyl group may be substituted by 1 to 3 substituents independently selected from R c Substituents are substituted, and the aryl, C5-C 10 -heteroaryl, and C4-C 10 - The heterocyclic group may be independently selected from 1 to 4 b Substituents substituted;
[0162] B. Hydrogen, C1-C4-alkyl, C3-C4-alkenyl, C3-C4-alkynyl, C3-C4-cycloalkyl-CH2, C5-C6-aryl-CH2, C9-C 10 -aryl-CH2, C5-C6-heteroaryl-CH2, C9-C 10 -heteroaryl-CH2, C4-C6-heterocyclyl-CH2, or C9-C 10 -heterocyclyl-CH2, the C1-C4-alkyl, C3-C4-alkenyl, and C3-C4-alkynyl groups may be replaced independently of one another by 1 to 3 groups independently selected from R a The cycloalkyl group may be substituted by 1 to 3 substituents independently selected from R c The aryl, heteroaryl, and heterocyclic groups may be substituted by 1 to 4 substituents independently selected from Rb or
[0163] C. Hydrogen, C1-C4-alkyl, C3-C4-alkenyl, C3-C4-alkynyl, C3-C4-cycloalkyl-CH2, C5-C6-aryl-CH2, C9-C 10 -aryl-CH2, C5-C6-heteroaryl-CH2, C9-C 10 -heteroaryl-CH2, C4-C6-heterocyclyl-CH2, or C9-C 10 -heterocyclyl-CH2, the C1-C4-alkyl, C3-C4-alkenyl, and C3-C4-alkynyl groups may be replaced independently of one another by 1 to 3 groups independently selected from R a The cycloalkyl group may be substituted by 1 to 3 substituents independently selected from R c The aryl, heteroaryl, and heterocyclic groups may be substituted by 1 to 4 substituents independently selected from R b or
[0164] D. hydrogen, C1-C3-alkyl, C3-C4-alkenyl, C3-C4-alkynyl, C3-C4-cycloalkyl-CH2, Ja-CH2 to Jdl-CH2, Ka-CH2 to Kbd-CH2, Ja-CH2CH2 to Jdl-CH2CH2, Ka-CH2CH2 to Kbd-CH2CH2, the C1-C3-alkyl, C3-C4-alkenyl, and C3-C4-alkynyl groups may be replaced independently by 1 to 3 groups independently selected from R a The cycloalkyl group may be substituted by 1 to 3 substituents independently selected from R c and these Ja to Jdl and Ka to Kbd rings may be independently substituted by 1 to 4 groups independently selected from R b or
[0165] E. hydrogen, C1-C3-alkyl, C3-C4-alkenyl, C3-C4-alkynyl, cyclopropylmethyl, Ja-CH2 to Jdl-CH2, Ka-CH2 to Kbd-CH2, Ja-CH2CH2 to Jdl-CH2CH2, or Ka-CH2CH2 to Kbd-CH2CH2, the C1-C3-alkyl, C3-C4-alkenyl, and C3-C4-alkynyl groups may be substituted independently by 1 to 3 substituents independently selected from chlorine, fluorine, cyano, and methoxy, the cyclopropyl group may be substituted by 1 to 3 substituents independently selected from chlorine, fluorine, cyano, methyl, and methoxy, and These J a to Jdl and Ka to Kbd rings may be substituted, independently of one another, by 1 to 4 substituents independently selected from the group consisting of halogen, cyano, C1-C3-alkyl, C1-C3-alkoxy, NH2C(O), (C1-C3-alkyl)N(H)C(O), NH2C(O)-C1-C3-alkoxy, (C1-C3-alkyl)SO2, benzyl, phenyl, phenoxy, C5-C6-heteroaryl, and C5-C6-heterocyclyl (the phenyl, phenoxy, heteroaryl or heterocyclyl may be substituted, independently of one another, by 1 to 4 substituents independently selected from the group consisting of halogen, cyano, and C1-C3-alkyl); or
[0166] F. hydrogen, C1-C3-alkyl, C3-C4-alkenyl, C3-C4-alkynyl, cyclopropylmethyl, Ja-CH2 to Jdl-CH2, Ka-CH2 to Kbd-CH2, Ja-CH2CH2 to Jdl-CH2CH2, or Ka-CH2CH2 to Kbd-CH2CH2, the C1-C3-alkyl, C3-C4-alkenyl, and C3-C4-alkynyl may be substituted independently of each other by 1 to 3 substituents independently selected from chlorine, fluorine, cyano, and methoxy, the cyclopropyl may be substituted by 1 to 3 substituents independently selected from chlorine, fluorine, cyano, methyl, and methoxy. substituted with a halogen group, and these Ja to Jdl and Ka to Kbd rings may be substituted independently of each other by 1 to 4 substituents independently selected from the following: fluorine, chlorine, cyano, methyl, ethyl, isopropyl, methoxy, NH2C(O), (methyl)N(H)C(O), NH2C(O)-methoxy, (methyl)SO2, benzyl, phenyl, phenoxy, C5-C6-heteroaryl, and C5-C6-heterocyclyl (the phenyl, phenoxy, C5-C6-heteroaryl, and C5-C6-heterocyclyl may be substituted independently of each other by 1 to 4 substituents independently selected from fluorine, chlorine, cyano, and methyl); or
[0167] G. hydrogen, methyl, ethyl, isopropyl, allyl, propargyl, cyclopropylmethyl, Ja-CH2, Ja-CH2CH2 to Jdl-CH2CH2, or Ka-CH2CH2 to Kbd-CH2CH2, the methyl, ethyl, isopropyl, allyl, and propargyl groups may be substituted independently by 1 to 3 substituents independently selected from chlorine, fluorine, cyano, and methoxy, the cyclopropyl group may be substituted by 1 to 3 substituents independently selected from chlorine, fluorine, cyano, methyl, and methoxy, and these Ja to Jdl-CH2CH2 to Kbd-CH2CH2 d1 and Ka to Kbd rings may be substituted, independently of each other, by 1 to 4 substituents independently selected from the group consisting of fluorine, chlorine, cyano, methyl, ethyl, isopropyl, methoxy, NH2C(O), (methyl)N(H)C(O), NH2C(O)-methoxy, (methyl)SO2, benzyl, phenyl, phenoxy, Ja to Jbn, and Ka to Kbd (the phenoxy, Ja to Jbn or Ka to Kbd rings may be substituted, independently of each other, by 1 to 4 substituents independently selected from the group consisting of fluorine, chlorine, cyano, and methyl); or
[0168] H. hydrogen, methyl, cyclopropylmethyl, Ja-CH2, Ja-CH2CH2 to Jdl-CH2CH2, or Ka-CH2CH2 to Kbd-CH2CH2, the methyl group may be substituted by 1 to 3 substituents independently selected from chlorine, fluorine, cyano, and methoxy, the cyclopropyl group may be substituted by 1 to 3 substituents independently selected from chlorine, fluorine, cyano, methyl, and methoxy, and these Ja to Jdl and Ka to Kbd rings may be substituted independently of each other. 1 to 4 substituents independently selected from the group consisting of fluorine, chlorine, cyano, methyl, ethyl, isopropyl, methoxy, NH2C(O), (methyl)N(H)C(O), NH2C(O)-methoxy, (methyl)SO2, benzyl, phenyl, phenoxy, Ja to Jbn, and Ka to Kbd (the phenoxy, Ja to Jbn, or Ka to Kbd rings may be substituted independently by 1-4 substituents independently selected from the group consisting of fluorine, chlorine, cyano, and methyl); or
[0169] I. hydrogen, Jaa-methyl, Jaf-ethyl, or Jaw-methyl, these J rings may be substituted independently by 1 to 4 substituents independently selected from the following: fluorine, chlorine, cyano, methyl, ethyl, isopropyl, methoxy, NH2C(O), (methyl)N(H)C(O), NH2C(O)-methoxy, (methyl)SO2, benzyl, phenyl, phenoxy, Ja to Jbn, and Ka to Kbd (the phenoxy, Ja to Jbn or Ka to Kbd rings may be substituted independently by 1-4 substituents independently selected from fluorine, chlorine, cyano, and methyl).
[0170] In an embodiment of each aspect of the invention, J is
[0171] A. C5-C6-aryl, C9-C 10 -aryl, C5-C6-heteroaryl, C9-C 10 -heteroaryl, C4-C6-heterocyclyl or C9-C 10 - heterocyclic group, the aryl, heteroaryl, and heterocyclic group may be independently substituted by 1 to 4 groups independently selected from R b or
[0172] B. Ja to Jdl or Ka to Kbd, these Ja to Jdl and Ka to Kbd rings can be replaced independently by 1 to 4 independently selected R b or
[0173] C. Ja, Jh, Jz, Jaa, Jag, Jas, Jat, Jaw, Jax, Jay, Jaz, Jba, Jbc, Jbd, Jbe, Jbj, Jbk, Jbl, Jbm, Jcj, Jck, Jcl, Jcy, Jdk, Jdl, Kaz, Kbb, Kbc, or Kbd, wherein the J ring and the K ring can be replaced by 1 to 4 independently selected R b or
[0174] D. Ja, Jh, Jz, Jaa, Jag, Jas, Jat, Jaw, Jax, Jay, Jaz, Jba, Jbc, Jbd, Jbe, Jbj, Jbk, Jbl, Jbm, Jcj, Jck, Jcl, Jcy, Jdk, Jdl, Kaz, Kbb, Kbc, or Kbd, wherein the J ring and the K ring may be substituted independently by 1 to 4 substituents independently selected from the group consisting of halogen, cyano, C1-C3 -alkyl, C1-C3-alkoxy, NH2C(O), (C1-C3-alkyl)N(H)C(O), NH2C(O)-C1-C3-alkoxy, (C1-C3-alkyl)SO2, benzyl, phenyl, phenoxy, C5-C6-heteroaryl, and C5-C6-heterocyclyl (the phenyl, phenoxy, heteroaryl or heterocyclyl may be substituted independently by 1 to 4 substituents independently selected from halogen, cyano, and C1-C3-alkyl); or
[0175] E. Ja, Jh, Jz, Jaa, Jag, Jas, Jat, Jaw, Jax, Jay, Jaz, Jba, Jbc, Jbd, Jbe, Jbj, Jbk, Jbl, Jbm, Jcj, Jck, Jcl, Jcy, Jdk, Jdl, Kaz, Kbb, Kbc, or Kbd, wherein the J ring and the K ring may be substituted independently by 1 to 4 substituents independently selected from the group consisting of halogen, cyano, Cl -C3-alkyl, C1-C3-alkoxy, NH2C(O), (C1-C3-alkyl)N(H)C(O), NH2C(O)-C1-C3-alkoxy, (C1-C3-alkyl)SO2, benzyl, phenyl, phenoxy, Ja to Jb1, and Ka to Kbd (the benzyl, phenoxy, Ja to Jbn or Ka to Kbd may be substituted independently by 1 to 4 substituents independently selected from fluorine, chlorine, cyano, and methyl); or
[0176] F. J a or J bj , the J a or J bj ring may be substituted, independently of one another, by 1 to 4 substituents independently selected from the group consisting of halogen, cyano, C1-C3-alkyl, C1-C3-alkoxy, NH2C(O), (C1-C3-alkyl)N(H)C(O), NH2C(O)-C1-C3-alkoxy, (C1-C3-alkyl)SO2, benzyl, phenyl, phenoxy, C5-C6-heteroaryl, and C5-C6-heterocyclyl (the phenyl, benzyl, phenoxy, heteroaryl, or heterocyclyl may be substituted, independently of one another, by 1 to 4 substituents independently selected from the group consisting of halogen, cyano, and C1-C3-alkyl); or
[0177] G. Ja or Jbj, the Ja or Jbj ring may be substituted independently by 1 to 4 substituents independently selected from the group consisting of fluorine, chlorine, cyano, methyl, ethyl, isopropyl, methoxy, NH2C(O), (methyl)N(H)C(O), NH2C(O)-methoxy, (methyl)SO2, benzyl, phenoxy, Ja to Jbn, and Ka to Kbd (the benzyl, phenoxy, J and K rings may be substituted independently by 1-4 substituents independently selected from the group consisting of fluorine, chlorine, cyano, and methyl); or
[0178] H.Ja or Jbj, the Ja or Jbj ring can be substituted independently by 1 to 4 substituents independently selected from the following: fluorine, chlorine, cyano, methyl, ethyl, isopropyl, methoxy, NH2C(O), (methyl)N(H)C(O), NH2C(O)-methoxy, (methyl)SO2, benzyl, phenyl, phenoxy, Kba, Jbm, and Jbn (the phenyl, phenoxy, J and K rings can be substituted independently by 1-4 substituents independently selected from fluorine, chlorine, cyano, and methyl).
[0179] In an embodiment of each aspect of the invention, J is
[0180] A. C1-C4-alkyl-C(O), C3-C4-cycloalkyl-C(O), aryl-C(O), C5-C 10 -heteroaryl-C(O), or C4-C 10 -heterocyclyl-C(O), the alkyl group may be 1 to 3 independently selected from R a The cycloalkyl group may be substituted by 1 to 3 substituents independently selected from R c The aryl, heteroaryl, and heterocyclic groups may be substituted by 1 to 4 substituents independently selected from R d or
[0181] B. C1-C3-alkyl-C(O), C3-C4-cycloalkyl-C(O), Ja-C(O) to Jdl-C(O), or Ka-C(O) to Kbd-C(O), wherein the alkyl group may be substituted by 1 to 3 independently selected R a The cycloalkyl group may be substituted by 1 to 3 substituents independently selected from R c and the Ja to Jdl, and Ka to Kbd may be independently substituted by 1 to 4 substituents independently selected from R d or
[0182] C. C1-C3-alkyl-C(O), C3-C4-cycloalkyl-C(O), Ja-C(O) to Jdl-C(O), or Ka-C(O) to Kbd-C(O), the alkyl group may be substituted by 1 to 3 substituents independently selected from chlorine, fluorine, cyano, and methoxy, the cycloalkyl group may be substituted by 1 to 3 substituents independently selected from chlorine, fluorine, cyano, methyl, and methoxy, and the Ja to Jdl, and Ka to Kbd may each be independently substituted by 1 to 4 substituents independently selected from the following or
[0183] D. C1-C3-alkyl-C(O), C3-C4-cycloalkyl-C(O), Ja-C(O) to Jdl-C(O), or Ka-C(O) to Kbd-C(O), the alkyl group may be substituted with 1 to 3 substituents independently selected from chlorine, fluorine, cyano, and methoxy, the cycloalkyl group may be substituted with 1 to 3 substituents independently selected from chlorine, fluorine, cyano, methyl, and methoxy, and the Ja to Jdl, and Ka to Kbd may each be independently substituted with 1 to 4 substituents independently selected from the following Substituents include: halogen, cyano, C1-C3-alkyl, C1-C3-alkoxy, NH2C(O), (C1-C3-alkyl)N(H)C(O), NH2C(O)-C1-C3-alkoxy, (C1-C3-alkyl)SO2, benzyl, phenyl, phenoxy, C5-C6-heteroaryl, and C5-C6-heterocyclyl (the phenyl, phenoxy, heteroaryl or heterocyclyl may be substituted independently by 1-4 substituents independently selected from fluorine, chlorine, cyano, and methyl).
[0184] In an embodiment of each aspect of the invention, J is
[0185] A. C1-C4-alkyl-S(O)2, C3-C4-cycloalkyl-S(O)2, aryl-S(O)2, C5-C 10 -heteroaryl-S(O)2, or C4-C 10 -heterocyclyl-S(O)2, the alkyl group may be 1 to 3 independently selected from R a The cycloalkyl group may be substituted by 1 to 3 substituents independently selected from R c The aryl, heteroaryl, and heterocyclic groups may be substituted by 1 to 4 substituents independently selected from R e or
[0186] B. C1-C3-alkyl-S(O)2, C3-C4-cycloalkyl-S(O)2, Ja-S(O)2 to Jdl-S(O)2, or Ka-S(O)2 to Kbd-S(O)2, wherein the alkyl group may be substituted by 1 to 3 independently selected R a The cycloalkyl group may be substituted by 1 to 3 substituents independently selected from R c and the aryl, Ja to Jdl, and Ka to Kbd may be independently substituted by 1 to 4 substituents independently selected from R e or
[0187] C. C1-C3-alkyl-S(O)2, C3-C4-cycloalkyl-S(O)2, Ja-S(O)2 to Jdl-S(O)2, or Ka-S(O)2 to Kbd-S(O)2, the alkyl group may be substituted by 1 to 3 substituents independently selected from chlorine, fluorine, cyano, and methoxy, the cycloalkyl group may be substituted by 1 to 3 substituents independently selected from chlorine, fluorine, cyano, methyl, and methoxy, and the Ja to Jdl, and Ka to Kbd may each be independently substituted by 1 to 4 substituents independently selected from the following substituted by: halogen, cyano, C1-C3-alkyl, C1-C3-alkoxy, NH2C(O), (C1-C3-alkyl)N(H)C(O), NH2C(O)-C1-C3-alkoxy, (C1-C3-alkyl)SO2, benzyl, phenyl, phenoxy, C5-C6-heteroaryl, and C5-C6-heterocyclyl (the phenyl, phenoxy, heteroaryl or heterocyclyl may be substituted independently by 1-4 substituents independently selected from halogen, cyano, and C1-C3-alkyl); or
[0188] D. C1-C3-alkyl-S(O)2, C3-C4-cycloalkyl-S(O)2, Ja-S(O)2 to Jdl-S(O)2, or Ka-S(O)2 to Kbd-S(O)2, the alkyl group may be substituted with 1 to 3 substituents independently selected from chlorine, fluorine, cyano, and methoxy, the cycloalkyl group may be substituted with 1 to 3 substituents independently selected from chlorine, fluorine, cyano, methyl, and methoxy, and the Ja to Jdl, and Ka to Kbd may each be independently substituted with 1 to 4 substituents independently selected from substituted with halogen, cyano, C1-C3-alkyl, C1-C3-alkoxy, NH2C(O), (C1-C3-alkyl)N(H)C(O), NH2C(O)-C1-C3-alkoxy, (C1-C3-alkyl)SO2, benzyl, phenyl, phenoxy, C5-C6-heteroaryl, and C5-C6-heterocyclyl (the phenyl, phenoxy, heteroaryl or heterocyclyl may be substituted with 1 to 4 substituents independently selected from fluorine, chlorine, cyano, and methyl); or
[0189] E. C1-C4-alkoxy, C3-C4-cycloalkyl-C1-C2-alkoxy, aryloxy, aryl-C1-C2-alkoxy, C5-C 10 -heteroaryl-C1-C2-alkoxy, or C4-C 10 -heterocyclyl-C1-C2-alkoxy, the alkoxy group may be 1 to 3 independently selected from R a The cycloalkyl group may be substituted by 1 to 3 substituents independently selected from R c The aryl, heteroaryl, and heterocyclic groups may be substituted by 1 to 4 substituents independently selected from R f or
[0190] F. C1-C3-alkoxy, C3-C4-cycloalkylmethoxy, C3-C4-cycloalkylethoxy, aryloxy, J a-methoxy to J dl-methoxy, J a-ethoxy to J dl-ethoxy, K a-methoxy to K bd-methoxy, or K a-ethoxy to K bd-ethoxy, the alkoxy group may be substituted by 1 to 3 independently selected a The cycloalkyl group may be substituted by 1 to 3 substituents independently selected from R c and the aryl, Ja to Jdl, and Ka to Kbd may be independently substituted by 1 to 4 substituents independently selected from R f or
[0191] G. C1-C3-alkoxy, C3-C4-cycloalkylmethoxy, aryloxy, aryl-methoxy, Ja-ethoxy to Jdl-ethoxy, or Ka-ethoxy to Kbd-ethoxy, the alkoxy may be substituted by 1 to 3 substituents independently selected from chlorine, fluorine, cyano, methyl and methoxy, the cycloalkyl may be substituted by 1 to 3 substituents independently selected from chlorine, fluorine, cyano, methyl and methoxy, and the aryl, Ja to Jdl, and Ka to Kbd may each be independently substituted by 1 to 4 substituents independently selected from or substituted by the following substituents: halogen, cyano, C1-C3-alkyl, C1-C3-alkoxy, NH2C(O), (C1-C3-alkyl)N(H)C(O), NH2C(O)-C1-C3-alkoxy, (C1-C3-alkyl)SO2, benzyl, phenyl, phenoxy, C5-C6-heteroaryl, and C5-C6-heterocyclyl (the phenyl, phenoxy, heteroaryl or heterocyclyl may be substituted independently by 1-4 substituents independently selected from halogen, cyano, and C1-C3-alkyl); or
[0192] H. C1-C3-alkoxy, C3-C4-cycloalkylmethoxy, phenyl-methoxy, Ja-ethoxy to Jdl-ethoxy, or Ka-ethoxy to Kbd-ethoxy, the alkoxy may be substituted by 1 to 3 substituents independently selected from chlorine, fluorine, cyano, methyl and methoxy, the cycloalkyl may be substituted by 1 to 3 substituents independently selected from chlorine, fluorine, cyano, methyl and methoxy, and the aryl, Ja to Jdl, and Ka to Kbd may each be independently substituted by 1 to 4 substituents independently selected from or substituted by the following substituents: halogen, cyano, C1-C3-alkyl, C1-C3-alkoxy, NH2C(O), (C1-C3-alkyl)N(H)C(O), NH2C(O)-C1-C3-alkoxy, (C1-C3-alkyl)SO2, benzyl, phenyl, phenoxy, C5-C6-heteroaryl, and C5-C6-heterocyclyl (the phenyl, phenoxy, heteroaryl or heterocyclyl may be substituted independently by 1-4 substituents independently selected from fluorine, chlorine, cyano, and methyl); or
[0193] I. methoxy, ethoxy, isopropoxy, propoxy, cyclopropylmethoxy, phenyl-methoxy (or benzyloxy), Ja-ethoxy to Jdl-ethoxy, or Ka-ethoxy to Kbd-ethoxy, the cyclopropyl group may be substituted by 1 to 3 substituents independently selected from chlorine, fluorine, cyano, methyl, and methoxy, and the aryl group, Ja to Jdl, and Ka to Kbd may each be independently substituted by 1 to 4 substituents independently selected from the following: halogen, cyano, C1-C3-alkyl, C1-C3-alkoxy, NH2C(O), (C1-C3-alkyl)N(H)C(O), NH2C(O)-C1-C3-alkoxy, (C1-C3-alkyl)SO2, benzyl, phenyl, phenoxy, C5-C6-heteroaryl, and C5-C6-heterocyclyl (the phenyl, phenoxy, heteroaryl or heterocyclyl may be substituted independently by 1-4 substituents independently selected from fluorine, chlorine, cyano, and methyl).
[0194] In an embodiment of each aspect of the invention, J is
[0195] A. Hydrogen, C1-C3-alkyl, C1-C3-alkoxy, aryl-C1-C2-alkoxy, C1-C3-alkyl-S(O)2, C3-C4-cycloalkyl-S(O)2, C3-C4-cycloalkyl-C1-C2-alkyl, C5-C 10 -heteroaryl, C4-C 10 -heterocyclic, aryl-C1-C2-alkyl, aryl, or C5-C 10-heteroaryl-C1-C2-alkyl, the alkyl may be substituted by 1 to 3 substituents independently selected from chlorine, fluorine, cyano, and methoxy, the alkoxy may be substituted by 1 to 3 substituents independently selected from chlorine, fluorine, cyano, methyl and methoxy, the cycloalkyl may be substituted by 1 to 3 substituents independently selected from chlorine, fluorine, cyano, methyl and methoxy, and the aryl, heteroaryl, and heterocyclic groups may be substituted independently of each other by 1 to 4 substituents independently selected from halogen, cyano, C1-C3-alkyl, C1-C3-alkoxy, NH2C(O), (C1-C3-alkyl)N(H)C(O), NH2C(O)-C1-C3-alkoxy, (C1-C3-alkyl)SO2, benzyl, phenyl, phenoxy, C5-C6-heteroaryl, and C5-C6-heterocyclyl (the phenyl, phenoxy, heteroaryl or heterocyclyl may be substituted independently by 1 to 4 substituents independently selected from fluorine, chlorine, cyano, and methyl); or
[0196] B. Hydrogen, methyl, ethyl, methoxy, ethoxy, aryl-methoxy, methyl-S(O)2, ethyl-S(O)2, cyclopropyl-S(O)2, C3-C4-cycloalkyl-methyl, C5-C 10 -heteroaryl, C4-C 10 -heterocyclic, aryl-C1-C2-alkyl, aryl, or C5-C 10 -heteroaryl-C1-C2-alkyl, the cycloalkyl may be substituted by 1 to 3 substituents independently selected from chlorine, fluorine, cyano, methyl, and methoxy, and the aryl, heteroaryl, and heterocyclyl may be substituted independently of each other by 1 to 4 substituents independently selected from the group consisting of halogen, cyano, C1-C3-alkyl, C1-C3-alkoxy, NH2C(O), (C1-C3-alkyl)N(H)C(O), NH2C(O)-C1-C3-alkoxy, (C1-C3-alkyl)SO2, benzyl, phenyl, phenoxy, C5-C6-heteroaryl, and C5-C6-heterocyclyl (the phenyl, phenoxy, heteroaryl, or heterocyclyl may be substituted independently of each other by 1 to 4 substituents independently selected from the group consisting of fluorine, chlorine, cyano, and methyl); or
[0197] C. hydrogen, methyl, ethoxy, phenyl, benzyl, phenyl-methoxy, methyl-S(O)2, cyclopropyl-S(O)2, cyclopropylmethyl, Jh, Jz, Jaa, Jag, Jas, Jat, Jaw, Jax, Jay, Jaz, Jba, Jbc, Jbd, Jbe, Jbj, Jbk, Jbl, Jbm, Jcj, Jck, Jcl, Jcy, Jdk, Jdl, Kaz, Kbb, Kbc, or Kbd, Jaa-methyl, Jaf-ethyl The phenyl group, benzyl group, J ring and K ring may be substituted independently by 1 to 4 substituents independently selected from the following: fluorine, chlorine, cyano, methyl, ethyl, methoxy, NH2C(O), (methyl)N(H)C(O), NH2C(O)-methoxy, (methyl)SO2, benzyl, phenyl, phenoxy, Kba, Jbm, and Jbn (the phenyl group, J and K ring may be substituted independently by 1-4 substituents independently selected from fluorine, chlorine, cyano, and methyl).
[0198]
[0199]
[0200]
[0201] In an embodiment of each aspect of the invention, T is
[0202] A. Hydrogen, C1-C4-alkyl, C3-C4-alkenyl, C3-C4-alkynyl, C3-C4-cycloalkyl-C1-C2-alkyl, aryl-C1-C2-alkyl, or C5-C 10 -heteroaryl-C1-C2-alkyl, the alkyl, C3-C4-alkenyl, and C3-C4-alkynyl groups may be replaced independently of one another by 1 to 3 groups independently selected from R a The cycloalkyl group may be substituted by 1 to 3 substituents independently selected from R c Substituents are substituted, and the aryl and C5-C 10 -heteroaryl may be substituted independently of each other by 1 to 4 independently selected g or
[0203] B. Hydrogen, C1-C3-alkyl, C3-C4-alkenyl, C3-C4-alkynyl, C3-C4-cycloalkyl-methyl, aryl-methyl, aryl-ethyl, C5-C 10 -heteroaryl-methyl, or C5-C 10 -heteroaryl-ethyl, the alkyl, C3-C4-alkenyl, C3-C4-alkynyl may be replaced independently of one another by 1 to 3 groups independently selected from R a The cycloalkyl group may be substituted by 1 to 3 substituents independently selected from Rc Substituents are substituted, and the aryl and C5-C 10 -heteroaryl may be substituted independently of each other by 1 to 4 independently selected g or
[0204] C. hydrogen, methyl, ethyl, isopropyl, propyl, allyl, propargyl, cyclopropylmethyl, benzyl, J a to J dl-methyl, or J a to J dl-ethyl, the methyl, ethyl, isopropyl, propyl, allyl, propargyl may be substituted independently by 1 to 3 substituents independently selected from fluorine, chlorine, cyano, and methoxy, the cyclopropyl may be substituted by 1 to 3 substituents independently selected from fluorine, chlorine, cyano, methyl, ethyl, and methoxy, and the benzyl and J a to J dl may be substituted independently by 1 to 4 substituents independently selected from R g or
[0205] D. hydrogen, methyl, ethyl, isopropyl, propyl, allyl, propargyl, cyclopropylmethyl, benzyl, J a to J dl-methyl, or J a to J dl-ethyl, the methyl, ethyl, isopropyl, propyl, allyl, propargyl being substituted independently by 1 to 3 substituents independently selected from fluorine, chlorine, cyano, and methoxy, the cyclopropyl being substituted by 1 to 3 substituents independently selected from fluorine, chlorine, cyano, methyl, ethyl, and methoxy, and the benzyl and J a to J dl being substituted independently by 1 to 4 substituents independently selected from fluorine, chlorine, cyano, methyl, ethyl, and methoxy; or
[0206] E. hydrogen, methyl, ethyl, isopropyl, propyl, allyl, propargyl, cyclopropylmethyl, benzyl, Jaa-methyl, Jaf-ethyl, or Jaw-methyl, the methyl, ethyl, isopropyl, propyl, allyl, propargyl may be substituted independently of each other with 1 to 3 substituents independently selected from fluorine, chlorine, cyano, and methoxy, the cyclopropyl may be substituted with 1 to 3 substituents independently selected from fluorine, chlorine, cyano, methyl, ethyl, and methoxy, and the benzyl and J ring may be substituted independently of each other with 1 to 4 substituents independently selected from fluorine, chlorine, cyano, methyl, ethyl, and methoxy.
[0207] In an embodiment of each aspect of the invention, R a Selected from
[0208] A. halogen, cyano, and C1-C3-alkoxy; or
[0209] B. Chloro, fluoro, cyano, and methoxy.
[0210] In an embodiment of each aspect of the invention, R c Selected from
[0211] A. halogen, cyano, C1-C3-alkyl, and C1-C3-alkoxy; or
[0212] B. Chloro, fluoro, cyano, methyl, and methoxy.
[0213] In an embodiment of each aspect of the invention, R b 、R d 、R e and R f Selected from
[0214] A. Halogen, cyano, C1-C3-alkyl, C1-C3-alkoxy, NH2C(O), (C1-C3-alkyl)N(H)C(O), NH2C(O)-C1-C3-alkoxy, (C1-C3-alkyl)SO2, benzyl, phenyl, phenoxy, C5-C6-heteroaryl and C4-C 10 - heterocyclyl (the phenyl, phenoxy, heteroaryl and heterocyclyl may be substituted independently of each other by 1 to 4 substituents independently selected from halogen, cyano, and C1-C3-alkyl); or
[0215] B. halogen, cyano, C1-C3-alkyl, C1-C3-alkoxy, NH2C(O), (C1-C3-alkyl)N(H)C(O), NH2C(O)-C1-C3-alkoxy, (C1-C3-alkyl)SO2, benzyl, phenyl, phenoxy, C5-C6-heteroaryl, and C5-C6-heterocyclyl (the phenyl, phenoxy, heteroaryl or heterocyclyl may be substituted independently of each other by 1 to 4 substituents independently selected from halogen, cyano, and C1-C3-alkyl); or
[0216] C. halogen, cyano, C1-C3-alkyl, C1-C3-alkoxy, NH2C(O), (C1-C3-alkyl)N(H)C(O), NH2C(O)-C1-C3-alkoxy, (C1-C3-alkyl)SO2, benzyl, phenyl, phenoxy, C5-C6-heteroaryl, and C5-C6-heterocyclyl (the phenyl, phenoxy, heteroaryl or heterocyclyl may be substituted independently by 1 to 4 substituents independently selected from fluorine, chlorine, cyano and methyl); or
[0217] D. fluorine, chlorine, cyano, methyl, ethyl, methoxy, NH2C(O), (methyl)N(H)C(O), NH2C(O)-methoxy, (methyl)SO2, benzyl, phenyl, phenoxy, C5-C6-heteroaryl, and C5-C6-heterocyclyl (the phenyl, heteroaryl or heterocyclyl may be substituted independently by 1 to 4 substituents independently selected from fluorine, chlorine, cyano, and methyl); or
[0218] E. Fluorine, chlorine, cyano, methyl, ethyl, methoxy, NH2C(O), (methyl)N(H)C(O), NH2C(O)-methoxy, (methyl)SO2, benzyl, phenyl, phenoxy, Kba, Jbm, and Jbn (the phenyl, J and K rings may be independently substituted with 1-4 substituents independently selected from fluorine, chlorine, cyano, and methyl).
[0219] In an embodiment of each aspect of the invention, R g Selected from
[0220] A. Halogen, cyano, C1-C3-alkyl, C1-C3-alkoxy, NH2C(O), (C1-C3-alkyl)N(H)C(O), NH2C(O)-C1-C3-alkoxy, (C1-C3-alkyl)SO2, benzyl, phenyl, phenoxy, C5-C6-heteroaryl and C4-C 10 - heterocyclyl (the phenyl, phenoxy, heteroaryl and heterocyclyl may be substituted independently of each other by 1 to 4 substituents independently selected from halogen, cyano, and C1-C3-alkyl); or
[0221] B. halogen, cyano, C1-C3-alkyl, C1-C3-alkoxy, benzyl, phenyl, and phenoxy; or
[0222] C. Fluoro, chlorine, cyano, methyl, ethyl, and methoxy.
[0223] Thus, the present invention makes it possible to obtain compounds of formula I wherein X, R 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 , Y and J are as defined above. Thus, for example, compounds of the first aspect having formula I can be obtained, wherein X is Example A (ie, O, S, SO, SO2, CH2, or SO(NH)); R 1 Example E (ie R 1 is hydrogen, chlorine, fluorine, methyl, trifluoromethyl or difluoromethyl); R 2 Example F (ie R 2 is hydrogen); R 3 Example F (ie R 3 is hydrogen); R 4 Example F (ie R 4 is hydrogen); R 5 Example E (ie R 5 is hydrogen, chlorine, fluorine, cyano, methyl, trifluoromethyl or difluoromethyl); R 6 Example F (ie R6 is hydrogen); R 7 Example F (ie R 7 is hydrogen); Y is embodiment C (ie, is hydrogen, methyl, ethyl, cyclopropylmethyl, benzyl, or methoxymethyl); and J is the first aspect, wherein R a is Example B (ie, selected from chloro, fluoro, cyano, and methoxy); R b is Example E (i.e., selected from fluorine, chlorine, cyano, methyl, ethyl, methoxy, NH2C(O), (methyl)N(H)C(O), NH2C(O)-methoxy, (methyl)SO2, benzyl, phenyl, phenoxy, Kba, Jbm, and Jbn (the phenyl group and the K ring may be independently substituted with 1-4 substituents independently selected from fluorine, chlorine, cyano, and methyl)); R c is Embodiment B (ie, selected from chloro, fluoro, cyano, methyl, and methoxy); and R d 、R e , and R f Each is Example A (i.e., selected from halogen, cyano, C1-C3-alkyl, C1-C3-alkoxy, NH2C(O), (C1-C3-alkyl)N(H)C(O), NH2C(O)-C1-C3-alkoxy, (C1-C3-alkyl)SO2, benzyl, phenyl, phenoxy, C5-C6-heteroaryl and C4-C 10 - heterocyclyl (the phenyl, phenoxy, heteroaryl and heterocyclyl may be substituted independently of each other by 1 to 4 substituents independently selected from halogen, cyano and C1-C3-alkyl)).
[0224] Thus, the present invention makes it possible to obtain compounds of formula II wherein X, R 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 , and T are as defined above. Thus, it is possible to obtain, for example, compounds of formula I wherein X is Example D (ie, O); R 1 Example E (ie R 1 is hydrogen, chlorine, fluorine, methyl, trifluoromethyl or difluoromethyl); R 2 Example F (ie R 2 is hydrogen); R 3 Example F (ie R 3 is hydrogen); R 4 Example F (ie R 4 is hydrogen); R 5 Example E (ie R 5is hydrogen, chlorine, fluorine, cyano, methyl, trifluoromethyl or difluoromethyl); R 6 Example F (ie R 6 is hydrogen); R 7 Example F (ie R 7 is hydrogen); and T is embodiment C (i.e., hydrogen, methyl, ethyl, isopropyl, propyl, allyl, propargyl, cyclopropylmethyl, benzyl, J a to J dl-methyl, or J a to J dl-ethyl, the methyl, ethyl, isopropyl, propyl, allyl, propargyl being independently substituted with 1 to 3 substituents independently selected from fluorine, chlorine, cyano, and methoxy, the cyclopropyl being substituted with 1 to 3 substituents independently selected from fluorine, chlorine, cyano, methyl, ethyl, and methoxy, and the benzyl and J a to J dl being independently substituted with 1 to 4 substituents independently selected from R g substituted by a substituent; wherein R g Example C (ie R g selected from fluoro, chloro, cyano, methyl, ethyl, and methoxy).
[0225] In an embodiment of each aspect of the present invention (except the second aspect), the compound of formula I has the following terms: X is O, or CH2; R 1 、R 2 、R 3 and R 4 R is independently selected from hydrogen, chlorine, fluorine, methyl, trifluoromethyl and difluoromethyl; 5 、R 6 , and R 7 are independently selected from hydrogen, chlorine, fluorine, cyano, methyl, trifluoromethyl and difluoromethyl; Y is hydrogen, methyl, ethyl, cyclopropylmethyl, benzyl, or methoxymethyl; and J is hydrogen, C1-C3-alkyl, C1-C3-alkoxy, aryl-C1-C2-alkoxy, C1-C3-alkyl-S(O)2, C3-C4-cycloalkyl-S(O)2, C3-C4-cycloalkyl-C1-C2-alkyl, C5-C 10 -heteroaryl, C4-C 10 -heterocyclic, aryl-C1-C2-alkyl, aryl, or C5-C 10-heteroaryl-C1-C2-alkyl, the C1-C3-alkyl may be substituted by 1 to 3 substituents independently selected from chlorine, fluorine, cyano, and methoxy, the C1-C3-alkoxy may be substituted by 1 to 3 substituents independently selected from chlorine, fluorine, cyano, methyl, and methoxy, the cycloalkyl may be substituted by 1 to 3 substituents independently selected from chlorine, fluorine, cyano, methyl, and methoxy, and the aryl, heteroaryl, and heterocyclyl may each be substituted by 1 to 4 substituents independently selected from Substitutents: halogen, cyano, C1-C3-alkyl, C1-C3-alkoxy, NH2C(O), (C1-C3-alkyl)N(H)C(O), NH2C(O)-C1-C3-alkoxy, (C1-C3-alkyl)SO2, benzyl, phenyl, phenoxy, C5-C6-heteroaryl, and C5-C6-heterocyclyl (the phenyl, phenoxy, heteroaryl or heterocyclyl may be substituted independently by 1-4 substituents independently selected from fluorine, chlorine, cyano, and methyl).
[0226] In an embodiment of each aspect of the present invention (except the second aspect), the compound of formula I has the following terms: X is O, or CH2; R 1 、R 2 、R 3 and R 4 Each is hydrogen; R 5 、R 6 , and R 7 Each is hydrogen; Y is hydrogen, methyl, ethyl, cyclopropylmethyl, benzyl, or methoxymethyl; and J is hydrogen, C1-C3-alkyl, C1-C3-alkoxy, aryl-C1-C2-alkoxy, C1-C3-alkyl-S(O)2, C3-C4-cycloalkyl-S(O)2, C3-C4-cycloalkyl-C1-C2-alkyl, C5-C 10 -heteroaryl, C4-C 10 -heterocyclic, aryl-C1-C2-alkyl, aryl, or C5-C 10-heteroaryl-C1-C2-alkyl, the C1-C3-alkyl may be substituted by 1 to 3 substituents independently selected from chlorine, fluorine, cyano, and methoxy, the C1-C3-alkoxy may be substituted by 1 to 3 substituents independently selected from chlorine, fluorine, cyano, methyl, and methoxy, the cycloalkyl may be substituted by 1 to 3 substituents independently selected from chlorine, fluorine, cyano, methyl, and methoxy, and the aryl, heteroaryl, and heterocyclyl may each be substituted by 1 to 4 substituents independently selected from Substitutents: halogen, cyano, C1-C3-alkyl, C1-C3-alkoxy, NH2C(O), (C1-C3-alkyl)N(H)C(O), NH2C(O)-C1-C3-alkoxy, (C1-C3-alkyl)SO2, benzyl, phenyl, phenoxy, C5-C6-heteroaryl, and C5-C6-heterocyclyl (the phenyl, phenoxy, heteroaryl or heterocyclyl may be substituted independently by 1-4 substituents independently selected from fluorine, chlorine, cyano, and methyl).
[0227] In an embodiment of each aspect of the present invention (except the second aspect), the compound of formula I has the following terms: X is O, or CH2; R 1 、R 2 、R 3 and R 4 Each is hydrogen; R 5 、R 6 , and R 7 Each is hydrogen; Y is hydrogen; and J is hydrogen, C1-C3-alkyl, C1-C3-alkoxy, aryl-C1-C2-alkoxy, C1-C3-alkyl-S(O)2, C3-C4-cycloalkyl-S(O)2, C3-C4-cycloalkyl-C1-C2-alkyl, C5-C 10 -heteroaryl, C4-C 10 -heterocyclic, aryl-C1-C2-alkyl, aryl, or C5-C 10-heteroaryl-C1-C2-alkyl, the C1-C3-alkyl may be substituted by 1 to 3 substituents independently selected from chlorine, fluorine, cyano, and methoxy, the C1-C3-alkoxy may be substituted by 1 to 3 substituents independently selected from chlorine, fluorine, cyano, methyl, and methoxy, the cycloalkyl may be substituted by 1 to 3 substituents independently selected from chlorine, fluorine, cyano, methyl, and methoxy, and the aryl, heteroaryl, and heterocyclyl may each be substituted by 1 to 4 substituents independently selected from Substitutents: halogen, cyano, C1-C3-alkyl, C1-C3-alkoxy, NH2C(O), (C1-C3-alkyl)N(H)C(O), NH2C(O)-C1-C3-alkoxy, (C1-C3-alkyl)SO2, benzyl, phenyl, phenoxy, C5-C6-heteroaryl, and C5-C6-heterocyclyl (the phenyl, phenoxy, heteroaryl or heterocyclyl may be substituted independently by 1-4 substituents independently selected from fluorine, chlorine, cyano, and methyl).
[0228] In an embodiment of each aspect of the present invention (except the second aspect), the compound of formula I has the following terms: X is O, or CH2; R 1 、R 2 、R 3 and R 4 Each is hydrogen; R 5 、R 6 , and R 7 each is hydrogen; Y is hydrogen; and J is hydrogen, methyl, ethoxy, benzyloxy, cyclopropyl-S(O)2, cyclopropylmethyl, Jh, Jz, Jaa, Jag, Jas, Jat, Jaw, Jax, Jay, Jaz, Jba, Jbc, Jbd, Jbe, Jbj, Jbk, Jbl, Jbm, Jcj, Jck, Jcl, Jcy, Jdk, Jdl, Kaz, Kbb, Kbc, Kbd, phenyl, benzyl, Jaa-methyl, Jaf-ethyl, or Jaw-methyl, the phenyl, benzyl, benzyloxy, J ring and K ring may be substituted independently by 1 to 4 substituents independently selected from the following: fluorine, chlorine, cyano, methyl, ethyl, methoxy, NH2C(O), (methyl)N(H)C(O), NH2C(O)-methoxy, (methyl)SO2, benzyl, phenyl, phenoxy, Kba, Jbm, and Jbn (the phenyl, J and K rings may be substituted independently by 1-4 substituents independently selected from fluorine, chlorine, cyano, and methyl).
[0229] In embodiments of each aspect of the invention (except the second aspect), the compound of formula I is represented by formula Ia (when X is CH2) or formula Iaa (when X is O), and in each case has the following terms: R 1 、R 2 、R3 and R 4 Each is hydrogen; R 5 、R 6 , and R 7 each is hydrogen; Y is hydrogen; and J is hydrogen, methyl, ethoxy, benzyloxy, cyclopropyl-S(O)2, cyclopropylmethyl, Jh, Jz, Jaa, Jag, Jas, Jat, Jaw, Jax, Jay, Jaz, Jba, Jbc, Jbd, Jbe, Jbj, Jbk, Jbl, Jbm, Jcj, Jck, Jcl, Jcy, Jdk, Jdl, Kaz, Kbb, Kbc, Kbd, phenyl, benzyl, Jaa-methyl, Jaf-ethyl, or Jaw-methyl, the phenyl, benzyl, benzyloxy, J ring and K ring may be substituted independently by 1 to 4 substituents independently selected from the following: fluorine, chlorine, cyano, methyl, ethyl, methoxy, NH2C(O), (methyl)N(H)C(O), NH2C(O)-methoxy, (methyl)SO2, benzyl, phenyl, phenoxy, Kba, Jbm, and Jbn (the phenyl, J and K rings may be substituted independently by 1-4 substituents independently selected from fluorine, chlorine, cyano, and methyl).
[0230] In embodiments of each aspect of the invention (except the second aspect), the compound of formula I is represented by formula Ia (when X is CH2) or formula Iaa (when X is O), and in each case has the following terms: R 1 、R 2 、R 3 and R 4 Each is hydrogen; R 5 、R 6 , and R 7 Each is hydrogen; Y is hydrogen; and J is hydrogen, Ja or Jbj, these J rings can be substituted independently by 1 to 4 substituents independently selected from the following: fluorine, chlorine, cyano, methyl, ethyl, methoxy, NH2C(O), (methyl)N(H)C(O), NH2C(O)-methoxy, (methyl)SO2, benzyl, phenyl, phenoxy, Kba, Jbm, and Jbn (the phenyl, J and K rings can be substituted independently by 1-4 substituents independently selected from fluorine, chlorine, cyano, and methyl).
[0231] In embodiments of each aspect of the invention (except the second aspect), the compound of formula I is represented by formula Ia (when X is CH2) or formula Iaa (when X is O), and in each case has the following terms: R 1 、R 2 、R 3 and R 4 Each is hydrogen; R 5 、R 6 , and R7 Each is hydrogen; Y is hydrogen; and J is hydrogen, Ja or Jbj, these J rings may be substituted independently of each other by 1 to 4 substituents independently selected from the group consisting of methyl, NH2C(O), (methyl)N(H)C(O), and phenyl.
[0232] In an embodiment of the second aspect of the invention, the compound of formula I has the following terms: X is O; R 1 、R 2 、R 3 and R 4 R is independently selected from hydrogen, chlorine, fluorine, methyl, trifluoromethyl and difluoromethyl; 5 、R 6 , and R 7 are independently selected from hydrogen, chlorine, fluorine, cyano, methyl, trifluoromethyl and difluoromethyl; Y is hydrogen, methyl, ethyl, cyclopropylmethyl, benzyl, or methoxymethyl; and J is hydrogen, C1-C3-alkyl, C1-C3-alkoxy, aryl-C1-C2-alkoxy, C1-C3-alkyl-S(O)2, C3-C4-cycloalkyl-S(O)2, C3-C4-cycloalkyl-C1-C2-alkyl, C5-C 10 -heteroaryl, C4-C 10 -heterocyclic, aryl-C1-C2-alkyl, aryl, or C5-C 10 -heteroaryl-C1-C2-alkyl, the C1-C3-alkyl may be substituted by 1 to 3 substituents independently selected from chlorine, fluorine, cyano, and methoxy, the C1-C3-alkoxy may be substituted by 1 to 3 substituents independently selected from chlorine, fluorine, cyano, methyl, and methoxy, the cycloalkyl may be substituted by 1 to 3 substituents independently selected from chlorine, fluorine, cyano, methyl, and methoxy, and the aryl, heteroaryl, and heterocyclyl may each be substituted by 1 to 4 substituents independently selected from Substitutents: halogen, cyano, C1-C3-alkyl, C1-C3-alkoxy, NH2C(O), (C1-C3-alkyl)N(H)C(O), NH2C(O)-C1-C3-alkoxy, (C1-C3-alkyl)SO2, benzyl, phenyl, phenoxy, C5-C6-heteroaryl, and C5-C6-heterocyclyl (the phenyl, phenoxy, heteroaryl or heterocyclyl may be substituted independently by 1-4 substituents independently selected from fluorine, chlorine, cyano, and methyl).
[0233] In an embodiment of the second aspect of the invention, the compound of formula I has the following terms: X is O; R 1 、R 2 、R 3 and R 4 Each is hydrogen; R 5 、R 6 , and R 7Each is hydrogen; Y is hydrogen, methyl, ethyl, cyclopropylmethyl, benzyl, or methoxymethyl; and J is hydrogen, C1-C3-alkyl, C1-C3-alkoxy, aryl-C1-C2-alkoxy, C1-C3-alkyl-S(O)2, C3-C4-cycloalkyl-S(O)2, C3-C4-cycloalkyl-C1-C2-alkyl, C5-C 10 -heteroaryl, C4-C 10 -heterocyclic, aryl-C1-C2-alkyl, aryl, or C5-C 10 -heteroaryl-C1-C2-alkyl, the C1-C3-alkyl may be substituted by 1 to 3 substituents independently selected from chlorine, fluorine, cyano, and methoxy, the C1-C3-alkoxy may be substituted by 1 to 3 substituents independently selected from chlorine, fluorine, cyano, methyl, and methoxy, the cycloalkyl may be substituted by 1 to 3 substituents independently selected from chlorine, fluorine, cyano, methyl, and methoxy, and the aryl, heteroaryl, and heterocyclyl may each be substituted by 1 to 4 substituents independently selected from Substitutents: halogen, cyano, C1-C3-alkyl, C1-C3-alkoxy, NH2C(O), (C1-C3-alkyl)N(H)C(O), NH2C(O)-C1-C3-alkoxy, (C1-C3-alkyl)SO2, benzyl, phenyl, phenoxy, C5-C6-heteroaryl, and C5-C6-heterocyclyl (the phenyl, phenoxy, heteroaryl or heterocyclyl may be substituted independently by 1-4 substituents independently selected from fluorine, chlorine, cyano, and methyl).
[0234] In an embodiment of the second aspect of the invention, the compound of formula I has the following terms: X is O; R 1 、R 2 、R 3 and R 4 Each is hydrogen; R 5 、R 6 , and R 7 Each is hydrogen; Y is hydrogen; and J is hydrogen, C1-C3-alkyl, C1-C3-alkoxy, aryl-C1-C2-alkoxy, C1-C3-alkyl-S(O)2, C3-C4-cycloalkyl-S(O)2, C3-C4-cycloalkyl-methyl, C5-C 10 -heteroaryl, C4-C 10 -heterocyclic, aryl-C1-C2-alkyl, aryl, or C5-C 10-heteroaryl-C1-C2-alkyl, the C1-C3-alkyl may be substituted by 1 to 3 substituents independently selected from chlorine, fluorine, cyano, and methoxy, the C1-C3-alkoxy may be substituted by 1 to 3 substituents independently selected from chlorine, fluorine, cyano, methyl, and methoxy, the cycloalkyl may be substituted by 1 to 3 substituents independently selected from chlorine, fluorine, cyano, methyl, and methoxy, and the aryl, heteroaryl, and heterocyclyl may each be substituted by 1 to 4 substituents independently selected from Substitutents: halogen, cyano, C1-C3-alkyl, C1-C3-alkoxy, NH2C(O), (C1-C3-alkyl)N(H)C(O), NH2C(O)-C1-C3-alkoxy, (C1-C3-alkyl)SO2, benzyl, phenyl, phenoxy, C5-C6-heteroaryl, and C5-C6-heterocyclyl (the phenyl, phenoxy, heteroaryl or heterocyclyl may be substituted independently by 1-4 substituents independently selected from fluorine, chlorine, cyano, and methyl).
[0235] In an embodiment of the second aspect of the invention, the compound of formula II has the following terms, X is O; R 1 、R 2 、R 3 and R 4 Each is hydrogen; R 5 、R 6 , and R 7 each is hydrogen; Y is hydrogen; and J is hydrogen, methyl, ethoxy, benzyloxy, cyclopropyl-S(O)2, cyclopropylmethyl, Jh, Jz, Jaa, Jag, Jas, Jat, Jaw, Jax, Jay, Jaz, Jba, Jbc, Jbd, Jbe, Jbj, Jbk, Jbl, Jbm, Jcj, Jck, Jcl, Jcy, Jdk, Jdl, Kaz, Kbb, Kbc, Kbd, phenyl, benzyl, Jaa-methyl, Jaf-ethyl, or Jaw-methyl, the phenyl, benzyl, benzyloxy, J ring and K ring may be substituted independently by 1 to 4 substituents independently selected from the following: fluorine, chlorine, cyano, methyl, ethyl, methoxy, NH2C(O), (methyl)N(H)C(O), NH2C(O)-methoxy, (methyl)SO2, benzyl, phenyl, phenoxy, Kba, Jbm, and Jbn (the phenyl, J and K rings may be substituted independently by 1-4 substituents independently selected from fluorine, chlorine, cyano, and methyl).
[0236] In an embodiment of the second aspect of the invention, the compound of formula II is represented by formula Iaa and has the following terms, R 1 、R 2 、R 3 and R 4 Each is hydrogen; R 5 、R6 , and R 7 each is hydrogen; Y is hydrogen; and J is hydrogen, methyl, ethoxy, benzyloxy, cyclopropyl-S(O)2, cyclopropylmethyl, Jh, Jz, Jaa, Jag, Jas, Jat, Jaw, Jax, Jay, Jaz, Jba, Jbc, Jbd, Jbe, Jbj, Jbk, Jbl, Jbm, Jcj, Jck, Jcl, Jcy, Jdk, Jdl, Kaz, Kbb, Kbc, Kbd, phenyl, benzyl, Jaa-methyl, Jaf-ethyl, or Jaw-methyl, the phenyl, benzyl, benzyloxy, J ring and K ring may be substituted independently by 1 to 4 substituents independently selected from the following: fluorine, chlorine, cyano, methyl, ethyl, methoxy, NH2C(O), (methyl)N(H)C(O), NH2C(O)-methoxy, (methyl)SO2, benzyl, phenyl, phenoxy, Kba, Jbm, and Jbn (the phenyl, J and K rings may be substituted independently by 1-4 substituents independently selected from fluorine, chlorine, cyano, and methyl).
[0237] In an embodiment of the second aspect of the invention, the compound of formula II is represented by formula Iaa and has the following terms, R 1 、R 2 、R 3 and R 4 Each is hydrogen; R 5 、R 6 , and R 7 Each is hydrogen; Y is hydrogen; and J is hydrogen, Ja or Jbj, these J rings can be substituted independently by 1 to 4 substituents independently selected from the following: fluorine, chlorine, cyano, methyl, ethyl, methoxy, NH2C(O), (methyl)N(H)C(O), NH2C(O)-methoxy, (methyl)SO2, benzyl, phenyl, phenoxy, Kba, Jbm, and Jbn (the phenyl, J and K rings can be substituted independently by 1-4 substituents independently selected from fluorine, chlorine, cyano, and methyl).
[0238] In an embodiment of the second aspect of the invention, the compound of formula II is represented by formula Iaa and has the following terms, R 1 、R 2 、R 3 and R 4 Each is hydrogen; R 5 、R 6 , and R 7 Each is hydrogen; Y is hydrogen; and J is hydrogen, Ja or Jbj, these J rings may be substituted independently of each other by 1 to 4 substituents independently selected from the group consisting of methyl, NH2C(O), (methyl)N(H)C(O), and phenyl.
[0239] In an embodiment of each aspect of the present invention, the compound of formula II has the following terms, X is O, or CH2; R 1 、R 2 、R 3 and R 4 R is independently selected from hydrogen, chlorine, fluorine, methyl, trifluoromethyl and difluoromethyl; 5 、R 6 , and R 7 are independently selected from hydrogen, chlorine, fluorine, cyano, methyl, trifluoromethyl and difluoromethyl; and T is hydrogen, methyl, ethyl, isopropyl, propyl, cyclopropylmethyl, benzyl, J a to J dl-methyl, or J a to J dl-ethyl, the methyl, ethyl, isopropyl, propyl, cyclopropylmethyl may be substituted with 1 to 3 substituents independently selected from fluorine, chlorine, cyano, methyl, ethyl, and methoxy, and the benzyl, and J a to J dl may each be independently substituted with 1 to 4 substituents independently selected from fluorine, chlorine, cyano, methyl, ethyl, and methoxy; provided that, when X in Formula II is CH2, T is not hydrogen, C1-C4-alkyl, 2-fluoroethyl, 2-methyl-4-pyrimidinyl)methyl, 2-(methylsulfonyl)phenyl]methyl, 2,6-di(tert-butyl)-4-methylphenyl, 1,4-dihydro-6-methyl-4-oxo-3-pyridazinyl)methyl, 1,3-dihydro-1,3-dioxo-2H-isoindol-2-yl, or tetrahydro-4,4-dimethyl-2-oxo-3-furanyl; or when X in Formula II is O, T is not hydrogen or C1-C2-alkyl.
[0240] In an embodiment of each aspect of the present invention, the compound of formula II has the following terms, X is O, or CH2; R 1 、R 2 、R 3 and R 4 R is independently selected from hydrogen, chlorine, fluorine, methyl, trifluoromethyl and difluoromethyl; 5 、R 6 , and R 7are independently selected from hydrogen, chlorine, fluorine, cyano, methyl, trifluoromethyl and difluoromethyl; and T is hydrogen, methyl, ethyl, isopropyl, propyl, cyclopropylmethyl, benzyl, Jaa-methyl, Jaf-ethyl, or Jaw-methyl, the methyl, ethyl, isopropyl, propyl, cyclopropylmethyl being substituted by 1 to 3 substituents independently selected from fluorine, chlorine, cyano, methyl, ethyl, and methoxy, and the benzyl and J ring being substituted by 1 to 4 substituents independently selected from fluorine, chlorine, cyano, methyl, ethyl, and methoxy; with the condition is, when X in formula II is CH2, T is not hydrogen, C1-C4-alkyl, 2-fluoroethyl, 2-methyl-4-pyrimidinyl)methyl, 2-(methylsulfonyl)phenyl]methyl, 2,6-di(tert-butyl)-4-methylphenyl, 1,4-dihydro-6-methyl-4-oxo-3-pyridazinyl)methyl, 1,3-dihydro-1,3-dioxo-2H-isoindol-2-yl, or tetrahydro-4,4-dimethyl-2-oxo-3-furanyl; or when X in formula II is O, T is not hydrogen or C1-C2-alkyl.
[0241] In a third aspect, the present invention makes available a composition comprising a compound of formula I or II as defined in the first aspect, one or more adjuvants and diluents, and optionally one or more other active ingredients. In an embodiment, the composition is a pesticide composition.
[0242] In a fourth aspect, the present invention makes available a method for protecting plant propagation material from attack by insects, mites, nematodes or molluscs, which method comprises treating the propagation material or the site in which the propagation material is planted with an effective amount of a compound of formula I or II as defined in the first aspect or a composition as defined in the third aspect.
[0243] 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 or II as defined in the first aspect or a composition as defined in the third aspect, or is treated with the compound or the composition, or has the compound or the composition attached thereto.
[0244] In embodiments of each aspect of the invention, the compound having formula I is represented by formula Ia or Ib (when X is CH2, S, SO, SO2, or SO(NH)); or by formula Iaa or Icc (when X is O).
[0245] In embodiments of each aspect of the invention, the compound of formula II is represented by formula IIa or IIb (when X is CH2, S, SO, SO2, or SO(NH)); or by formula IIaa or IIcc (when X is O).
[0246] In embodiments of each aspect of the invention, the compound having formula I is represented by formula Ia (when X is CH2, S, SO, SO2, or SO(NH)); or by formula Iaa (when X is O).
[0247] In an embodiment of each aspect of the invention, the compound having formula II is represented by formula IIa (when X is CH2, S, SO, SO2, or SO(NH)); or by formula IIaa (when X is O).
[0248] 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 as defined in the first aspect. The present invention further provides a method for controlling external parasites in an animal in need thereof, the method comprising administering an effective amount of a compound having Formula I or Formula II as defined in the first aspect. The present invention further provides a method for preventing and / or treating a disease transmitted by external parasites, the method comprising administering an effective amount of a compound having Formula I or Formula II as defined in the first aspect to an animal in need thereof.
[0249] Compounds of formula I and II can be prepared by those skilled in the art according to known methods. More specifically, compounds of formula I and II and intermediates thereof can be prepared as described below in the schemes and examples.
[0250] The process according to the invention for preparing compounds of formula I or formula II is carried out by methods known to those skilled in the art.
[0251] Compounds of formula I can be prepared, for example, as shown in Scheme 1.
[0252] Option 1:
[0253]
[0254] The reaction of a compound of formula IIa' with a compound of formula III gives a compound of formula I, wherein R 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7, J and Y are as defined above for compounds with formula I. Useful coupling reagents include, for example, dicyclohexylcarbodiimide, 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide (EDC) and carbonyldiimidazole. Other coupling reagents useful in this method include O-(7-azabenzotriazole-1-yl)-N, N, N', N'-tetramethyluronium hexafluorophosphate (HATU), 1-propanephosphonic anhydride (T3P), O-(7-azabenzotriazole-1-yl)-N, N, N', N'-tetramethyluronium tetrafluoroborate (TATU) and 2-(1H-benzotriazole-1-yl)-1,1,3,3-tetramethyluronium hexafluorophosphate (HBTU). These coupling reagents are usually used in the presence of a base such as triethylamine, pyridine, 4-(dimethylamino)pyridine or N, N-diisopropylethylamine. Typical reaction conditions include an anhydrous aprotic solvent such as ethyl acetate, dichloromethane, tetrahydrofuran or N,N-dimethylformamide, and a reaction temperature between room temperature and 80° C. For reaction conditions useful in the method of Scheme 1 and other well-known coupling conditions, see, for example, Bioorg. Med. Chem. 2015, 23(3), 564; J. Org. Chem. 2008, 73(7), 2731; Tetrahedron Lett. 2009, 50(45), 6200; and Org. Lett. 2011, 13(12), 2988. Compounds of formula III are known, or they can be prepared by methods known to those skilled in the art.
[0255] Additionally, compounds of formula I can be prepared, for example, as shown in Scheme 2.
[0256] Option 2:
[0257]
[0258] The reaction of a compound of formula IV with a compound of formula III gives a compound of formula I, wherein R 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7, J and Y are as defined above for compounds of formula I. Typical reaction conditions include an organic solvent such as ethyl acetate, dichloromethane, tetrahydrofuran or N,N-dimethylformamide, a reaction temperature between room temperature and 80°C, and the presence of an acid scavenger such as triethylamine, pyridine, 4-(dimethylamino)pyridine or N,N-diisopropylethylamine. Other scavengers include hydroxides such as sodium hydroxide and potassium hydroxide, or carbonates such as sodium carbonate and potassium carbonate. Compounds of formula III are known, or they can be prepared by methods known to those skilled in the art.
[0259] Compounds of formula IV can be prepared, for example, as shown in Scheme 3.
[0260] Option 3:
[0261]
[0262] Treatment of a compound of formula IIa with a chlorinating agent such as thionyl chloride, oxalyl chloride or phosphorus oxychloride in a solvent such as dichloromethane or toluene and optionally in the presence of a catalytic amount of N,N-dimethylformamide can provide the corresponding acid chloride of formula IV, wherein R 1 、R 2 、R 3 、R 4 、R 5 、R 6 , and R 7 is as defined above for the compound of formula I.
[0263] Compounds of formula IIa' can be prepared, for example, as shown in Scheme 4.
[0264] Option 4:
[0265]
[0266] Basic or acidic hydrolysis of compounds of formula II gives compounds of formula IIa, wherein R 1 、R 2 、R 3 、R 4 、R 5 、R 6 , and R 7is as defined above for compounds of formula II, and T is C1-C3-alkyl (e.g. methyl or ethyl), the hydrolysis reaction is preferably carried out using a slight excess of a hydroxide base (e.g. lithium hydroxide, sodium hydroxide, or potassium hydroxide) in a water-miscible solvent (e.g. methanol, ethanol, tetrahydrofuran or 1,4-dioxane) with or without water at a temperature between 0° C. and 80° C. The product can be isolated by adjusting the pH to about 1 to 3 and then filtering or extracting, optionally after removing the organic solvent by evaporation.
[0267] Compounds of formula II can be prepared, for example, as shown in Scheme 5.
[0268] Option 5:
[0269]
[0270] Treatment of a compound of formula V with a compound of formula VI in the presence of a transition metal catalyst such as Rh2OAc4 (i.e., rhodium(II) acetate dimer), Rh2oct4 (i.e., rhodium(II) octanoate dimer), Rh2esp2 (i.e., bis[rhodium(α,α,α',α'-tetramethyl-1,3-benzenedipropionic acid)]) or copper(II) sulfate gives a compound of formula II, wherein R 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 and T are as defined above for compounds with formula II. The reaction can be carried out with or without a solvent. More typically, the reaction is carried out in a liquid phase with a solvent (such as dichloromethane, hexane or toluene) and at a reaction temperature between -78°C and 110°C. The general procedure for making diazo ester cyclopropanation with olefins is described in detail in the chemical literature, for example, WO 1998 / 057968. Compounds with formulas V and VI are known, or they can be prepared by methods known to those skilled in the art.
[0271] Option 6:
[0272]
[0273] A compound of formula V (wherein R 1 、R 2 、R 3 、R 4 、R 5 , and R 6Each of the above is hydrogen, and X is S) can be prepared, for example, as shown in Scheme 6. This type of reaction is typically carried out using Ac2O in the presence of an acid catalyst such as p-toluenesulfonic acid or trifluoromethyl-acetic acid in a solvent such as dichloromethane, hexane, or toluene and at a reaction temperature between -78°C and 110°C. The general procedure for the Pummerer reaction is well documented in the chemical literature, see, for example, The Pummerer Reaction of Sulfinyl Compounds https: / / doi.org / 10.1002 / 0471264180.or040.03. Compounds of formula VII are known, or they can be prepared by methods known to those skilled in the art.
[0274] Option 7:
[0275]
[0276] The reaction of a compound of formula VIII with a compound of formula IX gives a compound of formula I, wherein R 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 , J and Y are as defined above for the compound having formula I, and Lg is a leaving group such as a halide (e.g., Cl, Br, I) or a sulfonate (e.g., mesylate, triflate, p-toluenesulfonate), or the like. Reactions of this type are typically carried out using a palladium catalyst such as palladium(II) acetate with a phosphine ligand such as t-BuBrettPhos (i.e., 2-(di-tert-butylphosphino)-2',4',6'-triisopropyl-3,6-dimethoxy-1,1'-biphenyl), or a copper catalyst such as copper(I) iodide with a diamine ligand such as trans-N,N'-dimethylcyclohexane-1,2-diamine. These reactions traditionally require the presence of a base such as potassium carbonate or potassium phosphate in an organic solvent such as tert-butanol, toluene, or dioxane and a reaction temperature between 80° C. and 110° C. (see, for example, Tetrahedron 2009, 65, 6576). Compounds of formula IX are known or they can be prepared by methods known to those skilled in the art.
[0277] Option 8:
[0278]
[0279] Alternatively, compounds of formula I can be prepared, for example as shown in Scheme 8, in the presence of a base such as sodium hydride or in the presence of a dilute acid such as hydrochloric acid, wherein R 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 , J and Y are as defined above for compounds of formula I, and Lg is a leaving group such as a halide (e.g., Cl, Br, I). This type of reaction is typically carried out in a solvent such as dimethyl sulfoxide, N,N-dimethylformamide, or tert-butanol at a temperature ranging from about room temperature to the reflux temperature of the reaction mixture.
[0280] Option 9:
[0281]
[0282] Ammonia can replace the compound of formula III in the reactions of Schemes 1 and 2 to produce a compound of formula Ia' wherein J and Y are H and R 1 、R 2 、R 3 、R 4 、R 5 、R 6 , and R 7 is as defined above for compounds of formula I. Acid chlorides of formula IV can also be generated in situ from compounds of formula II with thionyl chloride, optionally in the presence of a base (such as triethylamine or N,N-diisopropylethylamine) before adding ammonia. For reaction conditions useful in the method of Scheme 8, see, for example, J. Am. Chem. Soc. 2015, 137, 2042.
[0283] Option 10:
[0284]
[0285] Compounds of formula I can be prepared by rhodium-catalyzed oxidative amidation of alcohols of formula X with amines of formula III, wherein R 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7, J and Y are as defined above for the compound of formula I. This reaction is typically carried out in the presence of a catalyst such as Rh(COD)2BF4 (i.e., bis(1,5-cyclooctadiene)rhodium(I) tetrafluoroborate), a ligand such as 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene (i.e., Xantphos) or 1,4-bis(diphenyl-phosphino)butane (i.e., DPPB)), a hydrogen acceptor such as trifluoroacetophenone, and a base such as cesium acetate or cesium carbonate. The reaction can be carried out in an aprotic solvent such as tetrahydrofuran or dioxane at a temperature ranging from 0°C to 100°C (see, for example, ACS Catalysis [ACS Catalysis] 2016, 6, 8214). Alternatively, Compounds of formula I can be prepared by coupling an alcohol of formula X with an amine of formula III in the presence of a catalyst such as RuHClCO(AsPh3)3 (i.e., carbonyl chloride tris(triphenylarsine)ruthenium(II)) with a suitable thiocarboxamide ligand such as 2-pyridinethiocarboxamide. The reaction is typically carried out under aerobic conditions in an organic solvent such as ethanol at a temperature ranging from about room temperature to the reflux temperature of the solvent (see, e.g., Organometallics [Organometallics] 2014, 33, 4269). Alternatively, compounds of formula I can also be prepared by rhodium-catalyzed oxidative amidation of an aldehyde of formula XI with an amine of formula III.
[0286] Option 11:
[0287]
[0288] Alcohols of formula X and aldehydes of formula XI can be prepared from esters of formula II according to general methods known to those skilled in the art, wherein R 1 、R 2 、R 3 、R 4 、R 5 、R 6 , and R 7 is as defined above for compounds of formula I and wherein T is an alkyl group (e.g., methyl or ethyl). In one example, a suitable amount of a reducing agent (such as diisobutylaluminum hydride) in an aprotic solvent (such as dichloromethane or tetrahydrofuran) at a suitable temperature results in the conversion of compounds of formula V to compounds of formula X and XI.
[0289] Schemes 1 to 11 illustrate methods for preparing compounds of Formula I and II having various substituents. Compounds of Formula I and II having substituents other than those specifically noted for Schemes 1 to 11 can be prepared by general methods known in the art of synthetic organic chemistry, including methods analogous to those described for Schemes 1 to 11.
[0290] Those skilled in the art will recognize that various functional groups can be converted into other functional groups to provide different compounds with formula I and II.For example, there is a compound of formula I or an intermediate for its preparation can contain an aromatic nitro group, which can be reduced to an amino group, and then converted into various halides via reactions well known in the art (for example, Sandmeyer reaction). By similar known reactions, aromatic amines (aniline) can be converted into phenols via diazonium salts, and then these phenols can be alkylated to prepare compounds with formula I with alkoxy substituents. Similarly, aromatic halides (such as bromides or iodides) prepared via Sandmeyer reaction can react with alcohols (such as Ullmann reaction or its known improvements) under copper catalysis conditions to provide compounds with formula I containing alkoxy substituents. In addition, some halogen groups (such as fluorine or chlorine) can be substituted with alcohols under alkaline conditions to provide compounds with formula I containing corresponding alkoxy substituents. Compounds of formula I or precursors thereof containing a halide, preferably a bromide or iodide, are particularly useful intermediates for transition metal-catalyzed cross-coupling reactions to prepare compounds of formula I. These types of reactions are well documented in the literature; see, for example, Tsuji in Transition Metal Reagents and Catalysts: Innovations in Organic Synthesis, John Wiley and Sons, Chichester, 2002; Tsuji in Palladium in Organic Synthesis, Springer, 2005; and Miyaura and Buchwald in Cross Coupling Reactions: A Practical Guide, 2002; and references cited therein.
[0291] It should be recognized that some reagents and reaction conditions for preparing the compound with formula I or II may be incompatible with some functional groups present in the intermediate. In these cases, protection / deprotection sequence or functional group mutual conversion and incorporation into the synthesis will help to obtain the desired product. The use and selection of protecting groups will be clear to the technicians of chemical synthesis (see, for example, Greene, TW; Wuts, PGM Protective Groups in Organic Synthesis [protective groups in organic synthesis], 2nd edition; Wiley Press: New York, 1991). Those skilled in the art will recognize that, in some cases, after introducing the reagents described in the separate scheme, additional conventional synthesis steps not described in detail may be required to complete the synthesis of the compound with formula I or II. Those skilled in the art will also recognize that it may be necessary to carry out the combination of the steps described in the above scheme in an order different from the specific sequence presented by the compound with formula I or II.
[0292] Those skilled in the art will also recognize that the compounds of Formula I or II and intermediates described herein can be subjected to a variety of electrophilic, nucleophilic, free radical, organometallic, oxidation, and reduction reactions to add substituents or modify existing substituents.
[0293] Without further elaboration, it is believed that one skilled in the art can, using the preceding description, utilize the present invention to its fullest extent.
[0294] Depending on the procedure or reaction conditions, the reactants may be reacted in the presence of a base. Examples of suitable bases are alkali metal or alkaline earth metal hydroxides, alkali metal or alkaline earth metal hydrides, alkali metal or alkaline earth metal amides, alkali metal or alkaline earth metal alkoxides, alkali metal or alkaline earth metal acetates, alkali metal or alkaline earth metal carbonates, alkali metal or alkaline earth metal dialkylamides or alkali metal or alkaline earth metal alkylsilylamides, alkylamines, alkylenediamines, free or N-alkylated saturated or unsaturated cycloalkylamines, basic heterocycles, ammonium hydroxide and carbocyclic amines. Examples that may be mentioned are sodium hydroxide, sodium hydride, sodium amide, sodium methoxide, sodium acetate, sodium carbonate, potassium tert-butoxide, potassium hydroxide, potassium carbonate, potassium hydride, lithium diisopropylamide, potassium bis(trimethylsilyl)amide, calcium hydride, triethylamine, diisopropylethylamine, triethylenediamine, cyclohexylamine, N-cyclohexyl-N,N-dimethylamine, N,N-diethylaniline, pyridine, 4-(N,N-dimethylamino)pyridine, quinuclidine, N-methylmorpholine, benzyltrimethylammonium hydroxide and 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU).
[0295] These reactants can react with each other as is, i.e. without adding solvent or diluent. However, in most cases, it is advantageous to add an inert solvent or diluent or a mixture of these. If the reaction is carried out in the presence of a base, the base (such as triethylamine, pyridine, N-methylmorpholine or N,N-diethylaniline) used in excess can also serve as a solvent or diluent.
[0296] These reactions are advantageously carried out in a temperature range of from about -80°C to about +140°C, preferably from about -30°C to about +100°C, in many cases in a range between ambient temperature and about +80°C.
[0297] Depending on the reaction conditions and the choice of starting materials, which are appropriate in the respective case, it is possible, for example, to replace only one substituent with another substituent according to the invention in one reaction step, or to replace several substituents with other substituents according to the invention in one and the same reaction step.
[0298] The salts of the compounds of formula I and II can be prepared in a manner known per se. Thus, for example, acid addition salts of the compounds of formula I and II are obtained by treatment with a suitable acid or a suitable ion exchanger reagent, and salts with bases are obtained by treatment with a suitable base or with a suitable ion exchanger reagent.
[0299] Salts of compounds of the formula I and II can be converted in a customary manner into the free compounds I and II, respectively, or into acid addition salts (for example by treatment with suitable basic compounds or with suitable ion exchange reagents) and into salts with bases (for example by treatment with suitable acids or with suitable ion exchange reagents).
[0300] The salts of the compounds of the formulae I and II can be converted in a manner known per se into other salts of the compounds of the formulae I and II, respectively, and into acid addition salts, for example into other acid addition salts, for example by treating salts of inorganic acids (such as hydrochloric acid) with suitable metal salts of the acid (such as sodium, barium or silver salts, for example with silver acetate) in a suitable solvent in which the inorganic salt formed (such as silver chloride) is insoluble and therefore precipitates from the reaction mixture.
[0301] Depending on the procedure or reaction conditions, compounds of the formulae I and II having salt-forming properties can be obtained in free form or in salt form.
[0302] Depending on the number of asymmetric carbon atoms present in the molecule, the absolute and relative configuration and / or on the configuration of non-aromatic double bonds present in the molecule, the compounds of the formulae I and II and, where appropriate, their tautomers (in each case in free form or in salt form) can be present in the form of one of the possible isomers or as a mixture of these, for example in the form of pure isomers, such as enantiomers and / or diastereomers, or as isomer mixtures, such as enantiomeric mixtures, for example racemates, diastereomeric mixtures or racemic mixtures; the present invention relates to the pure isomers and also to all possible isomer mixtures, and the above and below are to be understood as such in each case, even if stereochemical details are not explicitly mentioned in each case.
[0303] Diastereomeric mixtures or racemic mixtures of compounds of formula I or II in free form or in salt form, which may be obtained depending on the starting materials and procedures chosen, can be separated in a known manner into the pure diastereomers or racemates on the basis of the physicochemical differences of the components, for example by fractional crystallization, distillation and / or chromatography.
[0304] Enantiomeric mixtures obtainable in an analogous manner (e.g. racemates) can be resolved into the optical antipodes by known methods, for example by recrystallization from optically active solvents; by chromatography on chiral adsorbents, for example high performance liquid chromatography (HPLC) on acetylcellulose; by cleavage with specific immobilized enzymes with the aid of suitable microorganisms; by formation of inclusion compounds, for example using chiral crown ethers, in which only one enantiomer is complexed; or by conversion into diastereomeric salts, for example by reacting the basic end product racemate with an optically active acid (e.g. a carboxylic acid, for example camphoric acid, tartaric acid or malic acid, or a sulfonic acid, for example camphorsulfonic acid) and separating the diastereomeric mixtures obtainable in this way, for example by fractional crystallization on the basis of their different solubilities, thereby obtaining the diastereomers from which the desired enantiomer can be freed by the action of suitable reagents (e.g. a basic reagent).
[0305] Pure diastereomers or enantiomers can be obtained according to the invention not only by separation of the appropriate isomer mixtures, but also by generally known methods of diastereoselective or enantioselective synthesis, for example by carrying out the method according to the invention with starting materials having the appropriate stereochemistry.
[0306] N-oxides can be prepared by reacting a compound of formula I or II with a suitable oxidizing agent (e.g. H O / urea adduct) in the presence of an anhydride (e.g. trifluoroacetic anhydride). Such oxidations are known from the literature, for example from J. Med. Chem., 32 (12), 2561-73, 1989 or WO 2000 / 15615.
[0307] If the individual components have different biological activities, it is advantageous to isolate or synthesize the biologically more effective isomers, such as enantiomers or diastereomers or isomer mixtures, such as enantiomeric mixtures or diastereomeric mixtures, in each case.
[0308] If appropriate, the compounds of the formulae I and II and, where appropriate, their tautomers (in each case in free form or in salt form) can also be obtained in the form of hydrates and / or include other solvents, such as those which can be used for crystallization of compounds present in solid form.
[0309] The compounds of formula I according to the following tables A-1 to A-36 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).
[0310]
[0311] Each of Tables A-1 to A-36 contains 57 compounds of formula (IA) wherein J is indicated in Table Z and X and Y are given in the relevant Table A-1 to A-36.
[0312] Table A-1 There are provided 57 compounds A-1.001 to A-1.057 of formula IA, wherein X is O, Y is H, and J is as defined in Table Z. For example, A-1.001 is
[0313]
[0314] Table A-2 Provided are 57 compounds A-2.001 to A-2.057 of formula IA wherein X is O, Y is CH 3 , and J is as defined in Table Z.
[0315] Table A-3 Provided are 57 compounds A-3.001 to A-3.057 of formula IA wherein X is O, Y is CH2-CH3, and J is as defined in Table Z.
[0316] Table A-4Provided are 57 compounds A-4.001 to A-4.057 of formula IA wherein X is O, Y is CH2-phenyl, and J is defined in Table Z.
[0317] Table A-5 Provided are 57 compounds A-5.001 to A-5.057 of formula IA wherein X is O, Y is CH2-cyclopropyl, and J is defined in Table Z.
[0318] Table A-6 Provided are 57 compounds A-6.001 to A-6.057 of Formula IA wherein X is O, Y is CH2-O-CH3, and J is defined in Table Z.
[0319] Table A-7 Provided are 57 compounds A-7.001 to A-7.057 of Formula IA wherein X is CH2, Y is H, and J is defined in Table Z.
[0320] Table A-8 Provided are 57 compounds A-8.001 to A-8.057 of Formula IA wherein X is CH2, Y is CH3, and J is defined in Table Z.
[0321] Table A-9 Provided are 57 compounds A-9.001 to A-9.057 of Formula IA wherein X is CH2, Y is CH2-CH3, and J is defined in Table Z.
[0322] Table A-10 Provided are 57 compounds A-10.001 to A-10.057 of Formula IA wherein X is CH2, Y is CH2-phenyl, and J is defined in Table Z.
[0323] Table A-11 Provided are 57 compounds A-11.001 to A-11.057 of Formula IA wherein X is CH2, Y is CH2-cyclopropyl, and J is defined in Table Z.
[0324] Table A-12 Provided are 57 compounds A-12.001 to A-12.057 of Formula IA wherein X is CH2, Y is CH2-O-CH3, and J is defined in Table Z.
[0325] Table A-13 Provided are 57 compounds A-13.001 to A-13.057 of Formula IA wherein X is S, Y is H, and J is defined in Table Z.
[0326] Table A-14 Provided are 57 compounds A-14.001 to A-14.057 of Formula IA wherein X is S, Y is CH 3 , and J is as defined in Table Z.
[0327] Table A-15 Provided are 57 compounds A-15.001 to A-15.057 of Formula IA, wherein X is S, Y is CH2-CH3, and J is defined in Table Z.
[0328] Table A-16 Provided are 57 compounds A-16.001 to A-16.057 of Formula IA wherein X is S, Y is CH2-phenyl, and J is defined in Table Z.
[0329] Table A-17 Provided are 57 compounds A-17.001 to A-17.057 of Formula IA wherein X is S, Y is CH2-cyclopropyl, and J is defined in Table Z.
[0330] Table A-18 Provided are 57 compounds A-18.001 to A-18.057 of Formula IA, wherein X is S, Y is CH2-O-CH3, and J is defined in Table Z.
[0331] Table A-19 Provided are 57 compounds A-19.001 to A-19.057 of Formula IA, wherein X is SO, Y is H, and J is defined in Table Z.
[0332] Table A-20 Provided are 57 compounds A-20.001 to A-20.057 of Formula IA, wherein X is SO, Y is CH 3 , and J is defined in Table Z.
[0333] Table A-21 Provided are 57 compounds A-21.001 to A-21.057 of Formula IA, wherein X is SO, Y is CH2-CH3, and J is defined in Table Z.
[0334] Table A-22 Provided are 57 compounds A-22.001 to A-22.057 of formula IA wherein X is SO, Y is CH2-phenyl, and J is defined in Table Z.
[0335] Table A-23 Provided are 57 compounds A-23.001 to A-23.057 of formula IA wherein X is SO, Y is CH2-cyclopropyl, and J is defined in Table Z.
[0336] Table A-24 Provided are 57 compounds A-24.001 to A-24.057 of Formula IA wherein X is SO, Y is CH2-O-CH3, and J is defined in Table Z.
[0337] Table A-25 Provided are 57 compounds A-25.001 to A-25.057 of Formula IA wherein X is SO2, Y is H, and J is defined in Table Z.
[0338] Table A-26 Provided are 57 compounds A-26.001 to A-26.057 of Formula IA wherein X is SO2, Y is CH3, and J is defined in Table Z.
[0339] Table A-27 Provided are 57 compounds A-27.001 to A-27.057 of Formula IA wherein X is SO2, Y is CH2-CH3, and J is defined in Table Z.
[0340] Table A-28 Provided are 57 compounds A-28.001 to A-28.057 of Formula IA wherein X is SO2, Y is CH2-phenyl, and J is defined in Table Z.
[0341] Table A-29 Provided are 57 compounds A-29.001 to A-29.057 of formula IA wherein X is SO2, Y is CH2-cyclopropyl, and J is defined in Table Z.
[0342] Table A-30 Provided are 57 compounds A-30.001 to A-30.057 of Formula IA, wherein X is SO2, Y is CH2-O-CH3, and J is defined in Table Z.
[0343] Table A-31 Provided are 57 compounds A-31.001 to A-31.057 of formula IA, wherein X is SONH, Y is H, and J is defined in Table Z.
[0344] Table A-32 Provided are 57 compounds A-32.001 to A-32.057 of Formula IA, wherein X is SONH, Y is CH3, and J is defined in Table Z.
[0345] Table A-33Provided are 57 compounds A-33.001 to A-33.057 of Formula IA, wherein X is SONH, Y is CH2-CH3, and J is defined in Table Z.
[0346] Table A-34 Provided are 57 compounds A-34.001 to A-34.057 of formula IA wherein X is SONH, Y is CH2-phenyl, and J is defined in Table Z.
[0347] Table A-35 Provided are 57 compounds A-35.001 to A-35.057 of formula IA, wherein X is SONH, Y is CH2-cyclopropyl, and J is defined in Table Z.
[0348] Table A-36 Provided are 57 compounds A-36.001 to A-36.057 of Formula IA, wherein X is SONH, Y is CH2-O-CH3, and J is defined in Table Z.
[0349] Table Z: Definition of substituents for J:
[0350]
[0351]
[0352]
[0353] The compounds of formula II according to the following tables B-1 to B-30 can be prepared according to the methods described above. The following examples are intended to illustrate the invention and show preferred compounds of formula II (in the form of compounds of formula II-B).
[0354]
[0355] Table B-1 Provided is a compound B-1.001 having formula II-B, wherein X is O and T is H. For example, B-1.001 is
[0356]
[0357] Table B-2 Provided is compound B-2.001 having formula II-B, wherein X is O and T is CH 3 .
[0358] Table B-3 Provided is compound B-3.001 having formula II-B, wherein X is O, and T is CH2-CH3.
[0359] Table B-4 Provided is a compound B-4.001 having formula II-B, wherein X is O and T is CH2-phenyl.
[0360] Table B-5 Provided is compound B-5.001 having formula II-B, wherein X is O and T is CH2-cyclopropyl.
[0361] Table B-6 Compound B-6.001 having formula II-B, wherein X is CH 2 and T is H, is provided.
[0362] Table B-7 Provided is compound B-7.001 having formula II-B, wherein X is CH2, and T is CH3.
[0363] Table B-8 Provided is compound B-8.001 having formula II-B, wherein X is CH2, and T is CH2-CH3.
[0364] Table B-9 Provided is a compound B-9.001 having formula II-B, wherein X is CH2, and T is CH2-phenyl.
[0365] Table B-10 Provided is a compound B-10.001 having formula II-B, wherein X is CH2, and T is CH2-cyclopropyl.
[0366] Table B-11 Compound B-11.001 having formula II-B, wherein X is S and T is H, is provided.
[0367] Table B-12 Provided is compound B-12.001 having formula II-B, wherein X is S, and T is CH 3 .
[0368] Table B-13 Provided is compound B-13.001 having formula II-B, wherein X is S, and T is CH2-CH3.
[0369] Table B-14 Provided is a compound B-14.001 having formula II-B, wherein X is S and T is CH2-phenyl.
[0370] Table B-15 Provided is compound B-15.001 having formula II-B, wherein X is S, and T is CH2-cyclopropyl.
[0371] Table B-16 Compound B-16.001 having formula II-B, wherein X is SO and T is H, is provided.
[0372] Table B-17 Provided is compound B-17.001 having formula II-B, wherein X is SO and T is CH 3 .
[0373] Table B-18 Provided is compound B-18.001 having formula II-B, wherein X is SO, and T is CH2-CH3.
[0374] Table B-19 Provided is a compound B-19.001 having formula II-B, wherein X is SO and T is CH2-phenyl.
[0375] Table B-20 Provided is compound B-20.001 having formula II-B, wherein X is SO and T is CH2-cyclopropyl.
[0376] Table B-21 Compound B-21.001 having formula II-B, wherein X is SO 2 and T is H, is provided.
[0377] Table B-22 Provided is compound B-22.001 having formula II-B, wherein X is SO2, and T is CH3.
[0378] Table B-23 Provided is compound B-23.001 having formula II-B, wherein X is SO2, and T is CH2-CH3.
[0379] Table B-24 Provided is a compound B-24.001 having formula II-B, wherein X is SO2, and T is CH2-phenyl.
[0380] Table B-25 Provided is compound B-25.001 having formula II-B, wherein X is SO2, and T is CH2-cyclopropyl.
[0381] Table B-26 Compound B-26.001 having formula II-B, wherein X is SONH and T is H, is provided.
[0382] Table B-27 Provided is compound B-27.001 having formula II-B, wherein X is SONH, and T is CH3.
[0383] Table B-28 Provided is compound B-28.001 having formula II-B, wherein X is SONH, and T is CH2-CH3.
[0384] Table B-29Provided is a compound B-29.001 having formula II-B, wherein X is SONH and T is CH2-phenyl.
[0385] Table B-30 Provided is compound B-30.001 having formula II-B, wherein X is SONH, and T is CH2-cyclopropyl.
[0386] Certain compounds of formula III and VI are novel.
[0387] Therefore, the present invention also makes it possible to obtain compounds of formula IIIa
[0388]
[0389] Y is H, and J is a substituent as defined in Table J;
[0390] Y is CH3, and J is a substituent as defined in Table J;
[0391] Y is CH2-CH3, and J is a substituent as defined in Table J;
[0392] Y is CH2-phenyl, and J is a substituent as defined in Table J; and
[0393] • Y is CH2-O-CH3, and J is a substituent as defined in Table J.
[0394] The present invention further makes it possible to obtain compounds of formula VIa
[0395]
[0396] wherein T is selected from Tables B-1 to B-5.
[0397] The compounds of formula I or II 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. The active ingredients according to the invention act on all or individual developmental stages of normally sensitive as well as 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., destruction of the pest occurs immediately or only after a certain period of time (e.g., during molting); or indirectly, for example, by reducing egg laying and / or hatching rates.
[0398] Examples of the animal pests mentioned above are:
[0399] From the order Acarina, e.g.
[0400] Acalitus spp., Aculus spp., Acaricalus spp., Aceria spp., Acarus siro, Amblyomma spp., Argas spp., Boophilus spp., Brevipalpus spp., Bryobia spp., Calipitrimerus spp., Chorioptes spp., Dermanyssus gallinae, 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.;
[0401] From the order Phthirus, e.g.
[0402] Haematopinus spp., Linognathus spp., Pediculus spp., Pemphigus spp., and Phylloxera spp.;
[0403] From the order Coleoptera, e.g.
[0404] Agriotes spp., Amphimallon majale, Anomala orientalis, Anthonomus spp., Aphodius spp., Astylus atromaculatus, Ataenius spp., Atomaria linearis, Chaetocnema tibialis, Cerotomas spp., Conoderus spp.,
[0405] Cosmopolites spp., Cotinis nitida, Curculio spp., Cyclocephala spp., 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. spp.), Melighetes aeneus, Melolontha spp., Myochrous armatus, Orycaephilus spp., Otiorhynchus spp., Phyllophaga spp., Phlyctinus spp., Popillia spp., Psylliodes spp., Rhyssomatus aubtilis, Rhizopertha spp., Scarabeidae, Sitophilus spp., Sitotrogas spp., Somaticus spp.), Cryptorhynchus species, Sternechus subsignatus, Tenebrio spp., Tribolium spp., and Trogoderma spp.;
[0406] From the order Diptera, e.g.
[0407] 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., Drosophila melanogaster, 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., Riveria quadrifasciata, Scatella spp., Sciara spp., Stomoxys spp., Tabanus spp., Tannia spp.) and Tipula spp.;
[0408] From the order Hemiptera, e.g.
[0409] Acanthocoris scabrator, Acrosternum spp., Adelphocoris lineolatus, Aleurodes spp., Amblypeltanitida, Bathycoelia thalassina, Acanthocoris spp., Clavigralla tomentosicollis, Creontiades spp., Dichelops furcatus, Edessa spp., Euchistus spp., Eurydema pulchrum, Acrosternum spp., Brown-winged stink bug, Horcias nobilellus), rice stink bug species, grass stink bug species, tropical scale bug species, cabbage stink bug (Murgantia histrionic), new long-margin stink bug species, tobacco blind bug (Nesidiocoris tenuis), green stink bug species, Nysius simulans, island stink bug, skin stink bug species, wall stink bug species, red assassin bug species, cocoa stink bug, chestnut stink bug (Scaptocoris castanea), black stink bug species (Scotinophara spp.), Thyanta spp., trypanosoma species, cassava web stink bug (Vatiga illudens);
[0410] Acyrthosium pisum, Adalges species, Agalliano ensigera, Targuiron vein psyllid, Aleurodicus species, Aleurocanthus species, sugarcane hole whitefly, Aleurothrixus floccosus, Aleyrodes brassicae, Amarasca biguttula, lemon leafhopper, Nephrodisiac species, Aphididae, Aphid species, Aspidiotus species, eggplant groove 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), Cryptophyllum 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), cabbage constrictor aphid (Hyadaphis pseudobrassicae), large tail aphid species (Hyalopterus spp.), Hyperomyzus pallidus, lemon green leafhopper (Idioscopus clypealis), African leafhopper, Laodelphax striatellus species, water-hard scale, oyster shield scale species, radish aphid (Lopaphis erysimi), Lyogenys maidis, Aphid species, Cicada species, Metcalfa pruinosa, Aphid, Cicada, Aphid species, Neotoxoptera sp, Blacktail leafhopper species, Nilaparvata spp.), pear green aphid, Odonaspis ruthae, sugarcane cotton aphid, bayberry whitefly, Caulis psyllid, Shield scale species, Gall aphid species, Corn waxhopper, Flat-horned planthopper species, Hob wart aphid, Phylloxera species, Mosella species, Mulberry white scale species, Mealybug species, Cotton blind bug (Pseudatomoscelis seriatus), Psyllid species, Cotton scale (Pulvinaria aethiopica), Toothed scale species, Quesada gigas, Electric leafhopper (Recilia dorsalis), Constrictor aphid species, Black helmet scale species, Banded leafhopper species, Aphid species, Sitobion spp., White-backed planthopper, Spissistilus triangularis festinus), Tarophagus Proserpina, aphid species, whitefly species, Tridiscus sporoboli, Trionymus spp., African psyllids, scaly scale, flame leafhopper, and Zyginidia scutellaris.
[0411] From the order Hymenoptera, e.g.
[0412] Acromyrmex, Arge spp., Atta spp., Cephus spp., Diprion spp., Diprionidae, Gilpinia polytoma, Hoplocampa spp., Lasius spp., Monomorium pharaonis, Neodiprions spp., Pogonomyrmex spp., imported fire ants, Solenopsis spp., and Vespa spp.
[0413] From the order Isoptera, e.g.
[0414] Coptotermes spp., Corniternes cumulans, Incisitermes spp., Macrotermes spp., Mastotermes spp., Microtermes spp., Reticulitermes spp.; Tropical fire ants (Solenopsis geminate)
[0415] From the order Lepidoptera, for example,
[0416] Species of the genus Long-winged Roller Moth, species of the genus Brown-banded Roller Moth, species of the genus Clearwing Moth, species of the genus Noctua, cotton leafworm, species of the genus Amylois, species of the genus Mucuna, species of the genus Yellow Roller Moth, species of the genus Argyresthia, species of the genus Banded Roller Moth, species of the genus Spodoptera, species of cotton miner, corn armyworm, powdery moth, peach fruit moth, species of the genus Graminus, species of the genus Color Roller Moth, Chrysoteuchia topiaria, grape fruit moth, species of the genus Leaf Roller, species of the genus Cloud Roller, species of the genus Striped Roller Moth, species of the genus Sheath Moth, Colias lesbia, Cosmophila flava), grass borer species, cabbage borer, apple cyclops, boxwood moth, cyclops species, boxwood moth, stem borer species, Sudan cotton bollworm, Spodoptera species, South American corn seedling borer (Elasmopalpus lignosellus), sweet potato stem borer, mealybug species, leaf cyclops species (Epinotia spp.), salt marsh moth (Etiella zinckinella), flower cyclops species, ring needle cyclops, yellow tussock moth species, root cutter species, Feltia jaculiferia, Grapholita spp., clouded broad-winged cyclops, Heliothis species, cabbage borer, leaf cutter species (Herpetogramma spp.), American 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., Noctuidae species, fall moth 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 ash moth (Rachiplusianu), western bean incense (Richia albicosta), white grain borer species (Scirpophaga spp.), Spodoptera species, Cyprinodon species, Spodoptera species, Cotton leaf roller, Cnaphalocrocis species, Heteroptera species, Trichoplusia species, Tomato leafminer, and Lymantria species;
[0417] From the order Mallophaga, for example,
[0418] Damalina spp. and Trichodectes spp.;
[0419] From the order Orthoptera, for example,
[0420] Blatta, Blattella, Mole Cricket, Madeira Cockroach, Locust, American Mole Cricket (Neocurtillahexadactyla), Periplaneta, Mole Cricket (Scapteriscus spp.), and Desert Locust;
[0421] From the order Psocoptera, for example,
[0422] Liposcelis spp.;
[0423] From the order Siphonaptera, for example,
[0424] Ceratophyllus spp., Ctenocephalides spp., and Xenopsylla cheopis;
[0425] From the order Thysanoptera, for example,
[0426] Calliothrips phaseoli, Frankliniella spp., Heliothrips spp., Hercinothrips spp., Parthenothrips spp., Scirtothrips aurantii, Sericothrips variabilis, Taeniothrips spp., Thrips spp.
[0427] From the order of the Thysanura, for example, Lepisma saccharina.
[0428] In a further aspect, the present invention may also relate to a method of controlling damage to plants and parts thereof by plant-parasitic nematodes (endoparasitic nematodes, semi-endoparasitic nematodes 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 Meloidogyne; cyst-forming nematodes, Globodera rostochiensis and other species of Globodera; Heterodera avenae, Heteroderaglycines, Heterodera exigua and other species of Globodera; schachtii), Heterodera trifolii, and other Heterodera species; Seed gall nematodes, Anguina species; Stem and foliar nematodes, Aphelenchoides species; Sting nematodes, Belonolaimus longicaudatus, 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 species of the genera Hemicriconemoides; Hirshmanniella species; 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 Trichodorus species, Paratrichodorus species; Stunt nematodes, Tylenchorhynchus claytoni, Tylenchorhynchus dubius, and other Tylenchorhynchus species;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.
[0429] The compounds of the present invention may also have activity against mollusks. Examples include, for example, the family Pomacea; Arion (A. ater, A. circumscriptus, A. hortensis, A. rufus); Bradybaenidae (Bradybaena fruticum); Cepaea (Cepaea hortensis, C. nemoralis); Ochlodina; Deroceras (C. spp.); Gray slugs (D. agrestis, D. empiricorum, D. laeve, D. reticulatum); Discus (D. rotundatus); Euomphalia; Galba (G. trunculata); Helicelia (H. itala, H. obvia); Helicidae (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.
[0430] The active ingredients according to the invention can be used for controlling, i.e. suppressing or destroying harmful organisms of the above-mentioned type, which occur in particular on plants, especially on useful and ornamental plants in agriculture, horticulture and forestry, or on organs of such 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 harmful organisms.
[0431] In particular, suitable target crops are cereals, such as wheat, barley, rye, oats, rice, maize 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, olives, sunflower, coconut, castor, cocoa, beans or peanuts; cucurbits 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, sugarcane, tea, pepper, grapevines, hops, plantago, and latex plants.
[0432] In particular embodiments, compounds of Formula I or II 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.
[0433] The compositions and / or methods of the present invention may also be used on any ornamental and / or vegetable crop, including flowers, shrubs, broadleaf trees, and evergreen plants.
[0434] For example, the present invention can be used on any of the following ornamental plant species: Ageratum species, Alonsoa species, Anemone species, Anisodontea capsenisis, Anthemis species, Antirrhinum species, Aster species, Begonia species (e.g., Rieger Begonia, Begonia sempervirens, Begonia tubéreux), Bougainvillea species, Brachycome species, Brassica species (ornamental plants), Calceolaria species, Capsicum species, 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.), Lisianthus, Forsythia species, Fuchsia species, Geranium gnaphalium, Gerbera species, Globe amaranth, Heliotrope species, Sunflower species, Hibiscus species, Hydrangea species, Hydrangea species, Rhododendron, Impatiens species (African balsam), Amaranth species (Iresines spp.), Kalanchoe species, Lantana, March flower, Lion's ear, Lilium species, Mesembryanthemum species, Physalis species, Monarda species, Dracaena species, Marigold species, Dianthus species (carnation), Canna species, Oxalis species, Daisy species, Pelargonium species (Shieldleaf Pelargonium, Horseshoe Pelargonium), Viola species (Viola tricolor), Petunia species, Phlox species, Plecthranthus species spp.), Poinsettia species, Parthenocissus species (five-leaf creeper, Parthenocissus quinquefolia), Primula species, Ranunculus species, Azalea species, Rosa species (roses), Rudbeckia species, African violet species, Salvia species, Scaevola aemola, Schizonepeta tenuifolia z anthuswisetonensis), Sedum species, Solanum species, Surfinia spp., Marigold species, Nicotiana species, Verbena species, Zinnia species, and other bedding plants.
[0435] For example, the present invention can be used on any of the following vegetable species: Allium species (garlic, onion, shallot (A.oschaninii), leek, shallot, scallion), beet parsley, celery, asparagus, beet, Brassica species (cabbage, Chinese cabbage, turnip), peppers, chickpeas, endive, chicory species (radicchio, endive), watermelon, Cucurbita species (cucumber, melon), Cucurbita species (zucchini, Indian pumpkin), Cynara species (artichoke, cardoon), carrot, fennel, Hypericum species, lettuce, Lycopersicon species (tomato, cherry tomato), mint species, basil, parsley, Phaseolus species (bean, pea), pea, radish, edible rhubarb, rosemary species, sage species, black salsify, eggplant, spinach, Valerian species (V. eriocarpa), and broad beans.
[0436] Preferred ornamental plant species include African violet, begonia, dahlia, gerbera, hydrangea, verbena, rose, kalanchoe, poinsettia, aster, cornflower, coreopsis, delphinium, monarda, phlox, rudbeckia, sedum, petunia, violet, impatiens, geranium, chrysanthemum, ranunculus, fuchsia, salvia, hydrangea, rosemary, sage, St. John's wort, mint, sweet pepper, tomato, and cucumber.
[0437] The active ingredients according to the invention are particularly suitable for controlling the bean aphid, cucumber leaf beetle (Diabrotica balteata), tobacco budworm, peach aphid, diamondback moth and sea worm on cotton, vegetables, corn, rice and soybean crops. The active ingredients according to the invention are also particularly suitable for controlling the cabbage looper (preferably on vegetables), the codling moth (preferably on apples), the green leafhopper (preferably on vegetables, in vineyards), the potato beetle (Leptinotarsa) (preferably on potatoes) and the striped stem borer (preferably on rice).
[0438] The compounds of formula I or II are particularly suitable for controlling mites, spider mites and rust mites. In an embodiment, the compound TX of the invention (as defined below) is particularly suitable for controlling pests selected from the group consisting of: Acarina spp; Wurtz's bee shield mite; Thick-legged flour mite; Acarina spp; Citrus gall mite; Citrus citrus tick; Acarina spp; Steinberg's needle gall mite; Acarina spp; Pseudo-amyseius; Brevipalpus spp; Purple-red short-palpus mite; Alfalfa moss mite; Fruit moss mite; Wood mites spp; Chelicerus buccae; Chelicerus spp; Asger's chelicerus mite; Cattle itch mite; Demodex spp ... caballi; Demodex canis; Demodex goat; Demodex equi; Demodex ovis; Demodex spp.; Demodex suis; Dermanysus gallinae; Dermanysus spp.; Eotetranychus spp.; Eotetranychus wei; Pear gall mite; Ribes chinensis gall mite; Eotetranychus spp.; Grape gall mite; Tetranychus spp.; Halotydeus destructor; Hemithorax spp.; Sarcoptes spp.; Chicken chick mite; Yak mite; Sarcoptes spp.; Neoschongastiaxerothermobia; Neotrombicula autumnalis; Neotrombicula desaleri; Cat ear mite; Otomitus spp.; Coffee mite; Holly mite ilicis); Micrognathus species; Aviphyllum species; Aviphyllum spp.; Aviphyllum species; Aviphyllum spp.; Aviphyllum spp.; Acanthophrys ... caninum); Polyphagous Tarsonemes; Polyphagous Tarsonemes species; Psorergatesovis; Psorergatesovis species; Psorergatesovis spp ... mali).
[0439] The compounds TX according to the invention (as defined below) are particularly suitable for controlling pests selected from the group consisting of Acalitus spp., Aculus spp., Acaricalus spp., Aceria spp., Acarus siro, Amblyommas spp., Argas spp., Boophilus spp., Brevipalpus spp., Bryobia spp., Calipitrimerus spp., Chorioptes spp., Dermanyssus gallinae, Dermatophagoides spp., Eotetranychus spp. spp.), Eriophyes spp., Hemitarsonemus spp., Hyalomma spp., Ixodes spp., Olygonychus spp., Ornithodoros spp., Polyphagotarsonemus spp., Panonychus spp., Phyllocoptruta oleivora, Phytonemus spp., Polyphagotarsonemus spp., Psoroptes spp., Rhipicephalus spp., Rhizoglyphus spp.), Sarcoptes spp., Steneotarsonemus spp., Tarsonemus spp., and Tetranychus spp.
[0440] In an embodiment of the first aspect of the invention, compound TX of the invention (as defined below) is suitable for controlling one or more of: citrus gall mite; tomato needle gall mite (Aculus lycopersici); Peet's needle gall mite; Steinni's needle gall mite; purple short-palped mite; Short-palped mite spp.; fruit moss mite; Carpinus hornbeam spider mite; Eriophyes spp.; pear gall mite; Eriophyes piri; Eriophyes spp.; grape gall mite; African true spider mite; Oriental true spider mite; Small clawed mites of the grassland; Citrus citrus mites; Apple citrus mites; Grape rust mite; Citrus rue rust mite; Lateral polyphagous tarsonemus; Cinnabarinus spider mite; Kanzawa's spider mite; Tetranychus spp.; and two-spotted spider mite.
[0441] The compound TX (as defined below) of the present invention is suitable for controlling pests selected from the group consisting of Acanthocoris scabrator, Acrosternum spp., Adelphocoris lineolatus, Aleurodes spp., Amblypelta nitida, Bathycoelia thalassina, Acanthocoris spp., Cimex spp., Clavigrallatomentosicollis, Creontiades spp., Dichelops furcatus, Acanthocoris spp., Edessa spp., Euchistus spp., Eurydema spp. pulchrum), flat shield bug species, brown-winged stink bug, Horcias nobilellus, rice-margined stink bug species, grass stink bug species, tropical scale species, Murgantia histrionic, new long-margined stink bug species, tobacco blind bug (Nesidiocoris tenuis), green stink bug species, Nysius simulans, island stink bug, skin stink bug species, wall stink bug species, red assassin bug species, cocoa brown stink bug, chestnut soil stink bug (Scaptocoris castanea), black stink bug species (Scotinophara spp.), Thyanta spp., trypanosoma species, cassava web stink bug (Vatiga illudens);
[0442] Acyrthosium pisum, Adalges species, Agalliano ensigera, Targuiron vein psyllid, Aleurodicus species, Aleurocanthus species, sugarcane hole whitefly, Aleurothrixus floccosus, Aleyrodes brassicae, Amarasca biguttula, lemon leafhopper, Nephrodisiac species, Aphididae, Aphid species, Aspidiotus species, eggplant groove 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), Cryptophyllum 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), cabbage constrictor aphid (Hyadaphis pseudobrassicae), large tail aphid species (Hyalopterus spp.), Hyperomyzus pallidus, lemon green leafhopper (Idioscopus clypealis), African leafhopper, Laodelphax striatellus species, water-hard scale, oyster shield scale species, radish aphid (Lopaphis erysimi), Lyogenys maidis, Aphid species, Cicada species, Metcalfa pruinosa, Aphid, Cicada, Aphid species, Neotoxoptera sp, Blacktail leafhopper species, Nilaparvata spp.), pear green aphid, Odonaspis ruthae, sugarcane cotton aphid, bayberry whitefly, Caulis psyllid, Shield scale species, Gall aphid species, Corn waxhopper, Flat-horned planthopper species, Hob wart aphid, Phylloxera species, Mosella species, Mulberry white scale species, Mealybug species, Cotton blind bug (Pseudatomoscelis seriatus), Psyllid species, Cotton scale (Pulvinaria aethiopica), Toothed scale species, Quesada gigas, Electric leafhopper (Recilia dorsalis), Constrictor aphid species, Black helmet scale species, Banded leafhopper species, Aphid species, Sitobion spp., White-backed planthopper, Spissistilus triangularis festinus), Tarophagus Proserpina, aphid species, whitefly species, Tridiscus sporoboli, Trionymus spp., African psyllids, scaly scale, flame leafhopper, and Zyginidia scutellaris.
[0443] The term "crops" is to be understood as also including crop plants which have been transformed by the use of recombinant DNA techniques so as to enable them to synthesize one or more selectively acting toxins, such as are known, for example, from toxigenic bacteria, in particular those of the genus Bacillus.
[0444] Toxins that can be expressed by such transgenic plants include, for example, insecticidal proteins, for example, insecticidal proteins 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, luffain, saporin or bryophyllin; steroid metabolizing enzymes, such as 3-hydroxysteroid oxidase, ecdysteroid-UDP-glycosyl-transferase, cholesterol oxidase, ecdysteroid inhibitors, 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.
[0445] In the context of the present invention, δ-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, but are not limited to, mixed toxins, truncated toxins, and modified toxins. Mixed toxins are recombinantly produced by combining 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 be 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).
[0446] 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.
[0447] Methods for preparing such transgenic plants are generally known to those 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.
[0448] The toxins contained in the transgenic plants confer tolerance 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).
[0449] Transgenic plants comprising one or more genes encoding insecticide resistance and expressing one or more toxins are known and some are commercially available. Examples of such plants are: (Zea mays variety expressing Cry1Ab toxin); YieldGard (maize variety expressing Cry3Bb1 toxin); YieldGard (Zea mays varieties expressing Cry1Ab and Cry3Bb1 toxins); (Zea mays variety expressing Cry9C toxin); Herculex (a maize 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); (cotton varieties expressing Cry1Ac and Cry2Ab toxins); (cotton variety expressing Vip3A and Cry1Ab toxins); (potato variety expressing Cry3A toxin); GT Advantage (GA21 glyphosate tolerance trait), CB Advantage (Bt11 corn borer (CB) trait) and
[0450] Further examples of such genetically modified crops are:
[0451] 1. Bt11 maize, from Syngenta Seeds SAS, 27 Chemin de l'Hobit, F-31 790 St. Sauveur, France, registration number C / FR / 96 / 05 / 10. This genetically modified maize is resistant to attack by the European corn borer (Ostrinia nubilalis and Sesamia inermis) by transgenic expression of a truncated Cry1Ab toxin. Bt11 maize also transgenicly expresses the PAT enzyme to confer tolerance to the herbicide glufosinate-ammonium.
[0452] 2. Bt176 maize, from Syngenta Seeds, 27 Rue de Hobbit, F-31 790 Saint-Sauveur, France, registration number C / FR / 96 / 05 / 10. This genetically modified maize is resistant to attack by the European corn borer (Ostrinia nubilalis and Sesamia inermis) by transgenic expression of the Cry1Ab toxin. Bt176 maize also transgenicly expresses the PAT enzyme to confer tolerance to the herbicide glufosinate-ammonium.
[0453] 3. MIR604 maize, from Syngenta Seeds, 27 Rue de Hobbit, F-31 790 Saint-Sauveur, France, registration number C / FR / 96 / 05 / 10. This maize plant is rendered insect-resistant by transgenic expression of a modified Cry3A toxin. This toxin is Cry3A055, modified by insertion of a cathepsin G protease recognition sequence. The preparation of these transgenic maize plants is described in WO 03 / 018810.
[0454] 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 confers resistance to certain coleopteran insects.
[0455] 5. IPC 531 cotton, from Monsanto Europe SA, 270-272 Avenue Tervuren, B-1150 Brussels, Belgium, registration number C / ES / 96 / 02.
[0456] 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.
[0457] 7. NK603×MON 810 maize, from Monsanto Europe, 270-272 Boulevard Tervuren, B-1150 Brussels, Belgium, registration number C / GB / 02 / M3 / 03. This is a conventionally bred hybrid maize variety, constructed 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, conferring herbicide tolerance. (contains glyphosate), and also the Cry1Ab toxin obtained from Bacillus thuringiensis subsp. kurstakia, which confers resistance to certain lepidopteran insects, including the European corn borer.
[0458] 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.
[0459] The term "crop" should be understood to also include crop plants that have been transformed using recombinant DNA technology to enable them to synthesize selectively acting antipathogenic substances, 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-0 353 191. 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.
[0460] Crops can also be modified to enhance 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.
[0461] Crops also include those with enhanced resistance to nematodes, such as Heterodera glycines.
[0462] Crops with tolerance to abiotic stress include those with enhanced tolerance to drought, high salinity, high temperature, cold, frost or light radiation, for example, through expression of NF-YB or other proteins known in the art.
[0463] 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 which are involved in plant pathogen defense (so-called "plant disease resistance genes", as described in WO 03 / 000906).
[0464] Further areas of use of the compositions according to the invention are the protection of stored goods and storage rooms and the protection of raw materials such as wood, textiles, floor coverings or buildings, and also in the hygiene sector, in particular the protection of humans, domestic animals and productive livestock from pests of the types mentioned.
[0465] 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 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.
[0466] The present invention provides the use of the compound of the first aspect for the manufacture of a medicament for controlling parasites in or on the body of an animal. The present invention further provides the use of the compound of the first aspect for the manufacture of a medicament for controlling parasites on the body of an animal. The present invention further provides the use of the compound of the first aspect for the manufacture of a medicament for preventing and / or treating diseases transmitted by parasites on the body.
[0467] The present invention provides a use of the compound of the first aspect in controlling parasites in or on the body of an animal. The present invention further provides a use of the compound of the first aspect in controlling parasites on the body of an animal.
[0468] 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.
[0469] When used in the context of parasites in or on animals, the term "treat" means to inhibit, slow, halt or reverse the progression or severity of existing symptoms or disease.
[0470] 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.
[0471] When used in the context of parasites in or on animals, the term "animal" may refer to both 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.
[0472] Pets include, but are not limited to, dogs, cats, and rabbits.
[0473] A "parasite" is a harmful organism that lives in or on a host animal and benefits by obtaining nutrients at the host animal's expense. An "endoparasite" is a parasite that lives inside the host animal. An "ectoparasite" is a parasite that lives on the host animal's body. Ectoparasites include, but are not limited to, ticks, insects, and crustaceans (e.g., sea lice). The subclass Ixodida (or Acarina) includes ticks and mites. Ticks include, but are not limited to, members of the genera 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 genera: Dermestes, such as P. calves; P. spp., such as P. goat; Cheyletus; Dermatophagida; such as Dermatophagida gallinae; Ortnithonyssus; Demodex, such as Demodex canis; Sarcoptes, such as Sarcoptes hominis; and Psoralea. Insects include, but are not limited to, members of the orders: Siphonaptera, Diptera, Trichoderma, Lepidoptera, Coleoptera, and Homoptera. Members of Siphonaptera include, but are not limited to, Ctenocephatides cati 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 species of the genus Tabunus and species of the genus Tabunus; black horn flies, such as blood flies; biting flies; green flies; midges; and mosquitoes. Members of the order Trichoderma include, but are not limited to, blood-sucking lice and chewing lice, such as the wool louse (Bovicola Ovis) and the bovine feather louse.
[0474] The term "effective amount," when used in the context of parasites in or on an animal, refers to an 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. An effective amount can be readily determined by the attending diagnostician (being one skilled in the art) by using known techniques and by observing results obtained in similar circumstances. In determining an effective amount, the attending diagnostician considers a number of factors, including, but not limited to: the species of mammal; its size, age, and general health; the parasite to be controlled and the degree of infestation; the specific disease or condition involved; the extent or severity of the disease or condition; the individual's response; the specific compound to be 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.
[0475] 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. Preparations suitable for topical administration include, for example, solutions, emulsions and suspensions, and can be poured, dotted, sprayed, sprayed, or immersed in the form of a spray race. In an alternative, the compounds of the present invention can be given by ear tags or collars.
[0476] 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 compound of the present invention easily changes into salt using technology and conditions known to those of ordinary skill in the art, and can be used as salt (such as hydrochloride) to separate.In addition, it will be appreciated by those skilled in the art that the compound of the present invention easily changes into corresponding free alkali, and can be used as corresponding free alkali to separate from corresponding salt.
[0477] The present invention also provides a method 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, to their locus, or to a surface or substrate by painting, rolling, spraying, spreading, or dipping. By way of example, IRS (indoor residual spraying) application to surfaces (such as walls, ceilings, or floor surfaces) is contemplated by the methods of the present invention. In another embodiment, application of such compositions to substrates, such as nonwoven or fabric materials in the form of (or for use in the manufacture of) netting, coverings, bedding, curtains, and tents is contemplated.
[0478] In one embodiment, the method for controlling this type of harmful organism comprises to target harmful organism, to their place or to surface or substrate using the composition of the present invention of pesticidal effective dose, so that on this surface or substrate, effective retained pesticidal activity is provided.This application can be carried out by brushing, rolling, spraying, spreading or dipping pesticidal composition of the present invention.By way of example, considered by method of the present invention that the IRS of surface (as wall, ceiling or floor surface) is used, so that on this surface, effective retained pesticidal activity is provided.In another embodiment, considered using this type of composition for the residual control of the harmful organism on substrate, this substrate is as the fabric material with the form (or can be used in the manufacture of these articles) of netting, covering, quilt, curtain and tent.
[0479] 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 treating textiles 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.
[0480] A further field of use of the compositions according to the invention is the field of tree injection / trunk treatment of all ornamental trees and all kinds of fruit and nut trees.
[0481] 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 and from the orders Coleoptera mentioned above, in particular against the wood-boring insects listed in Tables A and B below:
[0482] Table A. Examples of economically important exotic wood-boring insects.
[0483]
[0484]
[0485] Table B. Examples of economically important native wood-boring insects.
[0486]
[0487]
[0488]
[0489]
[0490] 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 stink bugs, and white grubs. The present invention can be used to control insect pests at all stages of their life cycle, including eggs, larvae, nymphs, and adults.
[0491] In particular, the present invention can be used to control insect pests that feed on the roots of turfgrasses, including grubs (such as Cyclocephala spp. (e.g., marked beetles, C. lurida), Rhizotrogus spp. (e.g., European beetles, European root beetles (R. majalis)), Cotinus spp. (e.g., Green June beetles, C. nitida), Popillia spp. (e.g., Japanese beetles, P. japonica), Phyllophaga spp. (e.g., May / June beetles), Ataenius spp. (e.g., Black turfgrass ataenius, A. spretulus), Maladera spp. (e.g., Asiatic garden beetles, A. spp.), and other insect pests. beetle, M. castanea, and Tomarus genera), ground pearls (Margarodes spp.), mole crickets (tawny, southern, and short-winged; Scapteriscus spp., Gryllotalpa africana), and leatherjackets (European crane fly, Tipula spp.).
[0492] The present invention can also be used to control insect pests of turfgrass in thatched homes, including armyworms (such as the fall armyworm Spodoptera frugiperda, and the common armyworm Pseudaletia unipuncta), cutworms, weevils (Sphenophorus spp., such as S. venatus vertitus and S. parvulus), and meadow moths (such as Crambus spp. and the tropical meadow moth, Herpetogramma phaeopteralis).
[0493] The present invention can also be used to control insect pests in turfgrasses 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.
[0494] The present invention can also be used to control other pests in turfgrass, such as introduced fire ants (Solenopsis invicta) that create nests in lawns.
[0495] In the hygiene sector, the compositions according to the invention are effective against epiparasites such as hard ticks, soft ticks, scabies, autumn mites, flies (biting and licking), parasitic fly larvae, lice, hair lice, bird lice and fleas.
[0496] Examples of such parasites are:
[0497] From the order of the Pediculus: Haemaphysalis spp., Linognathus spp., Pediculus hominis spp., and Phtirus spp., Phitirus spp.
[0498] From the order Trichophagus: Felicola species, Felicola species, Felicola species, Felicola species, Werneckiella spp., Lepikentron spp., Felicola species, Felicola species, and Felicola species.
[0499] Of the order Diptera and the suborders 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. spp.), Braula spp., Musca spp., Hydrotaea spp., Biting flies, 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 Melophagus spp.
[0500] From the order of the Siphonapterida, for example, Pulex spp., Ctenocephalides spp., Xenopsylla spp., Ceratophyllum spp.
[0501] From the order of the Heteropterida, for example, Cimex spp., Triatominae spp., Panstrongylus spp.
[0502] From the order of the Blattarida, for example, Blatta orientalis, Periplaneta americana, Blattelagermanica and Supella spp.
[0503] Subclass Acaria (family Acarida) and orders Meta-stigmata and Meso-stigmata, for example, Argas spp., Ornithodorus spp., Otobius spp., Ixodes spp., Amblyommas spp., Boophilus spp., Dermacentor spp., Haemophysalis spp., Hyalomma spp., Rhipicephalus spp., Dermanyssus spp., Raillietia spp., Pneumonyssus spp. spp.), Sternostoma spp., and Varroa spp.
[0504] From the orders Actinedida (Prostigmata) and Acaridida (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., Sarcooptes spp., Notoedress spp., Knemidocoptes spp., Cytodites spp., and Laminosioptes spp.
[0505] The compositions according to the invention are also suitable for protecting materials such as wood, textiles, plastics, adhesives, glues, paints, paper and card, leather, floor coverings and construction materials from infestation by insects.
[0506] In preferred embodiments of each aspect, the compound TX (defined below) controls
[0507] One or more of the following: Spodoptera littoralis, Plutella xylostella, Western Flower Thrips, Thrips tabaci, American hero stink bug, codling moth, brown rice hopper, green peach aphid, soybean looper, bean aphid, cucumber leaf beetle, cereal aphid, and striped rice borer (Chilosuppressalis), 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, green peach aphid+TX, soybean looper+TX, bean aphid+TX, cucumber leaf beetle+TX, cereal aphid+TX, and striped rice borer+TX.
[0508] In an embodiment of each aspect, compound TX is suitable for controlling Spodoptera littoralis, Plutella xylostella, western flower thrips, Thrips tabaci, hero stink bug, codling moth, brown rice hopper, green peach aphid, soybean looper, bean aphid, cucumber leaf beetle, cereal aphid, and striped stem borer on cotton, vegetables, corn, corn, rice, and soybean crops.
[0509] In an embodiment, compound TX 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).
[0510] The compounds according to the present invention may have any number of benefits, including, among others, 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 discovered that certain compounds of Formula I or II can exhibit favorable safety profiles against non-target arthropods, particularly pollinators such as honey bees, solitary bees, and bumblebees. Most particularly, against the Italian honey bee (Apis mellifera).
[0511] The compounds according to the invention can be used as pesticides in unmodified form, but they are generally formulated into compositions in various ways using formulation adjuvants such as carriers, solvents and surfactants. These formulations may be in different physical forms, for example, in the form of dusts, gels, wettable powders, water-dispersible granules, water-dispersible tablets, effervescent compressed tablets, emulsifiable concentrates, microemulsifiable concentrates, oil-in-water emulsions, mobile 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 known forms, for example, from the 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 diluted before use. Dilution can be performed with, for example, water, liquid fertilizers, micronutrients, biological organisms, oils or solvents.
[0512] These formulations can be prepared, for example, by mixing the active ingredient with formulation adjuvants in order to obtain compositions in the form of finely divided solids, granules, solutions, dispersions or emulsions. The active ingredients can also be formulated with other adjuvants such as finely divided solids, mineral oils, oils of vegetable or animal origin, modified oils of vegetable or animal origin, organic solvents, water, surface-active substances or combinations thereof.
[0513] These active ingredients can also be contained in very fine microcapsules. Microcapsules contain active ingredients in porous carriers. This allows the active ingredient to be released (e.g., slowly released) into the environment in a controlled amount. Microcapsules typically have a diameter of 0.1 to 500 microns. The amount of active ingredient they contain is about 25% to 95% of the capsule weight by weight. These active ingredients can be in the form of a holistic 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 copolymer, 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 ingredient is contained in a solid matrix of a base material in the form of finely dispersed particles, but these microcapsules themselves are not wrapped.
[0514] Formulation adjuvants suitable for preparing the compositions according to the invention are known per se. As liquid carriers, water, toluene, xylene, petroleum ether, vegetable oils, acetone, methyl ethyl ketone, cyclohexanone, acid 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, glyceryl acetate, glyceryl diacetate, glyceryl triacetate, decaglycerol Hexadecane, Hexanediol, Isoamyl Acetate, Isobornyl Acetate, Isooctane, Isophorone, Cumene, Isopropyl Myristate, Lactic Acid, Lauramine, Mesityl Oxide, Methoxypropanol, Methyl Isoamyl Ketone, Methyl Isobutyl Ketone, Methyl Laurate, Methyl Caprylate, Methyl Oleate, Methylene Chloride, 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, xylenesulfonic 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.
[0515] 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, soy flour, pumice, wood flour, ground walnut shells, lignin, and similar materials.
[0516] Many surface-active substances can be used advantageously in both solid and liquid formulations, especially those which can be diluted with a carrier before use. Surface-active substances can be anionic, cationic, nonionic or polymeric and they can act as emulsifiers, wetting agents or suspending agents or for other purposes. Typical surface-active substances include, for example, salts of alkyl sulfates, such as diethanolammonium laurylsulfate; 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 sorbitol oleate; quaternary amines, 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 further substances, such as are described, for example, in McCutcheon's Detergents and Emulsifiers Annual, MC Publishing Company. Corp., Ridgewood New Jersey (1981).
[0517] Additional adjuvants that can be used in pesticidal formulations include crystallization inhibitors, viscosity regulators, suspending agents, dyes, antioxidants, foaming agents, light absorbers, mixing aids, defoamers, complexing agents, substances and buffers that neutralize or vary the pH, corrosion inhibitors, fragrances, wetting agents, absorption enhancers, micronutrients, plasticizers, glidants, lubricants, dispersants, thickeners, antifreeze agents, microbicides, and liquid and solid fertilizers.
[0518] The composition according to the invention may contain additives comprising oils of plant or animal origin, mineral oils, alkyl esters of such oils or mixtures of such oils with oil derivatives. The amount of 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 oils or oils 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 C8-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.
[0519] The compositions of the present invention generally contain from 0.1% to 99% by weight, especially from 0.1% to 95% by weight, of a compound of the present invention and from 1% to 99.9% by weight of formulation adjuvants, preferably including from 0 to 25% by weight of surfactants. While commercial products may preferably be formulated as concentrates, the end user will generally employ dilute formulations.
[0520] 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 dictated by the application method, the time of application, and the target crop. In general, the compound can be applied at a rate of 1 l / ha to 2000 l / ha, in particular 10 l / ha to 1000 l / ha.
[0521] A preferred formulation may have the following composition (wt %):
[0522] Emulsifiable concentrates :
[0523] Active ingredient: 1% to 95%, preferably 60% to 90%
[0524] Surfactant: 1% to 30%, preferably 5% to 20%
[0525] Liquid carrier: 1% to 80%, preferably 1% to 35%
[0526] dust powder :
[0527] Active ingredient: 0.1% to 10%, preferably 0.1% to 5% Solid carrier: 99.9% to 90%, preferably 99.9% to 99%
[0528] Suspension concentrate:
[0529] Active ingredient: 5% to 75%, preferably 10% to 50%
[0530] Water: 94% to 24%, preferably 88% to 30%
[0531] Surfactant: 1% to 40%, preferably 2% to 30%
[0532] wettable powder :
[0533] Active ingredient: 0.5% to 90%, preferably 1% to 80% Surfactant: 0.5% to 20%, preferably 1% to 15%
[0534] Solid carrier: 5% to 95%, preferably 15% to 90%
[0535] Granules:
[0536] Active ingredient: 0.1% to 30%, preferably 0.1% to 15%
[0537] Solid carrier: 99.5% to 70%, preferably 97% to 85%
[0538] The following examples further illustrate (but do not limit) the present invention.
[0539] wettable powder a) b) c) Active ingredient 25% 50% 75% Sodium lignin sulfonate 5% 5% - Sodium lauryl sulfate 3% - 5% Sodium diisobutylnaphthyl sulfonate - 6% 10% Phenol polyglycol ether (7-8 mol of ethylene oxide) - 2% - Highly dispersed silicic acid 5% 10% 10% Kaolin 62% 27% -
[0540] The combination is thoroughly mixed with the adjuvants and the mixture is thoroughly ground in a suitable grinder to obtain a wettable powder which can be diluted with water to give a suspension of the desired concentration.
[0541] Powder for dry seed treatment a) b) c) Active ingredient 25% 50% 75% Light mineral oil 5% 5% 5% Highly dispersed silicic acid 5% 5% - Kaolin 65% 40% - talc - 20%
[0542] The combination is thoroughly mixed with the adjuvants and the mixture is thoroughly ground in a suitable grinder to obtain a dust that can be used directly for seed treatment.
[0543] Emulsifiable concentrates Active ingredient 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%
[0544] Emulsions of any desired dilution which can be used in plant protection can be obtained from these concentrates by dilution with water.
[0545] Dust powder a) b) c) Active ingredient 5% 6% 4% talc 95% - - Kaolin - 94% - Mineral fillers - - 96%
[0546] 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.
[0547]
[0548]
[0549] The combination is mixed and ground with the adjuvants, and the mixture is moistened with water.
[0550] The mixture is extruded and then dried in a stream of air.
[0551] <![CDATA[ Coated granules ]]> Active ingredient 8% Polyethylene glycol (molecular weight 200) 3% Kaolin 89%
[0552] The 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.
[0553] Suspension concentrates
[0554] Active ingredient 40% Propylene glycol 10% Nonylphenol polyglycol ether (15 mol of ethylene oxide) 6% Sodium lignin sulfonate 10% Carboxymethyl cellulose 1% Silicone oil (as a 75% emulsion in water) 1% water 32%
[0555] The finely ground combination is intimately mixed with adjuvants to give a suspension concentrate from which suspensions of any desired dilution can be obtained by dilution with water. Using such dilutions, living plants as well as plant propagation materials can be treated and protected against microbial infestation by spraying, pouring or immersion.
[0556] Flowable concentrate for seed treatment
[0557]
[0558]
[0559] The finely ground combination is intimately mixed with adjuvants to give a suspension concentrate from which suspensions of any desired dilution can be obtained by dilution with water. Using such dilutions, living plants as well as plant propagation materials can be treated and protected against microbial infestation by spraying, pouring or immersion.
[0560] Extended-release capsule suspension
[0561] 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, 2.8 parts of a mixture of 1,6-hexanediamine in 5.3 parts of water are added. The mixture is stirred until polymerization is complete. The resulting capsule suspension is stabilized by adding 0.25 parts of a thickener and 3 parts of a dispersant. The capsule suspension formulation contains 28% 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.
[0562] Formulation types include emulsion concentrates (EC), suspension concentrates (SC), suspoemulsions (SE), capsule suspensions (CS), water-dispersible granules (WG), emulsifiable granules (EG), water-in-oil emulsions (EO), oil-in-water emulsions (EW), microemulsions (ME), oil dispersions (OD), oil suspensions (OF), oil-soluble concentrates (OL), soluble concentrates (SL), ultra-low volume suspensions (SU), ultra-low volume concentrates (UL), finished products (TK), dispersible concentrates (DC), wettable powders (WP), soluble granules (SG), or any technically feasible formulation in combination with agriculturally acceptable adjuvants.
[0563] For the naming of compounds of Formula I and II (where X is O), relative stereodescriptors from the Chemical Abstracts Service have been used. The configuration of cyclic molecules (including suitable polycyclic systems) with several stereogenic centers is described whereby the α side of the reference plane is the side with the substituent having a CIP priority located on the lowest numbered stereogenic center. The other side is β. This type of nomenclature is well documented in the literature; see, for example, Pure & Appl. Chem. 1996, 68(12), 2193.
[0564] The following examples further illustrate (but do not limit) the present invention. One skilled in the art will readily recognize from these procedures appropriate variations on reactants and on reaction conditions and techniques.
[0565] Throughout this specification, temperatures are given in degrees Celsius (° C.) The following abbreviations are used: s = singlet; br s = broad singlet; d = doublet; br d = broad doublet; dd = double of doublets; dt = double of triplets; t = triplet, tt = triplet of triplets, q = quartet, quin = quintet, sept = septet; m = multiplet.
[0566] Preparation example:
[0567] The LC / MS and GC / MS apparatus and methods are:
[0568] Method 1:
[0569] 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: 41 V, extractor: 2.00 V, source temperature: 150°C, desolvation temperature: 500°C, cone gas flow: 50 l / h, desolvation gas flow: 1000 l / h, mass range: 110 to 800 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 x 2.1 mm, temperature: 40° C., PDA wavelength range (nm): 200 to 400, solvent gradient: A = water + 5% acetonitrile + 0.1% HCOOH, B = acetonitrile + 0.05% HCOOH, gradient: 10%-100% B in 1.3 min; flow rate (ml / min) 0.6.
[0570] Method 2:
[0571] Spectra were recorded on a Trace 1310 gas chromatograph with a 1:1 split between the FID detector and an ISQ LT single quadrupole mass spectrometer. Injector temperature: 250°C. Column: ZA-5ms, 15 m, 0.25 mm diameter, 0.25 μm (Phenomenex) (GC conditions: 40°C initial temperature hold for 2 minutes, followed by a 40°C / min gradient to 320°C. Mass
[0572] Spectrometer conditions: EI at 70 eV, mass range: 50-650 Da).
[0573] Method 3:
[0574] Spectra were recorded on a Trace 1310 gas chromatograph with a 1:1 split between the FID detector and an ISQ LT single quadrupole mass spectrometer. Injector temperature: 250°C. Column: ZA-5ms, 15 m, 0.25 mm diameter, 0.25 μm (Phenomenex). (GC conditions: 35°C initial temperature hold for 3 minutes, followed by a 40°C / min gradient to 320°C. Mass spectrometer conditions: CI with methane, mass range: 50–650 Da).
[0575] Method 4:
[0576] Spectra were recorded on a GC 2010PLUS (SHIMADZU), column: SH-Rxi 17Sil MS (L: 30 m, thickness: 0.25 mm, diameter 0.25 mm), oven temperature (°C): 40, injection volume (mL): 0.1, injection temperature (°C): 250, injection mode: split, split ratio: 50.0, flow control mode: pressure, pressure (kPa): 48.0, total flow (mL / min): 52, column flow (mL / min): 1.0, purge flow (mL / min): 2.0, linear velocity (cm / sec): 35.7, run time: 15 min.
[0577] Temperature program:
[0578] rate Temperature (℃) Holding time (min) 40 1.00 25 280 4.40
[0579] Mass spectrometer: GCMS-QP2010Ultra (Shimadzu Corporation), ionization mode: electron impact (EI), source temperature (°C): 200, interface temperature (°C): 220, solvent cutoff time (min): 3.5, detector gain mode: 0.0, acquisition mode: scan, event time (s): 0.30, scan speed: 2500, mass range (m / z): 50-650.
[0580] Method 5:
[0581] Spectra were recorded on a Waters mass spectrometer (SQD2 or QDA single quadrupole mass spectrometer) equipped with an electrospray source (polarity: positive and negative switching, capillary: 0.8-3.00 kV, cone range: 25 ° C., source temperature: 120 ° C.-150 ° C., desolvation temperature: 500 ° C.-600 ° C., cone gas flow: 50 L / h, desolvation gas flow: 1000 L / h, mass range: 110 to 850 Da) and an Acquity UPLC from Waters: quaternary solvent manager, heated column compartment, diode array detector. Column:
[0582] Acquity UPLC HSS T3 C18, 1.8 μm, 30 x 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.min-0.2 min 10%-50% B; 0.2 min-0.6 min 50%-100% B; 0.6 min-1.3 min 100% B; 1.3 min-1.4 min 100%-10% B; 1.4 min-1.6 min 10% B; flow rate (mL / min) 0.6.
[0583] Method 6:
[0584] Spectra were recorded on an ACQUITY mass spectrometer from Waters (SQD or SQDII single quadrupole mass spectrometer) 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 with a solvent degasser, binary pump, heated column compartment, and diode array detector. Column: Waters UPLC HSS T3, 1.8 μm, 30x2.1 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 3.0 min; flow rate (ml / min) 0.75.
[0585] Example P1: Preparation of rel-(1S,6S,7S)-2-oxabicyclo[4.1.0]heptane-7-carboxamide (P1)
[0586]
[0587] Step A: Preparation of rel-(1S,6S,7S)-2-oxabicyclo[4.1.0]heptane-7-carboxylic acid ethyl ester (I-1)
[0588]
[0589] To a stirred solution of copper sulfate (0.44 g, 2.8 mmol, 0.05 equivalent) in 3,4-dihydro-2H-pyrans (24 mL) was added a solution of ethyl 2-diazoacetate (6.5 mL, 56 mmol, 1.0 equivalent) in 3,4-dihydro-2H-pyrans (10 mL) using a syringe pump over a period of 2.5 hours at 82 ° C. The resulting reaction mixture was stirred under reflux for another 2 hours. After cooling to room temperature, diethyl ether (10 mL) was added to the reaction mixture, and the resulting suspension was filtered through a PTFE syringe filter. The solvent was concentrated at room temperature under reduced pressure to obtain rel-(1S, 6S, 7S)-2-oxabicyclo[4.1.0]heptane-7-ethyl carboxylate (9.2 g) as a brown oil.
[0590] GC-MS (Method 3): retention time 7.50 min
[0591] 1 H NMR (400 MHz, chloroform-d) δ ppm 4.07-4.15 (m, 2H) 3.88-3.94 (m, 1H) 3.57-3.65 (m, 1H) 3.37 (td, J = 11.08, 2.18 Hz, 1H) 1.92-2.04 (m, 2H) 1.72-1.78 (m, 2H) 1.43-1.58 (m, 2H) 1.23-1.28 (m, 3H)
[0592] Step B: Preparation of rel-(1S,6S,7S)-2-oxabicyclo[4.1.0]heptane-7-carboxylic acid (I-2)
[0593]
[0594] To a stirred solution of rel-(1S, 6S, 7S)-2-oxabicyclo [4.1.0] heptane-7-carboxylic acid ethyl ester (5.70 g, 33.5 mmol, 1.0 equivalent) in tetrahydrofuran (100 mL) and water (34 mL) was added lithium hydroxide monohydrate (3.27 g, 134 mmol, 4.0 equivalents). The reaction mixture was stirred at room temperature for 18 hours. Lithium hydroxide monohydrate (3.27 g, 134 mmol, 4.0 equivalents) was added again and stirred at room temperature for another 4 hours. The reaction mixture was poured into water and extracted three times with ethyl acetate. The water layer was acidified with 4M HCl and extracted three times with diethyl ether. The combined organic layers were dried over sodium sulfate, filtered and concentrated under reduced pressure. Grinding in pentane gave rel-(1S, 6S, 7S)-2-oxabicyclo [4.1.0] heptane-7-carboxylic acid (2.30 g) as a white solid.
[0595] GC-MS (Method 3): retention time 7.40 min
[0596] 1 H NMR(400MHz,DMSO-d6)δppm 12.05(br s,1H)3.70(dd,J=7.08,2.00Hz,1H)3.47-3.53(m,1H)3.20-3.31(m,1H)1.86-1.95(m,2H)1.57-1.64(m,2H)1.32-1.49(m,2H)
[0597] Step C: Preparation of rel-(1S,6S,7S)-2-oxabicyclo[4.1.0]heptane-7-carboxamide (P1)
[0598]
[0599] In a closed vial, a mixture of rel-(1S, 6S, 7S)-2-oxabicyclo [4.1.0] heptane-7-carboxylic acid ethyl ester (0.400 g, 2.35 mmol, 1.0 equivalent) and ammonium hydroxide (28% in water, 9.4 mL) was stirred at room temperature for 24 hours, then stirred at 50 ° C overnight. After cooling to room temperature, the reaction mixture was concentrated under reduced pressure. The crude product was purified by flash chromatography (ethyl acetate in cyclohexane), then precipitated in diisopropyl ether and ground in pentane to give rel-(1S, 6S, 7S)-2-oxabicyclo [4.1.0] heptane-7-carboxamide (0.118 g) as a beige solid.
[0600] GC-MS (method 2): retention time 6.54 min
[0601] 1 H NMR (400 MHz, chloroform-d) δ ppm 5.32-5.71 (m, 2H) 3.89 (dd, J = 7.27, 1.45 Hz, 1H) 3.61 (dt, J = 10.90, 3.09 Hz, 1H) 3.38 (td, J = 11.26, 1.82 Hz, 1H) 1.95-2.05 (m, 2H) 1.74-1.84 (m, 1H) 1.51-1.61 (m, 2H) 1.35-1.51 (m, 1H)
[0602] Example P2: rel-(1S,6S,7S)-N-[2-(methylcarbamoyl)phenyl]-2-oxabicyclo[4.1.0]heptyl Preparation of alkane-7-carboxamide (P2)
[0603]
[0604] To a stirred solution of rel-(1S, 6S, 7S)-2-oxabicyclo[4.1.0]heptane-7-carboxylic acid (I-1) (0.300 g, 2.11 mmol, 1.0 equivalent) in ethyl acetate (32 mL) was added 2-amino-N-methyl-benzamide (0.356 g, 2.32 mmol, 1.1 equivalents), 1-propanephosphonic anhydride (2.24 mL, 3.80 mmol, 1.80 equivalents) and N,N-diisopropylethylamine (1.11 mL, 6.33 mmol, 3.00 equivalents). The reaction mixture was stirred at room temperature overnight. It was then poured into a mixture of water and a saturated aqueous sodium bicarbonate solution and extracted three times with diethyl ether. The combined organic layer was dried over sodium sulfate, filtered, and concentrated under reduced pressure. The crude product was purified by flash chromatography (ethyl acetate in cyclohexane) to give rel-(1S,6S,7S)-N-[2-(methylcarbamoyl)phenyl]-2-oxabicyclo[4.1.0]heptane-7-carboxamide (0.400 g) as a white solid.
[0605] LC-MS (method 1): retention time 0.73 min, m / z 275 [M+H + ]
[0606] 1 H NMR (400MHz, chloroform-d) δppm 11.19 (br s, 1H) 8.52 (d, J = 7.99Hz, 1H) 7.39-7.45 (m, 2H) 7.01-7.06 (m, 1H) 6.32 (br s,1H)3.97(dd,J=7.45,1.63Hz,1H)3.61-3.68(m,1H)3.40(td,J=10.72,2.91Hz,1H)3.03(d,J= 5.09Hz,3H)1.95-2.09(m,2H)1.84-1.91(m,1H)1.76(dd,J=5.81,1.45Hz,1H)1.44-1.62(m,2H)
[0607] Example P3: rel-(1S,6S,7S)-N-(1-methyl-2-oxo-3-pyridinyl)-2-oxabicyclo[4.1.0]heptyl Preparation of alkane-7-carboxamide (P3)
[0608]
[0609] To a stirred solution of rel-(1S, 6S, 7S)-2-oxabicyclo[4.1.0]heptane-7-carboxylic acid (I-1) (0.300 g, 2.11 mmol, 1.0 equivalent) in ethyl acetate (32 mL) was added (1-methyl-2-oxo-3-pyridyl)ammonium chloride (0.373 g, 2.32 mmol, 1.1 equivalents), 1-propanephosphonic anhydride (2.24 mL, 3.80 mmol, 1.80 equivalents) and N,N-diisopropylethylamine (1.30 mL, 7.39 mmol, 3.50 equivalents). The reaction mixture was stirred at room temperature overnight. It was then poured into a mixture of water and a saturated aqueous sodium bicarbonate solution and extracted three times with diethyl ether. The combined organic layer was dried over sodium sulfate, filtered, and concentrated under reduced pressure. The crude product was purified by flash chromatography (ethyl acetate in cyclohexane) to give rel-(1S,6S,7S)-N-(1-methyl-2-oxo-3-pyridinyl)-2-oxabicyclo[4.1.0]heptane-7-carboxamide (0.250 g) as a white solid.
[0610] LC-MS (method 1): retention time 0.64 min, m / z 249 [M+H + ]
[0611] 1 H NMR (400 MHz, chloroform-d) δ ppm 8.56 (br s, 1H) 8.27 (dd, J = 7.63, 1.82 Hz, 1H) 6.96 (dd, J = 6.90, 1.82 Hz, 1H) 6.17-6.23 (m, 1H) 3.94-3.98 (m, 1H) 3.62-3.67 (m, 1H) 3.61 (s, 3H) 3.39 (td, J = 11.26, 2.18 Hz, 1H) 2.00-2.05 (m, 2H) 1.83-1.89 (m, 1H) 1.77 (dd, J = 5.81,
[0612] 1.82Hz,1H)1.43-1.63(m,2H)
[0613] Example P4: rel-(1S,6S,7S)-N-(2-oxo-1-phenyl-3-pyridinyl)-2-oxabicyclo[4.1.0]heptyl Preparation of alkane-7-carboxamide (P4)
[0614]
[0615] To a stirred solution of rel-(1S, 6S, 7S)-2-oxabicyclo[4.1.0]heptane-7-carboxylic acid (0.320 g, 2.25 mmol, 1.0 equivalent) in ethyl acetate (34 mL), 3-amino-1-phenyl-pyridine-2-one (0.461 g, 2.48 mmol, 1.1 equivalents), 1-propanephosphonic anhydride (2.39 mL, 4.05 mmol, 1.80 equivalents) and N,N-diisopropylethylamine (1.39 mL, 7.88 mmol, 3.50 equivalents) were added. The reaction mixture was stirred at room temperature overnight. The mixture was then poured into a mixture of water and a saturated sodium bicarbonate aqueous solution and extracted three times with ethyl acetate. The combined organic layer was washed with water and brine, dried over sodium sulfate, filtered, and concentrated under reduced pressure. The crude product was purified by flash chromatography (ethyl acetate in cyclohexane) to give rel-(1S,6S,7S)-N-(2-oxo-1-phenyl-3-pyridinyl)-2-oxabicyclo[4.1.0]heptane-7-carboxamide (0.400 g) as a white foam.
[0616] LC-MS (method 1): retention time 0.83 min, m / z 311 [M+H + ]
[0617] 1 H NMR (400 MHz, chloroform-d) δ ppm 8.58 (br s, 1H) 8.36 (dd, J = 7.27, 1.82 Hz, 1H) 7.49-7.55 (m, 2H) 7.42-7.49 (m, 1H) 7.38-7.42 (m, 2H) 7.05 (dd, J = 6.90, 1.82 Hz, 1H) 6.30 (t, J = 7.27 Hz, 1H) 3.98 (dd, J = 7.45 ,1.63Hz,1H)3.64(dt,J=10.81,3.13Hz,1H)3.40(td,J=11.17,2.00Hz,1H)1.9 8-2.07(m,2H)1.83-1.93(m,1H)1.75(dd,J=5.81,1.82Hz,1H)1.42-1.57(m,2H)
[0618] Example P5: (1α, 6α, 7α)- Preparation of 2,5-dioxabicyclo[4.1.0]heptane-7-carboxamide (P5)
[0619]
[0620] Step A: (1α,6α,7α)- Preparation of ethyl 2,5-dioxabicyclo[4.1.0]heptane-7-carboxylate (I-3)
[0621]
[0622] To a stirred solution of copper sulfate (0.068 g, 0.43 mmol, 0.05 equivalent) in 1,4-dioxene (1.6 mL) was added a solution of ethyl 2-diazoacetate (1.0 mL, 8.6 mmol, 1.0 equivalent) in 1,4-dioxene (1.6 mL) using a syringe pump over a period of 2.5 hours at 82 ° C. The resulting reaction mixture was stirred under reflux for another 2 hours. After cooling to room temperature, diethyl ether (10 mL) was added to the reaction mixture, and the resulting suspension was filtered through a PTFE syringe filter. The solvent was concentrated at room temperature under reduced pressure to obtain (1α, 6α, 7α)-2,5-dioxabicyclo [4.1.0] heptane-7-carboxylic acid ethyl ester (1.49 g) as a green oil.
[0623] GC-MS (Method 3): retention time 7.15 min
[0624] 1 H NMR (400 MHz, chloroform-d) δ ppm 4.07-4.16 (m, 2H) 3.95 (d, J = 3.27 Hz, 2H) 3.67-3.72 (m, 2H) 3.60-3.66 (m, 2H) 2.16 (t, J = 3.09 Hz, 1H) 1.22-1.27 (m, 3H)
[0625] Step B: (1α,6α,7α)- Preparation of 2,5-dioxabicyclo[4.1.0]heptane-7-carboxylic acid (I-4)
[0626]
[0627] To a stirred solution of (1α, 6α, 7α)-2,5-dioxabicyclo [4.1.0] heptane-7-carboxylic acid ethyl ester (0.750 g, 4.36 mmol, 1.0 equivalent) in tetrahydrofuran (10 mL) and water (10 mL) was added lithium hydroxide monohydrate (0.426 g, 17.4 mmol, 4.0 equivalents). The reaction mixture was stirred at room temperature for 18 hours. Lithium hydroxide monohydrate (0.426 g, 17.4 mmol, 4.0 equivalents) was added again and stirred at room temperature for another 24 hours. The reaction mixture was poured into water and extracted three times with diethyl ether. The aqueous layer was acidified with 4M HCl and extracted three times with diethyl ether. The combined organic layers were dried over sodium sulfate, filtered and concentrated under reduced pressure to give (1α, 6α, 7α)-2,5-dioxabicyclo [4.1.0] heptane-7-carboxylic acid (0.370 g) as a white-yellow solid.
[0628] 1H NMR (400MHz, DMSO-d6) δppm 12.24 (br s, 1H) 3.80 (d, J = 2.91Hz, 2H) 3.59 (s, 4H) 2.09-2.12 (m, 1H)
[0629] Step C: (1α,6α,7α)- Preparation of 2,5-dioxabicyclo[4.1.0]heptane-7-carboxamide (P5)
[0630]
[0631] In a closed vial, a mixture of (1α, 6α, 7α)-2,5-dioxabicyclo [4.1.0] heptane-7-carboxylic acid ethyl ester (0.750 g, 4.36 mmol, 1.0 equivalent) and ammonium hydroxide (28% in water, 18 mL) was stirred at room temperature for 24 hours and then stirred at 50 ° C overnight. After cooling to room temperature, the reaction mixture was concentrated under reduced pressure. The crude product was purified by flash chromatography (ethyl acetate in cyclohexane) to give (1α, 6α, 7α)-2,5-dioxabicyclo [4.1.0] heptane-7-carboxamide (0.180 g) as a white solid.
[0632] 1 H NMR (400 MHz, chloroform-d) δ ppm 5.57 (br s, 2H) 3.98 (d, J = 2.91 Hz, 2H) 3.68-3.75 (m, 2H) 3.60-3.68 (m, 2H) 1.98 (t, J = 2.91 Hz, 1H)
[0633] Example P6: (1α, 6α, 7α) -(N-[2-(methylcarbamoyl)phenyl]-2,5-dioxabicyclo[4.1.0]heptyl Preparation of alkane-7-carboxamide (P6)
[0634]
[0635] To a stirred solution of (1R, 6S)-2,5-dioxabicyclo[4.1.0]heptane-7-carboxylic acid (I-4) (0.360 g, 2.50 mmol, 1.0 equivalent) in ethyl acetate (38 mL) was added 2-amino-N-methyl-benzamide (0.421 g, 2.75 mmol, 1.1 equivalents), 1-propanephosphonic anhydride (2.65 mL, 4.50 mmol, 1.80 equivalents) and N,N-diisopropylethylamine (1.32 mL, 7.49 mmol, 3.00 equivalents). The reaction mixture was stirred at room temperature overnight. It was then poured into a mixture of water and a saturated aqueous sodium bicarbonate solution and extracted three times with ethyl acetate. The combined organic layers were dried over sodium sulfate, filtered, and concentrated under reduced pressure. The crude product was purified by flash chromatography (ethyl acetate in cyclohexane) followed by reverse phase chromatography (acetonitrile in water) to give (1α,6α,7α)-2,5-dioxabicyclo[4.1.0]heptane-7-carboxylic acid (0.135 g) as a red solid.
[0636] LC-MS (method 1): retention time 0.64 min, m / z 277 [M+H + ]
[0637] 1 H NMR (400MHz, chloroform-d) δppm 11.26 (br s, 1H) 8.46 (d, J = 7.99Hz, 1H) 7.38-7.46 (m, 2H) 7.01-7.09 (m, 1H) 6.34 (br s,1H)4.05(d,J=2.91Hz,2H)3.64-3.77(m,4H)3.02(d,J=4.72Hz,3H)2.20(t,J=2.91Hz,1H)
[0638] Table P: Examples of compounds of formula I:
[0639]
[0640]
[0641]
[0642]
[0643]
[0644]
[0645]
[0646]
[0647] By adding other insecticides, acaricides and / or fungicidal active ingredients, the activity of the composition according to the present invention can be significantly widened and adapted to prevailing conditions. Mixtures of compounds of Formula I or II with other insecticides, acaricides and / or fungicidal active ingredients can also have other unexpected advantages, which can also be described as synergistic in a broader sense. For example, better tolerance of plants, reduced phytotoxicity, insects can be controlled at their different developmental stages, or better behavior during their production (e.g., during grinding or mixing, during their storage or during their use).
[0648] Suitable active ingredients for addition 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.
[0649] Disclosed herein is a list of compound TX consisting of:
[0650] A. the compounds listed in Table P; and
[0651] B. Compounds defined in Tables A-1 to A-36; and
[0652] C. Compounds defined in Tables A-7 to A-36 (wherein Formula IA is represented by Formula Ia (when X is CH2, S, SO, SO2, or SO(NH))); and
[0653] D. Compounds defined in Tables A-1 to A-6 (wherein Formula IA is represented by Formula Iaa (when X is O)); and
[0654] E. Compounds defined in Tables B-7 to B-30 (wherein Formula II-A is represented by Formula IIa (when X is CH2, S, SO, SO2, or SO(NH))); and
[0655] F.; and
[0656] G. Compounds defined in Tables B-1 to B-6 (wherein Formula II-A is represented by Formula IIaa (when X is O)).
[0657] The present invention also makes available mixtures of a compound of the present invention and another active agent (chemical or biological) in a 1 to 1 weight ratio. Thus, disclosed herein are mixtures of a compound of the present invention as defined by TX and an active agent (chemical or biological) as disclosed below in List A in a 1 to 1 weight ratio.
[0658] List A
[0659] An auxiliary agent selected from the group consisting of: petroleum (alias) (628) + TX;
[0660] Abamectin + TX, acetamiprid + TX, acetamiprid + TX, flumethrin + TX, acynonapyr + TX, bifenapyr + TX, afoxolaner + TX, cotton bell carbendazim + TX, allethrin + TX, α-cypermethrin + TX, alpha-cypermethrin + TX, sulfamethoxazole + TX, cypermethrin + TX, triazotin + TX, sulfamethoxazole + TX, benzyltrimethoxam + TX, benzpyrimoxan + TX, β-cyfluthrin + TX, β-cypermethrin + TX, bifenazate + TX, bifenthrin + TX, binapacryl + TX, bioallethrin + TX, S-bioallethrin + TX, bio-resmethrin + TX, bistrifluan + TX, broflanilide + TX, brofluthrin + TX, bromophos-ethyl + TX, buprofezin + TX, butacarb + TX, cadusafos + TX, carbaryl + TX, butacarb + TX, batan + 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.: 2095470-94-1+TX, CAS No.: 2377084 -09-6+TX、CAS No.:1445683-71-5+TX、CAS No.:2408220-94-8+TX、CAS No.:2408220-91-5+TX、CAS No.:1365070-72-9+TX、CAS No.:2171099-09-3+TX、CAS No.:2396747-83-2+TX、CAS No.:2133042-31-4+TX、CAS No.:2133042-44-9+TX、CAS No.:1445684-82-1+TX、CAS No.:1445684-82-1+TX、CAS No.:1922957-45-6+TX、CAS No.:1 922957-46-7+TX、CAS No.:1922957-47-8+TX、CAS No.:1922957-48-9+TX、CAS No.:2415706-16-8+TX、CAS No.:1594624-87-9+TX、CAS No.:1594637-65-6+TX、CAS No.:1594626-19-3+TX、CAS No.:1990457-52-7+TX、CAS No.:1990457-55-0+TX、CAS No.:1990457-57-2+TX、CAS No.:1990457-77-6+TX、CAS No.:1990457-66-3+TX、CAS No.: 1990457-85-6+TX, CAS No.: 2220132-55-6+TX, CAS No.: 1255091-74-7+TX, CAS No.: 2719848-60-7+TX, CAS No.: 1956329-03-5+TX, chlorantraniliprole+TX, chlordane+TX, chlorfenapyr+TX, chlorpromazide+TX, chloranil+TX, chlorfenapyr+TX, chlorfenapyr+TX, clenpyrine+TX, cloethocarb+TX, clothianidin+TX, 2-chlorophenyl N-methylcarbamate (CPMC)+TX, benzonitrile+TX, cyanantraniliprole+TX, cyclobromofenapyr+TX, cyclobutrifluanid+TX ram)+TX, pyrethroids+TX, cycloxanthrin+TX, cytoxanil+TX, cyetpyrafen+TX, cyetpyrafen or etpyrafen+TX, cyfluthrin+TX, cyhalodiamide+TX, cyhalothrin+TX, cypermethrin+TX, cyproflanilide+TX, cyromazine+TX, deltamethrin+TX, cypermethrin+TX, cyproflanilide+TX, cyromazine+TX, deltamethrin+TX, cypermethrin+TX, chlorpyrifos+TX, chlorfenapyr+TX, chlorfenapyr+TX, dibrom+TX, dichlorothiazine+TX, fluazifop+TX, diflubenzuron+TX, methicillin+TX Dimpropyridaz + TX, diprofenac + TX, dinotefuran + TX, vesifloxacin + TX, emamectin (or emamectin benzoate) + TX, d-epsilon + TX, epsilon-momfluorothrin + TX, epsilon-metofluthrin + TX, cypermethrin + TX, ethion + TX, ethiprole + TX, ethomethrin + TX, etoxazole + TX, fenmethrin + TX, fenazaquin + TX, pentothrin + TX, fenmezoditiaz + TX, fenitrothion + TX, famoxadone + TX, fenthiocarb + TX, fenoxycarb + TX, cypermethrin + TX, fenpyroximate (fenpyroximate) + TX, fenpyrophos + TX, fenthion + TX, yesalin + TX, cypermethrin + TX, fipronil + TX, flometoquin + TX, flonicamid + TX, pyrimidifen + TX, fluazaindolizine + TX, flupyrimid + TX, flufenoxamide + TX, fluchlordiniliprole + TX, flucitrinate + TX, flufenoxamide + TX, flucythrin + TX, fluthiazolin + TX, flumethrin + TX, flumethrin + TX, butenefipronil + TX,Fluhexafon + TX, fluchlorfenapyr + TX, fluopyram + TX, flupentiofenox + TX, flupyronil + TX, flupyrimin + TX, fluralaner + TX, fluvalinate + TX, fluxametamide + TX, thiamethoxam + TX, γ-cyhalothrin + TX, pyrimidine + TX, chlorfenapyr + TX, benzyl ammonium chloride + TX, heptafluthrin + TX, hexathiazox + TX, hydrazone + TX, imicyafos + TX, γ-cyhalothrin + TX, pyrimidine + TX, chlorfenapyr + TX, benzyl ammonium chloride + TX, heptafluthrin + TX, hexathiazox + TX, hydrazone + TX, imicyafos os)+TX, imidacloprid+TX, imiprodinil+TX, indazapyroxamet+TX, indoxacarb+TX, iodomethane+TX, iprodione+TX, isocycloseram+TX, isosulfuron+TX, ivermectin+TX, kappa-bifenthrin+TX, kappa-tefluthrin+TX, lambda-cyhalothrin+TX, ledprona+TX, lepidomectin+TX, lotilaner+TX, chlorfenuron+TX, metaflumizone+TX, metaldehyde+TX, methomyl+TX, methomyl+TX, methoxyfenozide+TX, metofluthrin+TX, cypermethrin+TX, chlorfenapyr ... X, acaricide + TX, momfluorothrin + TX, cypermethrin + TX, nicofluprole + TX; nitenpyram + TX, nithiazine + TX, omethoate + TX, oxamyl + TX, oxazosulfyl + TX, parathion-ethyl + TX, permethrin + TX, phenothrin + TX, phosphamidon + TX, piperonyl butoxide + TX, pirimicarb + TX, pirimiphos-ethyl + TX, pirimiphos-methyl + TX, polyhedrosis virus + TX, prallethrin + TX, profenofos + TX, profluthrin + TX, propargite + TX, chlorpyrifos + TX, propoxur + TX, prothiophos + TX, protrifenbute + TX, pyflubumide + TX, pymetrozine + TX, pyraclofos + TX, pyrafluprole + TX, pyridaben + TX, pyridalyl + TX, pyrifluquinazon + TX, pyrimidine + TX, pyriminostrobin + TX, pyraclostrobin + TX, pyraclostrobin + TX, pyraclostrobin + TX, pyrimethrin + TX, pyriproxyfen + TX, resmethrin + TX, sarolaner + TX, selamectin + TX, silafluthrin + TX, spinosad + TX, spinosad + TX,Spirobudifen + TX; spirobudifen + TX, spiromesifen + TX, spiropidion + TX, spirotetramat + TX, spidoxamat + TX, sulfonecarb + TX, tebufenozide + TX, tebufenpyrad + TX, tebupirimiphos + TX, tefluthrin + TX, temephos + TX, tetracycline + TX, tetracycline sulfone + TX, tetramethrin + TX, tetracycline + TX, cyfluthrin + TX, fluazifop + TX +TX, θ-cypermethrin +TX, thiacloprid +TX, thiamethoxam +TX, thiodicarb +TX, long-lasting carb +TX, methyl benzyl sulfate +TX, sulfometuron +TX, tigolaner +TX, tiorantraniliprole +TX; tioxazafen +TX, tolfenpyrad +TX, toxaphene +TX, tralomethrin +TX, transfluthrin +TX, triazophos +TX, trichlorfon +TX, trichlorfon +TX, triflumuron (, trifluenfuronate)+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-21 618)+TX, Bacillus firmus+TX, Bacillus kurstak 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 (subspec.Kurstaki) BMP 123+TX, Beauveria bassiana+TX, D-limonene+TX, Granulovirus+TX, Harpin+TX, Helicoverpa armigera nuclear polyhedrosis virus+TX, Heliothis corneum nuclear polyhedrosis virus+TX, Heliothis virescens nuclear polyhedrosis virus+TX, Australian Helicoverpa armigera nuclear polyhedrosis virus+TX, Metarhizium species+TX, Muscodor albus 620 (NRRL accession number 30547)+TX, Muscodor albus 620 (NRRL accession number 30547)+TX, roseus) A3-5 (NRRL accession number 30548) + TX, neem-based products + TX, Paecilomyces fumosorum + TX, Paecilomyces lilacinus + TX, Pasteuria szabalensis + TX, Pasteuria penetrantus + TX, Pasteuria mycoides + 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, QRD460 (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 sp. (NRRL Accession No. B-30145) + TX, terpenoid blend + TX, and Verticillium sp. + TX;
[0661] 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, endoxan (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) + TX, and triphenyltin hydroxide (IUPAC name) (347) + TX;
[0662] Anthelmintics selected from the group consisting of: avermectin (1) + TX, clefonate (1011) + TX, cybutaflutol + TX, doramectin (alias) [CCN] + TX, emamectin (291) + TX, emamectin benzoate (291) + TX,
[0663] Eprinomectin (alias) [CCN] + TX, ivermectin (alias) [CCN] + TX, milbemycinoxime (alias) [CCN] + TX, moxidectin (alias) [CCN] + TX, piperazine [CCN] + TX, selamectin (alias) [CCN] + TX, spinosad (737) + TX, and thiophanate (1435) + TX; an avicide selected from the group consisting of chloralose (127) + TX, endrin (1122) + TX, fenthion (346) + TX, pyridin-4-amine (IUPAC name) (23) + TX, and strychnine (745) + TX;
[0664] Bactericide selected from the group consisting of: 1-hydroxy-1H-pyridine-2-thione (IUPAC name) (1222) + TX, 4-(quinoxalin-2-ylamino)benzenesulfonamide (IUPAC name) (748) + TX, 8-hydroxyquinoline sulfate (446) + TX, bronopol (97) + TX, copper dioctanoate (IUPAC name) (170) + TX, copper hydroxide (IUPAC name) (169) + TX, cresol [CCN] + TX, dichlorophen (232) + TX, dipyrithione (1105) + TX, dodesine (1112) + TX, fenaminosulf (1144) + TX, formaldehyde (404) + TX, mercaptophenone (IUPAC name) + TX, 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, chlorpheniramine (766) + TX, and thimerosal (other name) [CCN] + TX;
[0665] 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, NPV of celery budworm (alias) (28) + TX, Anagrus atomus (alias) (29) + TX, Aphelinus abdominalis (alias) (33) + TX, Aphidius colemani (alias) (34) + TX, Aphidoletes aphidimyza (alias) (35) + TX, NPV of lucerne budworm (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.ai zawai)(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)(other name)(53)+TX、Beauveria brongniartii)(other name)(54)+TX、Chrysoperla carnea)(alias)(151)+TX、Cryptolaemus montrouzieri)(alias)(178)+TX、GV of the codling moth(alias)(191)+TX、Dacnusa sibirica(alias)(212)+TX、Diglyphus isaea(alias)(254)+TX、Eretmocerus sibirica(scientific name)(293)+TX、Eretmocerus sibirica 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, Spodoptera exigua 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, Neodiprion sertifer NPV and N. lecontei NPV (alias) (575) + TX, species of the genus Pseudomonas (alias) (596) + TX, Paecilomyces fumosoroseus (alias) (613) + TX, Phytoseiulus persimlis (alias) (644) + TX, Spodoptera exigua multicapsid nuclear polyhedrosis virus (scientific name) (741) + TX, Steinernema bibionis (alias) (742) + TX, Steinernema carpocapsae) (alias) (742) + TX, Steinernema molitor (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) + TX, and Verticillium lecanii (alias) (848) + TX;
[0666] Soil disinfectants selected from the group consisting of iodomethane (IUPAC name) (542) + TX, and bromomethane (537) + TX;
[0667] A chemical sterilant selected from the group consisting of: apholanate [CCN] + TX, bisazir (alias) [CCN] + TX, busulfan (alias) [CCN] + TX, diflubenzuron (250) + TX, dimatif (alias) [CCN] + TX, hemel [CCN] + TX, hempa [CCN] + TX, metepa [CCN] + TX, methiotepa [CCN] + TX, methyl apholanate [CCN] + TX, methyl bisazir ... apholate) [CCN] + TX, morzid [CCN] + TX, penfluron (other name) [CCN] + TX, tepa [CCN] + TX, thiohempa (other name) [CCN] + TX, thiohexamethylenetepa (other name) [CCN] + TX, trotamide (other name) [CCN] + TX, and urethaneimide (other name) [CCN] + TX;
[0668] 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)-hexadecan-11-enal (IUPAC name) (436) + TX, (Z)-hexadecan-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, codlemone (alias) (167) + TX, cuelure (alias) ( 179)+TX, disparlure (277)+TX, dodec-8-en-1-yl acetate (IUPAC name) (286)+TX, dodec-9-en-1-yl acetate (IUPAC name) (287)+TX, dodec-8+TX, 10-dien-1-yl acetate (IUPAC name) (284)+TX, dominicalure (alias) [CCN]+TX, ethyl 4-methyloctanoate (IUPAC name) (317)+TX, eugenol (alias) [CCN]+TX, southern pine beetle aggregation pheromone (frontalin) (alias) [CCN]+TX, (Alternative name; a 1:1 mixture of (Z,E) and (Z,Z) isomers of hexadeca-7,11-dien-1-yl acetate) (420) + TX, grandlure (421) + TX, grandlure I (alternative name) (421) + TX, grandlure II (alternative name) (421) + TX, grandlure III (alternative name) (421) + TX, grandlure IV (alternative name) (421) + TX, hexalure [CCN] + TX, ipsdienol (alternative name) [ 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, (3E,5Z)-tetradec-3,5-dienoic acid (megatomoic acid)(alias)[CCN]+TX、Methyl eugenol)(alias)(540)+TX、Muscalure(563)+TX、Octadec-2,13-dien-1-yl acetate(IUPAC name)(588)+TX、Octadec-3,13-dien-1-yl acetate(IUPAC name)(589)+TX、Orfralure(alias)[CCN]+TX、Coconut rhinoceros beetle aggregation pheromone(oryctalure)(alias)(317)+TX、Ostramone(alias)[CCN]+TX、Muscalure( siglure) [CCN] + TX, banana bulb weevil attractant (sordidin) (alias) (736) + TX, sulcatol (alias) [CCN] + TX, tetradec-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 B1 (alias) (839) + TX, Mediterranean fruit fly attractant B2 (alias) (839) + TX, Mediterranean fruit fly attractant C (alias) (839) TX, and trunc-call (alias) [CCN] + TX;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] + TX, and picaridin [CCN] + TX;
[0669] 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 (62 3) + 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) + TX, triphenyltin hydroxide (IUPAC name) (347) + TX, and pyriprole [394730-71-3] + TX;
[0670] 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) 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, AZ 60541 (compound code) + TX, benclothiaz[CCN] + TX, benomyl (62) + TX, butylpyridaben (alias) + TX, chlorpyrifos (109) + TX, carbofuran (118) + TX, carbon disulfide (945) + TX, carbofuran (119) + TX, chloropicrin (141) + TX, chlorpyrifos (145) + TX, Xianwei (999) + TX, cyclobutaflutol + 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, dibromoethane (316)+TX, fenamiphos (326)+TX, fenpyrad (alias)+TX, fensulfuron (1158)+TX, thiazophos (408)+TX, butasulfophos (1196)+TX, furfural Aldehyde (alias) [CCN] + TX, GY-81 (research code) (423) + TX, cypermethrin [CCN] + TX, iodomethane (IUPAC name) (542) + TX, isamidophos (1230) + TX, chlorfenapyr (1231) + TX, ivermectin (alias) [CCN] + TX, kinetin (alias) (210) + TX, methyl azomethasone (1258) + TX,Metamex (519) + TX, Metamex potassium salt (alias) (519) + TX, Metamex sodium salt (519) + TX, methyl bromide (537) + TX, methyl isothiocyanate (543) + TX, milbemycin oxime (alias) [CCN] + TX, moxidectin (alias) [CCN] + TX, Myrothecium verrucaria composition (alias) (565) + TX, NC-184 (compound code) + TX, oxamyl (602) + TX, methyl parathion (636) + TX, phosphamidon (639) + TX, phosphamidon [CCN] + TX, chlorpyrifos (alias) + TX, selamectin (alias) [CCN] ]+TX, spinosad (737)+TX, terbufos (alias)+TX, terbufos (773)+TX, tetrachlorothiophene (IUPAC / Chemical Abstracts name) (1422)+TX, thiafenox (alias)+TX, fenamiphos (1434)+TX, triazophos (820)+TX, triazuron (alias)+TX, dimethylol [CCN]+TX, YI-5302 (compound code)+TX and zeatin (alias) (210)+TX, fluensulfone [318290-98-1]+TX, and fluopyram+TX;
[0671] A nitrification inhibitor selected from the group consisting of potassium ethylxanthate [CCN] + TX and nitrapyrin (580) + TX;
[0672] A plant activator selected from the group consisting of acibenzolar (6) + TX, acibenzolar-S-methyl (6) + TX, probenazole (658) + TX, and Reynoutria sachalinensis extract (alias) (720) + TX;
[0673] Rodenticide selected from the group consisting of: 2-isovaleryl indan-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, bisulfamethoxazole (912) + TX, brodifacoum (89) + TX, bromadiolone (including α-Bromadiolone) + TX, Bromadiolamine (92) + TX, Calcium Cyanide (444) + TX, Chloralose (127) + TX, Chloralone (140) + TX, Cholecalciferol (alias) (850) + TX, Chlorodiol (1004) + TX, Cyclodextrin (1005) + TX, Cyclodextrin (175) + TX, Cyclodextrin (1009) + TX, Cyclodextrin (246) + TX, Cyclodextrin (249) + TX, Cyclodextrin (273) + TX, Calciferol (301) + TX, Fluorodiol Fluorothiazolin (357) + TX, 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 (1336) + TX )+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)+TX, and zinc phosphide (640)+TX;
[0674] Synergist, which is 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; piprotal (1343) + TX; propyl ester (1343) + TX isomer)(1358)+TX; S421(research code)(724)+TX; sesamex(1393)+TX; sesasmolin(1394)+TX, and sulfoxide(1406)+TX;
[0675] Animal repellents, which are selected from the group consisting of 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, salamine (804) + TX, trimethacarb (840) + TX, zinc cyclohexane [CCN] + TX, and ziram (856) + TX;
[0676] Virucidal agents selected from the group consisting of: imamin (alternative name) [CCN] and ribavirin (alternative name) [CCN] + TX;
[0677] A wound protection agent selected from the group consisting of mercuric oxide (512) + TX, octhilinone (590) + TX, and thiophanate-methyl (802) + TX;
[0678] Biologically active substances selected from 1,1-bis(4-chloro-phenyl)-2-ethoxyethanol+TX, 2,4-dichlorophenylbenzenesulfonate+TX, 2-fluoro-N-methyl-N-1-naphthylacetamide+TX, 4-chlorophenylphenylsulfone+TX, acetofenapyr+TX, aldisulfonyl+TX, sagofos+TX, fomanphos+TX, amitriptyline+TX, amitriptyline hydrogen oxalate+TX, amitraz+TX, cypermethrin+TX, arsenic trioxide+TX, azobenzene+TX, azophos+TX, benomyl+TX, benoxaphos+TX, benzyl benzoate+TX, bixafenthion+TX, bromothiophene+TX, bromothiophene+TX, bromothiophene+TX X, bromopyralid + TX, buprofezin + TX, butanone carbendazim + TX, butanone carbendazim + TX, butylpyridaben + TX, calcium polysulfide + TX, octachlorocamphene + TX, chlormethoxam + TX, trithion + TX, cypermethrin + TX, cypermethrin + TX, cypermethrin + TX, chlordimeform + TX, chlordimeform hydrochloride + TX, chlorfenapyr + TX, chlorfenapyr + TX, chlorfenapyr + TX, ethyl chlorfenapyr + TX, chlorfenapyr + TX, propyl chlorfenapyr + TX, chlorfenapyr + TX, cypermethrin I + TX, cypermethrin II + TX, cypermethrin + TX, closantel + TX, coumaphos + TX, crotamiton + TX, baclofos + T X, thiophanate + TX, chlorfenapyr + TX, DCPM + TX, DDT + TX, dinapyr + TX, dinapyr-O + TX, dinapyr-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, chlorfenapyr + TX, dichlorvos + TX, dicliphos + TX, dichlorvos + TX, dimethoate + TX, dimethoate + TX, dimethoate + TX, dinex + TX, dinex-diclexine + TX, dimethoate Pu-4+TX, diclofenac-6+TX, orthodimethoate+TX, nitropentyl+TX, nitrooctyl ester acaricide+TX, nitrobutyl+TX, dimethoate+TX, sulfodiphenyl+TX, disulfiram+TX, DNOC+TX, phenoxyacetic acid+TX, doramectin+TX, fenoxaphos+TX, eprinomectin+TX, phosphamidon+TX, ethimox+TX, anti-mite+TX, fenbutatin+TX, fenthiocarb+TX, fenpyrad+TX, fenpyraclostrobin+TX, fenamipyraclostrobin+TX, fenpyrad+TX, fluazifop+TX, flunitroaniline+TX, fluazifop+TX, flufenoxuron+TX, fluazifop+TX, FMC 1137+TX, fenvalerate+TX, fenvalerate hydrochloride+TX, carbendazim+TX, γ-HCH+TX, chlorpyrifos+TX, benzyl methoxyfen+TX, hexadecyl cyclopropane carboxylate+TX, isocarbophos+TX, jasmonate I+TX, jasmonate II+TX, iodonium sulfate+TX, lindane+TX, propanil+TX,Mefenacet + TX, dithiophos + TX, methylthiophene + TX, acarb + TX, methyl bromide + TX, methicillin + TX, chlorpyrifos + TX, milbemycin + TX, propylamine + TX, monocrotophos + TX, maoguo + TX, moxidectin + TX, dibromophos + TX, 4-chloro-2-(2-chloro-2-methyl-propyl)-5-[(6-iodo-3-pyridyl)methoxy]pyridazin-3-one + TX, fluazifop + TX, nikkomycin + TX, pentocyanamide + TX, pentocyanamide 1:1 zinc chloride complex + TX, omethoate + TX, isothiocarb + TX, sulfamethoxam + TX, pp'-DDT + TX, parathion + TX, permethrin + TX, fenthion + TX, phosalone + TX, thiophanate + TX, phosphamidon + TX, phosphamidon + TX, chlorinated turpentine + TX, acaricide + TX, proclonol + 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-1492 + TX, glyphosate + TX, rotenone + TX, octamidine + TX, clomar + TX, selamectin + TX, thiothion + TX, SSI-121 + TX, sulfluramid + TX, sulfotep + TX, sulfur + TX, fluazifop + TX, τ-fluvalinate + TX, TEPP + T X, terbucarb + TX, tetrachlorobenzene + TX, acarbicide + TX, thiafenox + TX, pyrimidine + TX, long-lasting chlorpyrifos + TX, methyl benzylphos + TX, chlorpyrifos + TX, thiamethoxam + TX, thiamethoxam + TX, triazophos + TX, chlorpyrifos + TX, triclosan + TX, triamcinol + TX, aphidoxam + TX, methyl fipronil + TX, pyrimidine + TX, copper dioctanoate + TX, copper sulfate + TX, cybutryne + TX, dichloronaphthoquinone + TX, dichlorophen + TX, endoxan + TX, triphenyltin + TX, slaked lime + TX, sodium mancozeb + TX, chlorpyrifos + TX, quinone + TX, simazine + TX, triphenyltin acetate + TX, triphenylhydrazine Tin oxide + TX, folate + TX, piperazine + TX, thiophanate + TX, chloralose + TX, fenthion + TX, pyridin-4-amine + TX, strychnine + TX, 1-hydroxy-1H-pyridine-2-thione + TX, 4-(quinoxalin-2-ylamino)benzenesulfonamide + TX, 8-hydroxyquinoline sulfate + TX, bronopol + TX, copper hydroxide + TX, cresol + TX, dipyrithione + TX, dodixan + TX, sodium disulfide + TX, formaldehyde + TX, mercury + TX, kasugamycin + TX, kasugamycin hydrochloride hydrate + TX, nickel bis(dimethyldithiocarbamate) + TX, trichloromethylpyridine + TX, octhiothione + TX, oxolinic acid + TX, oxytetracycline + TX, potassium hydroxyquinoline sulfate + TX,Thiabendazole+TX, Streptomycin+TX, Streptomycin sesquisulfate+TX, Chlorophyll+TX, Thimerosal+TX, GV of the cotton brown-banded tormentor+TX, Agrobacterium radiobacterium+TX, Amblyseius species+TX, Spodoptera exigua NPV+TX, Procera ceranae+TX, Aphididae short-spurred wasp+TX, Cotton aphid parasitoid wasp+TX, Aphid midge+TX, Spodoptera lucerne NPV+TX, Bacillus sphaericus+TX, Beauveria bassiana+TX, Common lacewing+TX, Cryptochilus mandshurica+TX, GV of the codling moth+TX, Siberian sibirica+TX, Pea leafminer+TX, Aphididae ensifolia+TX , Aphididae + TX, Bacteriotrophic Heterorhabditis elegans and Heterorhabditis elegans + TX, Spotted Long-legged Ladybird + TX, Scale Parasitoid Wasp + TX, Misty Bug + TX, Cabbage Lobelia NPV + TX, Yellow-stalked Jumping Lobelia + TX, Yellow-green Metarhizium + TX, Metarhizium anisopliae Microspore Var. + TX, New European Pine Sawfly NPV and New Red-headed Pine Sawfly NPV + TX, Small Flower Bug Species + TX, Fumosomolus Roseus + TX, Chilean Small Plant Mite + TX, Hairy Mosquito Nematode + TX, Small Rolled Moth Nematode + TX, Noctuid Moth Nematode + TX, Grill's Nematode + TX, Steinernema sharpiena + TX, Steinernema riobravis+TX, mole cricket Steinernema+TX, Steinernema species+TX, Trichogramma species+TX, western blind mite+TX, Verticillium lecanii+TX, zophosphine+TX, bis(aziridine)methylaminophosphonium sulfide+TX, busulfan+TX, dimethivin+TX, hexamethylmelamine+TX, hexamethylphosphine+TX, methyl thiophosphine+TX, methylzophosphine+TX, infertility pyridine + TX, flubendiamide + TX, thiamethoxam + TX, thiamethoxam + TX, trothamide + TX, urethaneimine + 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-diene- 1-yl acetate + TX, (Z)-dodec-7-en-1-yl acetate + TX, (Z)-hexadec-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 gathering pheromone + TX, dodecadienol + TX, caldoxime + TX, tardione + TX, epoxynonadecane + TX, dodec-8-en-1-yl acetate + TX, dodec-9-en-1-yl acetate + TX, dodec-8 + TX, 10-dien-1-yl acetate + TX, dominicalure + TX, ethyl 4-methyloctanoate + TX, eugenol + TX, southern pine beetle gathering pheromone + TX, tardione mixture + TX, tardione mixture I + TX, tardione mixture II + TX, tardione mixture III + TX, tardione mixture IV + TX, hexane + TX, tooth beetle dienol + TX, beetle dienol + TX, scarab sex attractant + TX, trimethyldioxytricyclononane + TX, litlure + TX, cabbage looper sex attractant + TX, trapping ester + TX, (3E,5Z)-tetradec-3,5-dienoic acid + TX, trapping ether + TX, trapping ene + TX, octadec-2,13-dien-1-yl acetate + TX, octadec-3,13-dien-1-yl acetate + TX, Hekangbi + TX, coconut rhinoceros beetle aggregation pheromone + TX, non-lecon + TX, trapping ring + TX, sordidin + TX, fungivorous acetic acid + TX, tetradec-11-en-1-yl acetate + TX, Mediterranean fruit fly attractant + TX, Mediterranean fruit fly Attractant A+TX, Mediterranean fruit fly attractant B1+TX, Mediterranean fruit fly attractant B2+TX, Mediterranean fruit fly attractant C+TX, trunc-call+TX, 2-(octylthio)ethanol+TX, dimethoate+TX, butoxy(polypropylene glycol)+TX, dibutyl adipate+TX, dibutyl phthalate+TX, dibutyl succinate+TX, DEET+TX, mosquito repellent+TX, dimethyl phthalate+TX, ethyl hexanediol+TX, hexyl urea+TX, mequindine+TX, methyl neodecylamide+TX, oxamate+TX, picaridin+TX, 1-dichloro-1-nitroethane+TX, 1,1-dichloro-2,2-bis(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)phenylmethylcarbamate + TX, 2-(4-chloro-3,5-xylyloxy)ethanol + TX, 2-chlorovinyl diethyl phosphate + TX, 2-imidazolidinone + TX, 2-isovalerylindan-1,3-dione + TX,2-Methyl (prop-2-ynyl) aminophenyl methylcarbamate + TX, 2-thiocyanatoethyl laurate + TX, 3-bromo-1-chloroprop-1-ene + TX, 3-methyl-1-phenylpyrazol-5-yl dimethylcarbamate + TX, 4-methyl (prop-2-ynyl) amino-3,5-xylylmethylcarbamate + TX, 5,5-dimethyl-3-oxocyclohex-1-enyl dimethylcarbamate + T X, acethion + TX, acrylonitrile + TX, aldrin + TX, aloamicin + TX, chlorpyrifos + TX, α-decadin + TX, aluminum phosphide + TX, chlorpyrifos + TX, neonicotinoids + TX, ethyl methidathion + TX, methyl pyrifos + TX, Bacillus thuringiensis δ-endotoxin + TX, barium hexafluorosilicate + TX, barium polysulfide + TX, cypermethrin + TX, Bayer 22 / 190 + TX, Bayer 22408 + T X, β-cyfluthrin + TX, β-cypermethrin + TX, pentocyclam + TX, biopermethrin + TX, bis(2-chloroethyl) ether + TX, borax + TX, bromophenazone + TX, bromo-DDT + TX, cypermethrin + TX, cyfluthrin + TX, temirphos + TX, butylphos + TX, calcium arsenate + TX, calcium cyanide + TX, carbon disulfide + TX, carbon tetrachloride + TX, cypermethrin hydrochloride + TX, servadine + TX, bornyl + TX, chlordane + TX, chlordecone + TX, chloroform + TX, chloropicrin + TX, chloranisole + TX, chlorpyrifos + TX, cis-resmethrin + TX, cismethrin + TX, cypermethrin + TX, copper acetylarensite + TX, copper arsenate + TX, copper oleate + TX, cypermethrin + TX, cryolite + TX, CS 708+TX, benzonitrile+TX, cypermethrin+TX, cypermethrin+TX, cypermethrin+TX, d-cypermethrin+TX, DAEP+TX, dazomethon+TX, demethylcarbofuran+TX, chloranil+TX, isochlorvinphos+TX, chloranil+TX, dicresyl+TX, cypermethrin+TX, dieldrin+TX, diethyl 5-methylpyrazol-3-yl phosphate+TX, thiophene+TX, tetrafluthrin+TX, demacarb+TX, pyrethrin+TX, methylchlorfenapyr+TX, difenocarb+TX, propanol+TX, pentotropol+TX, dinoseb+TX, fenpropathrin+TX, vegetable phosphorus+TX, thiopyraphos+TX, DSP+TX, ecdysterone+TX, EI 1642+TX, EMPC+TX, EPBP+TX, etaphos+TX, ethiobencarb+TX, ethyl formate+TX, dibromoethane+TX, dichloroethane+TX, ethylene oxide+TX, EXD+TX, ethiobencarb+TX, ethiobencarb+TX, fenitrothion+TX, pyrimidine+TX, cypermethrin+TX, fenthion+TX, ethylfenthion+TX, chlorpyrifos+TX, butylfenthion+TX, phosphamidon+TX,Butylthion + TX, Fusalcarb + TX, Pyrethroid + TX, Biguanidine salt + TX, Biguanidine acetate + TX, Sodium tetrathiocarbonate + TX, Benzofen + TX, HCH + TX, HEOD + TX, Heptachlor + TX, Methiothion + TX, HHDN + TX, Hydrogen cyanide + TX, Quinoline + TX, IPSP + TX, Cyclofos + TX, Carbochlorin + TX, Isoaldrin + TX, Isothiophos + TX, Transplanting agent + TX, Blasticide + T X, oxazophos + TX, juvenile hormone I + TX, juvenile hormone II + TX, juvenile hormone III + TX, chlorpentyl + TX, methoprene + TX, lead arsenate + TX, bromophenophos + TX, pyralidon + TX, thiazophos + TX, m-isopropyl methylcarbamate + TX, magnesium phosphide + TX, phosphorus azide + TX, methyl azoxyphos + TX, thiamethoxam + TX, mercurous chloride + TX, methyl sulfoxide + TX, metamifene + TX, metamifene potassium salt +TX, sodium salt of Metamex +TX, methylsulfonyl fluoride +TX, butenamidophos +TX, methoprene +TX, methylthiothrin +TX, methoxychlor +TX, methyl isothiocyanate +TX, methyl chloroform +TX, dichloromethane +TX, oxadiazine +TX, mirex +TX, napeptide +TX, naphthalene +TX, NC-170 +TX, nicotine +TX, nicotine sulfate +TX, nithiazine +TX, pronicotine +TX, O-5-dichloro-4-iodo Phenyl O-ethyl ethyl 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 dithiopyrophosphate + TX, oleic acid + TX, p-dichlorobenzene + TX, methyl parathion + TX, pentachlorophenol + TX, pentachlorophenyl laurate + TX, PH 60-38+TX, fenthion+TX, parachlorothion+TX, phosphine+TX, methyl phoxim+TX, methamidophos+TX, polychlorinated dicyclopentadiene isomers+TX, potassium arsenite+TX, potassium thiocyanate+TX, precocious plant I+TX, precocious plant II+TX, precocious plant III+TX, amidopyrimidin+TX, fluthrin+TX, fenvalerate+TX, prothiophos+TX, pyraclostrobin+TX, anti-pyrethroid+TX, quassia extract+TX, quinalphos-methyl+TX, fenvalerate+TX, iodophos+TX, Resmethrin + TX, Rotenone + TX, Thiamphenicol + TX, Ronitin + TX, Rianodin + TX, Veratrum sabalii + TX, Phosphate + TX, Clamine + TX, SI-0009 + TX, Thiaclonitrile + TX, Sodium arsenite + TX, Sodium cyanide + TX, Sodium fluoride + TX, Sodium hexafluorosilicate + TX, Sodium pentachlorophenol + TX, Sodium selenate + TX, Sodium thiocyanate + TX, Sulfonamide + TX, Sulfonamide sodium salt + TX, Sulfuryl fluoride + TX, Thiaprophos + TX, Tar + TX, Thiamethoxam + TX, TDE + TX,Butylpyrimidinphos + TX, bispyribac + TX, cypermethrin + TX, tetrachloroethane + TX, thiochlorvos + TX, cyclohexane + TX, cyclohexane oxalate + TX, cypermethrin + TX, cypermethrin sodium + TX, tralomethrin + TX, permethrin + TX, triazolam + TX, isothiocyanate + TX, chlorpyrifos + TX, cyclohexanone + TX, trifloxystrobin + TX, chlorpyrifos + TX, chlorpyrifos + TX, trifloxystrobin + TX, chlorpyrifos + TX, chlorpyrifos + TX, veratridine + TX, veratridine + TX, XMC + TX, zetamethrin + TX, zinc phosphide + TX, tolfenphos + TX, chlorfluanid + TX X, tetrafluthrin + TX, bis(tributyltin) oxide + TX, bromoacetamide + TX, ferric phosphate + TX, niclosamide-ethanolamine + TX, tributyltin oxide + TX, pyromorph + 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-thiadiazin-3-yl acetic acid + TX, 6-isopentenylaminopurine + TX, anisiflupurin + TX, benzochlorothiazide +TX, cytokinin +TX, DCIP +TX, furfural +TX, isoamidophos +TX, kinetin +TX, verrucous myristic fungus composition +TX, tetrachlorothiophene +TX, xylenol +TX, zeatin +TX, potassium ethylxanthate +TX, acibenzolar +TX, acibenzolar-S-methyl +TX, giant knotweed extract +TX, α-chlorohydrin +TX, anto +TX, barium carbonate +TX, bismuth urea +TX, brodifacoum +TX, bromadiolone +TX, bromodiolone +TX, chlordicarb +TX, cholecalciferol +TX, chlorfenapyr +TX, chlorambucil +TX, chloramphenicol +TX, chlorambucil +TX, chloramphenicol +TX, Pyridine + TX, Felodipine + TX, Thiazide + TX, Diphacin + TX, Calciferol + TX, Fludioxaline + TX, Fluacetamide + TX, Fludioxaline + TX, Fludioxaline hydrochloride + TX, Felodipine + TX, Felodipine + TX, Felodipine + TX, Phosphate + TX, Phosphate + TX, Felodipine + TX, Felodipine + TX, Felodipine + TX, Felodipine + TX, Felodipine glycoside + TX, Sodium fluoroacetate + TX, Thallium sulfate + TX, Felodipine + TX, 2-(2-butoxyethoxy)ethyl piperate + TX, 5-(1,3-benzodioxol-5-yl)-3-hexylcyclohex-2-enone + TX, Farnesol with nerolidol + TX, Synergistic alkynyl ether + TX, MGK 264+TX, piperonyl butoxide+TX, synergistic aldehyde+TX, propyl isomer+TX, S421+TX, synergistic powder+TX, sesame linolenic acid+TX, sulfoxide+TX, anthraquinone+TX, copper naphthenate+TX, copper oxychloride+TX, dicyclopentadiene+TX, ceram+TX, zinc naphthenate+TX, ziram+TX, imanin+TX, ribavirin+TX, chloroinconazide+TX, mercuric oxide+TX,Thiophanate methyl + TX, azaconazole + TX, bifenthiazolin + TX, oxadiazol + TX, cyproconazole + TX, difenoconazole + TX, diniconazole + TX, epoxiconazole + TX, fenbuconazole + TX, fluquinconazole + TX, flusilazole + TX, flutriafol + TX, furazolidone + TX, hexaconazole + TX, imazalil + TX, imidazole + TX, picronil + TX, metconazole + TX, myclobutrazol + TX, paclobutrazol + TX, blastifungin + TX, penconazole + TX, prothioconazole + TX, pyraclostrobin + TX, prochloraz + TX, propiconazole + TX, pyraclostrobin + TX, silyfenazole + TX, tebuconazole + TX, fluconazole + TX, triadimefon + TX, triadimenol + TX, triflumizole + TX, triticonazole + TX, pyrimidine Alcohol + TX, chlorfenapyr + TX, flufenapyr + TX, pyrimidine sulfonate + TX, mefenamic acid + TX, mefenamic acid + TX, dodecacyclic morpholine + TX, fenpropidin + TX, fenpropimorph + TX, spiroxafil + TX, tridemorph + TX, cyprodinil + TX, myxazinamide + TX, myxazinamide + TX, fenpiclonil + TX, fludioxonil + TX, bensulfuron + TX, furalaxyl + TX, metalaxyl + TX, R-metalaxyl + TX, furamide + TX, oxadixyl + TX, carbendazim + TX, imidacloprid + TX, maixin + TX, thiabendazole + TX, mefenamic acid + TX, sclerotinol + TX, mefenamic acid + TX, procymidone + TX, vinclozolin + TX, boscalid + TX, carboxin + TX, mefenamic acid Furoxamide + TX, Flutolanil + TX, Mefenamic Acid + TX, Oxycarboxin + TX, Penthiopyrad + TX, Thifuranil + TX, Dodine + TX, Biguanide + TX, Azoxystrobin + TX, Dioxastrobin + TX, Enstrobin + TX, Enstrobin + TX, Fluoxastrobin + TX, Dioxastrobin + TX, Dioxastrobin + TX, Dioxastrobin + TX, Dioxastrobin + TX, Dioxastrobin + TX, Picoxystrobin + TX, Pyraclostrobin + TX, Pyraclostrobin + TX, Pyraclostrobin + TX, Ferram + TX, Mancozeb + TX, Maneb + TX, Maneb + TX, Metiram + TX, Methionine + TX, Maneb + TX, Maneb + TX, Captafol + TX, Captan + TX, Fentan + TX, Folpet + TX, Tolylfluanid + TX , Bordeaux mixture + TX, copper oxide + TX, mancozeb + TX, quinoline copper + TX, phthalocyanine + TX, kewensan + TX, isoprene + TX, chlorpyrifos + TX, tolclofos-methyl + TX, difop-butyl + TX, benzathiapiprolin + TX, blasticidin-S + TX, dimethoate + TX, chlorothalonil + TX, cyfluanid + TX, cymoxanil + TX, cyclobutrifluram + TX, dichlorocyanamide + TX, pyraclostrobin + TX, chloranil + TX, ethofluanid + TX, dimethomorph + TX, flumorph + TX, dithianon + TX, ethidiumb + TX, oxadone + TX, famoxadone + TX, imidacloprid + TX, blastic amide + TX, pyrimidine + TX, fluazinam + TX,flumetylsulforim+TX, fluopyram+TX, fluoxytioconazole+TX, sulfaquinoxaline+TX, flupyrosamide+TX, -fenpyraclostrobin+TX, fosetyl-aluminum+TX, oxamexazole+TX, propineb+TX, saizoline+TX, sulfaquinoxaline+TX, mefenoxam+TX, pencuron+TX, phthalide+TX, polyoxin+TX, propamocarb+TX, pyraclostrobin+TX, iodoquinoxaline+TX, pyroquilon+TX, fenpyraclostrobin+TX, quinoxyfen+TX, pentachloronitrobenzene+TX, thiazolinone+TX, imidazolinone+TX, tricyclazole+TX, triamcinol+TX, validamycin+TX, valosin+TX, zoxamide+T X, dimethomorph + TX, flubeneteram + TX, pyraclostrobin + TX, flutoxafen + TX, benzovinflumizone + TX, flutoxafen + TX, 3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid (3',4',5'-trifluoro-biphenyl-2-yl)-amide + TX, isoflurane + TX, isothianid + TX, dipymetitrone + TX, 6-ethyl-5,7-dioxo-pyrrolo[4,5][1,4]dithia[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, dich lobentiazox+TX, Mandespin+TX, 3-(4,4-difluoro-3,4-dihydro-3,3-dimethylisoquinolin-1-yl)quinolone+TX, 2-[2-fluoro-6-[(8-fluoro-2-methyl-3-quinolinyl)oxy]phenyl]propan-2-ol+TX, thiophene+TX, N-[6-[[[(1-methyltetrazol-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-dihydroisoxazole oxazol-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, pyraclostrobin+TX, indazolesulfamyl+TX, fluopicolide+TX, (Z,2E)-5-[1-(4 -chlorophenyl) pyrazol-3-yl] oxy-2-methoxyimino-N,3-dimethyl-pent-3-enamine + TX, florylpicoxamid + TX, benzylpicoxamid + TX, metarylpicoxamid + TX, isobutylethoxyquinoline + TX, ipflufenoquin + TX, quinofumelin + TX, isopropylthiopyrad + TX, 1-[[4-[[2-(trifluoromethyl)-1,3-dioxolane-2-yl] methoxy] phenyl] methyl] pyrazole-3-carboxylic acid ethyl ester + TX (can be made from WO 2020 / 056090), 1-[[4-[(Z)-2-ethoxy-3,3,3-trifluoro-prop-1-enyloxy]phenyl]methyl]pyrazole-3-carboxylic acid ethyl ester + TX (can be prepared by the method described in WO2020 / 056090), N-[[4-[1-(4-cyclopropyl-2,6-difluoro-phenyl)pyrazol-4-yl]-2-methyl-phenyl]methyl]carbamic acid methyl ester + TX (can be prepared by the method described in WO 2020 / 097012),Methyl N-[[4-[1-(2,6-difluoro-4-isopropyl-phenyl)pyrazol-4-yl]-2-methyl-phenyl]methyl]carbamate + TX (can be prepared by the method described in WO 2020 / 097012), 6-chloro-3-(3-cyclopropyl-2-fluoro-phenoxy)-N-[2-(2,4-dimethylphenyl)-2,2-difluoro-ethyl]-5-methyl-pyridazine-4-carboxamide + TX (can be prepared by the method described in WO 2020 / 109391), 6-chloro-N-[2-(2-chloro-4-methyl-phenyl)-2,2-difluoro-ethyl]-3-(3-cyclopropyl-2-fluoro-phenoxy)-5-methyl-pyridazine-4-carboxamide + TX (can be prepared by the method described in WO 2020 / 109391), 6-chloro-3-(3-cyclopropyl-2-fluoro-phenoxy)-N-[2-(3,4-dimethylphenyl)-2,2-difluoro-ethyl]-5-methyl-pyridazine-4-carboxamide+TX (can be prepared by the method described in WO 2020 / 109391), N-[2-[2,4-dichloro-phenoxy]phenyl]-3-(difluoromethyl)-1-methyl-pyrazole-4-carboxamide+TX, N-[2-[2-chloro-4-(trifluoromethyl)phenoxy]phenyl]-3-(difluoromethyl)-1-methyl-pyrazole-4-carboxamide+TX, thiocyanatoxin+TX, cyproconazole+TX, 5-amino-1,3,4-thiadiazole-2-thiol zinc salt ( 2:1)+TX, fluopyram+TX, flufenoxadiazam+TX, fluthiazolinone+TX, fluopyram+TX, pyrapropoyne+TX, piperacodazole+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- Formamide + 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, 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 + TX, (Z) -3-methoxy-2- [2-methyl-5- [4- (trifluoromethyl) triazol-2-yl] phenoxy] prop-2-enoic acid methyl ester + TX, (Z) -3-methoxy-2- [2-methyl-5- (4-propyltriazol-2-yl) phenoxy] prop-2-enoic acid methyl ester + TX,(Z)-2-[5-(3-isopropylpyrazol-1-yl)-2-methyl-phenoxy]-3-methoxy-prop-2-enoic acid methyl ester + TX, (Z)-3-methoxy-2-[2-methyl-5-(3-propylpyrazol-1-yl)phenoxy]prop-2-enoic acid methyl ester + TX, (Z)-3-methoxy-2-[2-methyl-5-[3-(trifluoromethyl)pyrazol-1-yl]phenoxy]prop-2-enoic acid methyl ester + TX (these compounds can be prepared by the method described in WO 2020 / 079111), (Z)-2-(5-cyclohexyl-2-methyl-phenoxy)-3-methoxy-prop-2-enoic acid methyl ester + TX, (Z)-2-(5-cyclopentyl-2-methyl-phenoxy)-3-methoxy-prop-2-enoic acid methyl ester + TX (these compounds can be prepared by the method described in WO 2020 / 193387), 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- 1-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, syringostaryl + TX, zhongshengmycin + TX, thiophanate-methyl + TX, thiazole zinc + TX, amectotractin + TX, iprodione + TX, seboctylamine + TX; N'-[5-bromo-2-methyl-6-[(1S)-1-methyl-2-propoxy-ethoxy]-3-pyridinyl]-N-ethyl-N-methyl-formamidine + TX, N'-[5-bromo-2-methyl-6-[(1R)-1-methyl-2-propoxy-ethoxy]-3-pyridinyl]-N-ethyl-N-methyl-formamidine + TX, N'-[5-bromo-2-methyl-6-(1-methyl-2-propoxy-ethoxy)-3-pyridinyl]-N-ethyl-N-methyl-formamidine + TX, N'-[5-chloro-2-methyl-6-(1-methyl-2-propoxy-ethoxy)-3-pyridinyl]-N-ethyl-N-methyl-formamidine + TX,N'-[5-bromo-2-methyl-6-(1-methyl-2-propoxy-ethoxy)-3-pyridinyl]-N-isopropyl-N-methyl-formamidine + TX (these compounds can be prepared by WO 2015 / 155075); N'-[5-bromo-2-methyl-6-(2-propoxypropoxy)-3-pyridinyl]-N-ethyl-N-methyl-formamidine + TX (this compound can be prepared by the method described in IPCOM000249876D); N-isopropyl-N'-[5-methoxy-2-methyl-4-(2,2,2-trifluoro-1-hydroxy-1-phenyl-ethyl)phenyl]-N-methyl-formamidine + TX, N'-[4-(1-cyclopropyl-2,2,2-trifluoro-1-hydroxy-ethyl)-5-methoxy-2-methyl-phenyl]-N-isopropyl-N-methyl-formamidine + TX (these compounds can be prepared by the method described in WO 2018 / 228896); N-ethyl-N'-[5-methoxy-2-methyl-4-[(2-trifluoromethyl)oxetan-2-yl]phenyl]-N-methyl-formamidine + TX, N-ethyl-N'-[5-methoxy-2-methyl-4-[(2-trifluoromethyl)tetrahydrofuran-2-yl]phenyl]-N-methyl-formamidine + TX (these compounds can be prepared by WO 2019 / 110427); N-[(1R)-1-benzyl-3-chloro-1-methyl-but-3-enyl]-8-fluoro-quinoline-3-carboxamide + TX, N-[(1S)-1-benzyl-3-chloro-1-methyl-but-3-enyl]-8-fluoro-quinoline-3-carboxamide + TX, N-[(1R)-1-benzyl-3,3,3-trifluoro-1-methyl-propyl]-8-fluoro-quinoline-3-carboxamide + TX, N-[(1S)-1-benzyl-3,3,3-trifluoro-1-methyl-propyl]-8-fluoro-quinoline-3-carboxamide + TX, N-[(1R)-1-benzyl-3,3,3-trifluoro-1-methyl-propyl]-8-fluoro-quinoline-3-carboxamide + TX, N-[(1R)-1-benzyl-1,3-dimethyl-butyl]-7,8-difluoro-quinoline-3-carboxamide + TX, N-[(1S)-1 -benzyl-1,3-dimethyl-butyl]-7,8-difluoro-quinoline-3-carboxamide + TX, 8-fluoro-N-[(1R)-1-[(3-fluorophenyl)methyl]-1,3-dimethyl-butyl]quinoline-3-carboxamide + TX, 8-fluoro-N-[(1S)-1-[(3-fluorophenyl)methyl]-1,3-dimethyl-butyl]quinoline-3-carboxamide + TX, N-[(1R)-1-benzyl-1,3-dimethyl-butyl]-8-fluoro-quinoline-3-carboxamide + TX, N-[(1S)-1-benzyl-1,3-dimethyl-butyl]-8-fluoro-quinoline-3-carboxamide + TX, N-((1R)-1-benzyl-3-chloro-1-methyl-but-3-enyl)-8-fluoro-quinoline-3-carboxamide + TX,N-((1S)-1-benzyl-3-chloro-1-methyl-but-3-enyl)-8-fluoro-quinoline-3-carboxamide + TX (these compounds can be prepared by the method described in WO 2017 / 153380); 1-(6,7-dimethylpyrazolo[1,5-a]pyridin-3-yl)-4,4,5-trifluoro-3,3-dimethyl-isoquinoline + TX, 1-(6,7-dimethylpyrazolo[1,5-a]pyridin-3-yl)-4,4,6-trifluoro-3,3-dimethyl-isoquinoline + TX, 4,4-difluoro-3,3-dimethyl -1-(6-methylpyrazolo[1,5-a]pyridin-3-yl)isoquinoline+TX, 4,4-difluoro-3,3-dimethyl-1-(7-methylpyrazolo[1,5-a]pyridin-3-yl)isoquinoline+TX, 1-(6-chloro-7-methyl-pyrazolo[1,5-a]pyridin-3-yl)-4,4-difluoro-3,3-dimethyl-isoquinoline+TX (these compounds can be prepared by WO 2017 / 025510); 1-(4,5-dimethylbenzimidazol-1-yl)-4,4,5-trifluoro-3,3-dimethyl-isoquinoline+TX, 1-(4,5-dimethylbenzimidazol-1-yl)-4,4-difluoro-3,3-dimethyl-isoquinoline+TX, 6-chloro-4,4-difluoro-3,3-dimethyl-1-(4-methylbenzimidazol-1-yl)isoquinoline+TX, 4,4-difluoro-1-(5-fluoro-4-methyl-benzimidazol-1-yl)-3,3-dimethyl-isoquinoline+TX, 3-(4,4-difluoro-3,3-dimethyl-1-isoquinolyl)-7,8-dihydro-6H-cyclopenta[e]benzimidazole+TX (these compounds can be prepared by WO 2016 / 156085); N-methoxy-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]cyclopropanecarboxamide+TX, N,2-dimethoxy-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]propionamide+TX, N-ethyl-2-methyl-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]propionamide+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, N,N-dimethyl-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]-1,2,4-triazol-3-amine+TX. The compounds in this paragraph can be prepared by WO 2017 / 055473, WO 2017 / 055469,Prepared by the method described in WO 2017 / 093348 and WO 2017 / 118689; 2-[6-(4-chlorophenoxy)-2-(trifluoromethyl)-3-pyridyl]-1-(1,2,4-triazol-1-yl)propan-2-ol+TX (this 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 (this 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 (this 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 (this 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 (this 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)-tetraone + TX (this compound can be prepared by the method described in WO 2014 / 006945); 2011 / 138281); N-methyl-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide+TX; N-methyl-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide+TX; (Z,2E)-5-[1-(2,4-dichlorophenyl)pyrazol-3-yl]oxy-2-methoxyimino-N,3-dimethyl-pent-3-enamine+TX (this compound can be prepared by the method described in WO 2018 / 153707); N'-(2-chloro-5-methyl-4-phenoxy-phenyl)-N-ethyl-N-methyl-formamidine+TX; N'-[2-chloro-4-(2-fluorophenoxy)-5-methyl-phenyl]-N-ethyl-N-methyl-formamidine+TX (this compound can be prepared by the method described in WO 2016 / 202742); 2-(difluoromethyl)-N-[(3S)-3-ethyl-1,1-dimethyl-indan-4-yl]pyridine-3-carboxamide + TX (this compound can be prepared by the method described in WO2014 / 095675); (5-methyl-2-pyridyl)-[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methanone + TX,(3-methylisoxazol-5-yl)-[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methanone+TX (these compounds can be prepared by the method described in WO 2017 / 220485); 2-oxo-N-propyl-2-[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]acetamide+TX (this compound can be prepared by the method described in WO 2018 / 065414); 1-[[5-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]-2-thienyl]methyl]pyrazole-4-carboxylic acid ethyl ester+TX (this compound can be prepared by the method described in WO 2,2-difluoro-N-methyl-2-[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]acetamide+TX, N-[(E)-methoxyiminomethyl]-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide+TX, N-[(Z)-methoxyiminomethyl]-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide+TX, N-[N-methoxy-C-methyl-carbonimido]-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide+TX (these compounds can be prepared by the method described in WO 2018 / 202428);
[0679] Microorganisms, including: Acinetobacter lwoffii + TX, Acremonium + TX + TX, Cephalosporium acremonium + TX + TX, Acremonium diospyri + TX, Acremonium obclavatum + TX, and AdoxGV +TX, Agrobacterium radioactive strain K84 (Galltrol- )+TX, Alternaria+TX, Alternaria cassiae+TX, Alternaria destruens +TX, Parasitoid spores +TX, Aspergillus flavus AF36 +TX, Aspergillus flavus NRRL 21882 +TX, Aspergillus species +TX, Aureobasidium pullulans +TX, Azospirillum ( 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 (e.g. Biostart TM ,Before )+TX, Bacillus licheniformis strain 3086 ( Green )+TX, Bacillus circulans+TX, Bacillus firmus ( BioNem- )+TX, Bacillus firmus strain I-1582+TX, Bacillus macerans+TX, Bacillus marismortui+TX, Bacillus megaterium+TX, Bacillus mycoides strain AQ726+TX, Milky Spore )+TX, Bacillus pumilus species+TX, Bacillus pumilus strain GB34 (Yield )+TX, Bacillus pumilus strain AQ717+TX, Bacillus pumilus strain QST 2808( 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, 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, Bacillus thuringiensis Cry 2Ae+TX, Bacillus thuringiensis Cry1Ab+TX, Bacillus thuringiensis subsp. Aizawawai GC 91 +TX, Bacillus thuringiensis israelensis +TX, Bacillus thuringiensis kurstaki ( Scutella Turilav Dipel )+TX, Bacillus thuringiensis kurstaki BMP 123 +TX, Bacillus thuringiensis subsp. Kurstaki HD-1 (Bioprotec-CAF / )+TX, Bacillus thuringiensis strain BD#32+TX, Bacillus thuringiensis strain AQ52+TX, Bacillus thuringiensis var. aizawai +TX, Bacteria species ( X、 )+TX, bacteriophage of Clavipacter michiganensis +TX, +TX, Beauveria bassiana ( Brocaril )+TX, Beauveria bassiana GHA (Mycotrol Mycotrol )+TX, Beauveria brongniartii ( Schweizer )+TX, Beauveria spp.+TX, Botrytis cineria+TX, Bradyrhizobium japonicum +TX, Brevibacillus brevis +TX, Bacillus thuringiensis tenebrionis +TX, BtBooster+TX, Burkholderia cepacia Blue )+TX, Burkholderia gladii+TX, Burkholderia gladioli+TX, Burkholderia spp.+TX, Canadian thistle fungus (CBHCanadian )+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(Bio- )+TX, Candida sake+TX, Candida species+TX, Candida tenius+TX, Cedecea dravisae+TX, Cellulomonas flavigena+TX, Chaetomium cochliodes(Nova- )+TX, Chaetomium globosum (Nova- )+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 (CYD- )+TX, Cydia pomonella granulovirus ( Plus, Max, Carpovirusine )+TX、Cylindrobasidium laeve
[0680] +TX, Cylindrocladium +TX, Debaryomyceshansenii +TX, Drechslera hawaiinensis +TX, Enterobacter cloacae +TX, Enterobacteriaceae +TX, Entomophtora virulenta +TX, Epicoccum nigrum +TX, Epicoccum purpurascens +TX, Epicoccum spp. +TX, Filobasidium floriforme +TX, Fusarium umaminasium +TX, Fusarium chlamydosporum +TX, Fusarium oxysporum ( Biofox )+TX, Fusarium proliferatum+TX, Fusarium spp.+TX, Galactomyces geotrichum+TX, Gliocladium catenulatum +TX, Gliocladium roseum +TX, Gliocladium spp. +TX, Gliocladium virens +TX, Granulovirus +TX, Halobacillus halophilus +TX, Halobacillus litoralis +TX, Halobacillus trueperi +TX, Halomonas spp. +TX, Halomonas subglaciescola +TX, Halovibrio variabilis +TX, Hanseniaspora uvarum +TX, Helicoverpa armigera nucleopolyhedrovirus +TX, Helicoverpa zea nuclear polyhedrosis virus +TX, Isoflavone-formononetin +TX, Kloeckera apiculata +TX, Kloeckera spp. +TX, Lagenidium giganteum +TX, Lecanicillium longisporum +TX, Lecanicillium muscarium +TX, Lymantria Dispar nucleopolyhedrosis virus +TX, Marinococcus halophilus +TX, Meirageulakonigii +TX, Metarhizium anisopliae +TX, Metarhizium anisopliae (Destruxin )+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. ( Root )+TX, Myrothecium verrucaria strain AARC-0255 +TX、BROS +TX, Ophiostoma piliferum strain D97 +TX, Paecilomyces farinosus +TX, Paecilomyces fumosoroseus (PFR- )+TX, Paecilomyces linacinus (Biostat )+TX, Paecilomyces lilacinus strain 251 (MeloCon )+TX, Paenibacillus polymyxa+TX, Pantoea agglomerans (BlightBanC9- )+TX, Pantoea spp.+TX, Pasteuria spp. +TX, Pasteuria nishizawae+TX, Penicillium billai +TX, Penicillium brevicompactum +TX, Penicillium frequentans +TX, Penicillium griseofulvum +TX, Penicillium purpurogenum +TX, Penicillium spp. +TX, Penicillium viridicatum +TX, Phlebiopsis gigantean +TX, phosphate solubilizing bacteria +TX, Phytophthora cryptogea +TX, Phytophthora palmivora +TX, Pichia anomala +TX, Pichia guilermondii +TX, Pichia membranaefaciens +TX, Pichia onychis +TX, Pichia stipites +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 spp.+TX, Pseudomonas syringae (Bio- )+TX, Pseudomonas viridiflava+TX, Pseudomonas fluorescens +TX, Pseudozyma flocculosa strain PF-A22 UL (Sporodex )+TX、Puccinia canaliculata+TX、Puccinia thlaspeos(Wood )+TX, Pythium paroecandrum+TX, Pythium oligandrum +TX, Pythium periplocum +TX, Rhanella aquatilis +TX, Rhanella spp. +TX, Rhizobia +TX, Rhizoctonia +TX, Rhodococcus globerulus strain AQ719 +TX, Rhodosporidium diobovatum +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, Sclerotiniaminor +TX, Sclerotiniaminor +TX, Scytalidium spp.+TX, Scytalidium uredinicola+TX, Spodoptera exigua nuclear polyhedrosis virus (Spod- )+TX, Serratia marcescens+TX, Serratia plymuthica+TX, Serratia spp.+TX, Sordaria fimicola+TX, Spodoptera littoralis nucleopolyhedrovirus +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 (Trianum- PlantShield Trianum- )+TX, Trichoderma harzianum T-39 +TX, Trichoderma inhamatum +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 (Botry- )+TX, Ustilago maydis+TX, various bacteria and supplementary nutrients (Natural )+TX, various fungi (Millennium )+TX, Verticillium chlamydosporium+TX, Verticillium lecanii +TX、Vip3Aa20 +TX, Virgibaclillus marismortui+TX, Xanthomonas campestris pv.Poae +TX, Xenorhabdus burnetii +TX, and Xenorhabdus nematophila +TX;
[0681] Plant extracts, including pine oil +TX, Azadirachtin (PlasmaNeem Molt- )+TX, plant IGR +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 extracts (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, +TX, rotenone (Eco )+TX, Rutaceae plant extract +TX, soybean oil (Ortho )+TX, Melaleuca alternifolia extract (also known as 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 mixture (EF )+TX, Clove-Peppermint-Garlic Oil and Mint Blend (Soil )+TX, kaolin +TX, storage glucan of brown algae +TX;
[0682] Pheromones, including: 3M Sprayable Blackheaded Fireworm )+TX, codling moth pheromone (Paramount dispenser-(CM) / IsomateC- )+TX, Grape Leaf Roller Pheromone (3M MEC-GBM Sprayable )+TX, leaf roller pheromone (3M MEC-LR Sprayable )+TX, housefly pheromone (Muscamone)(Snip7Fly Starbar Premium Fly )+TX, 3M oriental fruitmoth sprayable )+TX, Peachtree Borer pheromone (Isomate- )+TX, Tomato Pinworm Pheromone (3M Sprayable )+TX, Entostat powder (from palm tree extract) (Exosex )+TX、(3E,8Z,11Z)-3,8,11-tetradecatriene acetate+TX、(7Z,11Z,13E)-7,11,13-hexadecatrienal+TX、(E,Z)-7,9-dodecadien-1-yl acetate+TX、2-methyl-1-butanol+TX、calcium acetate+TX、 +TX, +TX、Check- +TX, Lavandulyl senecioate+TX;
[0683] Macrobial agents include: Aphelinus septentrionalis + TX, Aphelinus albus, )+TX、Acerophagus papaya+TX、Adalia- )+TX, Coccinella bispotata +TX, Coccinella bispotata +TX, cocoon jumping wasp +TX, nest moth polyembryonic jumping wasp +TX, Anderson's blunt mite ( Andersoni- )+TX, Amblyseius californicus +TX, Amblyseius cucumber ( Bugline )+TX, Pseudo-Amblyseius +TX, Bugline Swirskii- )+TX, Amblyseius osbornei +TX, whitefly wasp+TX, original cherry-winged wasp+TX, dark-bellied long-line jumping wasp+TX, Kama long-line jumping wasp+TX, Anagyrus loecki+TX, mealybug long-line jumping wasp +TX, red wax scale flat-horned jumping wasp +TX, golden wasp +TX, woodland flower stink bug (Anthocoris- )+TX, short-spurred aphid wasp +TX, short-spurred aphid wasp+TX, cotton aphid parasitic wasp +TX, Alphididae +TX, tobacco aphid braconid +TX, peach red aphid aphid braconid (Aphipar- )+TX, aphid-eating gall midge +TX, aphid-eating gall midge +TX, Lingnan yellow aphid wasp +TX, Indian yellow aphid wasp +TX, Ha's long-tailed biting wasp +TX, ant-shaped winged beetle +TX, Bombus species +TX, European bumblebee (Natupol )+TX, European bumblebee +TX, coffee berry borer parasitic wasp+TX, black-backed ladybug+TX, common lacewing +TX, Common Lacewing +TX, Red Lacewing +TX, Delicate Flat Horned Wasp +TX, Four-banded Sergi Wasp +TX, White Star Orange Biting Wasp +TX, Eucalyptus Flat Horned Golden Green Wasp +TX, Flat Horned Golden Green Wasp Species +TX, Tiny Broad Shield Biting Wasp +TX, Aphididae spp.+TX, Aphididae spp.+TX, Aphididae spp.+TX, Aphididae spp.+TX, Aphididae spp.+TX, Cryptochilus spp. +TX, Japanese square-headed beetle+TX, Siberian gnathostome +TX, Siberian gnathostome +TX, Pea leafminer +TX, Little Black Ladybug +TX, Delphastus pusillus+TX, Diachasmimorpha krausii+TX, Diaparsis jucunda+TX, Ali louse-eating wasp+TX, Pea leafminer wasp+TX, Pea leafminer wasp +TX, Siberian Braconidia +TX, Encarsia species+TX, Encarsia longita +TX, Encarsia spp. En- )+TX, Aphididae +TX, Goden's aphid wasp+TX, Haidian's aphid wasp+TX, thin flat hoverfly +TX, Eretmocerissiphonini+TX, California scimitar wasp+TX, scimitar wasp ( Eretline )+TX, Aphididae +TX, Heinrich's aphid wasp+TX, Montessori's aphid wasp ( Eretline )+TX, Eretmocerus siphonini+TX, Four-spotted light-edged ladybird+TX, Mite-eating gall midge +TX, Acarina +TX, Alishan fly miner +TX, Fopius ceratitivorus +TX, Wirless )+TX, thrips slender waist +TX, Western Stachybotrys +TX, Scleroderma leontopodium +TX, Lycosa axyridis +TX, Harmonia axyridis +TX, Heterorhabditis species (Lawn )+TX, Heterorhabditis elegans (NemaShield Terranem- B- )+TX, Nemasys BioNem Exhibitline Larvanem- )+TX, spotted long-legged ladybug+TX, Aculeifer- Entomite- )+TX, Hypoline Entomite- )+TX, Black Branch Gall Wasp+TX, Lecanoideus floccissimus+TX, Lemophagus errabundus+TX, Tricolor Jumping Wasp+TX, Citrus Flour Scale Parasitic Wasp +TX, Longhorn Jumping Wasp+TX, Lindorus lophanthae+TX, Lipolexis oregmae+TX, Green Fly +TX, Tea-footed Aphid Wasp+TX, Mirical- Macroline )+TX, Mesoseiulus longipes+TX, Yellow broad-stalked jumping wasp+TX, Metaphycus lounsburyi+TX, Corner vein brown lacewing +TX, yellow-winged jumping wasp +TX, Muscidifurax raptorellus and Spalangia cameroni +TX, Neodryinustyphlocybae+TX, California Neoseiulus+TX, Cucumber Neoseiulus +TX, Nesideocoris tenuis +TX, Bronze Blackfly +TX, Thripor- Oriline )+TX, Thripor- Oriline )+TX, Oriline )+TX, Thripor- )+TX、Pauesia juniperorum+TX、Phasmarhabditis hermaphrodita+TX +TX, Phymastichus coffea+TX, Phytoseiidae coarse hair mite+TX, Phytoseiidae Chileanus ( Phytoline )+TX, Cypripedium scaly-bellied +TX, Pseudacteon curvatus+TX, Pseudacteon obtusus+TX, Pseudacteon tricuspis+TX, Pseudaphycus maculipennis+TX, Pseudleptomastix mexicana+TX, Psyttalia concolor (complex)+TX, Psyttalia species+TX, Rhyzobius lophanthae+TX, Australian ladybirds+TX, Rumina decollate+TX, Semielacher petiolatus+TX, Aphid +TX, Steinernema carinata (Nematac BioNem )+TX, Steinernema carinata ( Nemasys BioNem F, Steinernema- Exhibitline Scia- )+TX, Nemasys BioNem Exhibitline )+TX, Steinernia rapis +TX, Nematacornae )+TX, Steinernematid species+TX, Steinernematid species (Guardian )+TX, Deep-point mite-feeding ladybug +TX, Tricholine glaze wasp +TX, Chinese long-tailed wasp +TX, Thropobius semiluteus +TX, Chinese long-tailed wasp +TX, Tricholine brassicae trichogrammatid )+TX, Tricho- )+TX, Trichogramma striata+TX, Trichogramma microsporum+TX, Trichogramma ostriniae+TX, Trichogramma broad-veined+TX, Trichogramma short-tubed+TX, Trichogramma striata+TX;
[0684] Other biological agents, these other biological agents include: abscisic acid + TX, +TX, Chondrostereum purpureum (Chontrol )+TX, Colletotrichum spondyloticum +TX, copper octanoate +TX, Delta trap (Trapline )+TX, Erwinia amylovora (Harpin) ( Ni-HIBIT Gold )+TX, fatty acids derived from natural by-products of extra virgin olive oil Ferric phosphate +TX, Funnel trap (Trapline )+TX、 +TX, Grower's +TX, Homo-brassonolide +TX, Ferric Phosphate (Lilly Miller Worry Free Ferramol Slug & Snail )+TX、MCP hail trap (Trapline )+TX、parasitic insects Microctonus hyperodae+TX、Mycoleptodiscus terrestris(Des- )+TX、 +TX, +TX, +TX, Pheromone Net (Thripline )+TX, potassium bicarbonate +TX, potassium salt of fatty acids +TX, potassium silicate solution (Sil- )+TX, potassium iodide+potassium thiocyanate +TX、SuffOil- +TX, spider venom +TX, locust microsporidia (Semaspore Organic Grasshopper )+TX, Trapline Rebell )+TX and capture (Takitrapline y+ )+TX;
[0685] (1) An antibacterial agent selected from the group consisting of:
[0686] (1.1) Bacteria, examples of which are Bacillus mojavensis strain R3B (accession number NCAIM (P) B001389) (WO 2013 / 034938), from Certis USA LLC +TX; Bacillus pumilus, in particular strain BU F-33, with NRRL accession number 50185 (from BASF); EPA registration number 71840-19) + TX; Bacillus subtilis, in particular strain QST713 / AQ713 (SERENADE OPTI or SERENADE ASO from Bayer CropScience LP, USA, with NRRL registration number B21661, U.S. Patent No. 6,060,051) + TX; Bacillus subtilis strain BU1814, (from BASF SE PLUS, FLEX and EXTRA) + TX; Bacillus subtilis variant amyloliquefaciens strain FZB24, with registration number DSM 10271 (available as or ECO (EPA registration number 70127-5) obtained from Novozymes) + TX; Bacillus subtilis CX-9060 + TX from Certis USA LLC; Bacillus species, specifically strain D747 (available as DOUBLE obtained from Kumiai Chemical Industry Co., Ltd.) with accession number FERM BP-8234, U.S. Patent No. 7,094,592+TX; Paenibacillus sp. strains with accession number NRRL B-50972 or accession number NRRL B-67129, WO 2016 / 154297+TX; Paenibacillus polymyxa, particularly strain AC-1 (e.g., from Green Biotech Company Ltd.) ) + TX; Pantoea agglomerans, in particular strain E325 (accession number NRRL B-21856) (available as BLOOMTIME BIOLOGICAL TM FD BIOPESTICIDE (from Northwest Agri Products) + TX; Pseudomonas proradix (e.g., from Sourcon Padena) )+TX; and
[0687] (1.2) Fungi, examples of which are Aureobasidium pullulans, in particular blastospores of strain DSM 14940, blastospores of strain DSM 14941 or a mixture of blastospores of strains DSM 14940 and DSM 14941 (e.g., blastospores from bio-ferm, Switzerland). and BLOSSOM )+TX; Pseudozyma aphidis (as disclosed in WO 2011 / 151819 by Yissum Research Development Company of the Hebrew University of Jerusalem)+TX; Saccharomyces cerevisiae, in particular strains CNCM No. 1-3936, CNCM No. 1-3937, CNCM No. 1-3938 or CNCM No. 1-3939 (as disclosed in WO 2010 / 086790, from Lesaffre et Compagnie, France)+TX;
[0688] (2) Biofungicides selected from the group consisting of:
[0689] (2.1) Bacteria, an example of which is Agrobacterium radiobacterium strain K84 (e.g. GALLTROL- )+TX; radiobacterium strain K1026 (e.g. NOGALL from BASF TM )+TX; Bacillus subtilis variant amyloliquefaciens strain FZB24, with registration number DSM 10271 (available as or ECO (EPA registration number 70127-5) obtained from Novozymes) + TX; Bacillus amyloliquefaciens, specifically strain D747 (available as Double Nickel TM obtained from Kumihiko Chemical Industries, Ltd., with accession number FERM BP-8234, U.S. Patent No. 7,094,592) + TX; Bacillus amyloliquefaciens strain F727 (also known as strain MBI110) (NRRL accession number B-50768, WO 2014 / 028521) (from Marrone Bio Innovations )+TX; Bacillus amyloliquefaciens strain FZB42, registration number DSM 23117, (can be used as from ABiTEP, Germany) + TX; Bacillus amyloliquefaciens isolate B246 (e.g., AVOGREEN from the University of Pretoria); TM )+TX; Bacillus licheniformis, in particular strain SB3086, having accession number ATCC 55406, WO 2003 / 000051 (available as Biofungicides and Green Release TM Bacillus licheniformis FMCH001 and Bacillus subtilis FMCH002 (from FMC Corporation) (WG) and (WP)) + TX; Bacillus methylotrophicus strain BAC-9912 (from the Institute of Applied Ecology, Chinese Academy of Sciences) + TX; Bacillus mojavensis strain R3B (accession number NCAIM(P)B001389) (WO 2013 / 034938), from Certis USA, Inc. + TX; Bacillus mycoides isolate with accession number B-30890 (available as BMJ or WG and LifeGard TM obtained from Surtice USA) + TX; Bacillus pumilus, specifically strain QST2808 (available as obtained from Bayer CropScience, USA, with registration number NRRL B-30087 and described in US Pat. No. 6,245,551) + TX; Bacillus pumilus, in particular strain GB34 (available as Yield pumilus, in particular strain BU F-33, having NRRL accession number 50185 (available as part of the CARTISSA product from BASF, EPA accession number 71840-19) + TX; Bacillus subtilis, in particular strain QST713 / AQ713 (available as SERENADE OPTI or SERENADE ASO from Bayer CropScience in the United States, having NRRL accession number B21661, and described in U.S. Patent No. 6,060,051) + TX; Bacillus subtilis Y1336 (available as WP was obtained from Bion-Tech, Taiwan, China, and registered as a biofungicide in Taiwan under registration numbers 4764, 5454, 5096, and 5277) + TX; Bacillus subtilis strain MBI600 (available as SUBTILEX from BASF, with registration number NRRL B-50595, U.S. Patent No. 5,061,495) + TX; Bacillus subtilis strain GB03 (available as obtained from Bayer AG, Germany) + TX; Bacillus subtilis strain BU1814, (available as PLUS, FLEX and EXTRA obtained from BASF) + TX; Bacillus subtilis CX-9060 + TX from Certis USA LLC; Bacillus subtilis KTSB strain (from Donaghys )+TX; Bacillus subtilis IAB / BS03 (AVIV from STK Bio-Ag Technologies) TM , from Idai Nature )+TX; Bacillus subtilis strain Y1336 (can be used as WP was obtained from Biotech, Taiwan, China, and registered as a biofungicide in Taiwan under registration numbers 4764, 5454, 5096, and 5277) + TX; Paenibacillus epiphyticus (WO 2016 / 020371) from BASF + TX; Paenibacillus polymyxa plantarum species (WO 2016 / 020371) from BASF + TX; Paenibacillus species strains with registration number NRRL B-50972 or registration number NRRL B-67129, WO 2016 / 154297 + TX; Pseudomonas chlororaphis strain AFS009 with registration number NRRL B-50897, WO 2017 / 019448 (e.g., HOWLER from AgBiome Innovations, USA). TM and ) + TX; Pseudomonas chlororaphis strains, in particular strain MA342 (e.g., from Bioagri and Koppert) and )+TX; Pseudomonas fluorescens strain A506 (e.g., from NuFarm A506) + TX; Pseudomonas proradix (e.g., from Soconpadna ) + TX; Streptomyces griseoviridis strain K61 (also known as Streptomyces luteus strain K61) (accession number DSM 7206) (from Verdera BioWorks See Crop Protection 2006, 25, 468-475) + TX; Streptomyces lydicus strain WYEC108 (also known as Streptomyces lydicus strain WYCD108US) (ACTINO- and )+TX; and
[0690] (2.2) Fungi, an example of which is Pseudomonas aeruginosa, in particular strain AQ 10 (e.g. AQ from IntrachemBio Italia) ) + TX; Psoralea corylifolia strain AQ10, with accession number CNCM 1-807 (e.g., AQ from Intrachem Biologia Italia S.A. )+TX; Aspergillus flavus strain NRRL21882 (as AFLA- from Syngenta / ChemChina and known products) + TX; budding mold, especially the spores of strain DSM14940 + TX; budding mold, especially the spores of strain DSM 14941 + TX; budding mold, especially the mixture of spores of strains DSM14940 and DSM 14941 (for example, from Bio-Philippe Co., Ltd., Switzerland )+TX; Chaetomium cupreum (accession number CABI353812) (e.g., BIOKUPRUM from AgriLife TM )+TX; Chaetomium globosum (can be used as from Rivale) + TX; Cladosporium cladosporioides, strain H39, with accession number CBS122244, US2010 / 0291039 (from Wageningen Research Foundation (Stichting DienstLandbouwkundig Onderzoek)) + TX; Coniothyrium minitans, in particular strain CON / M / 91-8 (accession number DSM9660, e.g., from Bayer CropScience Biologics GmbH) + TX; )+TX; Cryptococcus flavescens, strain 3C (NRRL Y-50378), (B2.2.99)+TX; Dactylaria candida+TX; Dilophosphora alopecuri (can be used as TWIST Obtain) + TX; Fusarium oxysporum, strain Fo47 (can be used as obtained from Natural Plant Protection) + TX; Gliocladium catenulatum (synonym: Clonostachys rosea f. catenulate) strain J1446 (e.g., from Lallemand) )+TX; Gliocladium roseum (also known as Clonostachys rosea), in particular strain 321U from Adjuvants Plus, strain ACM941 as disclosed in Xue AG (Efficacy of Clonostachys rosea strain ACM941 and fungicide seed treatments for controlling the root tot complex of field pea, Can. J. Plant Sci. 2003, 83(3):519-524), or strain IK726 (Jensen DF et al. Development of a biocontrol agent for plant disease control with special emphasis on the nearcommercial fungal antagonist Clonostachys rosea). strain 'IK726' [with particular emphasis on the development of a biocontrol agent for plant disease control using the near-commercial fungal antagonist Gliocladium roseum strain 'IK726'], Australasian Plant Pathol. 2007, 36(2), 95-101) + TX; Lecanicillium lecanii (formerly known as Verticillium lecanii)
[0691] Conidia of strain KV01 (e.g., from Colbert / Arysta )+TX; Metschnikowia fructicola, in particular strain NRRL Y-30752, (B2.2.3)+TX; Microsphaeropsis ochracea+TX; Muscodor roseus, in particular strain A3-5 (accession number NRRL 30548)+TX; Penicillium steckii (DSM 27859, WO 2015 / 067800) from BASF+TX; Penicillium vermiculatum+TX; Phlebiopsis gigantea strain VRA 1992 (from Danstar Ferment) C) + TX; Pichia anomala, strain WRL-076 (NRRL Y-30842), U.S. Patent No. 7,579,183 + TX; Pseudozyma flocculosa, strain PF-A22UL (can be used as L obtained from Plant Products Co., California) + TX; Saccharomyces cerevisiae, specifically strain LASO2 (from Agro-Levures et Dérivés), strain LAS117 cell wall (from Lesaffre From BASF ), strains CNCM No. 1-3936, CNCM No. 1-3937, CNCM No. 1-3938, CNCM No. 1-3939 (WO 2010 / 086790) + TX from Lesaffre, France; Simplicillium lanosoniveum + TX; Talaromyces flavus, strain V117b + TX; Trichoderma asperelloides JM41R (registration number NRRL B-50759) (from TRICHO )+TX; Trichoderma asperellum, in particular strain kd (e.g., T-Gro from Andermatt Biocontrol)+TX; Trichoderma asperellum, in particular strain SKT-1, having accession number FERM P-16510 (e.g., ECO- ), strain T34 (e.g., T34 from Biocontrol Technologies SL, Spain) or strain ICC012+TX from Isagro; Trichoderma atroviride, in particular strain SC1 (accession number CBS122089, WO2009 / 116106 and U.S. Patent No. 8,431,120 (from Bi-PA), strain 77B (T77 from Andermat Biocontrol) or strain LU132 (e.g., Sentinel from Agrimm Technologies Limited)+TX; Trichoderma atroviride, strain CNCM 1-1237 (e.g., Sentinel from Agrauxine, France); WP) + TX; Trichoderma viride, strain No. V08 / 002387 + TX; Trichoderma viride, strain NMI No. V08 / 002388 + TX; Trichoderma viride, strain NMI No. V08 / 002389 + TX; Trichoderma viride, strain NMI No. V08 / 002390 + TX; Trichoderma viride, strain LC52 (e.g., Tenet from Agri-Mount Technology Co., Ltd.) + TX; Trichoderma viride, strain ATCC 20476 (IMI 206040) + TX; Trichoderma viride, strain T11 (IMI352941 / CECT20498) + TX; Trichoderma viride, strain SKT-1 (FERM P-16510), Japanese Patent Publication (Kokai) 11-253151A + TX; Trichoderma viride, strain SKT-2 (FERM P-16511), Japanese Patent Publication (Kokai) 11-253151A+TX; Dark green Trichoderma, strain SKT-3 (FERM P-17021), Japanese Patent Publication (Kokai) 11-253151A+TX; Trichoderma fertile (for example, the product TrichoPlus from BASF) + TX; Trichoderma gamsii (original green Trichoderma), strain ICC080 (IMI CC 392151CABI, for example, BioDerma from AGROBIOSOL DE MEXICO, SADE CV) + TX; Trichoderma gamsii (original green Trichoderma), strain ICC 080 (IMI CC 392151CABI) (can be used as obtained from Agribelso Mexico) + TX; Trichoderma harmatum + TX; Trichoderma harmatum, with accession number ATCC 28012 + TX; Trichoderma harzianum strain T-22 (e.g., Trianum-P from Andermatt Biocontrol or Kobert) or strain CepaSimbT5 (from Simbiose Agro) + TX; Trichoderma harzianum + TX; Trichoderma harzianum slant (rifai) T39 (e.g., from Makhteshim, USA) )+TX; Trichoderma harzianum, strain ITEM 908 (e.g., Trianum-P from Kobert)+TX; Trichoderma harzianum, strain TH35 (e.g., Root-Pro from Mycontrol)+TX; Trichoderma harzianum, strain DB 103 (can be used as T- 7456 from Dagutat Biolab) + TX; Trichoderma polysporum, strain IMI 206039 (e.g., Binab TF WP from BINAB Bio-Innovation AB, Sweden) + TX; Trichoderma stromaticum, with accession number Ts3550 (e.g., Tricovab from CEPLAC, Brazil) + TX; Trichoderma virens (also known as Gliocladium virens), in particular strain GL-21 (e.g., SoilGard from Certis, USA) + TX; Trichoderma virens strain G-41, formerly known as Gliocladium virens (accession number ATCC 20906) (e.g., from Biovox, USA) + TX; PLUS WP and PLUS WP) + TX; Trichoderma viride, strain TV1 (e.g., Trianum-P from Kobert) + TX; Trichoderma viride, in particular strain B35 (Pietr et al., 1993, Zesz. Nauk. A Rw Szczecinie [Science of the Agricultural University of Szczecin] 161: 125-137) + TX; a mixture of Trichoderma asperellum strain ICC 012 (also known as Trichoderma harzianum ICC 012) (with the accession number CABI CC IMI 392716) and Trichoderma gamsii (formerly Trichoderma viride) strain ICC 080 (with the accession number IMI 392151) (e.g., BIO-TAM from Esig USA, Inc. TM and from Agriberso Mexico )+TX; Ulocladium oudemansii strain U3, having accession number NM 99 / 06216 (e.g., BOTRY-Zen Ltd, New Zealand). and from Byworth )+TX; Verticillium albo-atrum (formerly V. dahliae), strain WCS850, having accession number WCS850, deposited with the Central Bureau for Fungi Cultures (e.g., by DUTCH, Tree Care Innovations) )+TX; Verticillium chlamydosporium+TX;
[0692] (3) Biological control agents having the effect of improving plant growth and / or plant health selected from the following group:
[0693] (3.1) Bacteria, an example of which is Azospirillum brasilense
[0694] (For example, from KALO, Inc. )+TX; Azospirillum lipoferum (e.g., VERTEX-IF from TerraMax, Inc.) TM )+TX; Azorhizobium caulinodans, in particular strain ZB-SK-5+TX; Azotobacter chroococcum, in particular strain H23+TX; Azotobacter vinelandii, in particular strain ATCC 12837+TX; a mixture of Azotobacter vinelandii and Clostridium pasteurianum (which can be used as from Agrinos) + TX; Bacillus amyloliquefaciens pm414 (LOLI- from Biofilm Crop Protection) )+TX; Bacillus amyloliquefaciens SB3281 (ATCC#PTA-7542, WO2017 / 205258)+TX; Bacillus amyloliquefaciens TJ1000 (can be used as Bacillus amyloliquefaciens, in particular strain IN937a+TX; Bacillus amyloliquefaciens, in particular strain FZB42 (e.g., from Abbott, Germany). ) + TX; Bacillus amyloliquefaciens BS27 (accession number NRRL B-5015) + TX; EE128 (NRRL No. B-50917) + TX; EE349 (NRRL No. B-50928) + TX; Bacillus cereus, in particular strain BP01 (ATCC 55675, for example, from Arysta Lifescience, USA ) + TX; Bacillus firmus, in particular strain CNMC 1-1582 (e.g., from BASF )+TX; Bacillus mycoides BT155 (NRRL No. B-50921)+TX; Bacillus mycoides EE118 (NRRL No. B-50918)+TX; Bacillus mycoides EE141 (NRRL No. B-50916)+TX; Bacillus mycoides BT46-3 (NRRL No. B-50922)+TX; Bacillus pumilus, in particular strain QST2808 (accession number NRRL No. B-30087)+TX; Bacillus pumilus, in particular strain GB34 (e.g., YIELD® from Bayer CropScience, Germany) )+TX; Bacillus siamensis, particularly strain KCTC 13613T+TX; Bacillus subtilis, particularly strain QST713 / AQ713 (having NRRL accession number B-21661 and described in U.S. Patent No. 6,060,051, can be used as OPTI or ASO was obtained from Bayer CropScience, Inc., USA) + TX; Bacillus subtilis, in particular strain AQ30002 (accession number NRRL No. B-50421 and described in U.S. patent application No. 13 / 330,576) + TX; Bacillus subtilis, in particular strain AQ30004 (and NRRL No. B-50455 and described in U.S. patent application No. 13 / 330,576) + TX; Bacillus subtilis strain BU1814 (available as from BASF), Bacillus subtilis rm303 (from Biofilm Crop Protection ) + TX; Bacillus thuringiensis BT013A (NRRL No. B-50924), also known as Bacillus thuringiensis 4Q7 + TX; a mixture of Bacillus licheniformis FMCH001 and Bacillus subtilis FMCH002 (can be used as (WG), (WP) obtained from FMC Corporation) + TX; Bacillus subtilis, in particular strain MBI 600 (e.g., from BASF )+TX; Bacillus tequilensis, in particular strain NII-0943+TX; Bradyrhizobium japonicum (e.g., from Novozymes )+TX; Delftia acidovorans, in particular strain RAY209 (e.g., from Brett Young Seeds )+TX; Mesorhizobium cicer (e.g., NODULATOR from BASF)+TX; Lactobacillus species (e.g., Lactobacillus from Latpafi) ) + TX; Rhizobium leguminosarium biovar viciae (eg, NODULATOR from BASF) + TX; Pseudomonas proradix (eg, from Sokolpadner ) + TX; Pseudomonas aeruginosa, in particular strain PN1 + TX; Rhizobium leguminosarum, in particular Rhizobium vitis vinifera (bv. viceae) strain Z25 (accession number CECT4585) + TX; Bacillus polymyxa, in particular strain AC-1 (e.g., from Green Biotechnology Co., Ltd. ) + TX; Serratia marcescens, in particular strain SRM (accession number MTCC8708) + TX; Sinorhizobium meliloti strain NRG-185-1 (from Bayer CropScience GOLD) + TX; Thiobacillus sp. (e.g., from Cropaid Ltd, UK) )+TX; and
[0695] (3.2) Fungi, examples of which are Purpureocillium lilacinum (formerly Paecilomyces lilacinus) strain 251 (AGAL 89 / 030550, e.g., BioAct from Bayer CropScience Bio) +TX; Penicillium bilaii, strain ATCC 22348 (e.g., from Acceleron BioAg); ), yellow basket fungus (Talaromyces flavus), strain V117b + TX; dark green Trichoderma strain CNCM 1-1237 (for example, from Aglaocosin, France) WP), Trichoderma viride, for example, strain B35 (Pietr et al., 1993, Zesz. Nauk. AR w Szczecinie [Science of the Agricultural University of Szczecin] 161: 125-137) + TX; Trichoderma atroviride strain LC52 (also known as Trichoderma atroviride strain LU132, for example, from Agri-Mountain Technology Ltd. )+TX; Trichoderma atroviride strain SC1 (described in WO 2009 / 116106)+TX; Trichoderma asperellum strain kd (e.g., T-Gro from Andermatt Biocontrol)+TX; Trichoderma asperellum strain (Eco-T from Plant Health Products of New Zealand)+TX, Trichoderma harzianum strain T-22 (e.g., Trianum-P from Andermatt Biocontrol or Corbett)+TX; Myrotheca verrucosa strain AARC-0255 (e.g., DiTera from Valent Biosciences) TM )+TX; Penicillium bilaii strain ATCC ATCC20851+TX; Pythium oligandrum strain M1 (ATCC 38472, for example, Polyversum from Bioprepraty, Czech Republic)+TX; Trichoderma virens strain GL-21 (for example, from Sertis, USA) )+TX; Verticillium albo-atrum (formerly V. dahliae) strain WCS850 (CBS276.92, for example, Dutch Trig from Tree Care Innovations)+TX; Trichoderma aureum, particularly strain No. V08 / 002387, strain No. NMI No. V08 / 002388, strain No. NMI No. V08 / 002389, strain No. NMI No. V08 / 002390+TX; Trichoderma harzianum strain ITEM 908, Trichoderma harzianum strain TSTh20+TX; Trichoderma harzianum strain 1295-22+TX; Pythium oligandrum strain DV74+TX; Rhizopogon amylopogon (for example, from Agri-Enterprise, LLC, formerly Helena Chemical Company) + TX; Rhizopogon fulvigleba (such as Myco-Sol from Agri-Enterprise, LLC, formerly Helena Chemical Company) + TX; Trichoderma virens strain GI-3 + TX;
[0696] (4) Insecticidal biological control agents selected from the following
[0697] (4.1) Bacteria, examples of which are Agrobacterium radiobacterium strain K84 (Galltrol from Egger Biochemicals) + TX; Bacillus amyloliquefaciens, in particular strain PTS-4838 (e.g., AVEO from Hualun Biosciences, USA) + TX; Bacillus firmus, in particular strain CNMC 1-1582 (e.g., from BASF ) + TX; Bacillus mycoides, isolate J. (e.g., BmJ from Certis USA LLC) + TX; Bacillus sphaericus, particularly serotype H5a5b strain 2362 (strain ABTS-1743) (e.g., from Hualun Biosciences, Inc., USA ) + TX; Bacillus thuringiensis subsp. aizawai, in particular strain ABTS-1857 (SD-1372, e.g., from Hualun Biosciences ) + TX; Bacillus thuringiensis subsp. aizawai, particularly serotype H-7 (e.g., from Hualun Biosciences, USA) WG) + TX; Bacillus thuringiensis israelensis strain BMP 144 (e.g., from Becker Microbial Products, Inc., Illinois); ) + TX; Bacillus thuringiensis subsp. israelensis (serotype H-14) strain AM65-52 (accession number ATCC 1276) (e.g., from Hualun Biosciences, USA )+TX; Bacillus thuringiensis subsp. aizawai strain GC-91+TX; Bacillus thuringiensis var. Colmeri (e.g., TIANBAOBTC from Changzhou Jianghai Chemical Factory)+TX; Bacillus thuringiensis Japonica strain Buibui+TX; Bacillus thuringiensis subsp. kurstaki strain BMP 123 (from Becker Microbial Products, Illinois, BARITONE from Bayer CropScience)+TX; Bacillus thuringiensis subsp. kurstaki strain HD-1 (e.g., from Hualun Biosciences, USA) ES) + TX; Bacillus thuringiensis var. kurstak strain EVB-113-19 (e.g., from AEF Global )+TX; Bacillus thuringiensis subsp. Kurstaki strain ABTS 351+TX; Bacillus thuringiensis subsp. Kurstaki strain PB 54+TX; Bacillus thuringiensis subsp. Kurstaki strain SA 11, (JAVELIN from Sertis, USA)+TX; Bacillus thuringiensis subsp. Kurstaki strain SA 12 (THURICIDE from Sertis, USA)+TX; Bacillus thuringiensis subsp. Kurstaki strain EG 2348 (from Sertis, USA) )+TX; Bacillus thuringiensis subsp. Kurstaki strain EG 7841 (from Sertis, USA ) + TX; Bacillus thuringiensis subsp. tenebrionis strain NB 176 (SD-5428, e.g., BioFa, Germany) FC) + TX; Brevibacillus laterosporus (from Ecolibrium Biological...
Claims
1. A method for combating and / or controlling animal pests to achieve the following: (i) reducing damage to plants, said method comprising applying an effective amount of a compound of formula I or formula II to said pest, to the locus of said pest, or to a plant susceptible to attack by said pest; or (ii) protecting plant propagation material, said method comprising treating said propagation material or the site where said propagation material is planted with an effective amount of a compound of formula I or formula II; Wherein the compound of formula I and formula II is in X, independently of Formula I or II, is O, S, SO, SO2, SO(NH), or CH2; R 1 、R 2 、R 3 and R 4 , independent of formula I or II, are each independently selected from hydrogen, halogen, cyano, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy, C1-C4-haloalkoxy, C1-C4-alkylthio, C1-C4-haloalkylthio, C1-C4-alkylsulfinyl, C1-C4-haloalkylsulfinyl, C1-C4-alkylsulfonyl, and C1-C4-haloalkylsulfonyl; R 5 、R 6 and R 7 , independent of formula I or II, are each independently selected from hydrogen, halogen, cyano, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy, C1-C4-haloalkoxy, C1-C4-alkylthio, C1-C4-haloalkylthio, C1-C4-alkylsulfinyl, C1-C4-haloalkylsulfinyl, C1-C4-alkylsulfonyl, and C1-C4-haloalkylsulfonyl; Y is hydrogen, C1-C6-alkyl, C3-C6-alkenyl, C3-C6-alkynyl, C3-C6-cycloalkyl-C1-C2-alkyl, aryl-C1-C2-alkyl, or C1-C4-alkoxy-C1-C2-alkyl; J is hydrogen, C1-C6-alkyl, C3-C6-alkenyl, C3-C6-alkynyl, or substituted by C3-C6-cycloalkyl, aryl, C5-C 10 -heteroaryl, or C4-C 10 -heterocyclyl-substituted C1-C2-alkyl, said C1-C6-alkyl, C3-C6-alkenyl, C3-C6-alkynyl may be substituted independently of one another by 1 to 3 groups independently selected from R a The C3-C6-cycloalkyl group may be substituted by 1 to 3 substituents independently selected from R c Substituents are substituted, and the aryl, C5-C 10 -heteroaryl, and C4-C 10 - The heterocyclic group may be independently selected from 1 to 4 b or J is aryl, C5-C 10 -heteroaryl, or C4-C 10 -heterocyclic group, the aryl, C5-C 10 -heteroaryl, and C4-C 10 - The heterocyclic group may be independently selected from 1 to 4 b or J is C1-C6-alkyl-C(O), C3-C6-cycloalkyl-C(O), aryl-C(O), C5-C 10 -heteroaryl-C(O), or C4-C 10 -heterocyclyl-C(O), wherein the alkyl group may be 1 to 3 independently selected from R a The cycloalkyl group may be substituted by 1 to 3 substituents independently selected from R c Substituents are substituted, and the aryl, C5-C 10 -heteroaryl, and C4-C 10 - The heterocyclic group may be independently selected from 1 to 4 d or J is C1-C6-alkyl-S(O)2, C3-C6-cycloalkyl-S(O)2, aryl-S(O)2, C5-C 10 -heteroaryl-S(O)2, or C4-C 10 -heterocyclyl-S(O)2, wherein the alkyl group may be 1 to 3 independently selected from R a The cycloalkyl group may be substituted by 1 to 3 substituents independently selected from R c Substituents are substituted, and the aryl, C5-C 10 -heteroaryl, and C4-C 10 - The heterocyclic group may be independently selected from 1 to 4 e or J is C1-C6-alkoxy, C3-C6-cycloalkyl-C1-C2-alkoxy, aryl-C1-C2-alkoxy, C5-C 10 -heteroaryl-C1-C2-alkoxy, or C4-C 10 -heterocyclyl-C1-C2-alkoxy, said alkoxy group may be 1 to 3 independently selected from R a The cycloalkyl group may be substituted by 1 to 3 substituents independently selected from R c Substituents are substituted, and the aryl, C5-C 10 -heteroaryl, and C4-C 10 - The heterocyclic group may be independently selected from 1 to 4 f Substituents substituted; T is hydrogen, C1-C6-alkyl, C3-C6-alkenyl, C3-C6-alkynyl, C3-C6-cycloalkyl-C1-C2-alkyl, aryl-C1-C2-alkyl, or C5-C 10 -heteroaryl-C1-C2-alkyl, said alkyl, C3-C6-alkenyl, C3-C6-alkynyl may be substituted independently of one another by 1 to 3 groups independently selected from R a The cycloalkyl group may be substituted by 1 to 3 substituents independently selected from R c Substituents are substituted, and the aryl, and C5-C 10 -heteroaryl may be substituted independently of each other by 1 to 4 independently selected g Substituents substituted; R a , independently of formula I or II, and independently of the substituent to which it is attached, is selected from halogen, cyano, and C1-C3-alkoxy; R b 、R d 、R e 、R f , and R g , independently of formula I or II and independently of the substituent to which it is attached, is selected from halogen, cyano, C1-C3-alkyl, C1-C3-alkoxy, NH2C(O), (C1-C3-alkyl)N(H)C(O), NH2C(O)-C1-C3-alkoxy, (C1-C3-alkyl)SO2, benzyl, phenyl, phenoxy, C5-C6-heteroaryl and C4-C 10 - heterocyclic group (the phenyl, phenoxy, heteroaryl and heterocyclic group may be substituted independently of each other by 1 to 4 substituents independently selected from halogen, cyano, and C1-C3-alkyl); R c , independently of formula I or II, is selected from halogen, cyano, C1-C3-alkyl, and C1-C3-alkoxy; or an agronomically acceptable salt, stereoisomer, tautomer and / or N-oxide of the compound of Formula I or Formula II.
2. A compound of formula II or formula II-I, in In Formula I, X is O, S, SO, SO2, or SO(NH); In Formula II, X is O, S, SO, SO2, SO(NH) or CH2; R 1 、R 2 、R 3 and R 4 , independent of formula I or II, are each independently selected from hydrogen, halogen, cyano, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy, C1-C4-haloalkoxy, C1-C4-alkylthio, C1-C4-haloalkylthio, C1-C4-alkylsulfinyl, C1-C4-haloalkylsulfinyl, C1-C4-alkylsulfonyl, and C1-C4-haloalkylsulfonyl; R 5 、R 6 and R 7 , independent of formula I or II, are each independently selected from hydrogen, halogen, cyano, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy, C1-C4-haloalkoxy, C1-C4-alkylthio, C1-C4-haloalkylthio, C1-C4-alkylsulfinyl, C1-C4-haloalkylsulfinyl, C1-C4-alkylsulfonyl, and C1-C4-haloalkylsulfonyl; Y is hydrogen, C1-C6-alkyl, C3-C6-alkenyl, C3-C6-alkynyl, C3-C6-cycloalkyl-C1-C2-alkyl, aryl-C1-C2-alkyl, or C1-C4-alkoxy-C1-C2-alkyl; J is C1-C6-alkyl, C3-C6-alkenyl, C3-C6-alkynyl, or is replaced by C3-C6-cycloalkyl, aryl, C5-C 10 -heteroaryl, or C4-C 10 -heterocyclyl-substituted C1-C2-alkyl, said C1-C6-alkyl, C3-C6-alkenyl, C3-C6-alkynyl may be substituted independently of one another by 1 to 3 groups independently selected from R a The C3-C6-cycloalkyl group may be substituted by 1 to 3 substituents independently selected from R c Substituents are substituted, and the aryl, C5-C 10 -heteroaryl, and C4-C 10 - The heterocyclic group may be independently selected from 1 to 4 b or J is aryl, C5-C 10 -heteroaryl, or C4-C 10 -heterocyclic group, the aryl, C5-C 10 -heteroaryl, and C4-C 10 - The heterocyclic group may be independently selected from 1 to 4 b or J is C1-C6-alkyl-C(O), C3-C6-cycloalkyl-C(O), aryl-C(O), C5-C 10 -heteroaryl-C(O), or C4-C 10 -heterocyclyl-C(O), wherein the alkyl group may be 1 to 3 independently selected from R a The cycloalkyl group may be substituted by 1 to 3 substituents independently selected from R c Substituents are substituted, and the aryl, C5-C 10 -heteroaryl, and C4-C 10 - The heterocyclic group may be independently selected from 1 to 4 d or J is C1-C6-alkyl-S(O)2, C3-C6-cycloalkyl-S(O)2, aryl-S(O)2, C5-C 10 -heteroaryl-S(O)2, or C4-C 10 -heterocyclyl-S(O)2, wherein the alkyl group may be 1 to 3 independently selected from R a The cycloalkyl group may be substituted by 1 to 3 substituents independently selected from R c Substituents are substituted, and the aryl, C5-C 10 -heteroaryl, and C4-C 10 - The heterocyclic group may be independently selected from 1 to 4 e or J is C1-C6-alkoxy, C3-C6-cycloalkyl-C1-C2-alkoxy, aryl-C1-C2-alkoxy, C5-C 10 -heteroaryl-C1-C2-alkoxy, or C4-C 10 -heterocyclyl-C1-C2-alkoxy, said alkoxy group may be 1 to 3 independently selected from R a The cycloalkyl group may be substituted by 1 to 3 substituents independently selected from R c Substituents are substituted, and the aryl, C5-C 10 -heteroaryl, and C4-C 10 - The heterocyclic group may be independently selected from 1 to 4 f Substituents substituted; T is hydrogen, C1-C6-alkyl, C3-C4-alkenyl, C3-C4-alkynyl, C3-C6-cycloalkyl-C1-C2-alkyl, aryl-C1-C2-alkyl, or C5-C 10 -heteroaryl-C1-C2-alkyl, said alkyl, C3-C4-alkenyl, and C3-C4-alkynyl being independently substituted by 1 to 3 groups independently selected from R a The cycloalkyl group may be substituted by 1 to 3 substituents independently selected from R c Substituents are substituted, and the aryl and C5-C 10 -heteroaryl may be substituted independently of each other by 1 to 4 independently selected g Substituents substituted; R a , independently of formula I or II, and independently of the substituent to which it is attached, is selected from halogen, cyano, and C1-C3-alkoxy; R b 、R d 、R e 、R f , and R g , independently of formula I or II and independently of the substituent to which it is attached, is selected from halogen, cyano, C1-C3-alkyl, C1-C3-alkoxy, NH2C(O), (C1-C3-alkyl)N(H)C(O), NH2C(O)-C1-C3-alkoxy, (C1-C4-alkyl)SO2, benzyl, phenyl, phenoxy, C5-C6-heteroaryl and C4-C 10 - heterocyclic group (the phenyl, phenoxy, heteroaryl and heterocyclic group may be substituted independently of each other by 1 to 4 substituents independently selected from halogen, cyano, and C1-C3-alkyl); R c , independently of Formula I or II, is selected from halogen, cyano, C1-C3-alkyl, and C1-C3-alkoxy; provided that when X in Formula II is CH2, T is not hydrogen, C1-C4-alkyl, 2-fluoroethyl, 2-methyl-4-pyrimidinyl)methyl, 2-(methylsulfonyl)phenyl]methyl, 2,6-di(tert-butyl)-4-methylphenyl, 1,4-dihydro-6-methyl-4-oxo-3-pyridazinyl)methyl, 1,3-dihydro-1,3-dioxo-2H-isoindol-2-yl, or tetrahydro-4,4-dimethyl-2-oxo-3-furanyl; or when X in Formula II is O, T is not hydrogen or C1-C2-alkyl; or an agronomically acceptable salt, stereoisomer, tautomer and / or N-oxide of the compound of Formula II or Formula II-I.
3. The method according to claim 1 or the compound according to claim 2, wherein J is hydrogen, C1-C3-alkyl, C1-C3-alkoxy, aryl-C1-C2-alkoxy, C1-C3-alkyl-S(O)2, C3-C4-cycloalkyl-S(O)2, C3-C4-cycloalkyl-C1-C2-alkyl, C5-C 10 -heteroaryl, C4-C 10 -heterocyclic, aryl-C1-C2-alkyl, aryl, or C5-C 10 -heteroaryl-C1-C2-alkyl, the alkyl may be substituted by 1 to 3 substituents independently selected from chlorine, fluorine, cyano, and methoxy, the alkoxy may be substituted by 1 to 3 substituents independently selected from chlorine, fluorine, cyano, methyl, and methoxy, the cycloalkyl may be substituted by 1 to 3 substituents independently selected from chlorine, fluorine, cyano, methyl, and methoxy, and the aryl, heteroaryl, and heterocyclic groups may each be substituted independently by 1 to 4 substituents independently selected from the following: halo halogen, cyano, C1-C3-alkyl, C1-C3-alkoxy, NH2C(O), (C1-C3-alkyl)N(H)C(O), NH2C(O)-C1-C3-alkoxy, (C1-C3-alkyl)SO2, benzyl, phenyl, phenoxy, C5-C6-heteroaryl, and C5-C6-heterocyclyl (the phenyl, phenoxy, heteroaryl or heterocyclyl may be substituted independently by 1 to 4 substituents independently selected from fluorine, chlorine, cyano, and methyl).
4. The method according to claim 1 or 3 or the compound according to claim 2 or 3, wherein X is O or CH2, and Y, R 1 、R 2 、R 3 、R 4 、R 5 、R 6 and R 7 Each is hydrogen.
5. The method according to claim 1, 3 or 4 or the compound according to claim 2, 3 or 4, wherein X is O.
6. The method according to any one of claims 1, 3 and 4 or the compound according to any one of claims 2, 3 and 4, wherein The compound is represented by Formula Ia or Ib (when X is CH2, S, SO, SO2, or SO(NH)); or by Formula Iaa or Icc (when X is O).
7. A composition comprising a compound of formula I, II, II or III-I as defined in any one of claims 1 to 6, one or more adjuvants and diluents, and optionally one or more other active ingredients.
8. The composition according to claim 7, wherein The compounds have Formula I or II and exist as a mixture of compounds having Formula Ia or Ib (when X is CH2, S, SO, SO2, or SO(NH)); or compounds represented by Formula Iaa or Icc (when X is O).
9. A method for protecting plant propagation material from attack by insects, mites, nematodes or molluscs, comprising treating the propagation material or the site where the propagation material is planted with an effective dose of a compound as defined in any one of claims 1 to 6 or a composition as claimed in claim 7 or 8.
10. A plant propagation material such as a seed comprising a compound as defined in any one of claims 1 to 6 or a composition according to claim 7 or 8, or treated with said compound or said composition, or having said compound or said composition attached thereto.
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