CN117412961A - Pesticidally active heteroaromatic compounds - Google Patents

Pesticidally active heteroaromatic compounds Download PDF

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Publication number
CN117412961A
CN117412961A CN202280011073.3A CN202280011073A CN117412961A CN 117412961 A CN117412961 A CN 117412961A CN 202280011073 A CN202280011073 A CN 202280011073A CN 117412961 A CN117412961 A CN 117412961A
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alkyl
formula
cycloalkyl
substituted
compounds
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J·P·基拉鲁
M·费德特
S·贝拉多兹
R·G·豪尔
V·A·伊奥苏布
A·珍格纳特
T·皮特纳
V·奎特格拉斯
M·魏斯
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Syngenta Crop Protection AG Switzerland
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Syngenta Crop Protection AG Switzerland
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Priority claimed from PCT/EP2022/051111 external-priority patent/WO2022157188A2/en
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Abstract

Compounds of formula (I) wherein the substituents are as defined in claim 1, as well as agrochemically acceptable salts, stereoisomers, enantiomers, tautomers and N-oxides of those compounds, can be used as insecticides.

Description

Pesticidally active heteroaromatic compounds
The present invention relates to pesticidally active (in particular insecticidal) compounds, to processes for their preparation, to compositions comprising those compounds, and to their use for controlling animal pests (including arthropods and in particular insects or representatives of the order acarina).
Novel pesticidally active compounds have now been found.
Accordingly, the present invention relates in a first aspect to compounds of formula I
Wherein:
x is O or S;
q is
T is phenyl, pyridine, pyrimidine, pyrazine, pyridazine or a five-or nine-membered heteroaromatic ring; or (b)
T is phenyl, pyridine, pyrimidine, pyrazine, pyridazine or a five-or nine-membered heteroaromatic ring, each independently of the other being selected from R independently of the others from one to three 2 Is substituted by a substituent of (a);
R 1a and R is 1b Independently selected from hydrogen, C 1 -C 6 Alkyl groups independently selected from CN, C 1 -C 3 Alkoxy, C (O) NH 2 、C(O)OH、NO 2 and-Si (CH) 3 ) 3 C substituted by one substituent of (C) 1 -C 6 Alkyl, C 1 -C 6 Haloalkyl, C 2 -C 6 Alkenyl, C 2 -C 6 Haloalkenyl, C 2 -C 6 Alkynyl, C 2 -C 6 Haloalkynyl, C 3 -C 4 cycloalkyl-C 1 -C 2 Alkyl, C substituted by 1 or 2 halogen atoms 3 -C 4 cycloalkyl-C 1 -C 2 Alkyl, oxetan-3-yl-CH 2 -，C 1 -C 6 Alkylcarbonyl, C 1 -C 6 Alkoxycarbonyl, phenyloxycarbonyl, benzyloxycarbonyl, benzyl and groups selected from halogen, C independently from 1 to 3 1 -C 6 Alkoxy and C 1 -C 6 A benzyl group substituted with a substituent of a haloalkyl group; or (b)
R 1a And R is 1b Taken together is selected from- (CH) 2 ) 2 -、-(CH 2 ) 3 -、-CH 2 -O-CH 2 -、-CH 2 -S-CH 2 -、
-CH 2 -S(＝O)-CH 2 -、-CH 2 -SO 2 -CH 2 -and-CH 2 -N(R Y )-CH 2 -, to form a 5-or 6-membered ring with the nitrogen atom to which they are attached;
R 1b and T together with the nitrogen atom forms a nine or ten membered bicyclic heterocycle which may be substituted with one to three substituents independently selected from the group consisting of: c (C) 1 -C 3 Alkyl, C 1 -C 3 Haloalkyl, C 1 -C 3 Alkoxy, C 3 -C 4 Cycloalkyl, halogen, hydroxy, cyano and C 1 -C 3 Haloalkoxy groups;
R 2 independently selected from: c (C) 1 -C 3 Alkyl, C 1 -C 3 Haloalkyl, C 1 -C 3 Haloalkylthio, C 1 -C 3 Alkoxy, C 1 -C 3 Haloalkoxy, halo, NO 2 、SF 5 、CN、C(O)NR 7 R 8 、C(O)OH、C(S)NH 2 、C 1 -C 4 Alkylsulfonylamino, aminosulfonyl, C 1 -C 4 Alkylaminosulfonyl, di (C) 1 -C 4 Alkyl) sulfamoyl, C 3 -C 6 Cycloalkyl sulfamoyl, C 3 -C 6 Cycloalkyl radicalsIs one to three independently selected from R x C substituted by substituent(s) 3 -C 6 Cycloalkyl, C 3 -C 6 Cycloalkyl carbonyl, phenyl, independently selected from one to three of R x Phenyl, heteroaryl substituted with one to three substituents independently selected from R x Heteroaryl groups substituted with substituents OR 6 Piperidin-2-one-1-yl, one to two independently selected from R x Piperidin-2-one-1-yl, pyridin-2-one-1-yl substituted with one or two substituents independently selected from R x Pyridin-2-one-1-yl, azetidin-1-yl, substituted with one or two substituents independently selected from R x Azetidin-1-yl, pyrrolidin-1-yl substituted with one or two substituents independently selected from R x Pyrrolidin-1-yl, C, substituted by substituents of (2) 3 -C 6 Cycloalkyl C 1 -C 4 Alkyl, independently selected from one to two of R z C substituted by substituent(s) 3 -C 6 Cycloalkyl C 1 -C 4 Alkyl, C 3 -C 6 Cycloalkyl C 1 -C 3 Alkoxy, one to two independently selected from R x C substituted by substituent(s) 3 -C 6 Cycloalkyl C 1 -C 3 Alkoxy, C 1 -C 5 Cyanoalkyl, C 1 -C 5 Cyanoalkoxy, C 1 -C 4 Alkylsulfonyl, one to two independently selected from R x C substituted by substituent(s) 1 -C 4 Alkylsulfonyl, C 1 -C 4 Alkylsulfinyl groups, one to two of which are independently selected from R x C substituted by substituent(s) 1 -C 4 Alkylsulfinyl, C 3 -C 6 Cycloalkyl sulfanyl, C 3 -C 6 Cycloalkyl sulfinyl, C 3 -C 6 Cycloalkyl sulfonyl; a divalent group selected from the group consisting of-O-C 1 -C 2 haloalkyldi-O-, -CH 2 -C(CH 3 ) 2 -O-、-CH 2 -C(CH 3 ) 2 -S-、-CH 2 -C(CH 3 ) 2 -SO 2 -wherein the divalent group is linked to T via two adjacent ring members of T; eight (eight)To twelve membered spiro heterocycles, which rings may be substituted with one or two substituents selected from the group consisting of: halo, C 1 -C 3 Alkyl, C 1 -C 3 Haloalkyl, and C 1 -C 3 An alkoxy group; or (b)
R 3 Is C 1 -C 3 Alkyl or C 1 -C 3 A haloalkyl group;
R 4 is pyridine, pyrimidine, pyrazine or pyridazine; or (b)
R 4 Is pyridine, pyrimidine, pyrazine or pyridazine, each independently of the other being substituted by one to two substituents independently selected from the group consisting of: c (C) 1 -C 3 Alkyl, C 1 -C 3 Haloalkyl, C 1 -C 3 Alkoxy, C 3 -C 4 Cycloalkyl, halo, hydroxy, CN, C 1 -C 6 Haloalkoxy, C 2 -C 6 Haloalkenyloxy, C 2 -C 6 Haloalkynyloxy, C 3 -C 4 Halogenated cycloalkoxy, NH 2 C(O)-、NH 2 C(S)-、(OH)N＝C(NH 2 ) -and a 5-membered heteroaryl ring optionally substituted with 1 to 3 substituents independently selected from: halogen, C 1 -C 3 Alkyl, C 1 -C 3 Haloalkyl, C 1 -C 3 Alkoxy and C 1 -C 3 Haloalkoxy groups;
R 4 is thiazol-2-yl, thiazol-4-yl, thiazol-5-yl, isothiazol-3-yl, isothiazol-4-yl, isothiazol-5-yl, 1,2, 4-thiadiazol-3-yl, 1,3, 4-thiadiazol-2-yl or 1,2, 4-thiadiazol-5-yl; or (b)
R 4 Is thiazol-2-yl, thiazol-4-yl, thiazol-5-yl, isothiazol-3-yl, isothiazol-4-yl, isothiazol-5-yl, 1,2, 4-thiadiazol-3-yl, 1,3, 4-thiadiazol-2-yl or 1,2, 4-thiadiazol-5-yl, each of which is independently substituted with one to two substituents independently selected from the group consisting of: c (C) 1 -C 3 Alkyl, C 1 -C 3 Haloalkyl, C 1 -C 3 Alkoxy, C 3 -C 4 Cycloalkyl, halo, hydroxy, CN, C 1 -C 6 Haloalkoxy group,C 2 -C 6 Haloalkenyloxy, C 2 -C 6 Haloalkynyloxy, C 3 -C 4 Halogenated cycloalkoxy, NH 2 C(O)-、NH 2 C(S)-、(OH)N＝C(NH 2 ) -and a 5-membered heteroaryl ring optionally substituted with 1 to 3 substituents independently selected from: halogen, C 1 -C 3 Alkyl, C 1 -C 3 Haloalkyl, C 1 -C 3 Alkoxy and C 1 -C 3 Haloalkoxy groups;
R 4a is pyridine, pyrimidine, pyrazine or pyridazine; or (b)
R 4a Is pyridine, pyrimidine, pyrazine or pyridazine, each independently of the other being substituted by one to three substituents independently selected from the group consisting of: c (C) 1 -C 3 Alkyl, C 1 -C 3 Haloalkyl, C 1 -C 3 Alkoxy, C 3 -C 4 Cycloalkyl, halogen, hydroxy, cyano and C 1 -C 3 Haloalkoxy groups; or (b)
R 4a Is Y1, Y2, Y3 or Y4
Wherein R 'is' 4a 、R’ 4b And R'. 4c Independently of each other and independently of Y1 to Y4, from hydrogen, halogen, CN, C 1 -C 3 Alkyl, C 1 -C 3 Haloalkyl, C 3 -C 4 Cycloalkyl, C 1 -C 3 Alkoxy and C 1 -C 3 Haloalkoxy groups;
R 4a is thiazol-2-yl, thiazol-4-yl, thiazol-5-yl, isothiazol-3-yl, isothiazol-4-yl, isothiazol-5-yl, 1,2, 4-thiadiazol-3-yl, 1,3, 4-thiadiazol-2-yl or 1,2, 4-thiadiazol-5-yl; or (b)
R 4a Is thiazol-2-yl, thiazol-4-yl, thiazol-5-yl, isothiazol-3-yl, isothiazol-4-yl, isothiazol-5-yl, 1,2, 4-thiadiazol-3-yl, 1,3, 4-thiadiazol-2-yl or 1,2, 4-thiadiazol-5-yl, which are independent of each other Each of the sites is substituted with one to two substituents independently selected from the group consisting of: c (C) 1 -C 3 Alkyl, C 1 -C 3 Haloalkyl, C 1 -C 3 Alkoxy, C 3 -C 4 Cycloalkyl, halogen, hydroxy, cyano, and C 1 -C 3 Haloalkoxy groups; r is R 5 Is hydrogen, C 1 -C 3 Alkyl, C 1 -C 3 Haloalkyl, C 3 -C 4 Cycloalkyl, C 1 -C 3 Alkoxy, C 3 -C 4 Alkoxy C (O) -, (C) 1 -C 3 Alkoxy group) 2 CH-, halogen, CN, NH 2 C (O), amino (i.e., NH) 2 )、(C 1 -C 3 Alkyl) amino, di (C) 1 -C 3 Alkyl) amino, hydroxy, C 3 -C 4 Halogenated cycloalkyl, C 3 -C 4 Cyanocycloalkyl, C 2 -C 6 Alkenyl, C 2 -C 6 Haloalkenyl, C 2 -C 6 Alkynyl, C 2 -C 6 Haloalkynyl, C 1 -C 4 Haloalkyl sulfanyl, C 1 -C 4 Haloalkyl sulfinyl, C 1 -C 4 Haloalkyl sulfonyl, C 1 -C 4 Alkyl sulfanyl, C 1 -C 4 Alkylsulfinyl, C 1 -C 4 Alkylsulfonyl, C 1 -C 3 alkoxy-C 1 -C 3 Alkyl, C 1 -C 3 alkoxy-C 1 -C 3 alkoxy-C 1 -C 3 Alkyl, (C) 1 -C 3 Alkyl) sulfonylamino, (C 1 -C 3 Alkyl) sulfonyl (C) 1 -C 3 Alkyl) amino, (C 1 -C 3 Alkyl) NHC (O), (C 1 -C 3 Alkyl group 2 NC(O)、(C 1 -C 3 Cycloalkyl) NHC (O), (C 1 -C 3 Cycloalkyl) (C) 1 -C 3 Alkyl) NC (O), (C 1 -C 3 Alkyl) C (O) (C 1 -C 3 Alkyl) N, (C 1 -C 3 Alkyl) C (O) NH, (C) 1 -C 3 Alkyl) C (O), (C 1 -C 3 Alkoxy) C (O), HC (O)) Benzophenone imine, C 1 -C 3 Haloalkoxy, phenyl, or a 5-membered heteroaromatic ring; or (b)
R 5 Is phenyl substituted with one to three substituents selected from the group consisting of: c (C) 1 -C 3 Alkyl, C 1 -C 3 Haloalkyl, C 1 -C 3 Alkoxy, C 3 -C 4 Cycloalkyl, halogen, CN, and hydroxy; or (b)
R 5 Is a 5-membered heteroaromatic ring substituted with one to three substituents selected from the group consisting of: c (C) 1 -C 3 Alkyl, C 1 -C 3 Haloalkyl, C 1 -C 3 Alkoxy, C 3 -C 4 Cycloalkyl, halogen, CN, and hydroxy;
R 5a and R is 5b Independently of each other selected from hydrogen, halogen, CN, C 1 -C 3 Alkyl, C 1 -C 3 Haloalkyl, C 3 -C 4 Cycloalkyl, C 1 -C 3 Alkoxy and C 1 -C 3 Haloalkoxy groups;
R 6 is phenyl, benzyl, heteroaryl, C 3 -C 6 Cycloalkyl, or C 3 -C 6 Cycloalkyl C 1 -C 3 An alkyl group; or (b)
R 6 Is phenyl, benzyl, heteroaryl, C 3 -C 6 Cycloalkyl, or C 3 -C 6 Cycloalkyl C 1 -C 3 Alkyl groups, each independently of the other, are selected from R x Is substituted by a substituent of (a);
R 7 is hydrogen, C 1 -C 3 Alkyl or C 3 -C 6 Cycloalkyl; or (b)
R 7 Is C 1 -C 3 Alkyl or C 3 -C 6 Cycloalkyl groups, each independently of the other, are selected from R independently of the others from one to three z Is substituted by a substituent of (a);
R 8 is hydrogen, C 1 -C 3 Alkyl or C 3 -C 6 Cycloalkyl; or (b)
R 8 Is C 1 -C 3 Alkyl or C 3 -C 6 Cycloalkyl groups, each independently of the other, are selected from R independently of the others from one to three z Is substituted by a substituent of (a); or (b)
R 7 And R is 8 Together are- (CH) 2 ) 2 -O-(CH 2 ) 2 -and forms a 6-membered ring with the nitrogen atom;
R x independently selected from halogen, C 1 -C 3 Alkyl, C 1 -C 3 Haloalkyl, C 1 -C 3 Alkoxy, C 1 -C 3 Haloalkoxy, NO 2 、SF 5 、CN、C(O)NH 2 、C(S)NH 2 、C 3 -C 6 Cycloalkyl, C 1 -C 4 Haloalkyl sulfanyl, C 1 -C 4 Haloalkyl sulfinyl, C 1 -C 4 Haloalkyl sulfonyl, C 1 -C 4 Alkyl sulfanyl, C 1 -C 4 Alkylsulfinyl and C 1 -C 4 An alkylsulfonyl group;
R Y is C 1 -C 4 Alkyl, C 3 -C 5 Alkenyl, C 3 -C 4 Cycloalkyl, C 2 -C 5 Alkynyl, or benzyl;
R z selected from oxo, halogen, C 1 -C 3 Alkyl, C 1 -C 3 Haloalkyl, C 1 -C 3 Alkoxy, C 1 -C 3 Haloalkoxy and CN; or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer and N-oxide of the compound of formula I.
Compounds of formula I having at least one basic center may for example form for example acid addition salts with: strong mineral acids (e.g. mineral acids such as perchloric acid, sulfuric acid, nitric acid, nitrous acid, phosphoric acid or hydrohalic acid), strong organic carboxylic acids (e.g. C, unsubstituted or substituted, e.g. by halogen) 1 -C 4 Alkanoic acids, e.g. acetic acid, e.g. saturated or unsaturated dicarboxylic acids, e.g. oxalic acid, malonic acid, succinic acid, maleic acid, fumaric acid or phthalic acidFormic acid, e.g. hydroxycarboxylic acids, e.g. ascorbic acid, lactic acid, malic acid, tartaric acid or citric acid, or e.g. benzoic acid), or organic sulphonic acids (e.g. C which is unsubstituted or substituted, e.g. by halogen 1 -C 4 Alkanesulfonic or arylsulfonic acids, for example methanesulfonic acid or p-toluenesulfonic acid). The compounds of the formula I having at least one acidic group may for example form salts, such as mineral salts, for example alkali metal or alkaline earth metal salts, such as sodium, potassium or magnesium salts, with bases; or with ammonia or an organic amine (e.g., morpholine, piperidine, pyrrolidine, mono-, di-or tri-lower alkylamine, such as ethylamine, diethylamine, triethylamine or dimethylpropylamine, or mono-, di-or tri-hydroxy lower alkylamine, such as monoethanolamine, diethanolamine or triethanolamine).
In each case, the compounds according to the invention of formula I are in free form, oxidized form, such as N-oxide, or in salt form (e.g. in agronomically useful salt form).
The N-oxide is an oxidized form of a tertiary amine or an oxidized form of a nitrogen-containing heteroaromatic compound. They are described, for example, in the books "Heterocholic N-oxides [ Heterocyclic N-oxides ]", CRC Press [ CRC Press ], boca Raton [ Bokaraton ]1991 by A.Albini and S.Pietra.
The compounds of formula I according to the invention also include hydrates which may form during salt formation.
As used herein, the term "C 1 -C n Alkyl "refers to a saturated straight or branched hydrocarbon group having 1 to n carbon atoms attached via any carbon atom, such as any of the following groups: methyl, ethyl, n-propyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2-dimethylpropyl, 1-ethylpropyl, n-hexyl n-pentyl, 1-dimethylpropyl, 1, 2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl 1, 1-dimethylbutyl, 1, 2-dimethylbutyl, 1, 3-dimethylbutyl, 2-dimethylbutyl, 2, 3-dimethylbutyl, 3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1, 2-trimethylpropyl, 1, 2-trimethylpropyl, 1-ethyl-1-methylpropyl, or1-ethyl-2-methylpropyl.
As used herein, the term "C 1 -C n Haloalkyl "refers to a straight or branched saturated alkyl group (as mentioned above) having from 1 to n carbon atoms attached via any one carbon atom, wherein some or all of the hydrogen atoms of these groups may be replaced by fluorine, chlorine, bromine and/or iodine, i.e., for example, any one of the following: chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 2-fluoroethyl, 2-chloroethyl, 2-bromoethyl 2-iodoethyl, 2-difluoroethyl, 2-trifluoroethyl, 2-chloro-2-fluoroethyl, 2-chloro-2, 2-difluoroethyl 2, 2-dichloro-2-fluoroethyl, 2-trichloroethyl, pentafluoroethyl, 2-fluoropropyl 3-fluoropropyl group, 2-difluoropropyl group, 2, 3-difluoropropyl group, 2-chloropropyl group, 3-chloropropyl group 2, 3-dichloropropyl, 2-bromopropyl, 3-trifluoropropyl, 3-trichloropropyl 2, 3-pentafluoropropyl, heptafluoropropyl, 1- (fluoromethyl) -2-fluoroethyl, 1- (chloromethyl) -2-chloroethyl, 1- (bromomethyl) -2-bromoethyl, 4-fluorobutyl, 4-chlorobutyl, 4-bromobutyl or nonafluorobutyl. Accordingly, the term "C 1 -C 2 Fluoroalkyl will mean C with 1,2, 3, 4 or 5 fluorine atoms 1 -C 2 Alkyl groups such as any of the following: difluoromethyl, trifluoromethyl, 1-fluoroethyl, 2-difluoroethyl 2, 2-trifluoroethyl, 1, 2-tetrafluoroethyl or pentafluoroethyl.
As used herein, the term "C 1 -C n Alkoxy "refers to a straight or branched saturated alkyl group (as mentioned above) having 1 to n carbon atoms, which is attached via an oxygen atom, i.e., for example, any of the following groups: methoxy, ethoxy, n-propoxy, 1-methylethoxy, n-butoxy, 1-methylpropoxy, 2-methylpropoxy or 1, 1-dimethylethoxy. The term "halo C", as used herein 1 -C n Alkoxy "means C 1 -C n Alkoxy groups in which one or more hydrogen atoms on the alkyl group are replaced by the same or different halogen atoms-examples include trifluoromethoxy, 2-fluoroethoxy, 3-fluoropropoxy, 3,3-trifluoropropoxy, 4-chlorobutoxy.
As used herein, the term "C 1 -C n Cyanoalkyl "means a straight-chain or branched saturated C having 1 to n carbon atoms 1 -C n Alkyl groups (as mentioned above), wherein one of the hydrogen atoms in these groups is replaced by a cyano group: such as cyanomethyl, 2-cyanoethyl, 2-cyanopropyl, 3-cyanopropyl, 1- (cyanomethyl) -2-ethyl, 1- (methyl) -2-cyanoethyl, 4-cyanobutyl, and the like.
As used herein, the term "C 3 -C n Cycloalkyl "refers to 3 to n membered cycloalkyl groups such as cyclopropane, cyclobutane, cyclopentane and cyclohexane.
As used herein, the term "C 3 -C n Cycloalkyl carbonyl "refers to a 3-n membered cycloalkyl attached to a carbonyl (c=o) group, which carbonyl group is attached to the remainder of the molecule. Similarly, as used herein, the term "C 1 -C n Alkylcarbonyl "," C 1 -C n Alkoxycarbonyl "," phenyloxycarbonyl "and" benzyloxycarbonyl "refer to alkyl, alkoxy, phenyloxy and benzyloxy groups attached to a carbonyl (c=o) group, which carbonyl group is attached to the remainder of the molecule.
As used herein, the term "C 3 -C 4 cycloalkyl-C 1 -C 2 Alkyl "refers to a 3 or 4 membered cycloalkyl group bearing a methylene or ethylene group attached to the remainder of the molecule. In this case C 3 -C 4 cycloalkyl-C 1 -C 2 Alkyl-is substituted and one or more substituents may be on cycloalkyl and/or alkyl.
As used herein, the term "C 3 -C 6 Cycloalkyl C 1 -C 4 Haloalkoxy "refers to a 3 to 6 membered cycloalkyl group attached to a 1 to 4 membered haloalkoxy group, which haloalkoxy group is attached to the remainder of the molecule.
As used herein, the term "aminocarbonyl C 1 -C n Alkyl "refers to an alkyl group in which one of the hydrogen atoms in the group is replaced with a CONH2 group.
As used herein, the term "hydroxycarbonyl C 1 -C n Alkyl "refers to an alkyl group in which one of the hydrogen atoms in the group is replaced by a COOH group.
As used herein, the term "C 1 -C n Alkylsulfanyl "refers to C linked through a sulfur atom 1 -C n An alkyl moiety. Similarly, as used herein, the term "C 1 -C n Haloalkylthio "or" C 1 -C n Haloalkylsulfanyl "refers to C attached through a sulfur atom 1 -C n A haloalkyl moiety. Similarly, the term "C 3 -C n Cycloalkyl sulfanyl "refers to a 3-n membered cycloalkyl moiety attached through a sulfur atom.
As used herein, the term "C 1 -C n Alkylsulfinyl "refers to C attached through the sulfur atom of the S (=o) group 1 -C n An alkyl moiety. Similarly, as used herein, the term "C 1 -C n Haloalkyl sulfinyl "or" C 1 -C n Haloalkyl sulfinyl "refers to C linked through the sulfur atom of the S (=o) group 1 -C n A haloalkyl moiety. Similarly, the term "C 3 -C n Cycloalkyl sulfinyl "refers to a 3-n membered cycloalkyl moiety attached through the sulfur atom of the S (=o) group.
As used herein, the term "C 1 -C n Alkylsulfonyl "means by S (=o) 2 C linked to sulfur atoms of radicals 1 -C n An alkyl moiety. Similarly, as used herein, the term "C 1 -C n Haloalkylsulfonyl "or" C 1 -C n Haloalkylsulfonyl "refers to a compound obtained by reacting S (=o) 2 C linked to sulfur atoms of radicals 1 -C n A haloalkyl moiety. Similarly, the term "C 3 -C n Cycloalkyl sulfonyl "means through S (=o) 2 A 3-n membered cycloalkyl moiety attached to the sulfur atom of the group.
As used herein, the term "trimethylsilane C 1 -C n Alkyl "means C 1 -C n Alkyl groups, where the radicals areIs one of the hydrogen atoms of (C) is-Si (CH) 3 ) 3 And (3) replacing groups.
As used herein, the term "C 1 -C 4 Alkylsulfonylamino "refers to C 1 -C n An alkylsulfonyl moiety linked through an amino (or NH) group; an example is methylsulfonylamino (MeS (O) 2 NH-)。
As used herein, the term "aminosulfonyl" refers to an amino moiety linked through a sulfonyl group, i.e., NH 2 S(O) 2 -。
As used herein, the term "C 1 -C 4 Alkylaminosulfonyl "means C 1 -C n An alkylamino moiety linked through a sulfonyl group; examples are, i.e., meNHS (O) 2 -、EtNHS(O) 2 。
The term "di (C 1 -C 4 Alkyl) sulfamoyl "refers to di (C 1 -C 4 Alkyl) amino moieties linked through sulfonyl; examples are, i.e., me 2 NS(O) 2 -、Et(Me)NS(O) 2 。
As used herein, the term "C 3 -C 6 Cycloalkyl sulfamoyl "means C 3 -C 6 A cycloalkylamino moiety linked through a sulfonyl group; examples are, i.e., cyclopropyl NHS (O) 2 -。
The term "-O-C, as used herein 1 -C 2 haloalkadiyl-O- "refers to a linear saturated halogenated divalent group attached through each oxygen atom and having 1 or 2 carbon atoms between the oxygen atoms. When referring to the T ring, -O-C 1 -C 2 haloalkadiyl-O-groups via-O-C 1 -C 2 The oxygen atoms of the haloalkadiyl-O-groups are attached to adjacent ring members of the T-ring (i.e., phenyl, pyridine, pyrimidine, pyrazine, pyridazine, or five-or nine-membered heteroaromatic ring) and these oxygen atoms are attached through 1 to 2 carbon atoms substituted with one or more halogen atoms. Examples include-OCF 2 O-and-OCF 2 CF 2 O-. Together with two adjacent ring members of the T ring to which it is attached, -O-C 1 -C 2 Haloalkylsthe-O-group thus forms a 5-or 6-membered ring.
As used herein, the term "C 2 -C n Alkenyl "refers to a straight or branched alkenyl chain having from two to n carbon atoms and one or two double bonds, such as vinyl, prop-1-enyl, but-2-enyl.
As used herein, the term "C 2 -C n Haloalkenyl "means C substituted by one or more halogen atoms which may be the same or different 2 -C n Alkenyl moieties.
As used herein, the term "C 2 -C n Alkynyl "refers to a straight or branched alkynyl chain having from two to n carbon atoms and one triple bond, such as ethynyl, prop-2-ynyl, but-3-ynyl.
As used herein, the term "C 2 -C n Haloalkynyl "refers to C substituted with one or more halogen atoms which may be the same or different 2 -C n Alkynyl moiety.
Halogen or "halo" is typically fluoro, chloro, bromo or iodo. This applies correspondingly to halogens, such as haloalkyl, in combination with other meanings.
As used herein, the term "heteroaryl" refers to a 5-or 6-membered aromatic monocyclic ring having 1 to 3 heteroatoms independently selected from N, O and S. Examples are heteroaryl groups J-1 to J-41 shown in scheme A below. Preferred heteroaryl groups are pyridinyl, pyrimidinyl and pyrazolyl.
Scheme a: heteroaryl groups J-1 to J-41:
examples of nine membered heteroaromatic rings of T are heteroaromatic compounds which consist of two rings, with 1 to 3 carbon atoms independently replaced by nitrogen, sulfur, or oxygen (these heteroatoms may be in one ring or distributed in both rings). Examples are purinyl, thieno [2,3-d ] pyrimidinyl, [1,2,4] triazolo [1,5-a ] pyrimidinyl, quinolinyl, cinnolinyl, quinoxalinyl, indolyl, indazolyl, benzimidazolyl, benzothienyl and benzothiazolyl.
The term "nine or ten membered bicyclic heterocycle" as used herein is defined as consisting of T and R 1b The context of a ring formed with an N atom refers to a partially or fully saturated ring; the ring optionally has 1 or 2 further heteroatoms selected from N and O in addition to the N atom. From R 1b An example of a 9-membered heterocyclic ring formed with T is indolinyl.
As used herein, the term "spiroheterocycle" refers to an 8-to 12-membered spiro ring, preferably a ten membered spiro ring, having 3 to 4 heteroatoms selected from N and O, the ring being partially or fully saturated. If substituted, the substituent may be on a carbon atom or a heteroatom. An example of a spiro-heterocycle is oxa-2, 8-diazaspiro [4.5] dec-2-en-3-yl.
R 4 And R is 4a The pyridine, pyrimidine, pyrazine and pyridazine groups (unsubstituted or substituted) of (i) are each attached to the remainder of the compound via a carbon atom on the corresponding ring.
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 the plant or to plant-derived products is reduced.
As herein for example at Q a And the staggered lines used in Y1, e.g., the arrows used in scheme a, represent the connection or attachment points to the remainder of the compound.
As used herein, the term "pest" refers to insects and mollusks found in the storage of agricultural, horticultural, forestry, plant-derived products (such as fruits, grains and wood); and those related to damage to man-made structures. The term pest encompasses all phases of the pest life cycle.
As used herein, the term "effective amount" refers to an amount of a compound or salt thereof that provides a desired effect upon single or multiple applications.
The effective amount is readily determined by one skilled in the art by using known techniques and by observing results obtained in similar circumstances. In determining an effective amount, a number of factors are considered, including but not limited to: the type of plant or derivative product to be applied; the pests to be controlled and their life cycle; the particular compound administered; type of application; and other related situations.
As will be appreciated by those of ordinary skill in the art, compounds having formula I contain a stereocenter, which is indicated by an asterisk in the following structure:
therein T, X, R 1a 、R 1b 、R 3 And Q is as defined in the first aspect.
Both racemates and individual enantiomers are contemplated by the present invention. Compounds with preferred stereochemistry are listed below.
Particularly preferred compounds of the invention are those having the formula I' a (wherein T, X, R 1a 、R 1b 、R 3 And Q is as defined in the first aspect), and stereoisomers, enantiomers, tautomers and N-oxides of the compounds having formula (I' a), and agrochemically acceptable salts thereof.
As used herein, the term "optionally substituted" means that the group referred to is unsubstituted or substituted with the specified substituent. For example, "C 3 -C 4 Cycloalkyl optionally substituted by 1 or 2 halogen atoms "means C 3 -C 4 Cycloalkyl, C substituted by 1 halogen atom 3 -C 4 Cycloalkyl and C substituted by 2 halogen atoms 3 -C 4 Cycloalkyl groups.
Embodiments according to the present invention are provided, as listed below.
In an embodiment of each aspect of the invention,
A.X is oxygen; or (b)
B.X is sulfur.
In embodiments of each aspect of the invention, R 1a Is that
A. Hydrogen, C 1 -C 6 Alkyl, C 1 -C 6 Cyanoalkyl, aminocarbonyl C 1 -C 6 Alkyl, hydroxycarbonyl C 1 -C 6 Alkyl, C 1 -C 6 Nitroalkyl, trimethylsilane C 1 -C 6 Alkyl, C 1 -C 3 alkoxy-C 1 -C 6 Alkyl, C 1 -C 6 Haloalkyl, C 2 -C 6 Alkenyl, C 2 -C 6 Haloalkenyl, C 2 -C 6 Alkynyl, C 2 -C 6 Haloalkynyl, C 3 -C 4 Cycloalkyl C 1 -C 2 Alkyl-, C 3 -C 4 Cycloalkyl C 1 -C 2 Alkyl- (wherein C) 3 -C 4 Cycloalkyl substituted by 1 or 2 halogen atoms), oxetan-3-yl-CH 2 -、C 1 -C 3 Alkylcarbonyl, C 1 -C 3 Alkoxycarbonyl, phenyloxycarbonyl, benzyloxycarbonyl, or benzyl; or (b)
B. Hydrogen, C 1 -C 6 Alkyl, C 1 -C 6 Cyanoalkyl, aminocarbonyl C 1 -C 6 Alkyl, hydroxycarbonyl C 1 -C 6 Alkyl, C 1 -C 6 Nitroalkyl, trimethylsilane C 1 -C 6 Alkyl, C 1 -C 3 alkoxy-C 1 -C 6 Alkyl, C 1 -C 6 Haloalkyl, C 2 -C 6 Alkenyl, C 2 -C 6 Haloalkenyl, C 2 -C 6 Alkynyl, C 2 -C 6 Haloalkynyl, C 3 -C 4 Cycloalkyl C 1 -C 2 Alkyl-, benzyloxycarbonyl, or benzyl; or (b)
C. Hydrogen, C 1 -C 6 Alkyl, C 1 -C 6 Cyanoalkyl, aminocarbonyl C 1 -C 6 Alkyl, hydroxycarbonyl C 1 -C 6 Alkyl, C 1 -C 3 alkoxy-C 1 -C 6 Alkyl, C 1 -C 6 Haloalkyl, C 2 -C 6 Alkenyl, C 2 -C 6 Haloalkenyl, C 2 -C 6 Alkynyl, C 2 -C 6 Haloalkynyl, C 3 -C 4 Cycloalkyl C 1 -C 2 Alkyl-, benzyloxycarbonyl, or benzyl; or (b)
D. Hydrogen, C 1 -C 6 Alkyl, C 1 -C 6 Cyanoalkyl, C 1 -C 3 alkoxy-C 1 -C 6 Alkyl, C 1 -C 6 Haloalkyl, C 2 -C 6 Alkenyl, C 2 -C 6 Haloalkenyl, C 2 -C 6 Alkynyl, C 2 -C 6 Haloalkynyl, C 3 -C 4 Cycloalkyl C 1 -C 2 Alkyl-, benzyloxycarbonyl, or benzyl; or (b)
E. Hydrogen, C 1 -C 4 Alkyl, C 1 -C 4 Cyanoalkyl, C 1 -C 4 alkoxy-C 1 -C 3 Alkyl, C 1 -C 4 Haloalkyl, C 2 -C 4 Alkenyl, C 2 -C 4 Haloalkenyl, C 2 -C 4 Alkynyl, C 2 -C 4 Haloalkynyl, C 3 -C 4 Cycloalkyl C 1 -C 2 Alkyl-, benzyloxycarbonyl, or benzyl; or (b)
F. Hydrogen, C 1 -C 3 Alkyl, C 1 -C 3 Cyanoalkyl, C 1 -C 3 alkoxy-C 1 -C 3 Alkyl, C 1 -C 3 Haloalkyl, C 2 -C 4 Alkenyl, C 2 -C 4 Haloalkenyl, C 2 -C 4 Alkynyl, C 2 -C 4 Haloalkynyl, C 3 -C 4 Cycloalkyl C 1 -C 2 Alkyl group-benzyloxycarbonyl, or benzyl; or (b)
G. Hydrogen, methyl, ethyl, cyanomethyl, methoxymethyl, cyclopropyl-methyl, allyl, propargyl, benzyloxycarbonyl, or benzyl; or (b)
H. Hydrogen, methyl, ethyl, allyl, propargyl, or cyclopropyl-methyl; or (b)
I. Hydrogen, methyl, propargyl, or cyclopropyl-methyl;
J. hydrogen, or methyl; or (b)
K. Hydrogen.
In embodiments of each aspect of the invention, R 1b Is that
A. Hydrogen, C 1 -C 6 Alkyl, C 1 -C 6 Cyanoalkyl, aminocarbonyl C 1 -C 6 Alkyl, hydroxycarbonyl C 1 -C 6 Alkyl, C 1 -C 6 Nitroalkyl, trimethylsilane C 1 -C 6 Alkyl, C 1 -C 3 alkoxy-C 1 -C 6 Alkyl, C 1 -C 6 Haloalkyl, C 2 -C 6 Alkenyl, C 2 -C 6 Haloalkenyl, C 2 -C 6 Alkynyl, C 2 -C 6 Haloalkynyl, C 3 -C 4 Cycloalkyl C 1 -C 2 Alkyl-, C 3 -C 4 Cycloalkyl C 1 -C 2 Alkyl- (wherein C) 3 -C 4 Cycloalkyl substituted by 1 or 2 halogen atoms), oxetan-3-yl-CH 2 -、C 1 -C 3 Alkylcarbonyl, C 1 -C 3 Alkoxycarbonyl, phenyloxycarbonyl, benzyloxycarbonyl, or benzyl; or (b)
B. Hydrogen, C 1 -C 6 Alkyl, C 1 -C 6 Cyanoalkyl, aminocarbonyl C 1 -C 6 Alkyl, hydroxycarbonyl C 1 -C 6 Alkyl, C 1 -C 6 Nitroalkyl, trimethylsilane C 1 -C 6 Alkyl, C 1 -C 3 alkoxy-C 1 -C 6 Alkyl, C 1 -C 6 Haloalkyl, C 2 -C 6 Alkenyl groups、C 2 -C 6 Haloalkenyl, C 2 -C 6 Alkynyl, C 2 -C 6 Haloalkynyl, C 3 -C 4 Cycloalkyl C 1 -C 2 Alkyl-, benzyloxycarbonyl, or benzyl; or (b)
C. Hydrogen, C 1 -C 6 Alkyl, C 1 -C 6 Cyanoalkyl, aminocarbonyl C 1 -C 6 Alkyl, hydroxycarbonyl C 1 -C 6 Alkyl, C 1 -C 3 alkoxy-C 1 -C 6 Alkyl, C 1 -C 6 Haloalkyl, C 2 -C 6 Alkenyl, C 2 -C 6 Haloalkenyl, C 2 -C 6 Alkynyl, C 2 -C 6 Haloalkynyl, C 3 -C 4 Cycloalkyl C 1 -C 2 Alkyl-, benzyloxycarbonyl, or benzyl; or (b)
D. Hydrogen, C 1 -C 6 Alkyl, C 1 -C 6 Cyanoalkyl, C 1 -C 3 alkoxy-C 1 -C 6 Alkyl, C 1 -C 6 Haloalkyl, C 2 -C 6 Alkenyl, C 2 -C 6 Haloalkenyl, C 2 -C 6 Alkynyl, C 2 -C 6 Haloalkynyl, C 3 -C 4 Cycloalkyl C 1 -C 2 Alkyl-, benzyloxycarbonyl, or benzyl; or (b)
E. Hydrogen, C 1 -C 4 Alkyl, C 1 -C 4 Cyanoalkyl, C 1 -C 4 alkoxy-C 1 -C 3 Alkyl, C 1 -C 4 Haloalkyl, C 2 -C 4 Alkenyl, C 2 -C 4 Haloalkenyl, C 2 -C 4 Alkynyl, C 2 -C 4 Haloalkynyl, C 3 -C 4 Cycloalkyl C 1 -C 2 Alkyl-, benzyloxycarbonyl, or benzyl; or (b)
F. Hydrogen, C 1 -C 3 Alkyl, C 1 -C 3 Cyanoalkyl, C 1 -C 3 alkoxy-C 1 -C 3 Alkyl, C 1 -C 3 Halogenated compoundsAlkyl, C 2 -C 4 Alkenyl, C 2 -C 4 Haloalkenyl, C 2 -C 4 Alkynyl, C 2 -C 4 Haloalkynyl, C 3 -C 4 Cycloalkyl C 1 -C 2 Alkyl-, benzyloxycarbonyl, or benzyl; or (b)
G. Hydrogen, methyl, ethyl, cyanomethyl, methoxymethyl, cyclopropyl-methyl, allyl, propargyl, benzyloxycarbonyl, or benzyl; or (b)
H. Hydrogen, methyl, ethyl, allyl, propargyl, or cyclopropyl-methyl; or (b)
I. Hydrogen, methyl, propargyl, or cyclopropyl-methyl; or (b)
J. Hydrogen, or methyl;
K. hydrogen.
In embodiments of each aspect of the invention, R 1a And R is 1b Taken together are
A. Selected from- (CH) 2 ) 2 -、-(CH 2 ) 3 -、-CH 2 -O-CH 2 -、-CH 2 -S-CH 2 -、-CH 2 -S(＝O)-CH 2 -, and-CH 2 -SO 2 -CH 2 -; or (b)
B. Selected from- (CH) 2 ) 3 -、-CH 2 -O-CH 2 -、-CH 2 -S-CH 2 -、-CH 2 -S(＝O)-CH 2 -, and-CH 2 -SO 2 -CH 2 -; or (b)
C. Selected from-CH 2 -O-CH 2 -、-CH 2 -S-CH 2 -、-CH 2 -S(＝O)-CH 2 -, and-CH 2 -SO 2 -CH 2 -; or (b)
D.-CH 2 -O-CH 2 -。
In an embodiment of each aspect of the invention, T is
A. Phenyl, pyridine, pyrimidine, pyrazine, pyridazine or a heteroaromatic ring selected from the group consisting of: j-13, J-16, J-22, J-25, J-26, J-27, J-28, J-31, J-36, J-37, J-38, J-39, J-40, J-41, thieno [2,3-d ]]Pyrimidinyl, [1,2,4 ]]Triazolo [1,5-a ]]Pyrimidinyl, and indazoleRadicals, independently of one another, are unsubstituted or are selected from R 2 Is substituted by a substituent of (a);
B. phenyl, pyridine, pyrimidine, pyrazine, pyridazine or a heteroaromatic ring selected from the group consisting of: j-13, J-16, J-22, J-25, J-26, J-27, J-28, J-31, J-36, J-37, J-38, J-39, J-40, J-41, thieno [2,3-d ]]Pyrimidinyl, [1,2,4 ]]Triazolo [1,5-a ]]Pyrimidinyl, and indazolyl, each independently of the other, are selected from R 2 Is substituted by a substituent of (a); or (b)
C. Phenyl, pyridine, pyrimidine or a heteroaromatic ring selected from the group consisting of: j-13, J-16, J-22, J-25, J-26, J-27, J-28, J-31, J-36, J-37, J-38, J-39, J-40, J-41, thieno [2,3-d ]]Pyrimidinyl, [1,2,4 ]]Triazolo [1,5-a ]]Pyrimidinyl, and indazolyl, each independently of the other, are selected from R 2 Is substituted by a substituent of (a); or (b)
D. Phenyl, pyridine, pyrimidine or a heteroaromatic ring selected from the group consisting of: j-16, J-26, J-27 and J-28, J-41, thieno [2,3-d ]]Pyrimidinyl, [1,2,4 ]]Triazolo [1,5-a ]]Pyrimidinyl, and indazolyl, each independently of the other, are selected from R 2 Is substituted by a substituent of (a); or (b)
E. Phenyl, pyridin-2-yl (or J-1), J-2, J-3, J-4, J-5, J-6, J-16, J-26, J-27, J-28, J-41, thieno [2,3-d ]]Pyrimidinyl, [1,2,4 ]]Triazolo [1,5-a ]]Pyrimidinyl, or indazolyl, each independently of the other, being selected from R 2 Is substituted by a substituent of (a); or (b)
F. Phenyl, pyridin-2-yl (or J-1), or J-2, each independently of the other, is selected from R 2 Is substituted by a substituent of (a); or (b)
G. Phenyl, pyridin-2-yl (or J-1), or J-2, each independently of the other, being substituted with one to three substituents independently selected from the group consisting of: halogen, C 1 -C 3 Alkyl, C 1 -C 3 Haloalkyl, C 1 -C 3 Alkoxy, C 1 -C 3 Haloalkoxy, CN, C 3 -C 4 Cycloalkyl, C 3 -C 6 Cycloalkyl carbonyl group,Phenyl, heteroaryl (selected from J-1 and J-41) (C 3 -C 4 Cycloalkyl, phenyl or heteroaryl are each, independently of one another, each by one to three substituents R x Substituted, OR 6 Piperidin-2-one-1-yl, pyridin-2-one-1-yl, azetidin-1-yl (optionally substituted with R x Substituted), pyrrolidin-1-yl, C 3 -C 6 Cycloalkyl C 1 -C 4 Alkyl (substituted by one or two substituents R Z Substitution, C 3 -C 6 Cycloalkyl C 1 -C 3 Alkoxy (optionally by R x Substitution, C 1 -C 5 Cyanoalkyl, C 1 -C 5 Cyanoalkoxy, C 1 -C 4 Alkylsulfanyl (optionally substituted with one to three substituents R x Substitution, C 1 -C 4 Alkylsulfonyl (optionally substituted with one to three substituents R x Substitution, C 1 -C 4 Alkylsulfinyl (optionally substituted with one to three substituents R x Substituted), C (O) NR 7 R 8 、C 1 -C 4 Alkylsulfonylamino, aminosulfonyl, C 1 -C 4 Alkylaminosulfonyl, di (C) 1 -C 4 Alkyl) sulfamoyl, C 3 -C 6 Cycloalkyl sulfamoyl, -O-C 1 -C 2 Halogenated alkyl-O-, and 10 membered optionally substituted spiroheterocycle; or (b)
H. Phenyl, pyridin-2-yl (or J-1), or J-2, each independently of the other, being substituted with one to three substituents independently selected from the group consisting of: halogen, C 1 -C 3 Alkyl, C 1 -C 3 Haloalkyl, C 1 -C 3 Alkoxy, C 1 -C 3 Haloalkoxy, CN, C 3 -C 4 Cycloalkyl, C 3 -C 6 Cycloalkyl carbonyl, phenyl, heteroaryl (selected from J-1, J-13 and J-25) (C 3 -C 4 Cycloalkyl, phenyl or heteroaryl are each, independently of one another, each by one to three substituents R x Substituted, OR 6 、C 3 -C 6 Cycloalkyl C 1 -C 4 Alkyl (substituted by one or two substituents R Z Substitution, C 3 -C 6 Cycloalkyl C 1 -C 3 Alkoxy (optionally by R x Substitution, C 1 -C 5 Cyanoalkyl, C 1 -C 5 Cyanoalkoxy, C 1 -C 4 Alkylsulfanyl (optionally substituted with one to three substituents R x Substitution, C 1 -C 4 Alkylsulfonyl (optionally substituted with one to three substituents R x Substitution, C 1 -C 4 Alkylsulfinyl (optionally substituted with one to three substituents R x Substituted), C (O) NR 7 R 8 、C 1 -C 4 Alkylsulfonylamino, aminosulfonyl, C 1 -C 4 Alkylaminosulfonyl, di (C) 1 -C 4 Alkyl) sulfamoyl, C 3 -C 6 Cycloalkyl sulfamoyl, -O-C 1 -C 2 haloalkyldi-O-, and C 1 -C 3 Alkoxy substituted 10 membered spiroheterocycles; or (b)
I. Phenyl, pyridin-2-yl (or J-1), or J-2, each independently of the other, being substituted with one to three substituents independently selected from the group consisting of: halogen, C 1 -C 3 Alkyl, C 1 -C 3 Haloalkyl, C 1 -C 3 Haloalkoxy, methoxy, CN, OR 6 (wherein R is 6 Is phenyl, J-1 or J-17, each of which may be independently selected from R from one to three x Substituted with substituents) and-O-C 1 -C 2 haloalkyldi-O-; or (b)
J. Phenyl, pyridin-2-yl (or J-1), or J-2, each independently of the other, being substituted with one to three substituents independently selected from the group consisting of: chlorine, fluorine, bromine, iodine, methyl, difluoromethyl, trifluoromethyl, difluoromethoxy, trifluoromethoxy, 1, 2-tetrafluoroethoxy, 1, 2-pentafluoroethoxy, cyano, O-CF 2 CF 2 -O-, and O-CF 2 -O-；
K. Phenyl, pyridin-2-yl (or J-1), or J-2, each independently of the other, being substituted with one to three substituents independently selected from the group consisting of: chlorine, fluorine, bromine, iodine, methyl, trifluoromethyl, difluoromethoxy, and 1, 2-tetrafluoroethoxy; or (b)
L.2 4-bis (trifluoromethyl) phenyl, 2, 4-chloro-5- (1, 2-tetrafluoroethoxy) phenyl, 2-bromo-4-chloro-5- (trifluoromethyl) phenyl, 4-bromo-2- (difluoromethoxy) -5-fluoro-phenyl, 2-bromo-4- (difluoromethoxy) phenyl, 2-iodo-4- (trifluoromethyl) phenyl, 3, 5-bis (trifluoromethyl) phenyl, 2-chloro-4- (trifluoromethyl) phenyl, 4-chloro-2- (trifluoromethyl) phenyl, 2, 4-dibromophenyl, 5-chloro-2- (trifluoromethyl) phenyl, 2-chloro-5- (trifluoromethyl) phenyl, 4-chloro-3- (trifluoromethyl) phenyl, 3-chloro-4- (trifluoromethyl) phenyl, 4-chloro-5-cyano-2-fluoro-phenyl, 2-methyl-4- (trifluoromethyl) phenyl, 4-chloro-6- (trifluoromethyl) -3-pyridinyl, 4, 6-dibromo-3-pyridinyl, 4-bromo-6- (trifluoromethyl) -3-pyridinyl, 3-fluoro-3-pyridinyl, 3-trifluoromethyl-3-pyridinyl, 3-fluoro-3-methyl-3-pyridinyl, 3-fluoro-3-pyridinyl, and, 4-methoxy-6- (trifluoromethyl) -3-pyridinyl, 3-chloro-5- (trifluoromethyl) -2-pyridinyl, 5-chloro-4- (trifluoromethyl) thiazol-2-yl, 4-methyl-6- (trifluoromethyl) -3-pyridinyl, or 4-methoxy-6- (trifluoromethyl) -3-pyridinyl; or (b)
M.2, 4-bis (trifluoromethyl) phenyl, 2, 4-chloro-5- (1, 2-tetrafluoroethoxy) phenyl, 2-bromo-4-chloro-5- (trifluoromethyl) phenyl, 2-bromo-4- (difluoromethoxy) phenyl, 2-iodo-4- (trifluoromethyl) phenyl, 3, 5-bis (trifluoromethyl) phenyl, 2-chloro-4- (trifluoromethyl) phenyl, 4-chloro-2- (trifluoromethyl) phenyl, 2, 4-dibromophenyl, 5-chloro-2- (trifluoromethyl) phenyl, 2-chloro-5- (trifluoromethyl) phenyl, 4-chloro-3- (trifluoromethyl) phenyl, 3-chloro-4- (trifluoromethyl) phenyl, 4-chloro-6- (trifluoromethyl) -3-pyridinyl, 4, 6-dibromo-3-pyridinyl, 3-chloro-5- (trifluoromethyl) -2-pyridinyl, 5-chloro-4- (trifluoromethyl) thiazol-2-yl, 4-methyl-6- (trifluoromethyl) -3-pyridinyl, or 4-methoxy-pyridinyl; or (b)
N.4-bromo-2- (difluoromethoxy) -5-fluoro-phenyl, 4-chloro-5-cyano-2-fluoro-phenyl, 2-methyl-4- (trifluoromethyl) phenyl, 4-chloro-6- (trifluoromethyl) -3-pyridinyl, 4, 6-dibromo-3-pyridinyl, 4-bromo-6- (trifluoromethyl) -3-pyridinyl, 4-methyl-6- (trifluoromethyl) -3-pyridinyl, 4-methoxy-6- (trifluoromethyl) -3-pyridinyl, 4-methyl-6- (trifluoromethyl) -3-pyridinyl, or 4-methoxy-6- (trifluoromethyl) -3-pyridinyl; or (b)
O.2,4- (trifluoromethyl) phenyl, 2, 4-chloro-5- (1, 2-tetrafluoroethoxy) phenyl, 2-bromo-4-chloro-5- (trifluoromethyl) phenyl, 2-bromo-4- (difluoromethoxy) phenyl, 2-iodo-4- (trifluoromethyl) phenyl, 4-chloro-6- (trifluoromethyl) -3-pyridinyl, 4, 6-dibromo-3-pyridinyl, 4-methyl-6- (trifluoromethyl) -3-pyridinyl, or 4-methoxy-6- (trifluoromethyl) -3-pyridinyl.
In embodiments of each aspect of the invention, R 1b And T is taken together with the nitrogen atom to form
A. Nine membered bicyclic heterocycle which may be substituted with one to three substituents independently selected from: c (C) 1 -C 3 Haloalkyl, C 1 -C 3 Alkoxy, C 3 -C 4 Cycloalkyl, halogen, and C 1 -C 3 Haloalkoxy groups; or (b)
B. Nine membered bicyclic heterocycle which may be substituted with one to three substituents independently selected from: trifluoromethyl, methoxy, trifluoromethoxy, cyclopropyl, chloro, fluoro, and bromo; or (b)
C. An indoline ring which may be substituted with one to three substituents independently selected from: trifluoromethyl, methoxy, trifluoromethoxy, cyclopropyl, chloro, fluoro, and bromo; or (b)
D. An indoline ring which may be substituted with one to three substituents independently selected from: trifluoromethyl, chloro, fluoro, and bromo; or (b)
E. An indoline ring substituted with one to three substituents independently selected from the group consisting of: trifluoromethyl, chloro, fluoro, and bromo.
In embodiments of each aspect of the invention, R 2 Independently of one another selected from
A. Halogen, C 1 -C 3 Alkyl, C 1 -C 3 Haloalkyl, C 1 -C 3 Alkoxy, C 1 -C 3 Haloalkoxy, CN, C 3 -C 4 Cycloalkyl, C 3 -C 6 Cycloalkyl carbonyl, phenyl, heteroaryl (selected from J-1 and J-41) (C 3 -C 4 Cycloalkyl, phenyl or heteroaryl are each, independently of one another, each by one to three substituents R x Substituted, OR 6 Piperidin-2-one-1-yl, pyridin-2-one-1-yl, azetidin-1-yl (optionally substituted with R x Substituted) is a,Pyrrolidin-1-yl, C 3 -C 6 Cycloalkyl C 1 -C 4 Alkyl (substituted by one or two substituents R Z Substitution, C 3 -C 6 Cycloalkyl C 1 -C 3 Alkoxy (optionally by R x Substitution, C 1 -C 5 Cyanoalkyl, C 1 -C 5 Cyanoalkoxy, C 1 -C 4 Alkylsulfanyl (optionally substituted with one to three substituents R x Substitution, C 1 -C 4 Alkylsulfonyl (optionally substituted with one to three substituents R x Substitution, C 1 -C 4 Alkylsulfinyl (optionally substituted with one to three substituents R x Substituted), C (O) NR 7 R 8 、C 1 -C 4 Alkylsulfonylamino, aminosulfonyl, C 1 -C 4 Alkylaminosulfonyl, di (C) 1 -C 4 Alkyl) sulfamoyl, C 3 -C 6 Cycloalkyl sulfamoyl, -O-C 1 -C 2 Halogenated alkyl-O-, and 10 membered optionally substituted spiroheterocycle; or (b)
B. Halogen, C 1 -C 3 Alkyl, C 1 -C 3 Haloalkyl, C 1 -C 3 Alkoxy, C 1 -C 3 Haloalkoxy, CN, C 3 -C 4 Cycloalkyl, C 3 -C 6 Cycloalkyl carbonyl, phenyl, heteroaryl (selected from J-1, J-13 and J-25), pyrazolyl (C 3 -C 4 Cycloalkyl, phenyl, heteroaryl and pyrazolyl are each, independently of one another, each substituted by one to three substituents R x Substituted, OR 6 Piperidin-2-one-1-yl, pyridin-2-one-1-yl, azetidin-1-yl (optionally substituted with R x Substituted), pyrrolidin-1-yl, C 3 -C 6 Cycloalkyl C 1 -C 4 Alkyl (optionally substituted with one or two substituents R Z Substitution, C 3 -C 6 Cycloalkyl C 1 -C 3 Alkoxy (optionally by R x Substitution, C 1 -C 5 Cyanoalkyl, C 1 -C 5 Cyanoalkoxy, C 1 -C 4 Alkylsulfanyl (optionally substituted with one to three substituents R x Substitution, C 1 -C 4 Alkylsulfonyl (optionally substituted with one to three substituents R x Substituted) and C 1 -C 4 Alkylsulfinyl (optionally substituted with one to three substituents R x Substituted), C (O) NR 7 R 8 、C 1 -C 4 Alkylsulfonylamino, C 1 -C 4 Alkylaminosulfonyl, di (C) 1 -C 4 Alkyl) sulfamoyl, C 3 -C 6 Cycloalkyl sulfamoyl, -O-C 1 -C 2 haloalkyldi-O-, and C 1 -C 3 Alkoxy substituted 10 membered spiroheterocycles; or (b)
C. Halogen, C 1 -C 3 Alkyl, C 1 -C 3 Haloalkyl, C 1 -C 3 Alkoxy, C 1 -C 3 Haloalkoxy, CN, C 3 -C 4 Cycloalkyl, C 3 -C 6 Cycloalkyl carbonyl, phenyl or pyrazolyl (C) 3 -C 4 Cycloalkyl, phenyl, pyrazolyl are each independently of one another substituted by one to two substituents R x Substituted, OR 6 Azetidin-1-yl (optionally substituted by R x Substitution, C 3 -C 6 Cycloalkyl C 1 -C 4 Alkyl (optionally substituted with one or two substituents R Z Substitution, C 3 -C 6 Cycloalkyl C 1 -C 3 Alkoxy (optionally by R x Substitution, C 1 -C 4 Alkylsulfanyl (optionally substituted with one to three substituents R x Substitution, C 1 -C 4 Alkylsulfonyl (optionally substituted with one to three substituents R x Substitution, C 1 -C 4 Alkylsulfinyl (optionally substituted with one to three substituents R x Substituted), C (O) NH (C) 1 -C 4 Alkyl group, C 1 -C 4 Alkylsulfonylamino, C 1 -C 4 Alkylaminosulfonyl, C 3 -C 6 Cycloalkyl sulfamoyl, and-O-C 1 -C 2 haloalkyldi-O-; or (b)
D. Halogen, C 1 -C 3 Alkyl, C 1 -C 3 Haloalkyl, C 1 -C 3 Alkoxy, C 1 -C 3 Haloalkoxy, CN, C 3 -C 4 Cycloalkyl, substituted by one or two substituents R x Substituted C 3 -C 4 Cycloalkyl, C 3 -C 6 Cycloalkyl carbonyl, OR 6 、C 3 -C 6 Cycloalkyl C 1 -C 4 Alkyl, substituted by one or two substituents R Z Substituted C 3 -C 6 Cycloalkyl C 1 -C 4 Alkyl, C 1 -C 4 Alkylsulfanyl, substituted by one to three substituents R x Substituted C 1 -C 4 Alkyl sulfanyl, C 1 -C 4 Alkylsulfonyl, substituted by one to three substituents R x Substituted C 1 -C 4 Alkylsulfonyl, C 1 -C 4 Alkylsulfinyl, substituted with one to three substituents R x Substituted C 1 -C 4 Alkylsulfinyl, C (O) NH (C) 1 -C 4 Alkyl group, C 1 -C 4 Alkylsulfonylamino, C 1 -C 4 Alkylaminosulfonyl, C 3 -C 6 Cycloalkyl sulfamoyl, and-O-C 1 -C 2 haloalkyldi-O-; or (b)
E. Halogen, C 1 -C 3 Alkyl, C 1 -C 3 Haloalkyl, C 1 -C 3 Alkoxy, C 1 -C 3 Haloalkoxy, CN, C 3 -C 4 Cycloalkyl, one to two of which are independently selected from halogen, C 1 -C 3 Alkyl and C 1 -C 3 Substituted C of haloalkyl 3 -C 4 Cycloalkyl, C 3 -C 4 Cycloalkyl carbonyl group, OR 6 ，C 3 -C 4 Cycloalkylmethyl radicals, one to two independently selected from oxo, halogen, C 1 -C 3 Alkyl and C 1 -C 3 Substituted C of haloalkyl 3 -C 4 Cycloalkylmethyl, C substituted by one to three halogens 1 -C 2 Alkylsulfanyl, C substituted by one to three halogens 1 -C 2 Alkylsulfonyl, C (O) NH (C) 1 -C 4 Alkyl), C 1 -C 4 Alkylsulfonylamino, C 1 -C 4 Alkyl sulfamoyl, C 3 -C 6 Cycloalkyl sulfamoyl, and-O-C 1 -C 2 haloalkyldi-O-; or (b)
F. Halogen, C 1 -C 3 Alkyl, C 1 -C 3 Haloalkyl, C 1 -C 3 Alkoxy, C 1 -C 3 Haloalkoxy, CN, cyclopropyl substituted with one to two substituents independently selected from halogen, methyl and trifluoromethyl, cyclopropylcarbonyl, OR 6 Cyclopropylmethyl substituted with one to two substituents independently selected from oxo, halo, and trifluoromethyl, C substituted with one to three halo 1- C 2 Alkylsulfanyl, C substituted by one to three halogens 1- C 2 Alkylsulfonyl, C (O) NH (C) 1 -C 4 Alkyl), C 1 -C 4 Alkylsulfonylamino, C 1 -C 4 Alkyl sulfamoyl, C 3 -C 6 Cycloalkyl sulfamoyl, and-O-C 1 -C 2 haloalkyldi-O-; or (b)
G. Halogen, C 1 -C 3 Alkyl, C 1 -C 3 Haloalkyl, C 1 -C 3 Haloalkylsulfanyl, C 1 -C 3 Alkoxy, C 1 -C 3 Haloalkoxy, CN, C 3 -C 6 Cycloalkyl groups, one to three of which are independently selected from C 1 -C 3 Alkyl, C 1 -C 3 Haloalkyl, cyano and halogen substituted C 3 -C 6 Cycloalkyl, cyclopropylcarbonyl, OR 6 ，C 3 -C 6 Cycloalkyl C 1 -C 4 Alkyl, one to five independently selected from oxo, C 1 -C 3 Alkyl, C 1 -C 3 Haloalkyl, cyano and halogen substituted C 3 -C 6 Cycloalkyl C 1 -C 4 Alkyl, C 1 -C 5 Cyanoalkyl, C 1 -C 4 Alkylsulfonyl, C 1 -C 4 Haloalkylsulfonyl, C 1 -C 4 Alkylsulfinyl, C 1 -C 4 Haloalkyl sulfinyl, C 3 -C 6 Cycloalkyl sulfanyl, C 3 -C 6 Cycloalkyl sulfinyl, C 3 -C 6 Cycloalkyl sulfonyl, C (O) NH (C) 1 -C 4 Alkyl), C 1 -C 4 Alkylsulfonylamino, C 1 -C 4 Alkyl sulfamoyl, C 3 -C 6 Cycloalkyl sulfamoyl, and-O-C 1 -C 2 haloalkyldi-O-; or (b)
H. Halogen, C 1 -C 3 Alkyl, C 1 -C 3 Haloalkyl, C 1 -C 3 Haloalkylsulfanyl, C 1 -C 3 Alkoxy, C 1 -C 3 Haloalkoxy, CN, C 3 -C 6 Cycloalkyl groups, one or two of which are independently selected from C 1 -C 3 Haloalkyl, cyano and halogen substituted C 3 -C 6 Cycloalkyl, C 3 -C 4 Cycloalkyl carbonyl group, OR 6 ，C 3 -C 6 Cycloalkyl C 1 -C 4 Alkyl, one to three independently selected from oxo, C 1 -C 3 Haloalkyl, cyano and halogen substituted C 3 -C 6 Cycloalkyl C 1 -C 4 Alkyl, C 1 -C 5 Cyanoalkyl, C 1 -C 4 Alkylsulfonyl, C 1 -C 4 Haloalkylsulfonyl, C 1 -C 4 Alkylsulfinyl, C 1 -C 4 Haloalkyl sulfinyl, C 3 -C 6 Cycloalkyl sulfanyl, C 3 -C 6 Cycloalkyl sulfinyl, C 3 -C 6 Cycloalkyl sulfonyl, C (O) NH (C) 1 -C 4 Alkyl), C 1 -C 4 Alkylsulfonylamino, C 1 -C 4 Alkyl sulfamoyl, C 3 -C 6 Cycloalkyl sulfamoyl, and-O-C 1 -C 2 haloalkyldi-O-; or (b)
I. Halogen, C 1 -C 3 Haloalkyl, C 1 -C 3 Haloalkylsulfanyl, C 1 -C 3 A halogen-substituted alkoxy group, which is a halogen-substituted alkoxy group,CN，C 3 -C 6 cycloalkyl groups, one or two of which are independently selected from C 1 -C 3 Haloalkyl, cyano and halogen substituted C 3 -C 6 Cycloalkyl, C 3 -C 4 Cycloalkyl carbonyl group, OR 6 ，C 3 -C 6 Cycloalkyl C 1 -C 4 Alkyl, one to three independently selected from oxo, C 1 -C 3 Haloalkyl, cyano and halogen substituted C 3 -C 6 Cycloalkyl C 1 -C 4 Alkyl, C 1 -C 5 Cyanoalkyl, C 1 -C 4 Alkylsulfonyl, C 1 -C 4 Haloalkylsulfonyl, C 1 -C 4 Alkylsulfinyl, C 1 -C 4 Haloalkyl sulfinyl, C 3 -C 6 Cycloalkyl sulfanyl, C 3 -C 6 Cycloalkyl sulfinyl, C 3 -C 6 Cycloalkyl sulfonyl, C (O) NH (C) 1 -C 4 Alkyl), C 1 -C 4 Alkylsulfonylamino, C 1 -C 4 Alkyl sulfamoyl, C 3 -C 6 Cycloalkyl sulfamoyl, and-O-C 1 -C 2 haloalkyldi-O-; or (b)
J. Halogen, C 3 -C 4 Cycloalkyl, C 3 -C 4 Cycloalkyl carbonyl optionally substituted with one or two substituents selected from oxo, halogen, C 1 -C 3 Alkyl and C 1 -C 3 Substituted C of haloalkyl 3 -C 4 cycloalkyl-C 1 -C 2 Alkyl, C 1 -C 3 Haloalkyl, OR 6 (wherein R is 6 Is phenyl, J-1 or J-17, each of which may be independently selected from R from one to three x Substituted by substituents of (2), C 1 -C 3 Haloalkylsulfanyl, C 1 -C 3 Haloalkylsulfonyl, C 1 -C 3 Alkoxy, C 1 -C 3 Haloalkoxy, CN, and-O-C 1 -C 2 haloalkyldi-O-; or (b)
K. Halogen, C 3 -C 4 Cycloalkyl, C 1 -C 3 Haloalkyl, OR 6 (wherein R is 6 Is phenyl, J-1 or J-17, each of which may be independently selected from R from one to three x Substituted by substituents of (C) 1 -C 3 Haloalkyl sulfanyl, C 1 -C 3 Haloalkylsulfonyl, -O-CF 2 -O-、-OCF 2 CF 2 O-, and C 1 -C 3 Haloalkoxy groups; or (b)
L, halogen, C 1 -C 2 Haloalkyl, C 1 -C 2 Haloalkyl sulfanyl, C 1 -C 2 Haloalkylsulfonyl, -O-CF 2 -O-、-OCF 2 CF 2 O-, and C 1 -C 2 Haloalkoxy groups; or (b)
M, chloro, fluoro, bromo, iodo, cyclopropyl, difluoromethyl, trifluoromethyl, trifluoromethylsulfanyl, trifluoromethylsulfonyl, difluoromethoxy, trifluoromethoxy, 1, 2-tetrafluoroethoxy, 1, 2-pentafluoroethoxy, -O-CF 2 CF 2 -O-, and-O-CF 2 -O-; or (b)
N, fluoro, chloro, bromo, iodo, difluoromethyl, trifluoromethyl, difluoromethoxy, trifluoromethoxy, 1, 2-tetrafluoroethoxy, 1, 2-pentafluoroethoxy, -O-CF 2 CF 2 -O-, and-O-CF 2 -O-; or (b)
O, fluorine, chlorine, bromine, iodine, trifluoromethyl, difluoromethoxy, 1, 2-tetrafluoroethoxy, -O-CF 2 CF 2 -O-, and-O-CF 2 -O-; or (b)
P, fluoro, chloro, bromo, iodo, trifluoromethyl, difluoromethoxy, and 1, 2-tetrafluoroethoxy.
When R is 2 Where T is a divalent group, T carries only one such divalent group as R 2 And the divalent group is linked to T via two adjacent ring members of T. Examples of divalent groups include-O-C 1 -C 2 haloalkyldi-O-, -CH 2 -C(CH 3 ) 2 -O-、-CH 2 -C(CH 3 ) 2 -S-、-CH 2 -C(CH 3 ) 2 -SO 2 。-O-C 1 -C 2 Examples of haloalkadiyl-O-include-O-CF 2 -CF 2 -O-、-O-CFH-CF 2 -O-、-O-CFH-CFH-O-、-OCH 2 -CHF-O-、-OCH 2 -CF 2 -O-、-O-CF 2 -O-, and-O-CFH-O-; preferably-O-CF 2 CF 2 -O-, and-O-CF 2 -O-. In embodiments, T is a phenyl, pyridine, pyrimidine, pyrazine, pyridazine, or five or nine membered heteroaromatic ring substituted via two adjacent ring members of the phenyl, pyridine, pyrimidine, pyrazine, pyridazine, or five or nine membered heteroaromatic ring with a divalent group selected from: -O-C 1 -C 2 haloalkyldi-O-, -CH 2 -C(CH 3 ) 2 -O-、-CH 2 -C(CH 3 ) 2 -S-、-CH 2 -C(CH 3 ) 2 -SO 2 Preferably selected from-O-CF 2 CF 2 -O-and-O-CF 2 -O-。
In embodiments of each aspect of the invention, R 3 Is that
A.C 1 -C 2 Alkyl or C 1 -C 2 A haloalkyl group; or (b)
B. Methyl or trifluoromethyl; or (b)
C. Methyl group.
In embodiments of each aspect of the invention, Q is
A.Q a The method comprises the steps of carrying out a first treatment on the surface of the Or (b)
B.Q b The method comprises the steps of carrying out a first treatment on the surface of the Or (b)
C. Selected from Q a -1 to Q a -16, or is selected from Q b -1 to Q b -13; or (b)
D. Selected from Q a -1、Q a -6、Q a -7、Q a -10、Q a -15 and Q b -1; or (b)
E.Q a -1、Q a -15, or Q b -1; or (b)
F.Q a -1, or Q b -1；
G.Q a -1; or (b)
H.Q b -1。
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In embodiments of each aspect of the invention, R 4 Is that
A. Pyridine, or pyrimidine; wherein the pyridine or pyrimidine are independently optionally substituted with one substituent selected from the group consisting of: c (C) 1 -C 3 Alkyl, C 1 -C 3 Haloalkyl, C 1 -C 3 Alkoxy, C 3 -C 4 Cycloalkyl, halo, hydroxy, CN, C 1 -C 6 Haloalkoxy, C 2 -C 6 Haloalkenyloxy, C 2 -C 6 Haloalkynyloxy, C 3 -C 4 Halogenated cycloalkoxy, C 3 -C 6 Cycloalkyl C 1 -C 4 Haloalkoxy, NH 2 C(O)-、NH 2 C(S)-、(OH)N＝C(NH 2 ) -, J-13 (optionally from 1 to 3 independently selected from halogen, C 1 -C 3 Alkyl, C 1 -C 3 Haloalkyl, C 1 -C 3 Alkoxy and C 1 -C 3 Substituted with 1 to 3 substituents independently selected from halogen, C), J-20 (optionally substituted with 1 to 3 substituents independently selected from halogen 1 -C 3 Alkyl, C 1 -C 3 Haloalkyl, C 1 -C 3 Alkoxy and C 1 -C 3 Substituted with a substituent of haloalkoxy) and 1H-tetrazol-5-yl; or (b)
B. Pyridine or pyrimidine, wherein the pyridine or pyrimidine are independently of each other optionally substituted with one substituent selected from the group consisting of: c (C) 1 -C 3 Alkyl, C 1 -C 3 Haloalkyl, C 1 -C 3 Alkoxy, C 3 -C 4 Cycloalkyl, halo, hydroxy, CN, C 1 -C 6 Haloalkoxy, C 2 -C 6 Haloalkenyloxy, C 2 -C 6 Haloalkynyloxy, C 3 -C 4 Halogenated cycloalkoxy, C 3 -C 6 Cycloalkyl C 1 -C 4 Haloalkoxy group, NH 2 C(O)-、NH 2 C(S)-、(OH)N＝C(NH 2 ) -, optionally by C 1 -C 3 Haloalkyl-substituted J-13, optionally C 1 -C 3 Haloalkyl-substituted J-20, and 1H-tetrazol-5-yl; or (b)
C. Pyridine, wherein the pyridine is optionally substituted with one substituent selected from the group consisting of: c (C) 1 -C 3 Alkyl, C 1 -C 3 Haloalkyl, C 1 -C 3 Alkoxy, C 3 -C 4 Cycloalkyl, halo, hydroxy, CN, C 1 -C 6 Haloalkoxy, C 2 -C 6 Haloalkenyloxy, C 2 -C 6 Haloalkynyloxy, C 3 -C 4 Halogenated cycloalkoxy, C 3 -C 6 Cycloalkyl C 1 -C 4 Haloalkoxy, NH 2 C(O)-、NH 2 C(S)-、(OH)N＝C(NH 2 ) -, optionally by C 1 -C 3 Haloalkyl-substituted J-13, optionally C 1 -C 3 Haloalkyl-substituted J-20, and 1H-tetrazol-5-yl; or (b)
D. Pyrimidine; wherein the pyrimidine is optionally substituted with one substituent selected from the group consisting of: c (C) 1 -C 3 Alkyl, C 1 -C 3 Haloalkyl, C 1 -C 3 Alkoxy, C 3 -C 4 Cycloalkyl, halo, hydroxy, CN, C 1 -C 6 Haloalkoxy, C 2 -C 6 Haloalkenyloxy, C 2 -C 6 Haloalkynyloxy, C 3 -C 4 Halogenated cycloalkoxy, C 3 -C 6 Cycloalkyl C 1 -C 4 Haloalkoxy, NH 2 C(O)-、NH 2 C(S)-、(OH)N＝C(NH 2 ) -, J-13 (optionally substituted with trifluoromethyl), J-20 (optionally substituted with trifluoromethyl) and 1H-tetrazol-5-yl; or (b)
E. A thiazole, pyridine, pyrimidine, pyrazine, or pyridazine, wherein the thiazole, pyridine, pyrimidine, pyrazine, or pyridazine is optionally substituted with one substituent selected from the group consisting of: c (C) 1 -C 3 Alkyl, C 1 -C 3 Haloalkyl, C 1 -C 3 Alkoxy group,C 3 -C 4 Cycloalkyl, F, cl, br, CN and C 1 -C 6 Haloalkoxy groups; or (b)
F. A thiazole, pyridine, pyrimidine, pyrazine, or pyridazine, wherein the thiazole, pyridine, pyrimidine, pyrazine, or pyridazine is optionally substituted with one substituent selected from the group consisting of: c (C) 1 -C 3 Alkyl, C 3 -C 4 Cycloalkyl, F, cl, br, CN and C 1 -C 6 Haloalkoxy groups; or (b)
G. A thiazole, pyridine, pyrimidine, pyrazine, or pyridazine, wherein the thiazole, pyridine, pyrimidine, pyrazine, or pyridazine is optionally substituted with one substituent selected from the group consisting of: cyclopropyl, F, cl, br, CN, trifluoromethoxy, difluoromethoxy, 2-difluoroethoxy and 2, 2-trifluoroethoxy;
H. thiazole, pyridine, or pyrimidine, wherein the pyridine or pyrimidine is optionally substituted with one substituent selected from the group consisting of: cyclopropyl, F, cl, br, CN, trifluoromethoxy, difluoromethoxy, 2-difluoroethoxy and 2, 2-trifluoroethoxy; or (b)
5-cyanothiazol-2-yl, 5-cyclopropyl-pyridine, 5-fluoropyridine, 5-chloropyridine, 5-bromopyridine, 5-difluoromethoxy-pyridine, 5-trifluoromethoxy-pyridine, 5-cyanopyridine, 5- (2, 2-difluoroethoxy) -pyridine, 5- (2, 2-trifluoroethoxy) -pyridine, 5-cyclopropyl-pyrimidine, 5-fluoropyrimidine, 5-chloropyrimidine, 5-bromopyrimidine, 5-difluoromethoxy-pyrimidine, 5-trifluoromethoxy-pyrimidine, 5-cyanopyrimidine, 5- (2, 2-difluoroethoxy) -pyrimidine, 5- (2, 2-trifluoroethoxy) -pyrimidine, or pyrimidine; or (b)
J.5-Cyanothiazol-2-yl, 5-cyclopropylpyridin-2-yl, 5-fluoropyridin-2-yl, 5-chloropyridin-2-yl, 5-bromopyridin-2-yl, 5-difluoromethoxy-pyridin-2-yl, 5-trifluoromethoxy-pyridin-2-yl, 5-cyanopyridin-2-yl, 5- (2, 2-difluoroethoxy-pyridin-2-yl, 5- (2, 2-trifluoroethoxy) -pyridin-2-yl, 5-cyclopropylpyrimidin-2-yl, 5-fluoropyrimidin-2-yl, 5-chloropyrimidin-2-yl, 5-bromopyrimidin-2-yl, 5-difluoromethoxy-pyrimidin-2-yl, 5-trifluoromethoxy-pyrimidin-2-yl, 5- (2, 2-difluoroethoxy) -pyrimidin-2-yl, 5- (2, 2-trifluoroethoxy) -pyrimidin-2-yl, or
K.5-cyanothiazol-2-yl, pyrimidin-2-yl, pyridin-2-yl, 5-bromopyrimidin-2-yl, 5-bromopyridin-2-yl, 5-cyanopyrimidin-2-yl, or 5-cyanopyridin-2-yl; or (b)
L.5-cyanothiazol-2-yl, pyrimidin-2-yl, 5-bromopyrimidin-2-yl, 5-bromopyridin-2-yl, or 5-cyanopyridin-2-yl; or (b)
M.5-cyanothiazol-2-yl, pyrimidin-2-yl, or 5-cyanopyridin-2-yl; or (b)
N.5-cyanothiazol-2-yl; or (b)
O, pyrimidin-2-yl; or (b)
P.5-cyanopyridin-2-yl.
In embodiments of each aspect of the invention, R 4a Is that
A. Thiazole, pyridine, pyrimidine, pyrazine or pyridazine, wherein the thiazole, pyridine, pyrimidine, pyrazine or pyridazine are independently of each other optionally substituted with one substituent selected from the group consisting of: c (C) 1 -C 3 Haloalkyl, C 3 -C 4 Cycloalkyl, halogen, cyano and C 1 -C 3 Haloalkoxy, or selected from Y1 to Y4; or (b)
B. Thiazole, pyridine, pyrimidine, pyrazine or pyridazine, wherein the thiazole, pyridine, pyrimidine, pyrazine or pyridazine are independently of each other optionally substituted with one substituent selected from the group consisting of: F. cl, br, CN, trifluoromethoxy, difluoromethoxy, 2-difluoroethoxy and 2, 2-trifluoroethoxy, or selected from Y1 to Y4; or (b)
C. A thiazole, pyridine or pyrimidine, wherein the thiazole, pyridine or pyrimidine is optionally substituted with one substituent selected from the group consisting of: c (C) 1 -C 3 Haloalkyl, C 3 -C 4 Cycloalkyl, halogen, cyano and C 1 -C 3 Haloalkoxy, or selected from Y1 to Y4; or (b)
D. A thiazole, pyridine or pyrimidine, wherein the thiazole, pyridine or pyrimidine is optionally substituted with one substituent selected from the group consisting of: cyclopropyl, F, cl, br, CN, trifluoromethoxy, difluoromethoxy, 2-difluoroethoxy and 2, 2-trifluoroethoxy, or selected from Y1 to Y4; or (b)
E.5-cyanothiazol-2-yl, 5-cyclopropyl-pyridine, 5-fluoropyridine, 5-chloropyridine, 5-bromopyridine, 5-difluoromethoxy-pyridine, 5-trifluoromethoxy-pyridine, 5-cyanopyridine, 5- (2, 2-difluoroethoxy) -pyridine, 5- (2, 2-trifluoroethoxy) -pyridine, 5-cyclopropyl-pyrimidine, 5-fluoropyrimidine, 5-chloropyrimidine, 5-bromopyrimidine, 5-difluoromethoxy-pyrimidine, 5-trifluoromethoxy-pyrimidine, 5-cyanopyrimidine, 5- (2, 2-difluoroethoxy) -pyrimidine, 5- (2, 2-trifluoroethoxy) -pyrimidine, or 1,2, 3-triazole; or (b)
F.5-cyanothiazol-2-yl, 5-cyclopropylpyridin-2-yl, 5-fluoropyridin-2-yl, 5-chloropyridin-2-yl, 5-bromopyridin-2-yl, 5-difluoromethoxy-pyridin-2-yl, 5-trifluoromethoxypyridin-2-yl, 5-cyanopyridin-2-yl, 5- (2, 2-difluoroethoxy) -pyridin-2-yl, 5- (2, 2-trifluoroethoxy) -pyridin-2-yl, 5-cyclopropylpyrimidin-2-yl, 5-fluoropyrimidin-2-yl, 5-chloropyrimidin-2-yl, 5-bromopyrimidin-2-yl, 5-difluoromethoxy-pyrimidin-2-yl, 5-trifluoromethoxy-pyrimidin-2-yl, 5- (2, 2-trifluoroethoxy) -pyrimidin-2-yl, or 1,2, 3-triazol-2-yl (Y); or (b)
5-cyanothiazol-2-yl, 1,2, 3-triazol-2-yl (or Y2), pyrimidin-2-yl, or 5-cyanopyridin-2-yl; or (b)
H.5-cyanothiazol-2-yl; or (b)
I. Pyrimidin-2-yl; or (b)
J.5-cyanopyridin-2-yl.
In an embodiment of each aspect of the invention, when Y1 is selected as R 4a When R 'is' 4a And R'. 4c Independent of each other
A. Selected from hydrogen, halogen, CN, C 1 -C 3 Alkyl, C 1 -C 3 Haloalkyl, C 3 -C 4 Cycloalkyl, C 1 -C 3 Alkoxy and C 1 -C 3 Haloalkoxy groups; or (b)
B. Selected from hydrogen, F, cl, br, CN, methyl, CF 3 Cyclopropyl, methoxy and difluoromethoxy; or (b)
C. Are all hydrogen.
In an embodiment of each aspect of the invention, when Y2 is selected as R 4a In the time-course of which the first and second contact surfaces,
A.R’ 4b and R'. 4c Independently of each other selected from hydrogen, halogen, CN, C 1 -C 3 Alkyl, C 1 -C 3 Haloalkyl, C 3 -C 4 Cycloalkyl, C 1 -C 3 Alkoxy and C 1 -C 3 Haloalkoxy groups; or (b)
B.R’ 4b And R'. 4c Independently of each other selected from hydrogen, F, cl, br, CN, methyl, CF 3 Cyclopropyl, methoxy and difluoromethoxy; or (b)
C.R’ 4b And R'. 4c Are all hydrogen; or (b)
D.R’ 4b Is hydrogen and R' 4c Is cyclopropyl.
In an embodiment of each aspect of the invention, when Y3 is selected to be R 4a When R 'is' 4a And R'. 4b Independent of each other
A. Is hydrogen, halogen, CN, C 1 -C 3 Alkyl, C 1 -C 3 Haloalkyl, C 3 -C 4 Cycloalkyl, C 1 -C 3 Alkoxy and C 1 -C 3 Haloalkoxy groups; or (b)
B. Is hydrogen, F, cl, br, CN, methyl, CF 3 Cyclopropyl, methoxy and difluoromethoxy; or (b)
C. Are all hydrogen.
In an embodiment of each aspect of the invention, when Y4 is selected as R 4a In the time-course of which the first and second contact surfaces,
A.R’ 4a 、R’ 4b and R'. 4c Independently of each other selected from hydrogen, halogen, CN, C 1 -C 3 Alkyl, C 1 -C 3 Haloalkyl, C 3 -C 4 Cycloalkyl, C 1 -C 3 Alkoxy and C 1 -C 3 Haloalkoxy groups; or (b)
B.R’ 4a 、R’ 4b And R'. 4c Independently of each other selected from hydrogen, F, cl, br, CN, methyl, CF 3 Cyclopropyl, methoxy and difluoromethoxy; or (b)
C.R’ 4a 、R’ 4b And R'. 4c Are all hydrogen; or (b)
D.R’ 4a And R'. 4c Is hydrogen and R' 4b Is CN.
In embodiments of each aspect of the invention, R 5 Is that
A. Hydrogen, C 1 -C 3 Alkyl, C 1 -C 3 Haloalkyl, C 3 -C 4 Cycloalkyl, C 1 -C 3 Alkoxy, halogen, C 1 -C 3 alkoxy-C 1 -C 3 Alkyl, C 1 -C 3 alkoxy-C 1 -C 3 alkoxy-C 1 -C 3 Alkyl, (C) 1 -C 3 Alkyl) C (O), (C 1 -C 3 Alkoxy) C (O), HC (O), C 1 -C 3 A haloalkoxy or 5-membered heteroaromatic ring, wherein the 5-membered heteroaromatic ring may be optionally substituted with one to three substituents selected from the group consisting of: c (C) 1 -C 3 Alkyl, C 1 -C 3 Haloalkyl, C 1 -C 3 Alkoxy, C 3 -C 4 Cycloalkyl, halogen, CN or hydroxy; or (b)
B. Hydrogen, C 1 -C 3 Alkyl, C 1 -C 3 Haloalkyl, C 3 -C 4 Cycloalkyl, C 1 -C 3 Alkoxy, halogen, C 1 -C 3 alkoxy-C 1 -C 3 Alkyl, C 1 -C 3 alkoxy-C 1 -C 3 alkoxy-C 1 -C 3 Alkyl, (C) 1 -C 3 Alkyl) C (O), (C 1 -C 3 Alkoxy) C (O), HC (O) or C 1 -C 3 Haloalkoxy groups; or (b)
C. Hydrogen, C 1 -C 3 Alkyl, C 1 -C 3 Haloalkyl, C 3 -C 4 Cycloalkyl, C 1 -C 3 Alkoxy, halogen, cl, br, C 1 -C 3 alkoxy-C 1 -C 3 Alkyl, C 1 -C 3 alkoxy-C 1 -C 3 alkoxy-C 1 -C 3 Alkyl, (C) 1 -C 3 Alkyl) C (O), (C 1 -C 3 Alkoxy) C (O), or C 1 -C 2 Haloalkoxy groups; or (b)
D. Hydrogen, C 1 -C 3 Alkyl, C 1 -C 3 Alkoxy, C 3 -C 4 Cycloalkyl, C 1 -C 3 Haloalkoxy, halogen, C 1 -C 3 alkoxy-C 1 -C 3 Alkyl, C 1 -C 3 alkoxy-C 1 -C 3 alkoxy-C 1 -C 3 Alkyl, (C) 1 -C 3 Alkyl) C (O), HC (O), or (C 1 -C 3 Alkoxy) C (O); or (b)
E. Hydrogen, C 1 -C 2 Alkyl, C 1 -C 2 Alkoxy, C 3 -C 4 Cycloalkyl, C 1 -C 2 Haloalkoxy, halogen, C 1 -C 2 alkoxy-C 1 -C 2 Alkyl, C 1 -C 2 alkoxy-C 1 -C 2 alkoxy-C 1 -C 2 Alkyl, (C) 1 -C 2 Alkyl) C (O), HC (O), or (C 1 -C 2 Alkoxy) C (O); or (b)
F. Hydrogen, methyl, trifluoromethoxy, methoxy, cyclopropyl, 2-difluoroethoxy, 2-trifluoroethoxy, difluoromethoxy, 2-trifluoroethyl, chloro, bromo, methoxyethoxy, methylcarbonyl, or methoxycarbonyl; or (b)
G. Hydrogen, methyl, or bromine; or (b)
H. A methyl group; or (b)
I. Bromine; or (b)
J. Hydrogen.
In embodiments of each aspect of the invention, R 5a Is that
A. Hydrogen, halogen, CN, C 1 -C 3 Alkyl, C 1 -C 3 Haloalkyl, C 3 -C 4 Cycloalkyl, C 1 -C 3 Alkoxy or C 1 -C 3 Haloalkoxy groups; or (b)
B. Hydrogen, halogen, CN, C 1 -C 3 Alkyl, C 1 -C 3 Haloalkyl, C 3 -C 4 Cycloalkyl or C 1 -C 3 An alkoxy group; or (b)
C. Hydrogen, halogen, CN, C 1 -C 3 Alkyl, C 1 -C 3 Haloalkyl or C 1 -C 3 An alkoxy group; or (b)
D. Hydrogen, halogen, CN, C 1 -C 3 Alkyl or C 1 -C 3 An alkoxy group; or (b)
E. Hydrogen or halogen; or (b)
F. Hydrogen.
In embodiments of each aspect of the invention, R 5b Is that
A. Hydrogen, halogen, CN, C 1 -C 3 Haloalkyl, C 3 -C 4 Cycloalkyl, C 1 -C 3 Alkoxy, or C 1 -C 3 Haloalkoxy groups; or (b)
B. Hydrogen, halogen or C 1 -C 3 An alkoxy group; or (b)
C. Hydrogen.
In embodiments of each aspect of the invention, R 6 Is that
A. Phenyl, benzyl, heteroaryl (selected from J-1 to J-41), C 3 -C 6 Cycloalkyl, or C 3 -C 6 Cycloalkyl C 1 -C 3 Alkyl groups, independently of each other, each optionally selected from R, independently of one to three x Is substituted by a substituent of (a); or (b)
B. Phenyl, benzyl, J-1, J-17, cyclopropyl, or cyclopropylmethyl, each independently of the other optionally being selected from R independently of the others from one to three x Is substituted by a substituent of (a); or (b)
C. Phenyl, benzyl, J-1, J-17, cyclopropyl, or cyclopropylmethyl, each independently of the other optionally substituted with one to three substituents independently selected from the group consisting of: halogen, C 1 -C 3 Alkyl, C 1 -C 3 Haloalkyl, C 1 -C 3 Alkoxy, C 1 -C 3 Haloalkoxy groupsC 3 -C 6 Cycloalkyl; or (b)
D. Phenyl, J-1, J-17, or cyclopropylmethyl, each independently of the other optionally substituted with one to three substituents independently selected from the group consisting of: halogen, C 1 -C 3 Alkyl, C 1 -C 3 Haloalkyl, C 1 -C 3 Alkoxy, C 1 -C 3 Haloalkoxy and C 3 -C 6 Cycloalkyl; or (b)
E. Phenyl, J-1, J-17, or cyclopropylmethyl, each independently of the other optionally substituted with one to three substituents independently selected from the group consisting of: F. cl, br, and cyclopropyl.
In embodiments of each aspect of the invention, R 7 Is that
A. Hydrogen, C 1 -C 3 Alkyl, or C 3 -C 6 Cycloalkyl group, wherein the C 1 -C 3 Alkyl or C 3 -C 6 Cycloalkyl groups are optionally selected from R independently of each other from one to three z Is substituted by a substituent of (a); or (b)
B. Hydrogen, C 1 -C 3 Alkyl, or C 3 -C 6 Cycloalkyl; or (b)
C. Hydrogen, methyl, cyclopropyl, cyclobutyl, or cyclopentyl; or (b)
D. Hydrogen.
In embodiments of each aspect of the invention, R 8 Is that
A. Hydrogen, C 1 -C 3 Alkyl, or C 3 -C 6 Cycloalkyl group, wherein the C 1 -C 3 Alkyl or C 3 -C 6 Cycloalkyl groups are optionally selected from R independently of each other from one to three z Is substituted by a substituent of (a); or (b)
B.C 1 -C 3 Alkyl, or C 3 -C 6 Cycloalkyl; or (b)
C. Methyl, cyclopropyl, cyclobutyl, or cyclopentyl; or (b)
D. A cyclopentyl group.
In embodiments of each aspect of the invention, R x Independently selected from
A. Halogen, C 1 -C 3 Haloalkyl, C 1 -C 3 Alkoxy, C 3 -C 6 Cycloalkyl, C 1 -C 3 Haloalkoxy and CN; or (b)
B.F、Cl、Br、OCF 2 H、CF 3 Cyclopropyl, OCH 3 And CN; or (b)
C.F, cl, br, and cyclopropyl.
In embodiments of each aspect of the invention, R Y Independently selected from
A.C 1 -C 3 Alkyl, C 3 -C 4 Alkenyl, C 3 -C 4 Cycloalkyl, C 2 -C 4 Alkynyl, or benzyl; or (b)
B. Methyl, vinyl, cyclopropyl, propargyl or benzyl.
In embodiments of each aspect of the invention, R Z Independently selected from
A. Oxo, halogen, C 1 -C 3 Haloalkyl, C 1 -C 3 Alkoxy, C 1 -C 3 Haloalkoxy or CN; or (b)
B. Oxo, F, cl, br, OCF 2 H、OCH 3 Or CN.
Thus, the invention makes it possible to obtain a compound having the substituents T, X, R as defined above in all combinations/permutations 1a 、R 1b 、R 3 And Q is a compound of formula I. Thus, it is made possible to obtain, for example, compounds having formula I, wherein X is oxygen; t is example B (i.e., T is phenyl, pyridine, pyrimidine, pyrazine, pyridazine, or a heteroaromatic ring selected from the group consisting of J-13, J-16, J-22, J-25, J-26, J-27, J-28, J-31, J-36, J-37, J-38, J-39, J-40, J-41, thieno [2, 3-d)]Pyrimidinyl, [1,2,4 ]]Triazolo [1,5-a ]]Pyrimidinyl, and indazolyl, each independently of the other, are selected from R 2 Substituted with substituents of (2), wherein R 2 Is example A (i.e., R 2 Independently of the number of rings and substituents, selected from halogen, C 1 -C 3 Alkyl, C 1 -C 3 Haloalkyl, C 1 -C 3 Alkoxy, C 1 -C 3 Haloalkoxy, CN, C 3 -C 4 Cycloalkyl, C 3 -C 6 Cycloalkyl carbonyl, phenyl, heteroaryl (selected from J-1 and J-41) (C 3 -C 4 Cycloalkyl, phenyl or heteroaryl are each, independently of one another, each by one to three substituents R x Substituted, OR 6 Piperidin-2-one-1-yl, pyridin-2-one-1-yl, azetidin-1-yl (optionally substituted with R x Substituted), pyrrolidin-1-yl, C 3 -C 6 Cycloalkyl C 1 -C 4 Alkyl (substituted by one or two substituents R Z Substitution, C 3 -C 6 Cycloalkyl C 1 -C 3 Alkoxy (optionally by R x Substitution, C 1 -C 5 Cyanoalkyl, C 1 -C 5 Cyanoalkoxy, C 1 -C 4 Alkylsulfanyl (optionally substituted with one to three substituents R x Substitution, C 1 -C 4 Alkylsulfonyl (optionally substituted with one to three substituents R x Substitution, C 1 -C 4 Alkylsulfinyl (optionally substituted with one to three substituents R x Substituted), C (O) NR 7 R 8 、C 1 -C 4 Alkylsulfonylamino, aminosulfonyl, C 1 -C 4 Alkylaminosulfonyl, di (C) 1 -C 4 Alkyl) sulfamoyl, C 3 -C 6 Cycloalkyl sulfamoyl, -O-C 1 -C 2 Halogenated alkyl-O-, and 10 membered optionally substituted spiroheterocycle); r is R 1a Is embodiment D (i.e., R 1a Is hydrogen, C 1 -C 6 Alkyl, C 1 -C 6 Cyanoalkyl, C 1 -C 3 alkoxy-C 1 -C 6 Alkyl, C 1 -C 6 Haloalkyl, C 2 -C 6 Alkenyl, C 2 -C 6 Haloalkenyl, C 2 -C 6 Alkynyl, C 2 -C 6 Haloalkynyl, C 3 -C 4 Cycloalkyl C 1 -C 2 Alkyl-, benzyloxycarbonyl, or benzyl); r is R 1b Is of example I (i.e., R 1b Hydrogen, methyl, propargyl, or cyclopropyl-methyl); r is R 3 Is embodiment B (i.e., R 3 Methyl or trifluoromethyl); and Q is embodiment F (i.e., Q is Q a -1, or Q b -1), wherein R 4 Is example K (i.e., R 4 Is pyrimidin-2-yl, pyridin-2-yl, 5-bromopyrimidin-2-yl, 5-bromopyridin-2-yl, 5-cyanopyrimidin-2-yl, or 5-cyanopyridin-2-yl); r is R 4a Is example G (i.e., R 4a Is 1,2, 3-triazol-2-yl (or Y2), pyrimidin-2-yl, or 5-cyanopyridin-2-yl); r is R 6 Is example E (i.e., R 6 Is phenyl, J-1, J-17, or cyclopropylmethyl, each independently of the other optionally substituted with one to three substituents independently selected from the group consisting of: F. cl, br, and cyclopropyl); r is R 7 Is embodiment D (i.e., R 7 Is hydrogen); r is R 8 Is embodiment D (i.e., R 8 Is cyclopentyl); r is R x Is embodiment B (i.e., R x Independently selected from F, cl, br, OCF 2 H、CF 3 Cyclopropyl, OCH 3 And CN); and R is Z Is embodiment B (i.e., R Z Independently selected from oxo, F, cl, br, OCF 2 H、OCH 3 And CN).
In an embodiment, the compounds of formula I are of formulas Iaa and Iab (asterisks indicate stereogenic centers), wherein T, R 1a 、R 1b 、R 3 Is as defined in the first aspect, and Q 1 Corresponding to Q as defined in the first aspect, each has a corresponding embodiment as described above. The preferred stereochemistry of compounds having formulas Iaa and Iab is that depicted in formula I' a above.
In an embodiment, Q 1 Is that
A. Selected from Q aa To Q ag And Q ba To Q bf The method comprises the steps of carrying out a first treatment on the surface of the Or (b)
B. Selected from Q aa To Q ag The method comprises the steps of carrying out a first treatment on the surface of the Or (b)
C. Selected from Q ba To Q bf The method comprises the steps of carrying out a first treatment on the surface of the Or (b)
D. Selected from the group consisting ofQ aa 、Q ab 、Q ac 、Q af 、Q ag 、Q ba 、Q bb 、Q bc 、Q bd 、Q be And Q bf The method comprises the steps of carrying out a first treatment on the surface of the Or (b)
E. Selected from Q aa 、Q ab 、Q ac 、Q af 、Q af 、Q ba 、Q bb And Q bf The method comprises the steps of carrying out a first treatment on the surface of the Or (b)
F. Selected from Q aa 、Q ab 、Q ac 、Q af 、Q ba 、Q bb And Q bf 。
Similarly, the invention makes it possible to obtain a compound having the substituents T, R as defined in all combinations/permutations 1a 、R 1b 、R 3 And Q1 has the formula Iaa and Iab.
In an embodiment of each aspect of the invention, the compound having formula I has oxygen or sulfur as X; phenyl, pyridine, or five or nine membered heteroaromatic rings as T, each independently of the other, may be selected from R independently of one to three 2 Is substituted by a substituent of (a); wherein R is 2 Independently of the number of rings and substituents, selected from halogen, C 1 -C 3 Alkyl, C 1 -C 3 Haloalkyl, C 1 -C 3 Alkoxy, C 1 -C 3 Haloalkoxy, CN, C 3 -C 4 Cycloalkyl, C 3 -C 6 Cycloalkyl carbonyl, phenyl, heteroaryl (selected from J-1 and J-41) (C 3 -C 4 Cycloalkyl, phenyl or heteroaryl are each, independently of one another, each by one to three substituents R x Substituted, OR 6 Piperidin-2-one-1-yl, pyridin-2-one-1-yl, azetidin-1-yl (optionally substituted with R x Substituted), pyrrolidin-1-yl, C 3 -C 6 Cycloalkyl C 1 -C 4 Alkyl (substituted by one or two substituents R Z Substitution, C 3 -C 6 Cycloalkyl C 1 -C 3 Alkoxy (optionally by R x Substitution, C 1 -C 5 Cyanoalkyl, C 1 -C 5 Cyanoalkoxy, C 1 -C 4 Alkylsulfanyl (optionally substituted with one to three substituents R x Substitution, C 1 -C 4 Alkylsulfonyl (optionally substituted with one to three substituents R x Substitution, C 1 -C 4 Alkylsulfinyl (optionally substituted with one to three substituents R x Substituted), C (O) NR 7 R 8 、C 1 -C 4 Alkylsulfonylamino, aminosulfonyl, C 1 -C 4 Alkylaminosulfonyl, di (C) 1 -C 4 Alkyl) sulfamoyl, C 3 -C 6 Cycloalkyl sulfamoyl, -O-C 1 -C 2 Halogenated alkyl-O-, and 10 membered optionally substituted spiroheterocycle; wherein R is 6 Is phenyl, benzyl, heteroaryl (selected from J-1 to J-41), C 3 -C 6 Cycloalkyl, or C 3 -C 6 Cycloalkyl C 1 -C 3 Alkyl groups, independently of each other, each optionally selected from R, independently of one to three x Is substituted by a substituent of (a); r is R 7 And R is 8 Independently of one another, are hydrogen, C 1 -C 3 Alkyl, or C 3 -C 6 Cycloalkyl group, wherein the C 1 -C 3 Alkyl or C 3 -C 6 Cycloalkyl groups are optionally selected from R independently of each other from one to three z Is substituted by a substituent of (a); wherein R is X Independently selected from halogen, C 1 -C 3 Haloalkyl, C 1 -C 3 Alkoxy, C 3 -C 6 Cycloalkyl, C 1 -C 3 Haloalkoxy and CN; wherein R is z Independently selected from oxo, halogen, C 1 -C 3 Haloalkyl, C 1 -C 3 Alkoxy, C 1 -C 3 Haloalkoxy and CN; as R 1a And R is 1b Hydrogen, methyl, ethyl, cyanomethyl, methoxymethyl (independently of each other),Cyclopropyl-methyl, allyl, propargyl, benzyloxycarbonyl, or benzyl, or as R 1a And R is 1b Taken together-CH 2 -O-CH 2 -; or T and R 1b Together are a nine membered bicyclic partially saturated heterocyclic ring (which is C-substituted 1 -C 3 Haloalkyl substitution); as R 3 Methyl or trifluoromethyl of (a); and as Q, is selected from Q a -1 to Q a -16 and Q b -1 to Q b -13; wherein R is 4 Is pyridine, or pyrimidine; wherein the pyridine or pyrimidine are independently optionally substituted with one substituent selected from the group consisting of: c (C) 1 -C 3 Alkyl, C 1 -C 3 Haloalkyl, C 1 -C 3 Alkoxy, C 3 -C 4 Cycloalkyl, halo, hydroxy, CN, C 1 -C 6 Haloalkoxy, C 2 -C 6 Haloalkenyloxy, C 2 -C 6 Haloalkynyloxy, C 3 -C 4 Halogenated cycloalkoxy, C 3 -C 6 Cycloalkyl C 1 -C 4 Haloalkoxy, NH 2 C(O)-、NH 2 C(S)-、(OH)N＝C(NH 2 ) -, J-13 (optionally from 1 to 3 independently selected from halogen, C 1 -C 3 Alkyl, C 1 -C 3 Haloalkyl, C 1 -C 3 Alkoxy and C 1 -C 3 Substituted with 1 to 3 substituents independently selected from halogen, C), J-20 (optionally substituted with 1 to 3 substituents independently selected from halogen 1 -C 3 Alkyl, C 1 -C 3 Haloalkyl, C 1 -C 3 Alkoxy and C 1 -C 3 Substituted with a substituent of haloalkoxy) and 1H-tetrazol-5-yl; and wherein R is 4a Is pyridine, pyrimidine, pyrazine or pyridazine, wherein the pyridine, pyrimidine, pyrazine or pyridazine are independently of each other optionally substituted with one substituent selected from the group consisting of: c (C) 1 -C 3 Haloalkyl, C 3 -C 4 Cycloalkyl, halogen, cyano and C 1 -C 3 Haloalkoxy, or selected from Y1 to Y4; wherein R 'is' 4a 、R’ 4b And R'. 4c Independently of each other and independently of Y1 to Y4, from hydrogen, halogen, CN, C 1 -C 3 Alkyl group、C 1 -C 3 Haloalkyl, C 3 -C 4 Cycloalkyl, C 1 -C 3 Alkoxy and C 1 -C 3 Haloalkoxy groups.
In an embodiment of each aspect of the invention, the compound having formula I has oxygen or sulfur as X; phenyl, pyridine, or five or nine membered heteroaromatic rings as T, each independently of the other, may be selected from R independently of one to three 2 Is substituted by a substituent of (a); wherein R is 2 Independently of the number of rings and substituents, selected from halogen, C 1 -C 3 Alkyl, C 1 -C 3 Haloalkyl, C 1 -C 3 Alkoxy, C 1 -C 3 Haloalkoxy, CN, C 3 -C 4 Cycloalkyl, C 3 -C 6 Cycloalkyl carbonyl, phenyl, heteroaryl (selected from J-1 and J-41) (C 3 -C 4 Cycloalkyl, phenyl or heteroaryl are each, independently of one another, each by one to three substituents R x Substituted, OR 6 Piperidin-2-one-1-yl, pyridin-2-one-1-yl, azetidin-1-yl (optionally substituted with R x Substituted), pyrrolidin-1-yl, C 3 -C 6 Cycloalkyl C 1 -C 4 Alkyl (substituted by one or two substituents R Z Substitution, C 3 -C 6 Cycloalkyl C 1 -C 3 Alkoxy (optionally by R x Substitution, C 1 -C 5 Cyanoalkyl, C 1 -C 5 Cyanoalkoxy, C 1 -C 4 Alkylsulfanyl (optionally substituted with one to three substituents R x Substitution, C 1 -C 4 Alkylsulfonyl (optionally substituted with one to three substituents R x Substitution, C 1 -C 4 Alkylsulfinyl (optionally substituted with one to three substituents R x Substituted), C (O) NR 7 R 8 、C 1 -C 4 Alkylsulfonylamino, aminosulfonyl, C 1 -C 4 Alkylaminosulfonyl, di (C) 1 -C 4 Alkyl) sulfamoyl, C 3 -C 6 Cycloalkyl sulfamoyl, -O-C 1 -C 2 Halogenated alkyl-O-, and 10 membered optionally substituted spiroheterocycle; wherein R is 6 Is phenyl, benzyl, heteroaryl (selected from J-1 to J-41), C 3 -C 6 Cycloalkyl, or C 3 -C 6 Cycloalkyl C 1 -C 3 Alkyl groups, independently of each other, each optionally selected from R, independently of one to three x Is substituted by a substituent of (a); r is R 7 And R is 8 Independently of one another, are hydrogen, C 1 -C 3 Alkyl, or C 3 -C 6 Cycloalkyl group, wherein the C 1 -C 3 Alkyl or C 3 -C 6 Cycloalkyl groups are optionally selected from R independently of each other from one to three z Is substituted by a substituent of (a); wherein R is X Independently selected from halogen, C 1 -C 3 Haloalkyl, C 1 -C 3 Alkoxy, C 3 -C 6 Cycloalkyl, C 1 -C 3 Haloalkoxy and CN; wherein R is z Independently selected from oxo, halogen, C 1 -C 3 Haloalkyl, C 1 -C 3 Alkoxy, C 1 -C 3 Haloalkoxy and CN; as R 1a And R is 1b Hydrogen, methyl, ethyl, cyanomethyl, methoxymethyl, cyclopropyl-methyl, allyl, propargyl, benzyloxycarbonyl, or benzyl (independently of each other), or as R 1a And R is 1b Taken together-CH 2 -O-CH 2 -; or T and R 1b Together are a nine membered bicyclic partially saturated heterocyclic ring (which is C-substituted 1 -C 3 Haloalkyl substitution); as R 3 Methyl or trifluoromethyl of (a); and as Q, is selected from Q aa To Q ag And Q ba To Q bf 。
In an embodiment of each aspect of the invention, the compound having formula I has oxygen or sulfur as X; phenyl, pyridine, or five or nine membered heteroaromatic rings as T, each independently of the other, may be selected from R independently of one to three 2 Is substituted by a substituent of (a); wherein R is 2 Independently of the number of rings and substituents, selected from halogen, C 1 -C 3 Alkyl, C 1 -C 3 Haloalkyl, C 1 -C 3 Alkoxy, C 1 -C 3 Haloalkoxy, CN, C 3 -C 4 Cycloalkyl radicals、C 3 -C 6 Cycloalkyl carbonyl, phenyl, heteroaryl (selected from J-1 and J-41) (C 3 -C 4 Cycloalkyl, phenyl or heteroaryl are each, independently of one another, each by one to three substituents R x Substituted, OR 6 Piperidin-2-one-1-yl, pyridin-2-one-1-yl, azetidin-1-yl (optionally substituted with R x Substituted), pyrrolidin-1-yl, C 3 -C 6 Cycloalkyl C 1 -C 4 Alkyl (substituted by one or two substituents R Z Substitution, C 3 -C 6 Cycloalkyl C 1 -C 3 Alkoxy (optionally by R x Substitution, C 1 -C 5 Cyanoalkyl, C 1 -C 5 Cyanoalkoxy, C 1 -C 4 Alkylsulfanyl (optionally substituted with one to three substituents R x Substitution, C 1 -C 4 Alkylsulfonyl (optionally substituted with one to three substituents R x Substitution, C 1 -C 4 Alkylsulfinyl (optionally substituted with one to three substituents R x Substituted), C (O) NR 7 R 8 、C 1 -C 4 Alkylsulfonylamino, aminosulfonyl, C 1 -C 4 Alkylaminosulfonyl, di (C) 1 -C 4 Alkyl) sulfamoyl, C 3 -C 6 Cycloalkyl sulfamoyl, -O-C 1 -C 2 Halogenated alkyl-O-, and 10 membered optionally substituted spiroheterocycle; wherein R is 6 Is phenyl, benzyl, heteroaryl (selected from J-1 to J-41), C 3 -C 6 Cycloalkyl, or C 3 -C 6 Cycloalkyl C 1 -C 3 Alkyl groups, independently of each other, each optionally selected from R, independently of one to three x Is substituted by a substituent of (a); r is R 7 And R is 8 Independently of one another, are hydrogen, C 1 -C 3 Alkyl, or C 3 -C 6 Cycloalkyl group, wherein the C 1 -C 3 Alkyl or C 3 -C 6 Cycloalkyl groups are optionally selected from R independently of each other from one to three z Is substituted by a substituent of (a); wherein R is X Independently selected from halogen, C 1 -C 3 Haloalkyl, C 1 -C 3 Alkoxy, C 3 -C 6 Cycloalkyl radicals、C 1 -C 3 Haloalkoxy and CN; wherein R is z Independently selected from oxo, halogen, C 1 -C 3 Haloalkyl, C 1 -C 3 Alkoxy, C 1 -C 3 Haloalkoxy and CN; as R 1a And R is 1b Hydrogen, methyl, ethyl, cyanomethyl, methoxymethyl, cyclopropyl-methyl, allyl, propargyl, benzyloxycarbonyl, or benzyl (independently of each other), or as R 1a And R is 1b Taken together-CH 2 -O-CH 2 -; or T and R 1b Together are a nine membered bicyclic partially saturated heterocyclic ring (which is C-substituted 1 -C 3 Haloalkyl substitution); as R 3 Methyl or trifluoromethyl of (a); and as Q, is selected from Q aa 、Q ab 、Q ba And Q bb 。
In an embodiment of each aspect of the invention, the compound having formula I has oxygen or sulfur as X; phenyl, pyridin-2-yl (or J-1), J-2, J-3, J-4, J-5, J-6, J16, J-26, J-27, J-28, J41, thieno [2,3-d ] as T]Pyrimidinyl, [1,2,4 ] ]Triazolo [1,5-a ]]Pyrimidinyl, or indazolyl, each independently of the other, being selected from R 2 Is substituted by a substituent of (a); wherein R is 2 Independently of the number of rings and substituents, selected from halogen, C 1 -C 3 Alkyl, C 1 -C 3 Haloalkyl, C 1 -C 3 Alkoxy, C 1 -C 3 Haloalkoxy, CN, C 3 -C 4 Cycloalkyl, heteroaryl (selected from J-1 and J-41) (C 3 -C 4 Cycloalkyl or heteroaryl are each, independently of one another, substituted by one to three substituents R x Substituted, OR 6 、C 3 -C 6 Cycloalkyl C 1 -C 4 Alkyl (substituted by one or two substituents R Z Substitution, C 3 -C 6 Cycloalkyl C 1 -C 3 Alkoxy (optionally by R x Substitution, C 1 -C 5 Cyanoalkyl, C 1 -C 5 Cyanoalkoxy, C 1 -C 4 Alkylsulfanyl (optionally substituted with one to three substituents R x Substitution, C 1 -C 4 Alkylsulfonic acidsAcyl (optionally substituted with one to three substituents R x Substitution, C 1 -C 4 Alkylsulfinyl (optionally substituted with one to three substituents R x Substituted), C (O) NR 7 R 8 、C 1 -C 4 Alkylsulfonylamino, aminosulfonyl, C 1 -C 4 Alkylaminosulfonyl, C 3 -C 6 Cycloalkyl sulfamoyl, -O-C 1 -C 2 Halogenated alkyl-O-, and 10 membered optionally substituted spiroheterocycle; wherein R is 6 Is phenyl, benzyl, heteroaryl (selected from J-1 to J-41), C 3 -C 6 Cycloalkyl, or C 3 -C 6 Cycloalkyl C 1 -C 3 Alkyl groups, independently of each other, each optionally selected from R, independently of one to three x Is substituted by a substituent of (a); r is R 7 And R is 8 Independently of one another, are hydrogen, C 1 -C 3 Alkyl, or C 3 -C 6 Cycloalkyl group, wherein the C 1 -C 3 Alkyl or C 3 -C 6 Cycloalkyl groups are optionally selected from R independently of each other from one to three z Is substituted by a substituent of (a); wherein R is X Independently selected from halogen, C 1 -C 3 Haloalkyl, C 1 -C 3 Alkoxy, C 3 -C 6 Cycloalkyl, C 1 -C 3 Haloalkoxy and CN; wherein R is z Independently selected from oxo, halogen, C 1 -C 3 Haloalkyl, C 1 -C 3 Alkoxy, C 1 -C 3 Haloalkoxy and CN; as R 1a And R is 1b Hydrogen, methyl, ethyl, cyanomethyl, methoxymethyl, cyclopropyl-methyl, allyl, propargyl, benzyloxycarbonyl, or benzyl (independently of each other), or as R 1a And R is 1b Taken together-CH 2 -O-CH 2 -; or T and R 1b Together are a nine membered bicyclic partially saturated heterocyclic ring (which is C-substituted 1 -C 3 Haloalkyl substitution); as R 3 Methyl or trifluoromethyl of (a); and as Q, is selected from Q aa 、Q ab 、Q ba And Q bb 。
In an embodiment of each aspect of the invention,the compound having formula I has oxygen or sulfur as X; phenyl, or pyridine as T, each independently of the other, is selected from R 2 Wherein R is substituted by a substituent of 2 Independently of the number of rings and substituents, is selected from trifluoromethyl, fluoro, iodo, bromo, chloro, OR 6 (wherein R is J-1 substituted with 1 to 2 substituents independently selected from chlorine and trifluoromethyl), difluoromethoxy, 1, 2-tetrafluoroethoxy, and-O-CF 2 O-; as R 1a And R is 1b Hydrogen or methyl (independently of each other); or T and R 1b Together are a nine membered bicyclic partially saturated heterocyclic ring (which is C-substituted 1 -C 3 Haloalkyl substitution); as R 3 Methyl of (c); q as Q aa Or Q ab 。
In an embodiment of each aspect of the invention, the compound having formula I is represented by formula I' a and has oxygen or sulfur as X; phenyl, or pyridine as T, each independently of the other, is selected from R 2 Wherein R is substituted by a substituent of 2 Independently of the number of rings and substituents, is selected from trifluoromethyl, fluoro, iodo, bromo, chloro, OR 6 (wherein R is J-1 substituted with 1 to 2 substituents independently selected from chlorine and trifluoromethyl), difluoromethoxy, 1, 2-tetrafluoroethoxy, and-O-CF 2 O-; as R 1a And R is 1b Hydrogen or methyl (independently of each other); or T and R 1b Taken together is indolinyl (covered by C 1 -C 3 Haloalkyl substitution); as R 3 Methyl of (c); q as Q aa Or Q ab 。
In an embodiment of each aspect of the invention, the compound having formula I has oxygen as X; phenyl, or pyridine as T, each independently of the other, is selected from R 2 Wherein R is substituted by a substituent of 2 Independently of the number of rings and substituents, is selected from trifluoromethyl, fluoro, iodo, bromo, chloro, difluoromethoxy, and 1, 2-tetrafluoroethoxy; as R 1a And R is 1b Is a hydrogen atom of (a) a hydrogen atom; as R 3 Methyl of (c); q as Q aa Or Q ab 。
In an embodiment of each aspect of the invention, the compound having formula I is represented by formula I' a and has oxygen as X; phenyl, or pyridine as T, each independently of the other, is selected from R 2 Wherein R is substituted by a substituent of 2 Independently of the number of rings and substituents, is selected from trifluoromethyl, fluoro, iodo, bromo, chloro, difluoromethoxy, and 1, 2-tetrafluoroethoxy; as R 1a And R is 1b Is a hydrogen atom of (a) a hydrogen atom; as R 3 Methyl of (c); q as Q aa Or Q ab 。
In a second aspect, the present invention makes available a composition comprising a compound having formula I as defined in the first aspect, one or more adjuvants and diluents, and optionally one or more other active ingredients.
In a third aspect, the present invention makes available a method of combating and controlling insects, acarines, nematodes or molluscs which comprises applying to a pest, to a locus of a pest, or to a plant susceptible to attack by a pest an insecticidally, acaricidally, nematicidally or molluscicidally effective amount of a compound as defined in the first aspect or a composition as defined in the second aspect.
In a fourth aspect, the present invention makes available a method for protecting plant propagation material from attack by insects, acarines, nematodes or molluscs, which comprises treating the propagation material or the locus in which the propagation material is planted with an effective amount of a compound of formula I as defined in the first aspect or a composition as defined in the second aspect.
In a fifth aspect, the present invention makes it possible to obtain a plant propagation material, such as a seed, comprising a compound of formula I as defined in the first aspect or a composition as defined in the second aspect, or treated with the compound or the composition, or having the compound or the composition adhered thereto.
In another aspect, the invention provides a method of controlling parasites in or on an animal in need thereof, the method comprising administering an effective amount of a compound of the first aspect. The present invention further provides a method of controlling ectoparasites in an animal in need thereof, said method comprising administering an effective amount of a compound having formula I as defined in the first aspect. The present invention further provides a method for the prophylaxis and/or treatment of diseases transmitted by ectoparasites, which method comprises administering to an animal in need thereof an effective amount of a compound of formula I as defined in the first aspect.
The compounds of formula I may be prepared by methods known to those skilled in the art. More specifically, compounds having formulas I and I' a and intermediates thereof can be prepared as described below in schemes and examples. For clarity, certain stereocenters are not indicated and are not intended to limit the teachings of these schemes in any way.
The process according to the invention for preparing the compounds of formula I is carried out by methods known to the person skilled in the art.
In another aspect (examples of which are illustrated in schemes 1 and 2), the present invention makes available a process for preparing compounds having formula I,
the method comprises reacting an amine having formula II
React with: (i) A compound of formula III, when R 1a When hydrogen (i.e., this corresponds to a compound having formula I-a)
Or (ii) a compound having formula IV,
therein X, R 3 、R 1a 、R 1b T and Q are as defined above for compounds having formula I.
In another aspect (examples of which are illustrated in scheme 4), the present invention makes available a process for preparing a compound having formula I,
the method comprises reacting an amine having the formula VI
With a compound having the formula VII,
therein X, R 3 、R 1a 、R 1b T and Q are as defined above for compounds having formula I.
The compounds of formula I can be prepared, for example, as shown in scheme 1.
Scheme 1:
reacting a compound having formula II with a compound having formula III gives a compound having formula I-a wherein X, R 3 、R 1b T and Q are as defined above for compounds having formula I. The reaction can be carried out neat or in a solvent, preferably in the presence or absence of an added base, such as an inorganic base (e.g. potassium carbonate) or an organic base (e.g. like triethylamine), in a temperature range of-100 ℃ to +300 ℃, preferably between ambient and 200 °cThe selection is performed in a solvent such as an organic solvent, e.g., acetonitrile. The compounds of the formulae II and III are known or they can be prepared by methods known to the person skilled in the art.
Scheme 2:
reacting a compound having formula II with a compound having formula IV gives a compound having formula I, wherein X, R 3 、R 1a 、R 1b T and Q are as defined above for compounds having formula I. The reaction may be carried out neat or in a solvent, preferably in a solvent such as an organic solvent e.g. acetonitrile, with or without the addition of a base such as an inorganic base (e.g. potassium carbonate) or an organic base (e.g. like triethylamine) in the temperature range of-100 ℃ to +300 ℃, preferably between ambient temperature and 200 ℃. The compounds of formula II are known or they can be prepared by methods known to those skilled in the art.
Scheme 3:
the compounds having formula IV can be prepared, for example, as shown in scheme 3. Treatment of a compound of formula V with an amine of formula VI gives a compound of formula IV, wherein X, R 3 、R 1a And Q is as defined above for compounds having formula I. The reaction may be carried out neat or in a solvent, preferably in a solvent such as an organic solvent e.g. acetonitrile, with or without the addition of a base such as an inorganic base (e.g. potassium carbonate) or an organic base (e.g. like triethylamine) in the temperature range of-100 ℃ to +300 ℃, preferably between ambient temperature and 200 ℃.
Scheme 4:
reacting a compound having formula VII with a compound having formula VI gives a compound having formula I wherein X, R 3 、R 1a 、R 1b T and Q are as defined above for compounds having formula I. The reaction may be carried out neat or in a solvent, preferably in a solvent such as an organic solvent e.g. acetonitrile, with or without the addition of a base such as an inorganic base (e.g. potassium carbonate) or an organic base (e.g. like triethylamine) in the temperature range of-100 ℃ to +300 ℃, preferably between ambient temperature and 200 ℃. The compounds of formula II are known or they can be prepared by methods known to those skilled in the art.
Scheme 5:
the compounds having formula VII may be prepared, for example, as shown in scheme 5. Treatment of a compound of formula V with an amine of formula II gives a compound of formula VII, wherein R 1b X and T are as defined above for compounds having formula I. The reaction may be carried out neat or in a solvent, preferably in a solvent such as an organic solvent e.g. acetonitrile, with or without the addition of a base such as an inorganic base (e.g. potassium carbonate) or an organic base (e.g. like triethylamine) in the temperature range of-100 ℃ to +300 ℃, preferably between ambient temperature and 200 ℃.
Scheme 6:
reacting a compound having formula VIII with a compound having formula VI gives a compound having formula I-b wherein X, R 3 、R 1a T and Q are as defined above for compounds having formula I. The reaction can be carried out in-100 ℃ to +300 ℃, preferably in a temperature range between ambient temperature and 200 ℃, with or without addition of a base such as an inorganic base (e.g. potassium carbonate) or an organic base (e.g. like triethylamine), neat or in a solvent, preferably in a solvent such as an organic solvent like acetonitrile. The compounds of formulae VIII and VI are known or they can be prepared by methods known to the person skilled in the art.
Scheme 7:
compounds of formula VI can be prepared, for example, as shown in scheme 7, wherein R 3 、R 1a And Q is as defined above for compounds having formula I. Treatment of a compound of formula VI-a (wherein X2 is a leaving group such as halogen or sulfonate, e.g. bromide) with an amine of formula XIX gives a compound of formula VI. The reaction may be carried out neat or in a solvent, preferably in a solvent such as an organic solvent e.g. acetonitrile, with or without the addition of a base such as an inorganic base (e.g. potassium carbonate) or an organic base (e.g. like triethylamine) in the temperature range of-100 ℃ to +300 ℃, preferably between ambient temperature and 200 ℃. Alternatively, treating a compound having formula VI-b with an amine having formula XIX gives a compound having formula VI. The reaction is carried out in the presence of a reducing agent (e.g., like hydrogen or a hydride like sodium borohydride) with or without a catalyst (e.g., a hydrogenation catalyst such as palladium on carbon), with or without an acid (e.g., acetic acid or a lewis acid such as zinc bromide), in a solvent (e.g., like methanol) or without a solvent. The reaction may be carried out at a temperature in the range of-100 ℃ to +300 ℃, preferably between ambient and 200 ℃. Such methods for the alkylation of amines and the reductive alkylation of amines and the range of conditions under which these methods are carried out are well known to those skilled in the art. Amines of formula XIX are known or they can be prepared by methods known to those skilled in the art.
Scheme 8:
compounds having the formula VI-a can be prepared, for example, as shown in scheme 8, wherein R 3 And Q is as defined above for compounds having formula I. Treatment of a compound having the formula VI-c with a halogenating agent (such as, for example, chlorine or bromine or N-bromosuccinimide) gives a compound having the formula VI-a wherein the leaving group X2 is a halogen, such as chloride or bromide. The reaction is carried out with or without a solvent, preferably in a solvent, with or without additives such as free radical initiators, for example, such as benzoyl peroxide or azoisobutyronitrile. The reaction may be carried out with or without exposure to visible or ultraviolet light, and may be carried out at a temperature in the range of-100 ℃ to +300 ℃, preferably between ambient and 200 ℃. Alternatively, the compound having formula VI-b may be treated with a reducing agent and then reacted with a sulfonyl chloride, such as methanesulfonyl chloride, to give the compound having formula VI-a wherein the leaving group X2 is a sulfonate, such as a mesylate. The reaction may be carried out in the presence or absence of a base (such as an inorganic base, e.g. potassium carbonate, or an organic base, e.g. an amine base, e.g. trimethylamine) or in the absence of a base, and it may be carried out at a temperature in the range of-100 ℃ to +300 ℃, preferably between ambient and 200 ℃. Suitable reducing agents may be, for example, hydrogen, or hydrides (such as sodium borohydride), with or without a catalyst (such as a hydrogenation catalyst, e.g., palladium on carbon), in the presence or absence of an acid (such as acetic acid or a lewis acid such as zinc bromide), in a solvent (such as methanol, for example) or in the absence of a solvent. The reaction may be carried out at a temperature in the range of-100 ℃ to +300 ℃, preferably between ambient and 200 ℃. Such processes for halogenating, reducing carbonyl compounds and sulfonylating alcohols and the range of conditions under which they are carried out are well known to those skilled in the art. Compounds of formula VI-b and compounds of formula VI-c are known, or they may be prepared by the art Prepared by methods known to the skilled artisan.
Scheme 9:
as shown in scheme 9, compounds having formula I-d (wherein T, X, R and Q are as defined for formula I) can be prepared from compounds having formula I-c by treating with a compound having formula IX (wherein X2a and X2b are leaving groups, such as a halogen or sulfonate, e.g., bromide or iodide, or tosylate or mesylate). The reaction may be carried out neat or in a solvent, preferably in a solvent such as an organic solvent e.g. acetonitrile, with or without the addition of a base such as an inorganic base (e.g. potassium carbonate) or an organic base (e.g. like triethylamine) in the temperature range of-100 ℃ to +300 ℃, preferably between ambient temperature and 200 ℃. Such transformations are known to those skilled in the art.
As shown in scheme 9, compounds having formula I-e (wherein T, X, R and Q are as defined for formula I) can be prepared from compounds having formula I-c by treating with a compound having formula X (wherein X2a and X2b are leaving groups, such as a halogen or sulfonate, e.g., bromide or iodide, or tosylate or mesylate). The reaction may be carried out neat or in a solvent, preferably in a solvent such as an organic solvent e.g. acetonitrile, with or without the addition of a base such as an inorganic base (e.g. potassium carbonate) or an organic base (e.g. like triethylamine) in the temperature range of-100 ℃ to +300 ℃, preferably between ambient temperature and 200 ℃. Such transformations are known to those skilled in the art.
As shown in scheme 9, compounds having formulas I-f (wherein T, X, R and Q are as defined for formula I) can be prepared from compounds having formulas I-c by treatment with formaldehyde. The reaction may be carried out neat or in a solvent, preferably in a solvent such as organic solvent e.g. 1, 2-dichloroethane, with or without the addition of an acid such as an inorganic acid (e.g. hydrochloric acid) or an organic base (e.g. like acetic acid or trifluoroacetic acid), in a temperature range of-100 ℃ to +300 ℃, preferably between ambient temperature and 200 ℃. Such transformations are known to those skilled in the art. Such transformations are described, for example, in Synthetic Communications [ synthetic communication ] (1996), 26 (17), 3217-3224.
As shown in scheme 9, compounds having formulas I-g (wherein T, X, R and Q are as defined for formula I) can be prepared from compounds having formulas I-c by treatment with formaldehyde and hydrogen sulfide. The reaction may be carried out neat or in a solvent, preferably in a solvent such as organic solvent e.g. chloroform, with or without the addition of an acid such as an inorganic acid (e.g. hydrochloric acid) or an organic base (e.g. p-toluene sulphonic acid) in a temperature range of-100 ℃ to +300 ℃, preferably between ambient temperature and 200 ℃. Such transformations are known to those skilled in the art. Such transformations are described, for example, in Journal of Heterocyclic Chemistry [ J. Heterocycler chemistry ] (1972), 9 (2), 231-4.
As shown in scheme 9, compounds having the formula I-h (wherein T, X, R and Q are as defined for formula I) can be prepared by reacting formaldehyde with an amine XI (wherein R y Having the same meaning as defined for the compounds of formula I) are prepared from the compounds of formula I-c. The amine may be used as such or in the form of a salt, such as for example in the form of the hydrochloride salt. The reaction may be carried out neat or in a solvent, preferably in a solvent such as an organic solvent e.g. ethanol or in water or in a mixture of solvents, with or without the addition of an acid such as an inorganic acid (e.g. hydrochloric acid) or an organic base (e.g. paratoluenesulfonic acid), in a temperature range of-100 ℃ to +300 ℃, preferably between ambient temperature and 200 ℃. Such transformations are known to those skilled in the art. Such transformations are described, for example, in Izvestiya Vysshikh Uchebnykh Zavedenii, khimiya i Khimicheskaya Tekhnologiya (2005), 48 (3), 106-108.
Scheme 10:
as shown in scheme 10, compounds having formula I-I (wherein T, X, R and Q are as defined for formula I) can be prepared from compounds having formula I-g by treatment with an oxidizing agent such as hydrogen peroxide or a peracid, e.g., m-chloroperoxybenzoic acid. The reaction may be carried out neat or in a solvent, preferably in a solvent such as an organic solvent, e.g. methylene chloride, with or without the addition of a catalyst, e.g. a metal catalyst, e.g. 12-tungstophosphoric acid, in a temperature range of-100 ℃ to +300 ℃, preferably between ambient temperature and 200 ℃. Such transformations are well known to those skilled in the art.
As shown in scheme 10, compounds having formula I-j (wherein T, X, R and Q are as defined for formula I) can be prepared from compounds having formula I-g by treatment with an oxidizing agent such as hydrogen peroxide or a peracid, e.g., m-chloroperoxybenzoic acid. The reaction may be carried out neat or in a solvent, preferably in a solvent such as an organic solvent, e.g. methylene chloride, with or without the addition of a catalyst, e.g. a metal catalyst, e.g. 12-tungstophosphoric acid, in a temperature range of-100 ℃ to +300 ℃, preferably between ambient temperature and 200 ℃. Such transformations are well known to those skilled in the art.
Alternatively, compounds of formula I-j (wherein T, X, R and Q are as defined for formula I) may be prepared from compounds of formula I-I by treatment with an oxidizing agent such as hydrogen peroxide or a peracid, e.g., m-chloroperoxybenzoic acid. The reaction may be carried out neat or in a solvent, preferably in a solvent such as an organic solvent, e.g. methylene chloride, with or without the addition of a catalyst, e.g. a metal catalyst, e.g. 12-tungstophosphoric acid, in a temperature range of-100 ℃ to +300 ℃, preferably between ambient temperature and 200 ℃. Such transformations are well known to those skilled in the art.
Scheme 11:
compounds of the formula I-k may be as described in scheme 11The preparation is shown. Reaction of a compound of formula X with a compound of formula VIII gives a compound of formula XVI wherein T and R 3 Has the same meaning as given above for the compounds of formula I. The reaction may be carried out neat or in a solvent, preferably in a solvent such as an organic solvent e.g. acetonitrile or N, N-dimethylformamide, in the presence or absence of a catalyst, e.g. a metal catalyst such as a palladium complex, and with or without the addition of a base such as an inorganic base (e.g. potassium carbonate) or an organic base (e.g. like triethylamine), in a temperature range of-100 ℃ to +300 ℃, preferably between ambient temperature and 200 ℃.
Subsequent treatment of compound XVI with the known compound XII gives a compound of formula XIII, wherein T and R 3 Has the same meaning as given above for the compounds of formula I. The reaction may be carried out neat or in a solvent, preferably in a solvent such as an organic solvent, e.g. dichloromethane, in the absence of a base or in the presence of a base such as an inorganic base (e.g. potassium carbonate) or an organic base (e.g. like triethylamine), preferably in a temperature range between-100 ℃ and +300 ℃, preferably between ambient temperature and 100 ℃ or between ambient temperature and 50 ℃.
Further reaction of compound XIII with hydrazine XIV gives compounds of the formula I-k, T, R 3 And R is 4 Has the same meaning as given above for the compounds of formula I. The reaction may be carried out neat or in a solvent, preferably in a solvent such as an organic solvent, for example 1, 4-dioxane or acetic acid or a mixture of 1, 4-dioxane and acetic acid, at-100 ℃ to +300 ℃, preferably at a temperature range between ambient temperature and 200 ℃ or between ambient temperature and 80 ℃. Within this conversion sequence, the intermediate compounds of formula XVI and formula XIII can be used as crude products in the subsequent steps or they can be purified, for example by chromatography, and used in purified form for the next conversion.
Scheme 12:
the compounds having the formula I-m can be prepared, for example, as shown in scheme 12. Compounds of formula XV (wherein X 05 Is a leaving group such as chlorine, bromine, iodine, arylsulfonate, alkylsulfonate, or trifluoromethanesulfonate) with an amine of formula XIX to give a compound of formula XVII in which R 1a And R is 3 Has the same meaning as given above for the compounds of formula I. The reaction is carried out in the presence of a reducing agent (e.g., like hydrogen or a hydride like sodium borohydride) with or without a catalyst (e.g., a hydrogenation catalyst such as palladium on carbon), with or without an acid (e.g., acetic acid or a lewis acid such as zinc bromide), in a solvent (e.g., like methanol) or without a solvent. The reaction may be carried out at a temperature in the range of-100 ℃ to +300 ℃, preferably between ambient and 200 ℃. Such methods for the reductive alkylation of amines and the range of conditions under which these methods are carried out are well known to those skilled in the art.
Subsequent reaction of the intermediate of formula XVII with the compound of formula VIII gives a compound of formula XIII, wherein T, R 1a And R is 3 Has the same meaning as given above for the compounds of formula I. The reaction may be carried out neat or in a solvent, preferably in a solvent such as an organic solvent e.g. acetonitrile, in the presence or absence of a catalyst (e.g. a metal catalyst such as a palladium complex) and with or without the addition of a base such as an inorganic base (e.g. potassium carbonate) or an organic base (e.g. like triethylamine) in the temperature range of-100 ℃ to +300 ℃, preferably between ambient temperature and 200 ℃.
Subsequently, the intermediate of formula XVIII is reacted with a compound of formula XX to give a compound of formula I-m, wherein T, R 1a 、R 3 And R is 4a Has the same meaning as given above for the compounds of formula I, and R 4a -M 1 M in (2) 1 Is a metal such as, for example, lithium, or-MgCl, or-ZnBr, or-B (OH) 2 The method comprises the steps of carrying out a first treatment on the surface of the Or R is 4a -M 1 Represents borates, e.g. pinacol esters of boric acid, or stannanes such as R 4a -Sn(n-Bu) 3 . Such transformations are known to the person skilled in the art as Suzuki-, xiong Tian (Kumada), root-bank (Negishi) -or stele (Stille) -coupling reactions, respectively. Such reactions are carried out in the presence of a catalyst, such as a metal catalyst, for example a palladium catalyst, and a ligand, such as for example a phosphine ligand or an N-heterocyclic carbene (NHC) ligand or a phosphite ligand, at a temperature in the range of-100 ℃ to +300 ℃, preferably between ambient temperature and 200 ℃. The reaction may be carried out in the presence or absence of an additional metal catalyst, such as, for example, a copper salt (e.g., cuI). The reaction is carried out with or without a base, which may be an inorganic base such as potassium carbonate or sodium hydroxide, or cesium carbonate, or an organic base such as an amine base, for example triethylamine. The reaction is carried out with or without a solvent, preferably in a solvent. In the case of heating the reaction mixture, the reaction can be carried out under microwave irradiation or with conventional heating, for example heating the reaction vessel in an oil bath.
By alternative routes, compound XV may be reacted with a compound of formula XX to give intermediate XXI, wherein R 3 And R is 4a Has the same meaning as given above for the compounds of formula I. The reaction is carried out under essentially the same range of conditions as described for the conversion of intermediate XVIII to the compound of formula I-m. Subsequently, intermediate XXI is reacted with amine XIX to give intermediate XVIIa, wherein R 1a 、R 3 And R is 4a Has the same meaning as given above for the compounds of formula I. The reaction is carried out in the presence of a reducing agent under essentially the same conditions as described above for the conversion of compound XV to intermediate XVII.
Subsequently, the intermediate of formula XVIIa is reacted with a compound of formula VIII to give a compound of formula I-m, wherein T, R 1a 、R 3 And R is 4a Has the same meaning as given above for the compounds of formula I. The reaction is carried out under essentially the same conditions as described above for the conversion of intermediate XVII to intermediate XVIII.
Within these different multi-step sequences, intermediate compounds having formulas XVII, XVIIa, XVIII and XXI can be used as crude products in the corresponding subsequent steps or they can be purified, for example by chromatography, and used in purified form for the next conversion. The compounds of formula XV are known or they can be prepared by methods known to those skilled in the art.
Compounds of formula I-n
Can be prepared by the reaction of: amines of formula XVIIb
Wherein R is 1a 、R 3 、R 4a 、R 5a And R is 5b Is as described in formula I, and a compound having formula VIII
Wherein T is as described in formula I.
The chemistry is described in more detail in scheme 6.
Scheme 13:
the amine of formula XVIic may be prepared by reacting an amine of formula XVIId (wherein R 3 、R 4a 、R 5a And R is 5b As defined in formula I). This may for example be used in an eventually immobilized form (e.g.435 Lipase, e.g. candida antarctica lipaseB or pseudomonas fluorescens lipase in the presence of an acyl donor (e.g., ethyl methoxyacetate or vinyl acetate) in a suitable solvent (e.g., acetonitrile or methyl t-butyl ether) at a temperature between 20 ℃ and 100 ℃. Such methods are described, for example, in J.org.chem. [ journal of organic chemistry ]]2007,72,6918-6923 or adv. Synth. Catalyst [ advanced synthesis and catalysis ]]2007,349,1481-1488. The expected stereochemical consequences of such enzymatic de-racemization are known to the person skilled in the art and are recorded in the literature, for example J.Org.chem. [ journal of organic chemistry]1991,56,2656-2665 or J.Am.chem.Soc. [ journal of the American society of chemistry ] ]2015,137,3996-4009.
Treatment of a compound of formula XVIic with an amine of formula XXII gives a compound of formula XVIb. The reaction is carried out in the presence of a reducing agent (e.g., like hydrogen or a hydride like sodium borohydride) with or without a catalyst (e.g., a hydrogenation catalyst such as palladium on carbon), with or without an acid (e.g., acetic acid or a lewis acid such as zinc bromide), in a solvent (e.g., like methanol) or without a solvent. The reaction may be carried out at a temperature in the range of-100 ℃ to +300 ℃, preferably between ambient and 200 ℃. Such methods for the alkylation of amines and the reductive alkylation of amines and the range of conditions under which these methods are carried out are well known to those skilled in the art.
In an alternative method, the compound of formula XVIc may be synthesized as described in scheme 14 from a compound of formula XVId (wherein R 3 、R 4a 、R 5a And R is 5b As described in formula I):
scheme 14:
the amine of formula XVIic may be prepared from an intermediate of formula XXV (wherein R 3 、R 4a 、R 5a And R is 5b Is as described in formula I and Z 3 Is NPhth or NBoc 2 ) Obtained. Such intermediates can be prepared from alcohols of formula XXIII by casting (Mitsunobu) reaction involving treatment of an alcohol having formula XXIII with diisopropyl azodicarboxylate in the presence of a phosphine such as triphenylphosphine or tributylphosphine and an amine such as phthalimide or bis (t-butoxycarbonyl) amine. The casting reaction is known by the person skilled in the art for carrying out the inversion of stereocenters, as for example chem.rev. [ chemical review ]2009,109,2551-2651. Then can be prepared by using hydrazine (if Z 3 =nphth) or with an acid, e.g. trifluoroacetic acid (if Z 3 ＝NBoc 2 ) Treatments were performed to convert the compounds of formula XXV to amines of formula XVIIb.
Alternatively, the amine of formula XVIc may be used to reduce an azide of formula XXIV (wherein R) by treatment with triphenylphosphine and water (Staudinger reaction) or hydrogenation, for example in the presence of hydrogen, using a palladium catalyst 3 、R 4a 、R 5a And R is 5b As described in formula I). Azides of formula XXIV can be prepared by treating an alcohol of formula XXIII (wherein R is 3 、R 4a 、R 5a And R is 5b As described in formula I). Such methods are known by the person skilled in the art for carrying out the inversion of stereocenters and are described in the literature, for example adv. Synth. Catalyst. [ advanced synthesis and catalysis ]]2018,360,2157-2165.
The alcohol of formula XXIII may be reacted with a ketone of formula XVa (wherein R 3 、R 4a 、R 5a And R is 5b Is as described in formula I). Such reduction may be in a hydrogen donor system (such as, for example, HCOOH/Et 3 N or HCO 2 NH 4 ) Using catalysts in the presence of (e.g. ruthenium or rhodium catalysts with chiral ligands such as RuCl [ (R, R) -TsDPEN)](mesitylene) or RuBF 4 [(R,R)-TsDPEN](p-cymene)). Such methods are described in the literature, for example J.Org.chem. [ journal of organic chemistry ]]2017,82,5607.
Alternatively, compounds having formula XVIIc can also be prepared as outlined in scheme 15.
Scheme 15:
the amine of formula XVIc can be prepared by reacting an amine of formula XXXI (wherein R is 3 、R 4a 、R 5a And R is 5b As described in formula I). The amine of formula XXXI can be prepared by reacting a diketone of formula XXIX (wherein R 3 And R is 4a Is as described in formula I) on a diamine of formula XXX (wherein R 5a And R is 5b As described in formula I). This condensation may occur in the presence of a suitable solvent (e.g., ethanol or isopropanol) in the presence of an oxidizing agent (e.g., air or DDQ). The diketones of formula XXIX can be prepared by oxidizing a hydroxy ketone of formula XXVIII (wherein R 3 And R is 4a As described in formula I). Such oxidation may involve, for example, SO in the presence of DMSO and a base (e.g., triethylamine) 3 Pyridine, or alternatively in a catalyst (e.g. TEMPO/Bu 4 NHSO 4 ) Sodium hypochlorite in the presence of. Examples of such oxidation can be found in the literature, e.g. Synlett [ synthetic flash ]2014,25,596 or J.Am.chem.Soc. [ journal of the American society of chemistry ]]1990,112,5290-5313. The hydroxy ketone having formula XXVIII may be reacted with an aldehyde having formula XXVII (wherein R 4a Is as described in formula I) with an aldehyde having the formula XXVI (wherein R 3 As described in formula I). Aldehydes of the formula XXVI are commercially available in chiral form, such as, for example, boc-L-alanyl aldehyde (CAS 79069-50-4) or N- [ (1S) -1- (cyclopropylmethyl) -2-oxo-ethyl]Tert-butyl carbamate (CAS 881902-36-9). The cross-benzoin condensation is carried out in the usual manner by using an organic catalyst, such as a triazolium salt or a thiazolium salt, in the presence of a base, such as potassium tert-butoxide or isopropyl diethylamine, in a suitable solvent, such as DCM or THF, at a temperature between-20 ℃ and the boiling point of the solvent. Examples of catalysts for such conversions have been described in the literature, for example j.am.chem.soc. [ american chemistryMagazine for meeting]2014,136,7539-7542 or org.Lett. [ organic flash report ]]2016,18,4518-4521.
Scheme 16:
the amine having the formula XVIIe may be racemized by biocatalysis to an amine having the formula XVIIf (wherein R 3 、R 5a And R is 5b Is as defined in formula I and X 07 Is a leaving group such as bromine, chlorine or iodine). This may for example be used in an eventually immobilized form (e.g. 435 For example candida antarctica lipase B or pseudomonas fluorescens lipase in the presence of an acyl donor (e.g. ethyl methoxyacetate or vinyl acetate) in a suitable solvent (e.g. acetonitrile or methyl tert-butyl ether) at a temperature between 20 ℃ and 100 ℃. Such methods are described, for example, in J.org.chem. [ journal of organic chemistry ]]2007,72,6918-6923 or adv. Synth. Catalyst [ advanced synthesis and catalysis ]]2007,349,1481-1488. The expected stereochemical consequences of such enzymatic de-racemization are known to the person skilled in the art and are recorded in the literature, for example J.Org.chem. [ journal of organic chemistry]1991,56,2656-2665 or J.Am.chem.Soc. [ journal of the American society of chemistry ]]2015,137,3996-4009.
Alternatively, resolution of the amine having formula xviii to give an amine having formula xviii can be accomplished using chiral auxiliary as described in scheme 17.
Scheme 17:
the amine of formula XVIII can be prepared from an intermediate of formula XXXIII (wherein R is 3 、R 5a And R 5b Is as followsIn the compounds of formula I, X 07 Is a leaving group such as bromine, chlorine or iodine, and X 12 * Is a chiral auxiliary). Chiral auxiliary having the formula XXXII is, for example, mandelic acid or (1R) -methyl chloroformate. Can be prepared by chiral auxiliary having the formula XXXII (wherein X 0 Is a leaving group such as chlorine) is coupled with an amine having formula xviii to form an intermediate having formula XXXIII. The reaction may be carried out neat or in a solvent, preferably in a solvent such as an organic solvent e.g. acetonitrile, in the presence or absence of a catalyst (e.g. a metal catalyst such as a palladium complex) and with or without the addition of a base such as an inorganic base (e.g. potassium carbonate) or an organic base (e.g. like triethylamine) in the temperature range of-100 ℃ to +300 ℃, preferably between ambient temperature and 200 ℃. Compounds having the formula XXXII are known or they can be prepared by methods known to those skilled in the art. Examples of such de-racemisation methods are reported in the literature, e.g. J.Org.chem. [ journal of organic chemistry ]]2007,72,485-493.
Alternatively, an amine having formula XVIIe can be formed as described in scheme 18.
Scheme 18:
alternatively, the amine of formula XVIie may be derived from an intermediate of formula XXVa (wherein R 3 、R 5a And R is 5b Is as described in formula I, X 07 Is a leaving group such as halogen or sulfonate (e.g. bromide) and Z 3 Is NPhth or NBoc 2 ) Obtained. Such intermediates may be prepared from alcohols having the formula XXIIIa (wherein R 3 、R 5a And R 5b Is as described in formula I and X 07 Is a leaving group) is obtained by a casting reaction involving treating an alcohol having the formula XXIIIa with diisopropyl azodicarboxylate in the presence of a phosphine such as triphenylphosphine or tributylphosphine and an amine such as phthalimide or bis (t-butoxycarbonyl) amine. The use of a mitsunobu reaction is known to those skilled in the artInversion of the stereocenter is performed as for example chem.rev. [ chemical review]2009,109,2551-2651. Then can be prepared by using hydrazine (if Z 3 =nphth) or with an acid such as TFA (if Z 3 ＝NBoc 2 ) Treatments were performed to convert amines of formula XXVa to amines of formula XVIIe.
Alternatively, the amine of formula XVIIe can be used to reduce an azide of formula XXIVa (wherein R) by treatment with triphenylphosphine and water (schargan reaction) or hydrogenation, for example in the presence of hydrogen, using a palladium catalyst 3 、R 5a And R 5b Is as described in formula I and X 07 Is a leaving group such as a halogen or sulfonate, e.g., bromide). Azides of formula XXIVa can be obtained by treating an alcohol of formula XXIIIa with an azide reagent (e.g. diphenylphosphorylazide) in the presence of a base (e.g. DBU) in a solvent (e.g. toluene or THF). Such methods are known by the person skilled in the art for carrying out the inversion of stereocenters and are described in the literature, for example adv. Synth. Catalyst. [ advanced synthesis and catalysis ] ]2018,360,2157-2165.
The alcohol of formula XXIIIa may be prepared by reacting a ketone of formula Xvb (wherein R 3 、R 5a And R 5b Is as described in formula I and X 07 Is a leaving group such as a halogen or sulfonate, e.g., bromide). Such reduction may be in a hydrogen donor system (such as, for example, HCOOH/Et 3 N or HCO 2 NH 4 ) Using catalysts in the presence of (e.g. ruthenium or rhodium catalysts with chiral ligands such as RuCl [ (R, R) -TsDPEN)](mesitylene) or RuBF 4 [(R,R)-TsDPEN](p-cymene)). Such methods are described in the literature, for example J.Org.chem. [ journal of organic chemistry ]]2017,82,5607.
Depending on the procedure or reaction conditions, the reactants may react 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 hydroxides and carbocyclic amines. Examples which 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-diethylaniline, pyridine, 4- (N, N-dimethylamino) pyridine, quinuclidine, N-methylmorpholine, benzyltrimethylammonium hydroxide and 1, 8-diazabicyclo [5.4.0] undec-7-ene (DBU).
These reactants may react with each other as they are, namely: no solvent or diluent is added. However, in most cases it is advantageous to add inert solvents or diluents or mixtures of these. These overused bases (such as triethylamine, pyridine, N-methylmorpholine or N, N-diethylaniline) can also act as solvents or diluents if the reaction is carried out in the presence of a base.
These reactions are advantageously carried out at temperatures ranging from about-80 ℃ to about +140 ℃, preferably from about-30 ℃ to about +100 ℃, in many cases ranging between ambient temperature and about +80 ℃.
Depending on the reaction conditions selected as appropriate for the respective case and the starting materials, it is possible, for example, to replace only one substituent with another substituent according to the invention in one reaction step, or to replace a plurality of substituents with other substituents according to the invention in the same reaction step.
Salts of the compounds of formula I can be prepared in a manner known per se. Thus, for example, the acid addition salts of the compounds of formula I are obtained by treatment with a suitable acid or a suitable ion exchanger reagent, and the salts with bases are obtained by treatment with a suitable base or with a suitable ion exchanger reagent.
Salts of the compounds of formula I can be converted in a conventional manner into the free compound I, acid addition salts (e.g. by treatment with a suitable basic compound or with a suitable ion exchanger reagent) and salts with bases (e.g. by treatment with a suitable acid or with a suitable ion exchanger reagent).
Salts of the compounds of formula I can be converted in a manner known per se into other salts, acid addition salts, for example into other acid addition salts, of the compounds of formula I, for example by treating salts of inorganic acids, such as the hydrochloride salt, with suitable metal salts of acids, 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 thus precipitates out of the reaction mixture.
These compounds of formula I having salifying properties can be obtained in free form or in salt form, depending on the procedure or reaction conditions.
Depending on the number, absolute and relative configuration of the asymmetric carbon atoms present in the molecule and/or on the configuration of the non-aromatic double bonds present in the molecule, the compounds of the formula I and, where appropriate, the tautomers thereof (in each case in free form or in salt form) may 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 an isomeric mixture, such as an enantiomeric mixture, for example a racemate, a diastereomeric mixture or a racemic mixture; the present invention relates to the pure isomers and also to all possible isomer mixtures and should be understood as such in each case above and below even if stereochemical details are not explicitly mentioned in each case.
Diastereomeric mixtures or racemate mixtures of compounds of the formula I in free form or in salt form, which may be obtained depending on the starting materials and procedures selected, can be separated into the pure diastereomers or racemates in a known manner on the basis of the physicochemical differences of these components, for example by fractional crystallization, distillation and/or chromatography.
Mixtures of enantiomers (e.g., racemates) that can be obtained in a similar manner can be resolved into the optical enantiomers by known methods, for example by recrystallization from optically active solvents; by chromatography on chiral adsorbents, for example High Performance Liquid Chromatography (HPLC) on acetyl cellulose; by cleavage with a specific immobilized enzyme by means of a suitable microorganism; by forming inclusion compounds, for example using chiral crown ethers, wherein only one enantiomer is complexed; or by conversion to a salt of a diastereomer, for example by reaction of the basic end product racemate with an optically active acid, such as a carboxylic acid, for example camphoric acid, tartaric acid or malic acid, or a sulfonic acid, for example camphorsulfonic acid, and separation of the diastereomeric mixture which can be obtained in this way, for example by fractional crystallization on the basis of their different solubilities, to give the diastereomer from which the desired enantiomer can be brought to the free form by the action of a suitable reagent, for example an alkaline reagent.
Pure diastereomers or enantiomers can be obtained according to the invention not only by separation of suitable 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 suitable stereochemistry.
By reacting a compound of formula I (when A2 and A3 are each N) with a suitable oxidizing agent (e.g., H 2 O 2 Urea adducts) are reacted in the presence of an anhydride (e.g., trifluoroacetic anhydride) to produce an N-oxide. Such oxidation is described in the literature, for example in J.Med.chem. [ J.Pharmacope., J.Chem.]Known from 32 (12), 2561-73,1989 or WO 2000/15615.
If the individual components have different biological activities, it is advantageous to separate or synthesize in each case the biologically more effective isomers, for example enantiomers or diastereomers or isomer mixtures, for example enantiomer mixtures or diastereomer mixtures.
If appropriate, the compounds of the formula I and, if appropriate, the tautomers thereof (in each case in free form or in salt form) can also be obtained in the form of hydrates and/or include other solvents, for example those which can be used for crystallizing compounds which are present in solid form.
The compounds of formula I-A according to tables A-1 to A-243 below can be prepared according to the methods described above. The examples which follow are intended to illustrate the invention and show preferred compounds of formula I (in the form of compounds of formula I-A).
Table A-18 compounds A-1.001 to A-1.008 of formula I-A are provided, wherein Ax is C-O-CF 2 CF 2 H，S 1 Is Cl, S 2 Is Cl, R 1b Is H, R 1a Is H, R 3 Is CH 3 And Q is as defined in table Z. For example, A-1.002 is
Table A-28 compounds A-2.001 to A-2.008 of formula I-A are provided, wherein Ax is C-O-CF 2 CF 2 H，S 1 Is Cl, S 2 Is Cl, R 1b Is H, R 1a Is CH 3 ，R 3 Is CH 3 And Q is as defined in table Z.
Table A-38 compounds A-3.001 to A-3.008 of the formula I-A are provided, wherein Ax is C-O-CF 2 CF 2 H，S 1 Is Cl, S 2 Is Cl, R 1b Is H, R 1a Is CH 2 -cyclopropyl, R 3 Is CH 3 And Q is as defined in table Z.
Table A-48 compounds A-4.001 to A-4.008 of the formula I-A are provided, wherein Ax is C-O-CF 2 CF 2 H，S 1 Is Cl, S 2 Is Cl, R 1b Is CH 3 ，R 1a Is H, R 3 Is CH 3 And Q is asDefined in table Z.
Table A-58 compounds A-5.001 to A-5.008 of the formula I-A are provided, wherein Ax is C-O-CF 2 CF 2 H，S 1 Is Cl, S 2 Is Cl, R 1b Is CH 3 ，R 1a Is CH 3 ，R 3 Is CH 3 And Q is as defined in table Z.
Table A-68 compounds A-6.001 to A-6.008 of the formula I-A are provided, wherein Ax is C-O-CF 2 CF 2 H，S 1 Is Cl, S 2 Is Cl, R 1b Is CH 3 ，R 1a Is CH 2 -cyclopropyl, R 3 Is CH 3 And Q is as defined in table Z.
Table A-78 compounds A-7.001 to A-7.008 of the formula I-A are provided, wherein Ax is C-O-CF 2 CF 2 H，S 1 Is Cl, S 2 Is Cl, R 1b Is CH 2 -cyclopropyl, R 1a Is H, R 3 Is CH 3 And Q is as defined in table Z.
Table A-88 compounds A-8.001 to A-8.008 of the formula I-A are provided, wherein Ax is C-O-CF 2 CF 2 H，S 1 Is Cl, S 2 Is Cl, R 1b Is CH 2 -cyclopropyl, R 1a Is CH 3 ，R 3 Is CH 3 And Q is as defined in table Z.
Table A-98 compounds A-9.001 to A-9.008 of the formula I-A are provided, wherein Ax is C-O-CF 2 CF 2 H，S 1 Is Cl, S 2 Is Cl, R 1b Is CH 2 -cyclopropyl, R 1a Is CH 2 -cyclopropyl, R 3 Is CH 3 And Q is as defined in table Z.
Table A-108 compounds A-10.001 to A-10.008 of the formula I-A are provided, wherein Ax is C-O-CF 2 CF 2 H，S 1 Is Cl, S 2 Is Br, R 1b Is H, R 1a Is H, R 3 Is CH 3 And Q is as defined in Table Z。
Table A-118 compounds A-11.001 to A-11.008 of the formula I-A are provided, wherein Ax is C-O-CF 2 CF 2 H，S 1 Is Cl, S 2 Is Br, R 1b Is H, R 1a Is CH 3 ，R 3 Is CH 3 And Q is as defined in table Z.
Tables A-128 compounds A-12.001 to A-12.008 of the formula I-A are provided, wherein Ax is C-O-CF 2 CF 2 H，S 1 Is Cl, S 2 Is Br, R 1b Is H, R 1a Is CH 2 -cyclopropyl, R 3 Is CH 3 And Q is as defined in table Z.
Table A-138 compounds A-13.001 to A-13.008 of the formula I-A are provided, wherein Ax is C-O-CF 2 CF 2 H，S 1 Is Cl, S 2 Is Br, R 1b Is CH 3 ，R 1a Is H, R 3 Is CH 3 And Q is as defined in table Z.
Tables A-148 compounds A-14.001 to A-14.008 of the formula I-A are provided, wherein Ax is C-O-CF 2 CF 2 H，S 1 Is Cl, S 2 Is Br, R 1b Is CH 3 ，R 1a Is CH 3 ，R 3 Is CH 3 And Q is as defined in table Z.
Tables A-158 compounds A-15.001 to A-15.008 of the formula I-A are provided, wherein Ax is C-O-CF 2 CF 2 H，S 1 Is Cl, S 2 Is Br, R 1b Is CH 3 ，R 1a Is CH 2 -cyclopropyl, R 3 Is CH 3 And Q is as defined in table Z.
Tables A-168 compounds A-16.001 to A-16.008 of the formula I-A are provided, wherein Ax is C-O-CF 2 CF 2 H，S 1 Is Cl, S 2 Is Br, R 1b Is CH 2 -cyclopropyl, R 1a Is H, R 3 Is CH 3 And Q is as defined in table Z.
Tables A-178 compounds A-17.001 to A-17.008 of the formula I-A are provided, wherein Ax is C-O-CF 2 CF 2 H，S 1 Is Cl, S 2 Is Br, R 1b Is CH 2 -cyclopropyl, R 1a Is CH 3 ，R 3 Is CH 3 And Q is as defined in table Z.
Tables A-18 8 compounds A-18.001 to A-18.008 of the formula I-A are provided, wherein Ax is C-O-CF 2 CF 2 H，S 1 Is Cl, S 2 Is Br, R 1b Is CH 2 -cyclopropyl, R 1a Is CH 2 -cyclopropyl, R 3 Is CH 3 And Q is as defined in table Z.
Tables A-198 compounds A-19.001 to A-19.008 of the formula I-A are provided, wherein Ax is C-O-CF 2 CF 2 H，S 1 Is Cl, S 2 Is CF (CF) 3 ，R 1b Is H, R 1a Is H, R 3 Is CH 3 And Q is as defined in table Z.
Tables A-208 compounds A-20.001 to A-20.008 of the formula I-A are provided, wherein Ax is C-O-CF 2 CF 2 H，S 1 Is Cl, S 2 Is CF (CF) 3 ，R 1b Is H, R 1a Is CH 3 ，R 3 Is CH 3 And Q is as defined in table Z.
Table A-218 compounds A-21.001 to A-21.008 of the formula I-A are provided, wherein Ax is C-O-CF 2 CF 2 H，S 1 Is Cl, S 2 Is CF (CF) 3 ，R 1b Is H, R 1a Is CH 2 -cyclopropyl, R 3 Is CH 3 And Q is as defined in table Z.
Tables A-228 compounds A-22.001 to A-22.008 of the formula I-A are provided, wherein Ax is C-O-CF 2 CF 2 H，S 1 Is Cl, S 2 Is CF (CF) 3 ，R 1b Is CH 3 ，R 1a Is H, R 3 Is CH 3 And Q is as defined in table Z.
Tables A-238 compounds A-23.001 to A-23.008 of the formula I-A are provided, wherein Ax is C-O-CF 2 CF 2 H，S 1 Is Cl, S 2 Is CF (CF) 3 ，R 1b Is CH 3 ，R 1a Is CH 3 ，R 3 Is CH 3 And Q is as defined in table Z.
Tables A-248 compounds A-24.001 to A-24.008 are provided having the formula I-A, wherein Ax is C-O-CF 2 CF 2 H，S 1 Is Cl, S 2 Is CF (CF) 3 ，R 1b Is CH 3 ，R 1a Is CH 2 -cyclopropyl, R 3 Is CH 3 And Q is as defined in table Z.
Tables A-258 compounds A-25.001 to A-25.008 of the formula I-A are provided, wherein Ax is C-O-CF 2 CF 2 H，S 1 Is Cl, S 2 Is CF (CF) 3 ，R 1b Is CH 2 -cyclopropyl, R 1a Is H, R 3 Is CH 3 And Q is as defined in table Z.
Tables A-268 compounds A-26.001 to A-26.008 of the formula I-A are provided, wherein Ax is C-O-CF 2 CF 2 H，S 1 Is Cl, S 2 Is CF (CF) 3 ，R 1b Is CH 2 -cyclopropyl, R 1a Is CH 3 ，R 3 Is CH 3 And Q is as defined in table Z.
Tables A-278 compounds A-27.001 to A-27.008 of the formula I-A are provided, wherein Ax is C-O-CF 2 CF 2 H，S 1 Is Cl, S 2 Is CF (CF) 3 ，R 1b Is CH 2 -cyclopropyl, R 1a Is CH 2 -cyclopropyl, R 3 Is CH 3 And Q is as defined in table Z.
Tables A-288 compounds A-28.001 to A-28.008 of the formula I-A are provided, wherein Ax is C-O-CF 2 CF 2 H，S 1 Is Br, S 2 Is Cl, R 1b Is H, R 1a Is H, R 3 Is CH 3 And Q is as defined in table Z.
Tables A-298 compounds A-29.001 to A-29.008 of the formula I-A are provided, wherein Ax is C-O-CF 2 CF 2 H，S 1 Is Br, S 2 Is Cl, R 1b Is H, R 1a Is CH 3 ，R 3 Is CH 3 And Q is as defined in table Z.
Tables A-308 compounds A-30.001 to A-30.008 of the formula I-A are provided, wherein Ax is C-O-CF 2 CF 2 H，S 1 Is Br, S 2 Is Cl, R 1b Is H, R 1a Is CH 2 -cyclopropyl, R 3 Is CH 3 And Q is as defined in table Z.
TABLE A-318 compounds A-31.001 to A-31.008 of the formula I-A are provided, wherein Ax is C-O-CF 2 CF 2 H，S 1 Is Br, S 2 Is Cl, R 1b Is CH 3 ，R 1a Is H, R 3 Is CH 3 And Q is as defined in table Z.
Table A-328 compounds A-32.001 to A-32.008 of the formula I-A are provided, wherein Ax is C-O-CF 2 CF 2 H，S 1 Is Br, S 2 Is Cl, R 1b Is CH 3 ，R 1a Is CH 3 ，R 3 Is CH 3 And Q is as defined in table Z.
Tables A-338 compounds A-33.001 to A-33.008 of the formula I-A are provided, wherein Ax is C-O-CF 2 CF 2 H，S 1 Is Br, S 2 Is Cl, R 1b Is CH 3 ，R 1a Is CH 2 -cyclopropyl, R 3 Is CH 3 And Q is as defined in table Z.
Tables A-348 compounds A-34.001 to A-34.008 of the formula I-A are provided, wherein Ax is C-O-CF 2 CF 2 H，S 1 Is Br, S 2 Is Cl, R 1b Is CH 2 -cyclopropyl, R 1a Is H, R 3 Is CH 3 And Q is as defined in table Z.
Tables A-358 compounds A-35.001 to A-35.008 of the formula I-A are provided, wherein Ax is C-O-CF 2 CF 2 H，S 1 Is Br, S 2 Is Cl, R 1b Is CH 2 -cyclopropyl, R 1a Is CH 3 ，R 3 Is CH 3 And Q is as defined in table Z.
Tables A-368 compounds A-36.001 to A-36.008 of the formula I-A are provided, wherein Ax is C-O-CF 2 CF 2 H，S 1 Is Br, S 2 Is Cl, R 1b Is CH 2 -cyclopropyl, R 1a Is CH 2 -cyclopropyl, R 3 Is CH 3 And Q is as defined in table Z.
Tables A-378 compounds A-37.001 to A-37.008 of the formula I-A are provided, wherein Ax is C-O-CF 2 CF 2 H，S 1 Is Br, S 2 Is Br, R 1b Is H, R 1a Is H, R 3 Is CH 3 And Q is as defined in table Z.
Tables A-388 compounds A-38.001 to A-38.008 of the formula I-A are provided, wherein Ax is C-O-CF 2 CF 2 H，S 1 Is Br, S 2 Is Br, R 1b Is H, R 1a Is CH 3 ，R 3 Is CH 3 And Q is as defined in table Z.
Tables A-398 compounds A-39.001 to A-39.008 of the formula I-A are provided, wherein Ax is C-O-CF 2 CF 2 H，S 1 Is Br, S 2 Is Br, R 1b Is H, R 1a Is CH 2 -cyclopropyl, R 3 Is CH 3 And Q is as defined in table Z.
Table A-408 compounds A-40.001 to A-40.008 of the formula I-A are provided, wherein Ax is C-O-CF 2 CF 2 H，S 1 Is Br, S 2 Is Br, R 1b Is CH 3 ，R 1a Is H, R 3 Is CH 3 And Q is as defined in table Z.
Tables A-418 compounds A-41.001 to A-41.008 of the formula I-A are provided, wherein Ax is C-O-CF 2 CF 2 H，S 1 Is Br, S 2 Is Br, R 1b Is CH 3 ，R 1a Is CH 3 ，R 3 Is CH 3 And Q is as defined in table Z.
Tables A-428 compounds A-42.001 to A-42.008 of the formula I-A are provided, wherein Ax is C-O-CF 2 CF 2 H，S 1 Is Br, S 2 Is Br, R 1b Is CH 3 ，R 1a Is CH 2 -cyclopropyl, R 3 Is CH 3 And Q is as defined in table Z.
Table A-438 compounds A-43.001 to A-43.008 of the formula I-A are provided, wherein Ax is C-O-CF 2 CF 2 H，S 1 Is Br, S 2 Is Br, R 1b Is CH 2 -cyclopropyl, R 1a Is H, R 3 Is CH 3 And Q is as defined in table Z.
Tables A-448 compounds A-44.001 to A-44.008 of the formula I-A are provided, wherein Ax is C-O-CF 2 CF 2 H，S 1 Is Br, S 2 Is Br, R 1b Is CH 2 -cyclopropyl, R 1a Is CH 3 ，R 3 Is CH 3 And Q is as defined in table Z.
Tables A-458 compounds A-45.001 to A-45.008 of the formula I-A are provided, wherein Ax is C-O-CF 2 CF 2 H，S 1 Is Br, S 2 Is Br, R 1b Is CH 2 -cyclopropyl, R 1a Is CH 2 -cyclopropyl, R 3 Is CH 3 And Q is as defined in table Z.
Tables A-468 compounds A-46.001 to A-46.008 of the formula I-A are provided, wherein Ax is C-O-CF 2 CF 2 H，S 1 Is Br, S 2 Is CF (CF) 3 ，R 1b Is H, R 1a Is H, R 3 Is CH 3 And Q is as defined in table Z.
Tables A-478 compounds A-47.001 to A-47.008 of the formula I-A are provided, wherein Ax is C-O-CF 2 CF 2 H，S 1 Is Br, S 2 Is CF (CF) 3 ，R 1b Is H, R 1a Is CH 3 ，R 3 Is CH 3 And Q is as defined in table Z.
Tables A-488 compounds A-48.001 to A-48.008 of the formula I-A are provided, wherein Ax is C-O-CF 2 CF 2 H，S 1 Is Br, S 2 Is CF (CF) 3 ，R 1b Is H, R 1a Is CH 2 -cyclopropyl, R 3 Is CH 3 And Q is as defined in table Z.
Tables A-498 compounds A-49.001 to A-49.008 of the formula I-A are provided, wherein Ax is C-O-CF 2 CF 2 H，S 1 Is Br, S 2 Is CF (CF) 3 ，R 1b Is CH 3 ，R 1a Is H, R 3 Is CH 3 And Q is as defined in table Z.
Table A-508 compounds A-50.001 to A-50.008 of the formula I-A are provided, wherein Ax is C-O-CF 2 CF 2 H，S 1 Is Br, S 2 Is CF (CF) 3 ，R 1b Is CH 3 ，R 1a Is CH 3 ，R 3 Is CH 3 And Q is as defined in table Z.
Table A-518 compounds A-51.001 to A-51.008 of the formula I-A are provided, wherein Ax is C-O-CF 2 CF 2 H，S 1 Is Br, S 2 Is CF (CF) 3 ，R 1b Is CH 3 ，R 1a Is CH 2 -cyclopropyl, R 3 Is CH 3 And Q is as defined in table Z.
Tables A-528 compounds A-52.001 to A-52.008 of the formula I-A are provided, wherein Ax is C-O-CF 2 CF 2 H，S 1 Is Br, S 2 Is CF (CF) 3 ，R 1b Is CH 2 -cyclopropyl, R 1a Is H, R 3 Is CH 3 And Q is as defined in Table Z。
Table A-538 compounds A-53.001 to A-53.008 of the formula I-A are provided, wherein Ax is C-O-CF 2 CF 2 H，S 1 Is Br, S 2 Is CF (CF) 3 ，R 1b Is CH 2 -cyclopropyl, R 1a Is CH 3 ，R 3 Is CH 3 And Q is as defined in table Z.
Tables A-548 compounds A-54.001 to A-54.008 of the formula I-A are provided, wherein Ax is C-O-CF 2 CF 2 H，S 1 Is Br, S 2 Is CF (CF) 3 ，R 1b Is CH 2 -cyclopropyl, R 1a Is CH 2 -cyclopropyl, R 3 Is CH 3 And Q is as defined in table Z.
Table A-558 compounds A-55.001 to A-55.008 of the formula I-A are provided, wherein Ax is C-O-CF 2 CF 2 H，S 1 Is CF (CF) 3 ，S 2 Is Cl, R 1b Is H, R 1a Is H, R 3 Is CH 3 And Q is as defined in table Z.
Tables A-568 compounds A-56.001 to A-56.008 of the formula I-A are provided, wherein Ax is C-O-CF 2 CF 2 H，S 1 Is CF (CF) 3 ，S 2 Is Cl, R 1b Is H, R 1a Is CH 3 ，R 3 Is CH 3 And Q is as defined in table Z.
Tables A-578 compounds A-57.001 to A-57.008 of the formula I-A are provided, wherein Ax is C-O-CF 2 CF 2 H，S 1 Is CF (CF) 3 ，S 2 Is Cl, R 1b Is H, R 1a Is CH 2 -cyclopropyl, R 3 Is CH 3 And Q is as defined in table Z.
Tables A-588 compounds A-58.001 to A-58.008 of the formula I-A are provided, wherein Ax is C-O-CF 2 CF 2 H，S 1 Is CF (CF) 3 ，S 2 Is Cl, R 1b Is CH 3 ，R 1a Is H, R 3 Is CH 3 And Q is as defined in table Z.
Tables A-598 compounds A-59.001 to A-59.008 of the formula I-A are provided, wherein Ax is C-O-CF 2 CF 2 H，S 1 Is CF (CF) 3 ，S 2 Is Cl, R 1b Is CH 3 ，R 1a Is CH 3 ，R 3 Is CH 3 And Q is as defined in table Z.
Table A-618 compounds A-61.001 to A-61.008 of the formula I-A are provided, wherein Ax is C-O-CF 2 CF 2 H，S 1 Is CF (CF) 3 ，S 2 Is Cl, R 1b Is CH 2 -cyclopropyl, R 1a Is H, R 3 Is CH 3 And Q is as defined in table Z.
Tables A-62 8 compounds A-62.001 to A-62.008 of the formula I-A are provided, wherein Ax is C-O-CF 2 CF 2 H，S 1 Is CF (CF) 3 ，S 2 Is Cl, R 1b Is CH 2 -cyclopropyl, R 1a Is CH 3 ，R 3 Is CH 3 And Q is as defined in table Z.
Tables A-638 compounds A-63.001 to A-63.008 of the formula I-A are provided, wherein Ax is C-O-CF 2 CF 2 H，S 1 Is CF (CF) 3 ，S 2 Is Cl, R 1b Is CH 2 -cyclopropyl, R 1a Is CH 2 -cyclopropyl, R 3 Is CH 3 And Q is as defined in table Z.
Tables A-648 compounds A-64.001 to A-64.008 of the formula I-A are provided, wherein Ax is C-O-CF 2 CF 2 H，S 1 Is CF (CF) 3 ，S 2 Is Br, R 1b Is H, R 1a Is H, R 3 Is CH 3 And Q is as defined in table Z.
Table A-658 compounds A-65.001 to A-65.008 of the formula I-A are provided, wherein Ax is C-O-CF 2 CF 2 H，S 1 Is CF (CF) 3 ，S 2 Is Br, R 1b Is H, R 1a Is CH 3 ，R 3 Is CH 3 And Q is as defined in table Z.
Tables A-668 compounds A-66.001 to A-66.008 of the formula I-A are provided, wherein Ax is C-O-CF 2 CF 2 H，S 1 Is CF (CF) 3 ，S 2 Is Br, R 1b Is H, R 1a Is CH 2 -cyclopropyl, R 3 Is CH 3 And Q is as defined in table Z.
Table A-678 compounds A-67.001 to A-67.008 of the formula I-A are provided, wherein Ax is C-O-CF 2 CF 2 H，S 1 Is CF (CF) 3 ，S 2 Is Br, R 1b Is CH 3 ，R 1a Is H, R 3 Is CH 3 And Q is as defined in table Z.
Tables A-688 compounds A-68.001 to A-68.008 of the formula I-A are provided, wherein Ax is C-O-CF 2 CF 2 H，S 1 Is CF (CF) 3 ，S 2 Is Br, R 1b Is CH 3 ，R 1a Is CH 3 ，R 3 Is CH 3 And Q is as defined in table Z.
Tables A-698 compounds A-69.001 to A-69.008 of the formula I-A are provided, wherein Ax is C-O-CF 2 CF 2 H，S 1 Is CF (CF) 3 ，S 2 Is Br, R 1b Is CH 3 ，R 1a Is CH 2 -cyclopropyl, R 3 Is CH 3 And Q is as defined in table Z.
Table A-708 compounds A-70.001 to A-70.008 of the formula I-A are provided, wherein Ax is C-O-CF 2 CF 2 H，S 1 Is CF (CF) 3 ，S 2 Is Br, R 1b Is CH 2 -cyclopropyl, R 1a Is H, R 3 Is CH 3 And Q is as defined in table Z.
Table A-718 compounds A-71.001 to A-71.008 of the formula I-A are provided, wherein Ax is C-O-CF 2 CF 2 H，S 1 Is CF (CF) 3 ，S 2 Is Br, R 1b Is CH 2 -cyclopropyl, R 1a Is CH 3 ，R 3 Is CH 3 And Q is as defined in table Z.
Tables A-728 compounds A-72.001 to A-72.008 of the formula I-A are provided, wherein Ax is C-O-CF 2 CF 2 H，S 1 Is CF (CF) 3 ，S 2 Is Br, R 1b Is CH 2 -cyclopropyl, R 1a Is CH 2 -cyclopropyl, R 3 Is CH 3 And Q is as defined in table Z.
Tables A-738 compounds A-73.001 to A-73.008 of the formula I-A are provided, wherein Ax is C-O-CF 2 CF 2 H，S 1 Is CF (CF) 3 ，S 2 Is CF (CF) 3 ，R 1b Is H, R 1a Is H, R 3 Is CH 3 And Q is as defined in table Z.
Table A-748 compounds A-74.001 to A-74.008 of the formula I-A are provided, wherein Ax is C-O-CF 2 CF 2 H，S 1 Is CF (CF) 3 ，S 2 Is CF (CF) 3 ，R 1b Is H, R 1a Is CH 3 ，R 3 Is CH 3 And Q is as defined in table Z.
Table A-758 compounds A-75.001 to A-75.008 of the formula I-A are provided, wherein Ax is C-O-CF 2 CF 2 H，S 1 Is CF (CF) 3 ，S 2 Is CF (CF) 3 ，R 1b Is H, R 1a Is CH 2 -cyclopropyl, R 3 Is CH 3 And Q is as defined in table Z.
Tables A-768 compounds A-76.001 to A-76.008 of the formula I-A are provided, wherein Ax is C-O-CF 2 CF 2 H，S 1 Is CF (CF) 3 ，S 2 Is CF (CF) 3 ，R 1b Is CH 3 ，R 1a Is H, R 3 Is CH 3 And Q is as defined in table Z.
Table A-778 compounds A-77.001 to A-77.008 of the formula I-A are provided, wherein Ax is C-O-CF 2 CF 2 H，S 1 Is CF (CF) 3 ，S 2 Is CF (CF) 3 ，R 1b Is CH 3 ，R 1a Is CH 3 ，R 3 Is CH 3 And Q is as defined in table Z.
Tables A-788 compounds A-78.001 to A-78.008 of the formula I-A are provided, wherein Ax is C-O-CF 2 CF 2 H，S 1 Is CF (CF) 3 ，S 2 Is CF (CF) 3 ，R 1b Is CH 3 ，R 1a Is CH 2 -cyclopropyl, R 3 Is CH 3 And Q is as defined in table Z.
Tables A-798 compounds A-79.001 to A-79.008 of the formula I-A are provided, wherein Ax is C-O-CF 2 CF 2 H，S 1 Is CF (CF) 3 ，S 2 Is CF (CF) 3 ，R 1b Is CH 2 -cyclopropyl, R 1a Is H, R 3 Is CH 3 And Q is as defined in table Z.
Table A-808 compounds A-80.001 to A-80.008 of the formula I-A are provided, wherein Ax is C-O-CF 2 CF 2 H，S 1 Is CF (CF) 3 ，S 2 Is CF (CF) 3 ，R 1b Is CH 2 -cyclopropyl, R 1a Is CH 3 ，R 3 Is CH 3 And Q is as defined in table Z.
Table A-81 8 compounds A-81.001 to A-81.008 of the formula I-A are provided, wherein Ax is C-O-CF 2 CF 2 H，S 1 Is CF (CF) 3 ，S 2 Is CF (CF) 3 ，R 1b Is CH 2 -cyclopropyl, R 1a Is CH 2 -cyclopropyl, R 3 Is CH 3 And Q is as defined in table Z.
Table A-828 compounds A-82.001 to A-82.008 of the formula I-A are provided, wherein Ax is C-CF 3 ，S 1 Is Cl, S 2 Is Cl, R 1b Is H, R 1a Is H, R 3 Is CH 3 And Q is as defined in table Z.
Tables A-838 compounds A-83.001 to A-83.008 of the formula I-A are provided, wherein Ax is C-CF 3 ，S 1 Is Cl, S 2 Is Cl, R 1b Is H, R 1a Is CH 3 ，R 3 Is CH 3 And Q is as defined in table Z.
Tables A-848 compounds A-84.001 to A-84.008 of the formula I-A are provided, wherein Ax is C-CF 3 ，S 1 Is Cl, S 2 Is Cl, R 1b Is H, R 1a Is CH 2 -cyclopropyl, R 3 Is CH 3 And Q is as defined in table Z.
Table A-858 compounds A-85.001 to A-85.008 of the formula I-A are provided, wherein Ax is C-CF 3 ，S 1 Is Cl, S 2 Is Cl, R 1b Is CH 3 ，R 1a Is H, R 3 Is CH 3 And Q is as defined in table Z.
Tables A-868 compounds A-86.001 to A-86.008 of the formula I-A are provided, wherein Ax is C-CF 3 ，S 1 Is Cl, S 2 Is Cl, R 1b Is CH 3 ，R 1a Is CH 3 ，R 3 Is CH 3 And Q is as defined in table Z.
Tables A-878 compounds A-87.001 to A-87.008 of the formula I-A are provided, wherein Ax is C-CF 3 ，S 1 Is Cl, S 2 Is Cl, R 1b Is CH 3 ，R 1a Is CH 2 -cyclopropyl, R 3 Is CH 3 And Q is as defined in table Z.
Tables A-888 compounds A-88.001 to A-88.008 of the formula I-A are provided, wherein Ax is C-CF 3 ，S 1 Is Cl, S 2 Is Cl, R 1b Is CH 2 -cyclopropyl, R 1a Is H, R 3 Is CH 3 And Q is as defined in table Z.
Table A-898 compounds A-89.001 to A-89.008 of the formula I-A are provided, wherein Ax is C-CF 3 ，S 1 Is Cl, S 2 Is Cl, R 1b Is CH 2 -cyclopropyl, R 1a Is CH 3 ，R 3 Is CH 3 And Q is as defined in table Z.
Tables A-908 compounds A-90.001 to A-90.008 of the formula I-A are provided, wherein Ax is C-CF 3 ，S 1 Is Cl, S 2 Is Cl, R 1b Is CH 2 -cyclopropyl, R 1a Is CH 2 -cyclopropyl, R 3 Is CH 3 And Q is as defined in table Z.
Tables A-918 compounds A-91.001 to A-91.008 of the formula I-A are provided, wherein Ax is C-CF 3 ，S 1 Is Cl, S 2 Is Br, R 1b Is H, R 1a Is H, R 3 Is CH 3 And Q is as defined in table Z.
Table A-928 compounds A-92.001 to A-92.008 of the formula I-A are provided, wherein Ax is C-CF 3 ，S 1 Is Cl, S 2 Is Br, R 1b Is H, R 1a Is CH 3 ，R 3 Is CH 3 And Q is as defined in table Z.
Table A-938 compounds A-93.001 to A-93.008 of the formula I-A are provided, wherein Ax is C-CF 3 ，S 1 Is Cl, S 2 Is Br, R 1b Is H, R 1a Is CH 2 -cyclopropyl, R 3 Is CH 3 And Q is as defined in table Z.
Table A-948 compounds A-94.001 to A-94.008 of the formula I-A are provided, wherein Ax is C-CF 3 ，S 1 Is Cl, S 2 Is Br, R 1b Is CH 3 ，R 1a Is H, R 3 Is CH 3 And Q is as defined in table Z.
Tables A-958 compounds A-95.001 to A-95.008 of the formula I-A are provided, wherein Ax is C-CF 3 ，S 1 Is Cl, S 2 Is Br, R 1b Is CH 3 ，R 1a Is CH 3 ，R 3 Is CH 3 And Q is as defined in Table ZAs defined herein.
Tables A-968 compounds A-96.001 to A-96.008 of the formula I-A are provided, wherein Ax is C-CF 3 ，S 1 Is Cl, S 2 Is Br, R 1b Is CH 3 ，R 1a Is CH 2 -cyclopropyl, R 3 Is CH 3 And Q is as defined in table Z.
Table A-978 compounds A-97.001 to A-97.008 of the formula I-A are provided, wherein Ax is C-CF 3 ，S 1 Is Cl, S 2 Is Br, R 1b Is CH 2 -cyclopropyl, R 1a Is H, R 3 Is CH 3 And Q is as defined in table Z.
Table A-988 compounds A-98.001 to A-98.008 of the formula I-A are provided, wherein Ax is C-CF 3 ，S 1 Is Cl, S 2 Is Br, R 1b Is CH 2 -cyclopropyl, R 1a Is CH 3 ，R 3 Is CH 3 And Q is as defined in table Z.
Table A-998 compounds A-99.001 to A-99.008 of the formula I-A are provided, wherein Ax is C-CF 3 ，S 1 Is Cl, S 2 Is Br, R 1b Is CH 2 -cyclopropyl, R 1a Is CH 2 -cyclopropyl, R 3 Is CH 3 And Q is as defined in table Z.
Table A-1008 compounds A-100.001 to A-100.008 of the formula I-A are provided, wherein Ax is C-CF 3 ，S 1 Is Cl, S 2 Is CF (CF) 3 ，R 1b Is H, R 1a Is H, R 3 Is CH 3 And Q is as defined in table Z.
Tables A-1018 compounds A-101.001 to A-101.008 of the formula I-A are provided, wherein Ax is C-CF 3 ，S 1 Is Cl, S 2 Is CF (CF) 3 ，R 1b Is H, R 1a Is CH 3 ，R 3 Is CH 3 And Q is as defined in table Z.
Tables A-1028 kinds of products having the formula are providedCompounds A-102.001 to A-102.008 of I-A, in which Ax is C-CF 3 ，S 1 Is Cl, S 2 Is CF (CF) 3 ，R 1b Is H, R 1a Is CH 2 -cyclopropyl, R 3 Is CH 3 And Q is as defined in table Z.
Tables A to 1038 compounds A-103.001 to A-103.008 of the formula I-A are provided, wherein Ax is C-CF 3 ，S 1 Is Cl, S 2 Is CF (CF) 3 ，R 1b Is CH 3 ，R 1a Is H, R 3 Is CH 3 And Q is as defined in table Z.
Tables A-1048 compounds A-104.001 to A-104.008 of the formula I-A are provided, wherein Ax is C-CF 3 ，S 1 Is Cl, S 2 Is CF (CF) 3 ，R 1b Is CH 3 ，R 1a Is CH 3 ，R 3 Is CH 3 And Q is as defined in table Z.
Tables A-1058 compounds A-105.001 to A-105.008 of the formula I-A are provided, wherein Ax is C-CF 3 ，S 1 Is Cl, S 2 Is CF (CF) 3 ，R 1b Is CH 3 ，R 1a Is CH 2 -cyclopropyl, R 3 Is CH 3 And Q is as defined in table Z.
Tables A-1068 compounds A-106.001 to A-106.008 of the formula I-A are provided, wherein Ax is C-CF 3 ，S 1 Is Cl, S 2 Is CF (CF) 3 ，R 1b Is CH 2 -cyclopropyl, R 1a Is H, R 3 Is CH 3 And Q is as defined in table Z.
Tables A-1078 compounds A-107.001 to A-107.008 of the formula I-A are provided, wherein Ax is C-CF 3 ，S 1 Is Cl, S 2 Is CF (CF) 3 ，R 1b Is CH 2 -cyclopropyl, R 1a Is CH 3 ，R 3 Is CH 3 And Q is as defined in table Z.
Tables A-1088 compounds A-108.001 to A of the formula I-A are providedA-108.008, wherein Ax is C-CF 3 ，S 1 Is Cl, S 2 Is CF (CF) 3 ，R 1b Is CH 2 -cyclopropyl, R 1a Is CH 2 -cyclopropyl, R 3 Is CH 3 And Q is as defined in table Z.
Tables A-1098 compounds A-109.001 to A-109.008 of the formula I-A are provided, wherein Ax is C-CF 3 ，S 1 Is Br, S 2 Is Cl, R 1b Is H, R 1a Is H, R 3 Is CH 3 And Q is as defined in table Z.
Tables A-1108 compounds A-110.001 to A-110.008 of the formula I-A are provided, wherein Ax is C-CF 3 ，S 1 Is Br, S 2 Is Cl, R 1b Is H, R 1a Is CH 3 ，R 3 Is CH 3 And Q is as defined in table Z.
Tables A-1118 compounds A-111.001 to A-111.008 of the formula I-A are provided, wherein Ax is C-CF 3 ，S 1 Is Br, S 2 Is Cl, R 1b Is H, R 1a Is CH 2 -cyclopropyl, R 3 Is CH 3 And Q is as defined in table Z.
Tables A-1128 compounds A-112.001 to A-112.008 of the formula I-A are provided, wherein Ax is C-CF 3 ，S 1 Is Br, S 2 Is Cl, R 1b Is CH 3 ，R 1a Is H, R 3 Is CH 3 And Q is as defined in table Z.
Table A-1138 compounds A-113.001 to A-113.008 of the formula I-A are provided, wherein Ax is C-CF 3 ，S 1 Is Br, S 2 Is Cl, R 1b Is CH 3 ，R 1a Is CH 3 ，R 3 Is CH 3 And Q is as defined in table Z.
Tables A-1148 compounds A-114.001 to A-114.008 of the formula I-A are provided, wherein Ax is C-CF 3 ，S 1 Is Br, S 2 Is Cl, R 1b Is CH 3 ，R 1a Is CH 2 -cyclopropyl, R 3 Is CH 3 And Q is as defined in table Z.
Tables A-1158 compounds A-115.001 to A-115.008 of the formula I-A are provided, wherein Ax is C-CF 3 ，S 1 Is Br, S 2 Is Cl, R 1b Is CH 2 -cyclopropyl, R 1a Is H, R 3 Is CH 3 And Q is as defined in table Z.
Tables A-1168 compounds A-116.001 to A-116.008 of the formula I-A are provided, wherein Ax is C-CF 3 ，S 1 Is Br, S 2 Is Cl, R 1b Is CH 2 -cyclopropyl, R 1a Is CH 3 ，R 3 Is CH 3 And Q is as defined in table Z.
Tables A-1178 compounds A-117.001 to A-117.008 of the formula I-A are provided, wherein Ax is C-CF 3 ，S 1 Is Br, S 2 Is Cl, R 1b Is CH 2 -cyclopropyl, R 1a Is CH 2 -cyclopropyl, R 3 Is CH 3 And Q is as defined in table Z.
Tables A-1188 compounds A-118.001 to A-118.008 of the formula I-A are provided, wherein Ax is C-CF 3 ，S 1 Is Br, S 2 Is Br, R 1b Is H, R 1a Is H, R 3 Is CH 3 And Q is as defined in table Z.
Tables A-1198 compounds A-119.001 to A-119.008 of the formula I-A are provided, wherein Ax is C-CF 3 ，S 1 Is Br, S 2 Is Br, R 1b Is H, R 1a Is CH 3 ，R 3 Is CH 3 And Q is as defined in table Z.
Tables A-1208 compounds A-120.001 to A-120.008 of the formula I-A are provided, wherein Ax is C-CF 3 ，S 1 Is Br, S 2 Is Br, R 1b Is H, R 1a Is CH 2 -cyclopropyl, R 3 Is CH 3 And Q is as defined in table Z.
Tables A-1218 compounds A-121.001 to A-121.008 of the formula I-A are provided, wherein Ax is C-CF 3 ，S 1 Is Br, S 2 Is Br, R 1b Is CH 3 ，R 1a Is H, R 3 Is CH 3 And Q is as defined in table Z.
Tables A-1228 compounds A-122.001 to A-122.008 of the formula I-A are provided, wherein Ax is C-CF 3 ，S 1 Is Br, S 2 Is Br, R 1b Is CH 3 ，R 1a Is CH 3 ，R 3 Is CH 3 And Q is as defined in table Z.
Tables A-1238 compounds A-123.001 to A-123.008 of the formula I-A are provided, wherein Ax is C-CF 3 ，S 1 Is Br, S 2 Is Br, R 1b Is CH 3 ，R 1a Is CH 2 -cyclopropyl, R 3 Is CH 3 And Q is as defined in table Z.
Tables A-1248 compounds A-124.001 to A-124.008 of the formula I-A are provided, wherein Ax is C-CF 3 ，S 1 Is Br, S 2 Is Br, R 1b Is CH 2 -cyclopropyl, R 1a Is H, R 3 Is CH 3 And Q is as defined in table Z.
Tables A-1258 compounds A-125.001 to A-125.008 of the formula I-A are provided, wherein Ax is C-CF 3 ，S 1 Is Br, S 2 Is Br, R 1b Is CH 2 -cyclopropyl, R 1a Is CH 3 ，R 3 Is CH 3 And Q is as defined in table Z.
Tables A-1268 compounds A-126.001 to A-126.008 of the formula I-A are provided, wherein Ax is C-CF 3 ，S 1 Is Br, S 2 Is Br, R 1b Is CH 2 -cyclopropyl, R 1a Is CH 2 -cyclopropyl, R 3 Is CH 3 And Q is as defined in table Z.
Table A-1278 kinds of products having the formula are providedCompounds A-127.001 to A-127.008 of I-A, wherein Ax is C-CF 3 ，S 1 Is Br, S 2 Is CF (CF) 3 ，R 1b Is H, R 1a Is H, R 3 Is CH 3 And Q is as defined in table Z.
Table A-1288 compounds A-128.001 to A-128.008 of the formula I-A are provided, wherein Ax is C-CF 3 ，S 1 Is Br, S 2 Is CF (CF) 3 ，R 1b Is H, R 1a Is CH 3 ，R 3 Is CH 3 And Q is as defined in table Z.
Tables A-1298 compounds A-129.001 to A-129.008 of the formula I-A are provided, wherein Ax is C-CF 3 ，S 1 Is Br, S 2 Is CF (CF) 3 ，R 1b Is H, R 1a Is CH 2 -cyclopropyl, R 3 Is CH 3 And Q is as defined in table Z.
Tables A-1308 compounds A-130.001 to A-130.008 of the formula I-A are provided, wherein Ax is C-CF 3 ，S 1 Is Br, S 2 Is CF (CF) 3 ，R 1b Is CH 3 ，R 1a Is H, R 3 Is CH 3 And Q is as defined in table Z.
Table A-1318 compounds A-131.001 to A-131.008 of the formula I-A are provided, wherein Ax is C-CF 3 ，S 1 Is Br, S 2 Is CF (CF) 3 ，R 1b Is CH 3 ，R 1a Is CH 3 ，R 3 Is CH 3 And Q is as defined in table Z.
Tables A-1328 compounds A-132.001 to A-132.008 of the formula I-A are provided, wherein Ax is C-CF 3 ，S 1 Is Br, S 2 Is CF (CF) 3 ，R 1b Is CH 3 ，R 1a Is CH 2 -cyclopropyl, R 3 Is CH 3 And Q is as defined in table Z.
Tables A-1338 compounds A-133.001 to A-133.008 of the formula I-A are provided, wherein Ax is C-CF 3 ，S 1 Is Br, S 2 Is CF (CF) 3 ，R 1b Is CH 2 -cyclopropyl, R 1a Is H, R 3 Is CH 3 And Q is as defined in table Z.
Tables A-1348 compounds A-134.001 to A-134.008 of the formula I-A are provided, wherein Ax is C-CF 3 ，S 1 Is Br, S 2 Is CF (CF) 3 ，R 1b Is CH 2 -cyclopropyl, R 1a Is CH 3 ，R 3 Is CH 3 And Q is as defined in table Z.
Tables A-1358 compounds A-135.001 to A-135.008 of the formula I-A are provided, wherein Ax is C-CF 3 ，S 1 Is Br, S 2 Is CF (CF) 3 ，R 1b Is CH 2 -cyclopropyl, R 1a Is CH 2 -cyclopropyl, R 3 Is CH 3 And Q is as defined in table Z.
Tables A-1368 compounds A-136.001 to A-136.008 of the formula I-A are provided, wherein Ax is C-CF 3 ，S 1 Is CF (CF) 3 ，S 2 Is Cl, R 1b Is H, R 1a Is H, R 3 Is CH 3 And Q is as defined in table Z.
Tables A-1378 compounds A-137.001 to A-137.008 of the formula I-A are provided, wherein Ax is C-CF 3 ，S 1 Is CF (CF) 3 ，S 2 Is Cl, R 1b Is H, R 1a Is CH 3 ，R 3 Is CH 3 And Q is as defined in table Z.
Tables A-1388 compounds A-138.001 to A-138.008 of the formula I-A are provided, wherein Ax is C-CF 3 ，S 1 Is CF (CF) 3 ，S 2 Is Cl, R 1b Is H, R 1a Is CH 2 -cyclopropyl, R 3 Is CH 3 And Q is as defined in table Z.
Tables A-1398 compounds A-139.001 to A-139.008 of the formula I-A are provided, wherein Ax is C-CF 3 ，S 1 Is CF (CF) 3 ，S 2 Is Cl, R 1b Is CH 3 ，R 1a Is H, R 3 Is CH 3 And Q is as defined in table Z.
Tables A-1408 compounds A-140.001 to A-140.008 of the formula I-A are provided, wherein Ax is C-CF 3 ，S 1 Is CF (CF) 3 ，S 2 Is Cl, R 1b Is CH 3 ，R 1a Is CH 3 ，R 3 Is CH 3 And Q is as defined in table Z.
Table A-1418 compounds A-141.001 to A-141.008 of the formula I-A are provided, wherein Ax is C-CF 3 ，S 1 Is CF (CF) 3 ，S 2 Is Cl, R 1b Is CH 3 ，R 1a Is CH 2 -cyclopropyl, R 3 Is CH 3 And Q is as defined in table Z.
Tables A-1428 compounds A-142.001 to A-142.008 of the formula I-A are provided, wherein Ax is C-CF 3 ，S 1 Is CF (CF) 3 ，S 2 Is Cl, R 1b Is CH 2 -cyclopropyl, R 1a Is H, R 3 Is CH 3 And Q is as defined in table Z.
Tables A-1438 compounds A-143.001 to A-143.008 of the formula I-A are provided, wherein Ax is C-CF 3 ，S 1 Is CF (CF) 3 ，S 2 Is Cl, R 1b Is CH 2 -cyclopropyl, R 1a Is CH 3 ，R 3 Is CH 3 And Q is as defined in table Z.
Tables A-1448 compounds A-144.001 to A-144.008 of the formula I-A are provided, wherein Ax is C-CF 3 ，S 1 Is CF (CF) 3 ，S 2 Is Cl, R 1b Is CH 2 -cyclopropyl, R 1a Is CH 2 -cyclopropyl, R 3 Is CH 3 And Q is as defined in table Z.
Tables A-1458 compounds A-145.001 to A-145.008 of the formula I-A are provided, wherein Ax is C-CF 3 ，S 1 Is CF (CF) 3 ，S 2 Is Br, R 1b Is H, R 1a Is H, R 3 Is CH 3 And Q is as defined in table Z.
Tables A-1468 compounds A-146.001 to A-146.008 of the formula I-A are provided, wherein Ax is C-CF 3 ，S 1 Is CF (CF) 3 ，S 2 Is Br, R 1b Is H, R 1a Is CH 3 ，R 3 Is CH 3 And Q is as defined in table Z.
Tables A-1478 compounds A-147.001 to A-147.008 of the formula I-A are provided, wherein Ax is C-CF 3 ，S 1 Is CF (CF) 3 ，S 2 Is Br, R 1b Is H, R 1a Is CH 2 -cyclopropyl, R 3 Is CH 3 And Q is as defined in table Z.
Table A-1488 compounds A-148.001 to A-148.008 of the formula I-A are provided, wherein Ax is C-CF 3 ，S 1 Is CF (CF) 3 ，S 2 Is Br, R 1b Is CH 3 ，R 1a Is H, R 3 Is CH 3 And Q is as defined in table Z.
Tables A-1498 compounds A-149.001 to A-149.008 of the formula I-A are provided, wherein Ax is C-CF 3 ，S 1 Is CF (CF) 3 ，S 2 Is Br, R 1b Is CH 3 ，R 1a Is CH 3 ，R 3 Is CH 3 And Q is as defined in table Z.
Tables A-1508 compounds A-150.001 to A-150.008 of the formula I-A are provided, wherein Ax is C-CF 3 ，S 1 Is CF (CF) 3 ，S 2 Is Br, R 1b Is CH 3 ，R 1a Is CH 2 -cyclopropyl, R 3 Is CH 3 And Q is as defined in table Z.
Tables A-1518 compounds A-151.001 to A-151.008 of the formula I-A are provided, wherein Ax is C-CF 3 ，S 1 Is CF (CF) 3 ，S 2 Is Br, R 1b Is CH 2 -cyclopropyl, R 1a Is H, R 3 Is CH 3 And Q is as defined in table Z.
Tables A-1528 compounds A-152.001 to A-152.008 of the formula I-A are provided, wherein Ax is C-CF 3 ，S 1 Is CF (CF) 3 ，S 2 Is Br, R 1b Is CH 2 -cyclopropyl, R 1a Is CH 3 ，R 3 Is CH 3 And Q is as defined in table Z.
Table A-1538 compounds A-153.001 to A-153.008 of the formula I-A are provided, wherein Ax is C-CF 3 ，S 1 Is CF (CF) 3 ，S 2 Is Br, R 1b Is CH 2 -cyclopropyl, R 1a Is CH 2 -cyclopropyl, R 3 Is CH 3 And Q is as defined in table Z.
Table A-1548 compounds A-154.001 to A-154.008 of the formula I-A are provided, wherein Ax is C-CF 3 ，S 1 Is CF (CF) 3 ，S 2 Is CF (CF) 3 ，R 1b Is H, R 1a Is H, R 3 Is CH 3 And Q is as defined in table Z.
Tables A-1558 compounds A-155.001 to A-155.008 of the formula I-A are provided, wherein Ax is C-CF 3 ，S 1 Is CF (CF) 3 ，S 2 Is CF (CF) 3 ，R 1b Is H, R 1a Is CH 3 ，R 3 Is CH 3 And Q is as defined in table Z.
Tables A-1568 compounds A-156.001 to A-156.008 of the formula I-A are provided, wherein Ax is C-CF 3 ，S 1 Is CF (CF) 3 ，S 2 Is CF (CF) 3 ，R 1b Is H, R 1a Is CH 2 -cyclopropyl, R 3 Is CH 3 And Q is as defined in table Z.
Tables A-1578 compounds A-157.001 to A-157.008 of the formula I-A are provided, wherein Ax is C-CF 3 ，S 1 Is CF (CF) 3 ，S 2 Is CF (CF) 3 ，R 1b Is CH 3 ，R 1a Is H, is a group of the formula,R 3 is CH 3 And Q is as defined in table Z.
Table A-1588 compounds A-158.001 to A-158.008 of the formula I-A are provided, wherein Ax is C-CF 3 ，S 1 Is CF (CF) 3 ，S 2 Is CF (CF) 3 ，R 1b Is CH 3 ，R 1a Is CH 3 ，R 3 Is CH 3 And Q is as defined in table Z.
Tables A-1598 compounds A-159.001 to A-159.008 of the formula I-A are provided, wherein Ax is C-CF 3 ，S 1 Is CF (CF) 3 ，S 2 Is CF (CF) 3 ，R 1b Is CH 3 ，R 1a Is CH 2 -cyclopropyl, R 3 Is CH 3 And Q is as defined in table Z.
Tables A-1608 compounds A-160.001 to A-160.008 of the formula I-A are provided, wherein Ax is C-CF 3 ，S 1 Is CF (CF) 3 ，S 2 Is CF (CF) 3 ，R 1b Is CH 2 -cyclopropyl, R 1a Is H, R 3 Is CH 3 And Q is as defined in table Z.
Tables A-1618 compounds A-161.001 to A-161.008 of the formula I-A are provided, wherein Ax is C-CF 3 ，S 1 Is CF (CF) 3 ，S 2 Is CF (CF) 3 ，R 1b Is CH 2 -cyclopropyl, R 1a Is CH 3 ，R 3 Is CH 3 And Q is as defined in table Z.
Tables A-1628 compounds A-162.001 to A-162.008 of the formula I-A are provided, wherein Ax is C-CF 3 ，S 1 Is CF (CF) 3 ，S 2 Is CF (CF) 3 ，R 1b Is CH 2 -cyclopropyl, R 1a Is CH 2 -cyclopropyl, R 3 Is CH 3 And Q is as defined in table Z.
Tables A-1638 compounds A-163.001 to A-163.008 of the formula I-A are provided, wherein Ax is N, S 1 Is Cl, S 2 Is Cl, R 1b Is H, R 1a Is H, R 3 Is CH 3 And Q is as defined in table Z.
Tables A-1648 compounds A-164.001 to A-164.008 of the formula I-A are provided, wherein Ax is N, S 1 Is Cl, S 2 Is Cl, R 1b Is H, R 1a Is CH 3 ，R 3 Is CH 3 And Q is as defined in table Z.
Tables A-1658 compounds A-165.001 to A-165.008 of the formula I-A are provided, wherein Ax is N, S 1 Is Cl, S 2 Is Cl, R 1b Is H, R 1a Is CH 2 -cyclopropyl, R 3 Is CH 3 And Q is as defined in table Z.
Table A-1668 compounds A-166.001 to A-166.008 of the formula I-A are provided, wherein Ax is N, S 1 Is Cl, S 2 Is Cl, R 1b Is CH 3 ，R 1a Is H, R 3 Is CH 3 And Q is as defined in table Z.
Tables A-167 8 compounds A-167.001 to A-167.008 of the formula I-A are provided, wherein Ax is N, S 1 Is Cl, S 2 Is Cl, R 1b Is CH 3 ，R 1a Is CH 3 ，R 3 Is CH 3 And Q is as defined in table Z.
Tables A-1688 compounds A-168.001 to A-168.008 of the formula I-A are provided, wherein Ax is N, S 1 Is Cl, S 2 Is Cl, R 1b Is CH 3 ，R 1a Is CH 2 -cyclopropyl, R 3 Is CH 3 And Q is as defined in table Z.
Tables A-1698 compounds A-169.001 to A-169.008 of the formula I-A are provided, wherein Ax is N, S 1 Is Cl, S 2 Is Cl, R 1b Is CH 2 -cyclopropyl, R 1a Is H, R 3 Is CH 3 And Q is as defined in table Z.
Tables A-1708 compounds A-170.001 to A-170.008 of the formula I-A are provided, in whichAx is N, S 1 Is Cl, S 2 Is Cl, R 1b Is CH 2 -cyclopropyl, R 1a Is CH 3 ，R 3 Is CH 3 And Q is as defined in table Z.
Table A-1718 compounds A-171.001 to A-171.008 of the formula I-A are provided, wherein Ax is N, S 1 Is Cl, S 2 Is Cl, R 1b Is CH 2 -cyclopropyl, R 1a Is CH 2 -cyclopropyl, R 3 Is CH 3 And Q is as defined in table Z.
Tables A-1728 compounds A-172.001 to A-172.008 of the formula I-A are provided, wherein Ax is N, S 1 Is Cl, S 2 Is Br, R 1b Is H, R 1a Is H, R 3 Is CH 3 And Q is as defined in table Z.
Tables A-173There are provided 8 compounds A-173.001 to A-173.008 of the formula I-A, wherein Ax is N, S 1 Is Cl, S 2 Is Br, R 1b Is H, R 1a Is CH 3 ，R 3 Is CH 3 And Q is as defined in table Z.
Tables A-1748 compounds A-174.001 to A-174.008 of the formula I-A are provided, wherein Ax is N, S 1 Is Cl, S 2 Is Br, R 1b Is H, R 1a Is CH 2 -cyclopropyl, R 3 Is CH 3 And Q is as defined in table Z.
Tables A-1758 compounds A-175.001 to A-175.008 of the formula I-A are provided, wherein Ax is N, S 1 Is Cl, S 2 Is Br, R 1b Is CH 3 ，R 1a Is H, R 3 Is CH 3 And Q is as defined in table Z.
Tables A-1768 compounds A-176.001 to A-176.008 of the formula I-A are provided, wherein Ax is N, S 1 Is Cl, S 2 Is Br, R 1b Is CH 3 ，R 1a Is CH 3 ，R 3 Is CH 3 And Q is as defined in table Z.
Tables A-1778 compounds A-177.001 to A-177.008 of the formula I-A are provided, wherein Ax is N, S 1 Is Cl, S 2 Is Br, R 1b Is CH 3 ，R 1a Is CH 2 -cyclopropyl, R 3 Is CH 3 And Q is as defined in table Z.
Tables A-1788 compounds A-178.001 to A-178.008 of the formula I-A are provided, wherein Ax is N, S 1 Is Cl, S 2 Is Br, R 1b Is CH 2 -cyclopropyl, R 1a Is H, R 3 Is CH 3 And Q is as defined in table Z.
Tables A-179 8 compounds A-179.001 to A-179.008 of the formula I-A are provided, wherein Ax is N, S 1 Is Cl, S 2 Is Br, R 1b Is CH 2 -cyclopropyl, R 1a Is CH 3 ，R 3 Is CH 3 And Q is as defined in table Z.
Tables A-1808 compounds A-180.001 to A-180.008 of the formula I-A are provided, wherein Ax is N, S 1 Is Cl, S 2 Is Br, R 1b Is CH 2 -cyclopropyl, R 1a Is CH 2 -cyclopropyl, R 3 Is CH 3 And Q is as defined in table Z.
Tables A-1818 compounds A-181.001 to A-181.008 of the formula I-A are provided, wherein Ax is N, S 1 Is Cl, S 2 Is CF (CF) 3 ，R 1b Is H, R 1a Is H, R 3 Is CH 3 And Q is as defined in table Z.
Tables A-1828 compounds A-182.001 to A-182.008 of the formula I-A are provided, wherein Ax is N, S 1 Is Cl, S 2 Is CF (CF) 3 ，R 1b Is H, R 1a Is CH 3 ，R 3 Is CH 3 And Q is as defined in table Z.
Tables A-1838 compounds A-183.001 to A-183.008 of the formula I-A are provided, wherein Ax is N, S 1 Is Cl, S 2 Is CF (CF) 3 ，R 1b Is H, R 1a Is CH 2 -cyclopropyl, R 3 Is CH 3 And Q is as defined in table Z.
Tables A-1848 compounds A-184.001 to A-184.008 of the formula I-A are provided, wherein Ax is N, S 1 Is Cl, S 2 Is CF (CF) 3 ，R 1b Is CH 3 ，R 1a Is H, R 3 Is CH 3 And Q is as defined in table Z.
Tables A-185 8 compounds A-185.001 to A-185.008 of the formula I-A are provided, wherein Ax is N, S 1 Is Cl, S 2 Is CF (CF) 3 ，R 1b Is CH 3 ，R 1a Is CH 3 ，R 3 Is CH 3 And Q is as defined in table Z.
Tables A-1868 compounds A-186.001 to A-186.008 of the formula I-A are provided, wherein Ax is N, S 1 Is Cl, S 2 Is CF (CF) 3 ，R 1b Is CH 3 ，R 1a Is CH 2 -cyclopropyl, R 3 Is CH 3 And Q is as defined in table Z.
Tables A-1878 compounds A-187.001 to A-187.008 of the formula I-A are provided, wherein Ax is N, S 1 Is Cl, S 2 Is CF (CF) 3 ，R 1b Is CH 2 -cyclopropyl, R 1a Is H, R 3 Is CH 3 And Q is as defined in table Z.
Table A-1888 compounds A-188.001 to A-188.008 of the formula I-A are provided, wherein Ax is N, S 1 Is Cl, S 2 Is CF (CF) 3 ，R 1b Is CH 2 -cyclopropyl, R 1a Is CH 3 ，R 3 Is CH 3 And Q is as defined in table Z.
Tables A-1898 compounds A-189.001 to A-189.008 of the formula I-A are provided, wherein Ax is N, S 1 Is Cl, S 2 Is CF (CF) 3 ，R 1b Is CH 2 -cyclopropyl, R 1a Is CH 2 -cyclopropyl, R 3 Is CH 3 And Q is as defined in table Z.
Tables A-1908 compounds A-190.001 to A-190.008 of the formula I-A are provided, wherein Ax is N, S 1 Is Br, S 2 Is Cl, R 1b Is H, R 1a Is H, R 3 Is CH 3 And Q is as defined in table Z.
Tables A-191 8 compounds A-191.001 to A-191.008 of the formula I-A are provided, wherein Ax is N, S 1 Is Br, S 2 Is Cl, R 1b Is H, R 1a Is CH 3 ，R 3 Is CH 3 And Q is as defined in table Z.
Tables A-1928 compounds A-192.001 to A-192.008 of the formula I-A are provided, wherein Ax is N, S 1 Is Br, S 2 Is Cl, R 1b Is H, R 1a Is CH 2 -cyclopropyl, R 3 Is CH 3 And Q is as defined in table Z.
Table A-1938 compounds A-193.001 to A-193.008 of the formula I-A are provided, wherein Ax is N, S 1 Is Br, S 2 Is Cl, R 1b Is CH 3 ，R 1a Is H, R 3 Is CH 3 And Q is as defined in table Z.
Tables A-1948 compounds A-194.001 to A-194.008 of the formula I-A are provided, wherein Ax is N, S 1 Is Br, S 2 Is Cl, R 1b Is CH 3 ，R 1a Is CH 3 ，R 3 Is CH 3 And Q is as defined in table Z.
Tables A-1958 compounds A-195.001 to A-195.008 of the formula I-A are provided, wherein Ax is N, S 1 Is Br, S 2 Is Cl, R 1b Is CH 3 ，R 1a Is CH 2 -cyclopropyl, R 3 Is CH 3 And Q is as defined in table Z.
Table A-1968 compounds A-196.001 to A-196.008 of the formula I-A are provided, wherein Ax is N, S 1 Is Br, S 2 Is Cl, R 1b Is CH 2 -cyclopropyl, R 1a Is H, R 3 Is CH 3 And Q is as defined in table Z.
Tables A-1978 compounds A-197.001 to A-197.008 of the formula I-A are provided, wherein Ax is N, S 1 Is Br, S 2 Is Cl, R 1b Is CH 2 -cyclopropyl, R 1a Is CH 3 ，R 3 Is CH 3 And Q is as defined in table Z.
Tables A-1988 compounds A-198.001 to A-198.008 of the formula I-A are provided, wherein Ax is N, S 1 Is Br, S 2 Is Cl, R 1b Is CH 2 -cyclopropyl, R 1a Is CH 2 -cyclopropyl, R 3 Is CH 3 And Q is as defined in table Z.
Tables A-1998 compounds A-199.001 to A-199.008 of the formula I-A are provided, wherein Ax is N, S 1 Is Br, S 2 Is Br, R 1b Is H, R 1a Is H, R 3 Is CH 3 And Q is as defined in table Z.
Tables A-2008 compounds A-200.001 to A-200.008 of the formula I-A are provided, wherein Ax is N, S 1 Is Br, S 2 Is Br, R 1b Is H, R 1a Is CH 3 ，R 3 Is CH 3 And Q is as defined in table Z.
Table A-2018 compounds A-201.001 to A-201.008 of the formula I-A are provided, wherein Ax is N, S 1 Is Br, S 2 Is Br, R 1b Is H, R 1a Is CH 2 -cyclopropyl, R 3 Is CH 3 And Q is as defined in table Z.
Table A-2028 compounds A-202.001 to A-202.008 of the formula I-A are provided, wherein Ax is N, S 1 Is Br, S 2 Is Br, R 1b Is CH 3 ，R 1a Is H, R 3 Is CH 3 And Q is as defined in table Z.
Tables A-2038 compounds A-203.0 having the formula I-A are provided01 to A-203.008, wherein Ax is N, S 1 Is Br, S 2 Is Br, R 1b Is CH 3 ，R 1a Is CH 3 ，R 3 Is CH 3 And Q is as defined in table Z.
Tables A-2048 compounds A-204.001 to A-204.008 of the formula I-A are provided, wherein Ax is N, S 1 Is Br, S 2 Is Br, R 1b Is CH 3 ，R 1a Is CH 2 -cyclopropyl, R 3 Is CH 3 And Q is as defined in table Z.
Tables A-2058 compounds A-205.001 to A-205.008 of the formula I-A are provided, wherein Ax is N, S 1 Is Br, S 2 Is Br, R 1b Is CH 2 -cyclopropyl, R 1a Is H, R 3 Is CH 3 And Q is as defined in table Z.
Tables A-2068 compounds A-206.001 to A-206.008 of the formula I-A are provided, wherein Ax is N, S 1 Is Br, S 2 Is Br, R 1b Is CH 2 -cyclopropyl, R 1a Is CH 3 ，R 3 Is CH 3 And Q is as defined in table Z.
Tables A-2078 compounds A-207.001 to A-207.008 of the formula I-A are provided, wherein Ax is N, S 1 Is Br, S 2 Is Br, R 1b Is CH 2 -cyclopropyl, R 1a Is CH 2 -cyclopropyl, R 3 Is CH 3 And Q is as defined in table Z.
Tables A-2088 compounds A-208.001 to A-208.008 of the formula I-A are provided, wherein Ax is N, S 1 Is Br, S 2 Is CF (CF) 3 ，R 1b Is H, R 1a Is H, R 3 Is CH 3 And Q is as defined in table Z.
Table A-2098 compounds A-209.001 to A-209.008 of the formula I-A are provided, wherein Ax is N, S 1 Is Br, S 2 Is CF (CF) 3 ，R 1b Is H, R 1a Is CH 3 ，R 3 Is CH 3 And Q is as defined in table Z.
Tables A-2108 compounds A-210.001 to A-210.008 of the formula I-A are provided, wherein Ax is N, S 1 Is Br, S 2 Is CF (CF) 3 ，R 1b Is H, R 1a Is CH 2 -cyclopropyl, R 3 Is CH 3 And Q is as defined in table Z.
Tables A-2118 compounds A-211.001 to A-211.008 of the formula I-A are provided, wherein Ax is N, S 1 Is Br, S 2 Is CF (CF) 3 ，R 1b Is CH 3 ，R 1a Is H, R 3 Is CH 3 And Q is as defined in table Z.
Tables A-2128 compounds A-212.001 to A-212.008 of the formula I-A are provided, wherein Ax is N, S 1 Is Br, S 2 Is CF (CF) 3 ，R 1b Is CH 3 ，R 1a Is CH 3 ，R 3 Is CH 3 And Q is as defined in table Z.
Table A-2138 compounds A-213.001 to A-213.008 of the formula I-A are provided, wherein Ax is N, S 1 Is Br, S 2 Is CF (CF) 3 ，R 1b Is CH 3 ，R 1a Is CH 2 -cyclopropyl, R 3 Is CH 3 And Q is as defined in table Z.
Table A-2148 compounds A-214.001 to A-214.008 of the formula I-A are provided, wherein Ax is N, S 1 Is Br, S 2 Is CF (CF) 3 ，R 1b Is CH 2 -cyclopropyl, R 1a Is H, R 3 Is CH 3 And Q is as defined in table Z.
Tables A-2158 compounds A-215.001 to A-215.008 of the formula I-A are provided, wherein Ax is N, S 1 Is Br, S 2 Is CF (CF) 3 ，R 1b Is CH 2 -cyclopropyl, R 1a Is CH 3 ，R 3 Is CH 3 And Q is as defined in table Z.
Tables A-216Provides 8 kinds of toolsCompounds of the formulae A-216.001 to A-216.008, in which Ax is N, S 1 Is Br, S 2 Is CF (CF) 3 ，R 1b Is CH 2 -cyclopropyl, R 1a Is CH 2 -cyclopropyl, R 3 Is CH 3 And Q is as defined in table Z.
Tables A-2178 compounds A-217.001 to A-217.008 of the formula I-A are provided, wherein Ax is N, S 1 Is CF (CF) 3 ，S 2 Is Cl, R 1b Is H, R 1a Is H, R 3 Is CH 3 And Q is as defined in table Z.
Tables A-2188 compounds A-218.001 to A-218.008 of the formula I-A are provided, wherein Ax is N, S 1 Is CF (CF) 3 ，S 2 Is Cl, R 1b Is H, R 1a Is CH 3 ，R 3 Is CH 3 And Q is as defined in table Z.
Table A-2198 compounds A-219.001 to A-219.008 of the formula I-A are provided, wherein Ax is N, S 1 Is CF (CF) 3 ，S 2 Is Cl, R 1b Is H, R 1a Is CH 2 -cyclopropyl, R 3 Is CH 3 And Q is as defined in table Z.
Tables A-2208 compounds A-220.001 to A-220.008 of the formula I-A are provided, wherein Ax is N, S 1 Is CF (CF) 3 ，S 2 Is Cl, R 1b Is CH 3 ，R 1a Is H, R 3 Is CH 3 And Q is as defined in table Z.
Table A-2218 compounds A-221.001 to A-221.008 of the formula I-A are provided, wherein Ax is N, S 1 Is CF (CF) 3 ，S 2 Is Cl, R 1b Is CH 3 ，R 1a Is CH 3 ，R 3 Is CH 3 And Q is as defined in table Z.
Tables A-2228 compounds A-222.001 to A-222.008 of the formula I-A are provided, wherein Ax is N, S 1 Is CF (CF) 3 ，S 2 Is Cl, R 1b Is CH 3 ，R 1a Is CH 2 -cyclopropyl, R 3 Is CH 3 And Q is as defined in table Z.
Tables A-2238 compounds A-223.001 to A-223.008 of the formula I-A are provided, wherein Ax is N, S 1 Is CF (CF) 3 ，S 2 Is Cl, R 1b Is CH 2 -cyclopropyl, R 1a Is H, R 3 Is CH 3 And Q is as defined in table Z.
Tables A-2248 compounds A-224.001 to A-224.008 of the formula I-A are provided, wherein Ax is N, S 1 Is CF (CF) 3 ，S 2 Is Cl, R 1b Is CH 2 -cyclopropyl, R 1a Is CH 3 ，R 3 Is CH 3 And Q is as defined in table Z.
Table A-2258 compounds A-225.001 to A-225.008 of the formula I-A are provided, wherein Ax is N, S 1 Is CF (CF) 3 ，S 2 Is Cl, R 1b Is CH 2 -cyclopropyl, R 1a Is CH 2 -cyclopropyl, R 3 Is CH 3 And Q is as defined in table Z.
Tables A-2268 compounds A-226.001 to A-226.008 of the formula I-A are provided, wherein Ax is N, S 1 Is CF (CF) 3 ，S 2 Is Br, R 1b Is H, R 1a Is H, R 3 Is CH 3 And Q is as defined in table Z.
Table A-2278 compounds A-227.001 to A-227.008 of the formula I-A are provided, wherein Ax is N, S 1 Is CF (CF) 3 ，S 2 Is Br, R 1b Is H, R 1a Is CH 3 ，R 3 Is CH 3 And Q is as defined in table Z.
Tables A-2288 compounds A-228.001 to A-228.008 of the formula I-A are provided, wherein Ax is N, S 1 Is CF (CF) 3 ，S 2 Is Br, R 1b Is H, R 1a Is CH 2 -cyclopropyl, R 3 Is CH 3 And Q is as defined in table Z.
Table A-2298 compounds A-229.001 to A-229.008 of the formula I-A are provided, wherein Ax is N, S 1 Is CF (CF) 3 ，S 2 Is Br, R 1b Is CH 3 ，R 1a Is H, R 3 Is CH 3 And Q is as defined in table Z.
Tables A-2308 compounds A-230.001 to A-230.008 of the formula I-A are provided, wherein Ax is N, S 1 Is CF (CF) 3 ，S 2 Is Br, R 1b Is CH 3 ，R 1a Is CH 3 ，R 3 Is CH 3 And Q is as defined in table Z.
Table A-2318 compounds A-231.001 to A-231.008 of the formula I-A are provided, wherein Ax is N, S 1 Is CF (CF) 3 ，S 2 Is Br, R 1b Is CH 3 ，R 1a Is CH 2 -cyclopropyl, R 3 Is CH 3 And Q is as defined in table Z.
Tables A-2328 compounds A-232.001 to A-232.008 of the formula I-A are provided, wherein Ax is N, S 1 Is CF (CF) 3 ，S 2 Is Br, R 1b Is CH 2 -cyclopropyl, R 1a Is H, R 3 Is CH 3 And Q is as defined in table Z.
Tables A-2338 compounds A-233.001 to A-233.008 of the formula I-A are provided, wherein Ax is N, S 1 Is CF (CF) 3 ，S 2 Is Br, R 1b Is CH 2 -cyclopropyl, R 1a Is CH 3 ，R 3 Is CH 3 And Q is as defined in table Z.
Table A-2348 compounds A-234.001 to A-234.008 of the formula I-A are provided, wherein Ax is N, S 1 Is CF (CF) 3 ，S 2 Is Br, R 1b Is CH 2 -cyclopropyl, R 1a Is CH 2 -cyclopropyl, R 3 Is CH 3 And Q is as defined in table Z.
Tables A-2358 compounds A-235.001 to A-235.00 of the formula I-A are provided8, wherein Ax is N, S 1 Is CF (CF) 3 ，S 2 Is CF (CF) 3 ，R 1b Is H, R 1a Is H, R 3 Is CH 3 And Q is as defined in table Z.
Tables A-2368 compounds A-236.001 to A-236.008 of the formula I-A are provided, wherein Ax is N, S 1 Is CF (CF) 3 ，S 2 Is CF (CF) 3 ，R 1b Is H, R 1a Is CH 3 ，R 3 Is CH 3 And Q is as defined in table Z.
Table A-2378 compounds A-237.001 to A-237.008 of the formula I-A are provided, wherein Ax is N, S 1 Is CF (CF) 3 ，S 2 Is CF (CF) 3 ，R 1b Is H, R 1a Is CH 2 -cyclopropyl, R 3 Is CH 3 And Q is as defined in table Z.
Tables A-2388 compounds A-238.001 to A-238.008 of the formula I-A are provided, wherein Ax is N, S 1 Is CF (CF) 3 ，S 2 Is CF (CF) 3 ，R 1b Is CH 3 ，R 1a Is H, R 3 Is CH 3 And Q is as defined in table Z.
Table A-2398 compounds A-239.001 to A-239.008 of the formula I-A are provided, wherein Ax is N, S 1 Is CF (CF) 3 ，S 2 Is CF (CF) 3 ，R 1b Is CH 3 ，R 1a Is CH 3 ，R 3 Is CH 3 And Q is as defined in table Z.
Tables A-2408 compounds A-240.001 to A-240.008 of the formula I-A are provided, wherein Ax is N, S 1 Is CF (CF) 3 ，S 2 Is CF (CF) 3 ，R 1b Is CH 3 ，R 1a Is CH 2 -cyclopropyl, R 3 Is CH 3 And Q is as defined in table Z.
Table A-2418 compounds A-241.001 to A-241.008 of the formula I-A are provided, wherein Ax is N, S 1 Is CF (CF) 3 ，S 2 Is CF (CF) 3 ，R 1b Is CH 2 -cyclopropyl, R 1a Is H, R 3 Is CH 3 And Q is as defined in table Z.
Tables A-2428 compounds A-242.001 to A-242.008 of the formula I-A are provided, wherein Ax is N, S 1 Is CF (CF) 3 ，S 2 Is CF (CF) 3 ，R 1b Is CH 2 -cyclopropyl, R 1a Is CH 3 ，R 3 Is CH 3 And Q is as defined in table Z.
Tables A-2438 compounds A-243.001 to A-243.008 of the formula I-A are provided, wherein Ax is N, S 1 Is CF (CF) 3 ，S 2 Is CF (CF) 3 ，R 1b Is CH 2 -cyclopropyl, R 1a Is CH 2 -cyclopropyl, R 3 Is CH 3 And Q is as defined in table Z.
The compounds of formula I-B according to tables B-1 to B-81 below can be prepared according to the methods described above. The examples which follow are intended to illustrate the invention and show preferred compounds of formula I (in the form of compounds of formula I-B).
Table B-18 compounds B-1.001 to B-1.008 of the formula I-B are provided, wherein A x Is C-O-CF 2 CF 2 H，S 1 Is Cl, S 2 Is Cl, W is a direct bond, R 3 Is CH 3 And Q is as defined in table Z.
Table B-28 compounds B-2.001 to B-2.008 of the formula I-B are provided, wherein A x Is C-O-CF 2 CF 2 H，S 1 Is Cl, S 2 Is Cl, W is CH 2 ，R 3 Is CH 3 And Q is as defined in table Z. For example, B-2.002 and B-2.003 are:
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table B-38 compounds B-3.001 to B-3.008 of the formula I-B are provided, wherein A x Is C-O-CF 2 CF 2 H，S 1 Is Cl, S 2 Is Cl, W is O, R 3 Is CH 3 And Q is as defined in table Z.
Table B-48 compounds B-4.001 to B-4.008 of the formula I-B are provided, wherein A x Is C-O-CF 2 CF 2 H，S 1 Is Cl, S 2 Is Br, W is a direct bond, R 3 Is CH 3 And Q is as defined in table Z.
Table B-58 compounds B-5.001 to B-5.008 of the formula I-B are provided, wherein A x Is C-O-CF 2 CF 2 H，S 1 Is Cl, S 2 Is Br, W is CH 2 ，R 3 Is CH 3 And Q is as defined in table Z.
Table B-68 compounds B-6.001 to B-6.008 of the formula I-B are provided, wherein A x Is C-O-CF 2 CF 2 H，S 1 Is Cl, S 2 Is Br, W is O, R 3 Is CH 3 And Q is as defined in table Z.
Table B-78 compounds B-7.001 to B-7.008 of the formula I-B are provided, wherein A x Is C-O-CF 2 CF 2 H，S 1 Is Cl, S 2 Is CF (CF) 3 W is a direct bond, R 3 Is CH 3 And Q is as defined in table Z.
Table B-88 compounds B-8.001 to B-8.008 of the formula I-B are provided, wherein A x Is C-O-CF 2 CF 2 H，S 1 Is Cl, S 2 Is CF (CF) 3 W is CH 2 ，R 3 Is CH 3 And Q is as defined in table Z.
Table B-98 compounds B-9.001 to B-9.008 of the formula I-B are provided, wherein A x Is C-O-CF 2 CF 2 H，S 1 Is Cl, S 2 Is CF (CF) 3 W is O，R 3 Is CH 3 And Q is as defined in table Z.
Table B-108 compounds B-10.001 to B-10.008 of the formula I-B are provided, wherein A x Is C-O-CF 2 CF 2 H，S 1 Is Br, S 2 Is Cl, W is a direct bond, R 3 Is CH 3 And Q is as defined in table Z.
Table B-118 compounds B-11.001 to B-11.008 of the formula I-B are provided, wherein A x Is C-O-CF 2 CF 2 H，S 1 Is Br, S 2 Is Cl, W is CH 2 ，R 3 Is CH 3 And Q is as defined in table Z.
Table B-128 compounds B-12.001 to B-12.008 of the formula I-B are provided, wherein A x Is C-O-CF 2 CF 2 H，S 1 Is Br, S 2 Is Cl, W is O, R 3 Is CH 3 And Q is as defined in table Z.
Table B-138 compounds B-13.001 to B-13.008 of the formula I-B are provided, wherein A x Is C-O-CF 2 CF 2 H，S 1 Is Br, S 2 Is Br, W is a direct bond, R 3 Is CH 3 And Q is as defined in table Z.
Table B-148 compounds B-14.001 to B-14.008 of the formula I-B are provided, wherein A x Is C-O-CF 2 CF 2 H，S 1 Is Br, S 2 Is Br, W is CH 2 ，R 3 Is CH 3 And Q is as defined in table Z.
Table B-158 compounds B-15.001 to B-15.008 of the formula I-B are provided, wherein A x Is C-O-CF 2 CF 2 H，S 1 Is Br, S 2 Is Br, W is O, R 3 Is CH 3 And Q is as defined in table Z.
Table B-16 8 compounds B-16.001 to B-16.008 of the formula I-B are provided, wherein A x Is C-O-CF 2 CF 2 H，S 1 Is Br, S 2 Is CF (CF) 3 W is a direct bond, R 3 Is CH 3 And Q is as defined in table Z.
Table B-178 compounds B-17.001 to B-17.008 of the formula I-B are provided, wherein A x Is C-O-CF 2 CF 2 H，S 1 Is Br, S 2 Is CF (CF) 3 W is CH 2 ，R 3 Is CH 3 And Q is as defined in table Z.
Table B-188 compounds B-18.001 to B-18.008 of the formula I-B are provided, wherein A x Is C-O-CF 2 CF 2 H，S 1 Is Br, S 2 Is CF (CF) 3 W is O, R 3 Is CH 3 And Q is as defined in table Z.
TABLE B-198 compounds B-19.001 to B-19.008 of the formula I-B are provided, wherein A x Is C-O-CF 2 CF 2 H，S 1 Is CF (CF) 3 ，S 2 Is Cl, W is a direct bond, R 3 Is CH 3 And Q is as defined in table Z.
Table B-208 compounds B-20.001 to B-20.008 of the formula I-B are provided, wherein A x Is C-O-CF 2 CF 2 H，S 1 Is CF (CF) 3 ，S 2 Is Cl, W is CH 2 ，R 3 Is CH 3 And Q is as defined in table Z.
Table B-218 compounds B-21.001 to B-21.008 of the formula I-B are provided, wherein A x Is C-O-CF 2 CF 2 H，S 1 Is CF (CF) 3 ，S 2 Is Cl, W is O, R 3 Is CH 3 And Q is as defined in table Z.
Table B-228 compounds B-22.001 to B-22.008 of the formula I-B are provided, wherein A x Is C-O-CF 2 CF 2 H，S 1 Is CF (CF) 3 ，S 2 Is Br, W is a direct bond, R 3 Is CH 3 And Q is as defined in table Z.
Table B-23There are provided 8 compounds of formula ICompounds B-23.001 to B-23.008 of B, wherein A x Is C-O-CF 2 CF 2 H，S 1 Is CF (CF) 3 ，S 2 Is Br, W is CH 2 ，R 3 Is CH 3 And Q is as defined in table Z.
Table B-248 compounds B-24.001 to B-24.008 of the formula I-B are provided, wherein A x Is C-O-CF 2 CF 2 H，S 1 Is CF (CF) 3 ，S 2 Is Br, W is O, R 3 Is CH 3 And Q is as defined in table Z.
Table B-258 compounds B-25.001 to B-25.008 of the formula I-B are provided, wherein A x Is C-O-CF 2 CF 2 H，S 1 Is CF (CF) 3 ，S 2 Is CF (CF) 3 W is a direct bond, R 3 Is CH 3 And Q is as defined in table Z.
Table B-268 compounds B-26.001 to B-26.008 of the formula I-B are provided, wherein A x Is C-O-CF 2 CF 2 H，S 1 Is CF (CF) 3 ，S 2 Is CF (CF) 3 W is CH 2 ，R 3 Is CH 3 And Q is as defined in table Z.
Table B-278 compounds B-27.001 to B-27.008 of the formula I-B are provided, wherein A x Is C-O-CF 2 CF 2 H，S 1 Is CF (CF) 3 ，S 2 Is CF (CF) 3 W is O, R 3 Is CH 3 And Q is as defined in table Z.
Table B-288 compounds B-28.001 to B-28.008 of the formula I-B are provided, wherein A x Is C-CF 3 ，S 1 Is Cl, S 2 Is Cl, W is a direct bond, R 3 Is CH 3 And Q is as defined in table Z.
Table B-298 compounds B-29.001 to B-29.008 of the formula I-B are provided, wherein A x Is C-CF 3 ，S 1 Is Cl, S 2 Is Cl, W is CH 2 ，R 3 Is CH 3 And Q is as in Table ZAs defined.
Table B-308 compounds B-30.001 to B-30.008 of the formula I-B are provided, wherein A x Is C-CF 3 ，S 1 Is Cl, S 2 Is Cl, W is O, R 3 Is CH 3 And Q is as defined in table Z.
Table B-318 compounds B-31.001 to B-31.008 of the formula I-B are provided, wherein A x Is C-CF 3 ，S 1 Is Cl, S 2 Is Br, W is a direct bond, R 3 Is CH 3 And Q is as defined in table Z.
Table B-328 compounds B-32.001 to B-32.008 of the formula I-B are provided, wherein A x Is C-CF 3 ，S 1 Is Cl, S 2 Is Br, W is CH 2 ，R 3 Is CH 3 And Q is as defined in table Z.
Table B-338 compounds B-33.001 to B-33.008 of the formula I-B are provided, wherein A x Is C-CF 3 ，S 1 Is Cl, S 2 Is Br, W is O, R 3 Is CH 3 And Q is as defined in table Z.
Table B-348 compounds B-34.001 to B-34.008 of the formula I-B are provided, wherein A x Is C-CF 3 ，S 1 Is Cl, S 2 Is CF (CF) 3 W is a direct bond, R 3 Is CH 3 And Q is as defined in table Z.
Table B-358 compounds B-35.001 to B-35.008 of the formula I-B are provided, wherein A x Is C-CF 3 ，S 1 Is Cl, S 2 Is CF (CF) 3 W is CH 2 ，R 3 Is CH 3 And Q is as defined in table Z.
Table B-368 compounds B-36.001 to B-36.008 of the formula I-B are provided, wherein A x Is C-CF 3 ，S 1 Is Cl, S 2 Is CF (CF) 3 W is O, R 3 Is CH 3 And Q is as defined in table Z.
Table B-378 compounds B-37.001 to B-37.008 of the formula I-B are provided, wherein A x Is C-CF 3 ，S 1 Is Br, S 2 Is Cl, W is a direct bond, R 3 Is CH 3 And Q is as defined in table Z.
Table B-388 compounds B-38.001 to B-38.008 of the formula I-B are provided, wherein A x Is C-CF 3 ，S 1 Is Br, S 2 Is Cl, W is CH 2 ，R 3 Is CH 3 And Q is as defined in table Z.
Table B-398 compounds B-39.001 to B-39.008 of the formula I-B are provided, wherein A x Is C-CF 3 ，S 1 Is Br, S 2 Is Cl, W is O, R 3 Is CH 3 And Q is as defined in table Z.
Table B-408 compounds B-40.001 to B-40.008 of the formula I-B are provided, wherein A x Is C-CF 3 ，S 1 Is Br, S 2 Is Br, W is a direct bond, R 3 Is CH 3 And Q is as defined in table Z.
Table B-418 compounds B-41.001 to B-41.008 of the formula I-B are provided, wherein A x Is C-CF 3 ，S 1 Is Br, S 2 Is Br, W is CH 2 ，R 3 Is CH 3 And Q is as defined in table Z.
Table B-428 compounds B-42.001 to B-42.008 of the formula I-B are provided, wherein A x Is C-CF 3 ，S 1 Is Br, S 2 Is Br, W is O, R 3 Is CH 3 And Q is as defined in table Z.
Table B-438 compounds B-43.001 to B-43.008 of the formula I-B are provided, wherein A x Is C-CF 3 ，S 1 Is Br, S 2 Is CF (CF) 3 W is a direct bond, R 3 Is CH 3 And Q is as defined in table Z.
Table B-448 compounds B-44.001 to B-44.008 of the formula I-B are providedIn A of x Is C-CF 3 ，S 1 Is Br, S 2 Is CF (CF) 3 W is CH 2 ，R 3 Is CH 3 And Q is as defined in table Z.
Table B-458 compounds B-45.001 to B-45.008 of the formula I-B are provided, wherein A x Is C-CF 3 ，S 1 Is Br, S 2 Is CF (CF) 3 W is O, R 3 Is CH 3 And Q is as defined in table Z.
Table B-468 compounds B-46.001 to B-46.008 of the formula I-B are provided, wherein A x Is C-CF 3 ，S 1 Is CF (CF) 3 ，S 2 Is Cl, W is a direct bond, R 3 Is CH 3 And Q is as defined in table Z.
Table B-478 compounds B-47.001 to B-47.008 of the formula I-B are provided, wherein A x Is C-CF 3 ，S 1 Is CF (CF) 3 ，S 2 Is Cl, W is CH 2 ，R 3 Is CH 3 And Q is as defined in table Z.
Table B-488 compounds B-48.001 to B-48.008 of the formula I-B are provided, wherein A x Is C-CF 3 ，S 1 Is CF (CF) 3 ，S 2 Is Cl, W is O, R 3 Is CH 3 And Q is as defined in table Z.
Table B-498 compounds B-49.001 to B-49.008 of the formula I-B are provided, wherein A x Is C-CF 3 ，S 1 Is CF (CF) 3 ，S 2 Is Br, W is a direct bond, R 3 Is CH 3 And Q is as defined in table Z.
Table B-508 compounds B-50.001 to B-50.008 of the formula I-B are provided, wherein A x Is C-CF 3 ，S 1 Is CF (CF) 3 ，S 2 Is Br, W is CH 2 ，R 3 Is CH 3 And Q is as defined in table Z.
Table B-518 compounds B-51.001 to B-51.008 of the formula I-B are providedIn A of x Is C-CF 3 ，S 1 Is CF (CF) 3 ，S 2 Is Br, W is O, R 3 Is CH 3 And Q is as defined in table Z.
Table B-528 compounds B-52.001 to B-52.008 of the formula I-B are provided, wherein A x Is C-CF 3 ，S 1 Is CF (CF) 3 ，S 2 Is CF (CF) 3 W is a direct bond, R 3 Is CH 3 And Q is as defined in table Z.
Table B-538 compounds B-53.001 to B-53.008 of the formula I-B are provided, wherein A x Is C-CF 3 ，S 1 Is CF (CF) 3 ，S 2 Is CF (CF) 3 W is CH 2 ，R 3 Is CH 3 And Q is as defined in table Z.
Table B-548 compounds B-54.001 to B-54.008 of the formula I-B are provided, wherein A x Is C-CF 3 ，S 1 Is CF (CF) 3 ，S 2 Is CF (CF) 3 W is O, R 3 Is CH 3 And Q is as defined in table Z.
Table B-558 compounds B-55.001 to B-55.008 of the formula I-B are provided, wherein A x Is N, S 1 Is Cl, S 2 Is Cl, W is a direct bond, R 3 Is CH 3 And Q is as defined in table Z.
Table B-568 compounds B-56.001 to B-56.008 of the formula I-B are provided, wherein A x Is N, S 1 Is Cl, S 2 Is Cl, W is CH 2 ，R 3 Is CH 3 And Q is as defined in table Z.
Table B-578 compounds B-57.001 to B-57.008 of the formula I-B are provided, wherein A x Is N, S 1 Is Cl, S 2 Is Cl, W is O, R 3 Is CH 3 And Q is as defined in table Z.
Table B-588 compounds B-58.001 to B-58.008 of the formula I-B are provided, wherein A x Is N, S 1 Is Cl, S 2 Is Br, W is a direct bond, R 3 Is CH 3 And Q is as defined in table Z.
Table B-598 compounds B-59.001 to B-59.008 of the formula I-B are provided, wherein A x Is N, S 1 Is Cl, S 2 Is Br, W is CH 2 ，R 3 Is CH 3 And Q is as defined in table Z.
Table B-608 compounds B-60.001 to B-60.008 of the formula I-B are provided, wherein A x Is N, S 1 Is Cl, S 2 Is Br, W is O, R 3 Is CH 3 And Q is as defined in table Z.
Table B-618 compounds B-61.001 to B-61.008 of the formula I-B are provided, wherein A x Is N, S 1 Is Cl, S 2 Is CF (CF) 3 W is a direct bond, R 3 Is CH 3 And Q is as defined in table Z.
Table B-628 compounds B-62.001 to B-62.008 of the formula I-B are provided, wherein A x Is N, S 1 Is Cl, S 2 Is CF (CF) 3 W is CH 2 ，R 3 Is CH 3 And Q is as defined in table Z.
Table B-638 compounds B-63.001 to B-63.008 of the formula I-B are provided, wherein A x Is N, S 1 Is Cl, S 2 Is CF (CF) 3 W is O, R 3 Is CH 3 And Q is as defined in table Z.
Table B-648 compounds B-64.001 to B-64.008 of the formula I-B are provided, wherein A x Is N, S 1 Is Br, S 2 Is Cl, W is a direct bond, R 3 Is CH 3 And Q is as defined in table Z.
Table B-658 compounds B-65.001 to B-65.008 of the formula I-B are provided, wherein A x Is N, S 1 Is Br, S 2 Is Cl, W is CH 2 ，R 3 Is CH 3 And Q is as defined in table Z.
Table B-668 compounds B-66.001 to B-66.008 of the formula I-B are provided, wherein A x Is N, S 1 Is Br, S 2 Is Cl, W is O, R 3 Is CH 3 And Q is as defined in table Z.
Table B-678 compounds B-67.001 to B-67.008 of the formula I-B are provided, wherein A x Is N, S 1 Is Br, S 2 Is Br, W is a direct bond, R 3 Is CH 3 And Q is as defined in table Z.
Table B-688 compounds B-68.001 to B-68.008 of the formula I-B are provided, wherein A x Is N, S 1 Is Br, S 2 Is Br, W is CH 2 ，R 3 Is CH 3 And Q is as defined in table Z.
Table B-698 compounds B-69.001 to B-69.008 of the formula I-B are provided, wherein A x Is N, S 1 Is Br, S 2 Is Br, W is O, R 3 Is CH 3 And Q is as defined in table Z.
Table B-708 compounds B-70.001 to B-70.008 of the formula I-B are provided, wherein A x Is N, S 1 Is Br, S 2 Is CF (CF) 3 W is a direct bond, R 3 Is CH 3 And Q is as defined in table Z.
Table B-71 8 compounds B-71.001 to B-71.008 of the formula I-B are provided, wherein A x Is N, S 1 Is Br, S 2 Is CF (CF) 3 W is CH 2 ，R 3 Is CH 3 And Q is as defined in table Z.
Table B-728 compounds B-72.001 to B-72.008 of the formula I-B are provided, wherein A x Is N, S 1 Is Br, S 2 Is CF (CF) 3 W is O, R 3 Is CH 3 And Q is as defined in table Z.
Table B-738 compounds B-73.001 to B-73.008 of the formula I-B are provided, wherein A x Is N, S 1 Is CF (CF) 3 ，S 2 Is Cl, W is a direct bond, R 3 Is CH 3 And Q is as defined in table Z.
Table B-748 compounds B-74.001 to B-74.008 of the formula I-B are provided, wherein A x Is N, S 1 Is CF (CF) 3 ，S 2 Is Cl, W is CH 2 ，R 3 Is CH 3 And Q is as defined in table Z.
Table B-758 compounds B-75.001 to B-75.008 of the formula I-B are provided, wherein A x Is N, S 1 Is CF (CF) 3 ，S 2 Is Cl, W is O, R 3 Is CH 3 And Q is as defined in table Z.
Table B-768 compounds B-76.001 to B-76.008 of the formula I-B are provided, wherein A x Is N, S 1 Is CF (CF) 3 ，S 2 Is Br, W is a direct bond, R 3 Is CH 3 And Q is as defined in table Z.
Table B-778 compounds B-77.001 to B-77.008 of the formula I-B are provided, wherein A x Is N, S 1 Is CF (CF) 3 ，S 2 Is Br, W is CH 2 ，R 3 Is CH 3 And Q is as defined in table Z.
Table B-788 compounds B-78.001 to B-78.008 of the formula I-B are provided, wherein A x Is N, S 1 Is CF (CF) 3 ，S 2 Is Br, W is O, R 3 Is CH 3 And Q is as defined in table Z.
Table B-798 compounds B-79.001 to B-79.008 of the formula I-B are provided, wherein A x Is N, S 1 Is CF (CF) 3 ，S 2 Is CF (CF) 3 W is a direct bond, R 3 Is CH 3 And Q is as defined in table Z.
Table B-808 compounds B-80.001 to B-80.008 of the formula I-B are provided, wherein A x Is N, S 1 Is CF (CF) 3 ，S 2 Is CF (CF) 3 W is CH 2 ，R 3 Is CH 3 And Q is as defined in table Z.
Table B-818 compounds B-81.001 to B-81.008 of the formula I-B are provided, wherein A x Is N, S 1 Is CF (CF) 3 ，S 2 Is CF (CF) 3 W is O, R 3 Is CH 3 And Q is as defined in table Z.
In tables A-1 to A-243 and tables B-1 to B-81, S 1 And S is 2 Does not represent a sulfur atom.
Table Z: substituent definition of Q:
the compounds of formula I according to table X below can be prepared according to the methods described above. The following examples are intended to illustrate the invention and illustrate preferred compounds of formula I.
Table X:
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it also makes available certain intermediate compounds having the formulae III, IV, VII, XIII and XVI, some of which are novel.
For example, the number of the cells to be processed,
a compound of formula III, wherein Q is selected from Q aa To Q ag And Q ba To Q bf ，R 3 Is methyl and X is oxygen;
a compound of formula III, wherein Q is selected from Q aa To Q ag And Q ba To Q bf ，R 3 Is methyl and X is sulfur;
a compound of formula IV wherein Q is selected from Q aa To Q ag And Q ba To Q bf ，R 3 Is methyl, R 1a Is hydrogen and X is oxygen;
a compound of formula IV wherein Q is selected from Q aa To Q ag And Q ba To Q bf ，R 3 Is methyl, R 1a Is hydrogen and X is sulfur;
a compound of formula VII wherein T is selected from the group consisting of 2, 4-bis (trifluoromethyl) phenyl, 2, 4-chloro-5- (1, 2-tetrafluoroethoxy) phenyl, 2-bromo-4-chloro-5- (trifluoromethyl) phenyl, 4-bromo-2- (difluoromethoxy) -5-fluoro-phenyl, 2-bromo-4- (difluoromethoxy) phenyl, 2-iodo-4- (trifluoromethyl) phenyl, 3, 5-bis (trifluoromethyl) phenyl, 2-chloro-4- (trifluoromethyl) phenyl, 4-chloro-2- (trifluoromethyl) phenyl, 2, 4-dibromophenyl, 5-chloro-2- (trifluoromethyl) phenyl, 2-chloro-5- (trifluoromethyl) phenyl, 4-chloro-3- (trifluoromethyl) phenyl, 3-chloro-4- (trifluoromethyl) phenyl, 4-chloro-5-cyano-2-fluoro-phenyl, 2-methyl-4- (trifluoromethyl) phenyl, 4-chloro-6- (trifluoromethyl) -3-pyridinyl, 4-bromo-6-trifluoromethyl) -pyridinyl, 3-bromo-3- (trifluoromethyl) -pyridinyl, 3-bromo-3-pyridinyl, 3-trifluoromethyl-pyridinyl 4-methoxy-6- (trifluoromethyl) -3-pyridinyl, 3-chloro-5- (trifluoromethyl) -2-pyridinyl, 5-chloro-4- (trifluoromethyl) thiazol-2-yl, 4-methyl-6- (trifluoromethyl) -3-pyridinyl and 4-methoxy-6- (trifluoromethyl) -3-pyridinyl, R1b is hydrogen and X is oxygen;
A compound of formula VII wherein T is selected from the group consisting of 2, 4-bis (trifluoromethyl) phenyl, 2, 4-chloro-5- (1, 2-tetrafluoroethoxy) phenyl, 2-bromo-4-chloro-5- (trifluoromethyl) phenyl, 4-bromo-2- (difluoromethoxy) -5-fluoro-phenyl, 2-bromo-4- (difluoromethoxy) phenyl, 2-iodo-4- (trifluoromethyl) phenyl, 3, 5-bis (trifluoromethyl) phenyl, 2-chloro-4- (trifluoromethyl) phenyl, 4-chloro-2- (trifluoromethyl) phenyl, 2, 4-dibromophenyl, 5-chloro-2- (trifluoromethyl) phenyl, 2-chloro-5- (trifluoromethyl) phenyl, 4-chloro-3- (trifluoromethyl) phenyl, 3-chloro-4- (trifluoromethyl) phenyl, 4-chloro-5-cyano-2-fluoro-phenyl, 2-methyl-4- (trifluoromethyl) phenyl, 4-chloro-6- (trifluoromethyl) -3-pyridinyl, 4-bromo-6-trifluoromethyl) -pyridinyl, 3-bromo-3- (trifluoromethyl) -pyridinyl, 3-bromo-3-pyridinyl, 3-trifluoromethyl-pyridinyl 4-methoxy-6- (trifluoromethyl) -3-pyridinyl, 3-chloro-5- (trifluoromethyl) -2-pyridinyl, 5-chloro-4- (trifluoromethyl) thiazol-2-yl, 4-methyl-6- (trifluoromethyl) -3-pyridinyl and 4-methoxy-6- (trifluoromethyl) -3-pyridinyl, R1b is hydrogen and X is sulfur; and
compounds of the formula XIII or of the formula XVI in which R 3 Is methyl and T is selected from the group consisting of 2, 4-bis (trifluoromethyl) phenyl, 2, 4-chloro-5- (1, 2-tetrafluoroethoxy) phenyl, 2-bromo-4-chloro-5- (trifluoromethyl) phenyl, 4-bromo-2- (difluoromethoxy) -5-fluoro-phenyl, 2-bromo-4- (difluoromethoxy) phenyl, 2-iodo-4- (trifluoromethyl) phenyl, 3, 5-bis (trifluoromethyl) phenyl, 2-chloro-4- (trifluoromethyl) phenyl, 4-chloro-2- (trifluoromethyl) phenyl, 2, 4-dibromophenyl, 5-chloro-2- (trifluoromethyl) phenyl, 2-chloro-5- (trifluoromethyl) phenyl, 4-chloro-3- (trifluoromethyl) phenyl, 3-chloro-4- (trifluoromethyl) phenyl, 4-chloro-5-cyano-2-fluoro-phenyl, 2-methyl-4- (trifluoromethyl) phenyl, 4-chloro-6- (trifluoromethyl) pyridinyl, 4, 6-bromo-3-bromo-6- (trifluoromethyl) pyridinyl, 3-bromo-6-methyl-3- (trifluoromethyl) pyridinyl, 3-bromo-6-pyridinyl, 3-methyl-3- (trifluoromethyl) phenyl and 3-chloro-4- (trifluoromethyl) phenyl 4-methoxy-6- (trifluoromethyl) -3-pyridinyl, 3-chloro-5- (trifluoromethyl) -2-pyridinyl, 5-chloro-4- (trifluoromethyl) thiazol-2-yl, 4-methyl-6- (trifluoromethyl) -3-pyridinyl and 4-methoxy-6- (trifluoromethyl) -3-pyridinyl.
In a further aspect, the invention accordingly makes available compounds of the formulae III, IV, VII, XIII and XVI, where in each case, where appropriate, X is sulfur or oxygen, R 1a 、R 1b 、R 3 Q and T are as defined for formula I in the first aspect. Furthermore, the corresponding embodiments shown for formula I are also applicable to those having formulas III, IV, VII, XIII and XVIA compound.
The compounds of formula I according to the invention are active ingredients of prophylactic and/or therapeutic value in the field of pest control, even at low application rates, they have a very favourable biocidal spectrum and are well tolerated by warm-blooded species, fish and plants. These active ingredients according to the invention act on all or individual developmental stages of normally sensitive and also resistant animal pests, such as insects or representatives of the order acarina. The insecticidal or acaricidal activity of the active ingredient according to the invention can manifest itself directly, i.e. the destruction of the pest occurs immediately or only after some time has elapsed (for example during molting); or indirectly, e.g., reducing spawning and/or hatching rate.
Examples of animal pests mentioned above are:
From the order Acarina, e.g.
The species of the genus goiter (Acalitus spp.), the species of the genus goiter (Aculus spp.), the species of the genus goiter (Acaricalus spp.), the species of the genus goiter (Aceria spp.), the species of the genus goiter (agarus siro), the species of the genus amblyphagus (amblyoma spp.), the species of the genus sharp-edged tick (Argas spp.), the species of the genus bovinus (Boophilus spp.), the species of the genus brevipus (brevipus spp.), the species of the genus sedge (bryobala spp), the species of the genus goiter (Calipitrimerus spp.), the species of the genus dermatophagoides (chord spp.), the species of the genus gallipot (Dermanyssus gallinae), the species of the genus epidermides (Dermatophagoides spp), the species of the genus goiter (Eotetranychus spp), the species of the genus goiter (eriopos spp.) half-tarsonemus species (Hemitarsonemus spp), phophagous species (Hyalomma spp.), hard tick species (Ixodes spp.), white-bristletail species (olygonichus spp), blunt-edge tick species (orthiodoros spp.), side-tarsonemus dorsi (Polyphagotarsone latus), panonychus species (Panonychus spp.), citrus brassica spp (Phyllocoptruta oleivora) plant mite species (Phytonemus spp.), phytophagus species (Polyphagotarsonemus spp), ixophagus species (Psorophtes spp.), rhipicephalus species (Rhipicephalus spp.), rhizoglyphus spp.), sarcopsis species (sarcophagus spp.), tarsophagus species (Steneotarsonemus spp), tarsonemus species (Tarsonemus spp.);
From the order of the lice, e.g.
The species of the genus sanguinea (haematoplus spp.), the species of the genus ulna (lingnathus spp.), the species of the genus Pediculus (Pediculus spp.), the species of the genus gomphrena (pepphigus spp.), and the species of the genus rhizobium (Phylloxera spp.);
from the order Coleoptera, e.g.
The species of kowtow (agriosphaera spp.), delphinium (Amphimallon majale), isophthys orientalis (Anomala orientalis), rhododendron (Anthonomus spp.), rhododendron (Aphodius spp), corn pseudoflower (Astylus atromaculatus), chafer (ataenus spp), beet cryptophaga (Atomaria linearis), beet shank flea (Chaetocnema tibialis), fluorima spp, amethyst (Conoderus spp), root neck spp, tortoise (cotinida), curculia spp, rhinococci sp, dermestoides spp, dipterex spp Argentina (Diloboderus abderus), pachyrhizus species (Epilochna spp.), eremus species, heidelaevis (Heteronychus arator), coffea minor (Hypothenemus hampei), lagria vilosa, solanum tuberosum (Leptinotarsa decemlineata), oryza species (Lisorhaponticus spp.), liogenys species, maecoaspis species, castanea (Maladera castanea), america species (Megascleis spp), rhizopus jalapas spp (Melighetes aeneus), pleuropus javensis spp (Melolochia spp), myochrous armatus, orycaeus spp, coral image species (Onagichos spp), phytophaga spp, phragon species (Philiops spp), philippia spp, the species of scarab (Popilia spp.), flea beetle (Psylliodes spp.), rhyssomatus aubtilis, rhizopus robberus (Rhizopertha spp.), scarabaeidae (Scarabidae), michelia (Sitophilus spp.), fagopsis (Sitotroga spp.), pseudocercospora (Somaticus spp.), cryptosporidium, glycine max (Sternechus subsignatus), pachyrhizus (Tenebrio spp.), tribolium spp;
From the order diptera, e.g.
Aedes species (Aedes spp.), anopheles species (Anopheles spp), sorghum mosquitos (Anopheles spp), olive fruit flies (bacteriocea) garden Mao Wen (bishoutulus), bradysia species (Bradysia spp.), red head flies (Calliphora erythrocephala), bactrocera species (cermetis spp.), chrysomyia species (Chrysomyia spp), culex species (Culex spp), huang Ying species (cutebra spp), oligochaeta species (Dacus spp), geotrichia species (Delia spp), drosophila melanogaster (drosophila melanogaster), toilet species (Fannia spp), gaster species (gasphagus spp), geomyza tripunctata @, 32 gloiopsis species (Glossina spp.), dermatophagoides species (Hypoderma spp.), luppoca species (hypobosaspp.), liriomyza spp.), green copperus species (Lucilia spp.), black copperus species (melamagromyza spp.), family copperus species (Musca spp.), rabies copperus species (Oestrus spp.), gall copperus species (oscillola spp.), swedish wheat straw fly (oscila flit), chenopodium (Pegomyia hyoscyami), tsetse species (phtbia spp.), round copperus species (rhagoetis spp.), rivelia quadrifasciata, scatopla species, scatela spp, scatica spp.), stingy species (Sciara spp.), stingy cop spp, st cop species (Stomox spp.), gall cop spp A taenia species (Tannia spp.);
From the order hemiptera, e.g.
Oncorhynchus (Acanthocoris scabrator), apostigma species (Acrosternum spp), apostigma lucorum (Adelphocoris lineolatus), aleurodes species, apostigma turcicum (Amblypelta nitida), apostigma glabra (Bathycoelia thalassina), apostigma species, ainsus species, clavigralla tomentosicollis, apostigma species (Cronetades spp.), theobroma cacao, dichelops furcatus, lepidus species, edessa spp, america species (Eunchistus spp.), hexalygus (Eurydema pulchrum), aleurodes species, theobroma sinensis, theobroma fumarus (Horcias nobilellus), alternus maculatus the plant species may be selected from the group consisting of a plant bug species, lygus species, tropical lygus species, cabbage plant bug (Murgantia histrionic), neo-lygus species, lygus lucorum (Nesidiocoris tenuis), lygus species, lygus lucorum (Nysius simuns), lygus salvinus, lygus species, lygus erythropolis species, theobroma, lygus lucorum (Scaptocoris castanea), black plant bug species (scotinopyhara spp.), thyantra species, trypanosoma species, tapioca (vactaga ilden);
alternaria pinnata (Acyrthosium pisum), adalges species, agalliana ensigera, talargevein psylla, aleyrodids species (Aleurodicus spp.), aleyrodids species (Aleuroculus spp.), saccharum officinarum, aleurodes fumosoroseus (Aleurothrixus floccosus), aleurodes brassicae (Aleyrodes brassicae), oncomelania (Amarasca biguttula), cynanchum aurantium, leptodermia species, aphididae, aphis species, verneed species (Aspidiotus spp.), alternaria sinica, solanum tuberosum/Solanum esculentum (Bactericera cockerelli), bemisia species, brevibacterium species (Brachycarpus spp.), brassica, kadsura species, pimenta biennis (Cavariella aegopodii Scop), lepidius species, gecko, orange brown, erinaceus, oncomen species, oncomelania (Cona) and Cona (Cona) plant Cryptotaenia species, ezebra species, philippia, zea mays Huang Chi Ezebra, bemisia species, citrus psyllium, mylabris, ceripola species, emotion Aphis, portugus species, gascadia species, eucalyptus rudis (Glycaspis brimblecombei), sinonotus (Hyadaphis pseudobrassicae), hyalopsis species (Hyalopterus spp.), ultrafrica species (Hyperomyzus pallidus), cyperus aurantii (Idioscopus clypealis), africa Eichhornia, ashbya species, gecko, pleurotus, raphani aphid (Lopaphia erysimi), lyogenys maidis, aphis, long tube, cicada species, ceraraceae (Metcalfa pruinosa), mylabris, myzus, nemaculata species, neotope species (Neotope), the species of the genus black leafhopper, brown planthopper (Nilaparvata spp.), green pear aphid, odonassis rutha, sugarcane cotton aphid, red bayberry leaf whitefly, psyllium coohnii, platanus species, pygeum gomphreni, corn wax cicada, delphaga species, verruca negundo, root nodule aphid (Phylloxa spp), pediococcus species, sang Baidun lecania species, lygus cotton plant bug (Pseudatomoscelis seriatus), diaphorina species, lecanii (Pulvinaria aethiopica), and combinations thereof the species of the genus Ericerus, quesada gigas, electro-optic leafhoppers (Recilia dorsalais), sinapis, hedychium, emblica, aphis, sitobion spp.), beacon plant hopper, tricopsis delphinidia (Spissistilus festinus), phaescion (Tarophagus Proserpina), aphis, bemisia, tridiscus sporoboli, gecko (Trionymus spp), african psyllium, toxocerus, toxocercus, zyginidia scutellaris;
From the order hymenoptera, e.g.
The genus acrophyllomyrmex (Acromyrmex), trichium species (range spp.), phyllomyrmen species (Atta spp.), phyllomyrtus species (Cephus spp.), melissa species (Diprionidus spp.), apriona (Gilpinia polytoma), apriona species (Hoplocalyxpa spp.), mao Yi species (Lasius spp.), yellow ant (Monomorium pharaonis), neophyllomyrtus species (neodopteran spp.), agricultural species (Pogonomomyrmem spp), red fire ants, water ant species (Solenopsis spp.), and wasp species (Vespa spp.);
from the order of Isoptera, e.g.
Coptermes spp, termites Corniternes cumulans, jacaragonis spp, macrotermes spp, australis spp, microctermes spp, rottermes spp, reticletes spp; fire ant tropical (Solenopsis geminate)
From the order Lepidoptera (Lepidoptera), for example,
the species of Philippia, spodoptera, cotton leaf worm, amylois, spodoptera, verticillium, argyrosphaera, agrocybe (Argyresthia spp.), philippia, spodoptera, cotton-leaf roller, corn earworm, pink moth, peach moth, graphoaphis, chrysosporium, cranbergii (Chrysoteuchia topiaria) the species of the genus of the panel, the species of the genus of the panel, the species of the genus of the panel of the genus panel, the genus of the panel the species of the genus Ostrinia, the species of the genus Plutella, the species of the species Plutella xylostella, the species of the species Leptoradix Tripterygii Wilfordii, the species of the species Plutella Sudana, the species of the species Spodoptera south america corn seedling borer (Elasmopalpus lignosellus), sweet potato stem borer, pink borer, leaf roller (ephotoria spp.), salt roller (Estigmene acrea), etiella zinckinella, flower roller, ring needle roller, cotton boll roller, cotton leaf, cotton Huang Due species, ceratoptera species, feltia jaculiferia, ceratoptera species (Grapholita spp.), plutella xylostella, spodoptera species, plutella xylostella, ceratoptera species, ceratoptera sedge, ceratoptera species (Herpetogmma spp.), ceratoptera species, ceratoptera petunia, ceratoptera species (Herpetogmma spp.); fall webworm, tomato moth, lasmopalpus lignosellus, leaf miner, grape wing moth, loxostege bifidalis, moth, fall webworm (Malcosoma spp.), cabbage looper, tobacco astromoth, armyworm (Mythimna spp.), noctuid, fall webworm, ornidodes indica, european corn borer, the species of the genus Phantom, the species Phantom plutella xylostella the red bell moth, the coffee leaf miner, the one-star armyworm, the potato moth, the white moth cabbage butterfly, pink butterfly, plutella, leptopetalum, mentha, rachipleusia nu cymbidium sibiricum (Richia albicosta), bai He borer species (Scirpophaga spp.), spodoptera species, cotton leaf roller, sphaerocephalus species, isotopsia species, sphaerocephalus species, spodoptera frugiperda, tomato spotted fly, and vicia species;
From the order of the pileata (Mallophaga), for example,
beasts species (Damalinea spp.) and trichomadillidium species (trichomadactes spp.);
from the order Orthoptera (Orthoptera), for example,
a Periplaneta species (Blatta spp.), a Periplaneta species (blattalla spp.), a mole cricket species (grylotalpa spp.), a madagago (Leucophaea maderae), a migratory locust species (Locusta spp.), north cricket (Neocurtilla hexadactyla), a Periplaneta species (Periplaneta spp.), a nevus cricket species (Scapteriscus spp.), and a desert locust species (Schistocerca spp.);
from the order of the rodentia (pseudoaltera), for example,
a species of the genus bezoa (Liposcelis spp.);
from the order of the fleas (Siphonaptera), for example,
a flea species (Ceratophyllus spp.), a Ctenocephalides spp, a queen flea (Xenopsylla cheopis);
from the order Thysanoptera (Thysanoptera), for example,
calliothrips phaseoli a Frankliniella species (Frankliniella spp.), a Frankliniella species (Heliothrips spp), a brown ribbon Thrips species (hercothrips spp.), a uniparent Thrips species (Parthenothrips spp.), a citrus reticulum (Scirtothrips aurantii), a soybean Thrips (Sericothrips variabilis), a ribbon Thrips species (Taeniothrips spp), a Thrips species (threps spp);
From the order of the Thysanora, for example, tuna (Lepisma saccharina).
In another aspect, the invention may also relate to a method of controlling damage to plants and parts thereof by plant parasitic nematodes (endoparasitic, semi-endoparasitic and exositic nematodes), in particular plant parasitic nematodes such as root-knot nematodes (root knot nematodes), northern root-knot nematodes (Meloidogyne hapla), southern root-knot nematodes (Meloidogyne incognita), javaroot-knot nematodes (Meloidogyne javanica), arachnids (Meloidogyne arenaria) and other root-knot nematode species; cyst forming nematodes (cyst-forming nematodes), golden-potato nematodes (Globodera rostochiensis), and other species of the genus saccharis (Globodera); cereal cyst nematodes (Heterodera avenae), soybean cyst nematodes (Heterodera glycines), beet cyst nematodes (Heterodera schachtii), heterodera rubra (Heterodera trifolii), and other Heterodera species; goiter species (Seed gall nematodes), caenorhabditis species (Anguina); stem and leaf nematodes (Stem and foliar nematodes), aphelenchoides (Aphelenchoides) species; trichina (Sting nemades), long tail nematodes (Belonolaimus longicaudatus) and other trichina (Belonolaimus) species; pine nematodes (Pine nemades), pine nematodes (Bursaphelenchus xylophilus) and other Bursaphelenchus (Bursaphelenchus) species; a species of the genus strongylus (Ring nematodes), a species of the genus strongylus (crimonema), a species of the genus strongylus (crimonemella), a species of the genus strongylus (crimonemeides), a species of the genus strongylus (mesomonema); stem and caenorhabditis elegans (Stem and bulb nematodes), rotting stem nematodes (Ditylenchus destructor), caenorhabditis elegans (Ditylenchus dipsaci) and other stem nematode (Ditylenchus) species; a Willonema (Awl nematodos), conus (Dolichodorus) species; spiralis (Spiral nematodes), multi-headed spiralis (Heliocotylenchus multicinctus), and other spiralis (spiralyenchus) species; sheath and sheath nematodes (Sheath and sheathoid nematodes), sheath nematode (hemacyclora) species and hemiwheel nematode (hemcicontoides) species; a submerged root nematode (hirschmanniella) species; a nematode (Lance nematodes), a Corona (Hoploaimus) species; pseudoroot knot nematode (false rootknot nematodes), pearl nematode (nacobus) species; needle nematodes (Needle nematodes), long-shank nematodes (Longidorus elongatus) and other long-shank nematode (longidolus) species; a Pratylenchus species; rotten nematodes (Lesion nematoddes), pratylenchus variabilis (Pratylenchus neglectus), pratylenchus prallensis (Pratylenchus penetrans), pratylenchus curvulus (Pratylenchus curvitatus), pratylenchus colognes (Pratylenchus goodeyi) and other brachyotus species; citrus perforins (Burrowing nematodes), radopholus (Radopholus similis) and other introgressing nematode (Radopholus) species; reniform nematodes (Reniform nematodes), luo Baishi spiral nematodes (Rotylenchus robustus) reniform nematodes (Rotylenchus reniformis) and others a species of the genus stromelitemia (Rotylenchus); a scenedema (Scutellonema) species; a root-worm (Stubby root nematodes), a primitive Bursaphelenchus (Trichodorus primitivus), and other Bursaphelenchus (Trichodorus) species, a Bursaphelenchus (Paratrix dorus) species; stunting nematodes (Stunt nemades), purslane stunting nematodes (Tylenchorhynchus claytoni), cis-trans stunting nematodes (Tylenchorhynchus dubius) and other stunting nematode (tylenchormchus) species; citrus nematodes (Citrus nematodes), piercing nematode (tyrenchus) species; a species of the genus xiphides (Xiphinema); other plant parasitic nematode species, such as the subtrenia species (subunguina spp.), the root knot nematode species (hypsomycete spp.), the macrocyclic nematode species (Macroposthonia spp.), the dwarf nematode species (Melinius spp.), the point cyst species (Punctodera spp.), and the pentadactyla species (quinsulcus spp.).
The compounds of the invention also have activity against molluscs. Examples thereof include, for example, the family of Pomacea canaliculata; slug family (aris) (black slug (a. Ter), annular slug (a. Circumscript), brown brave slug (a. Hortinsis), red slug (a. Rufus)); barbaceae (Bradybaenidae) (Bush snail (Bradybaena fruticum)); spring onions (Cepaea) (garden spring onions (c.hortens), forest spring onions (c nemorolia)); ochloridina; wild slug genus (Derocera) (wild ash slug (D. Agrestis), D. Empiricorum, smooth wild slug (D. Laeve), reticulate wild slug (D. Reticum)); disc snail (Discus) (circular disc snail); euomphalia; soil snail (Galba) (kerf soil snail (g.trunk); snails (helicobacter) (itara snail (h.itala), buwei snail (h.obvia)); snail (Helicidae) Helicigona arbustorum); a helicobacter; snail (Helix) (open snail (h.aperta)); slug genus (Limax) (Li Maike slug (l. Cinereoniger), huangyu (l. Flavus), edge slug (l. Marginalis), large slug (l. Maximus), flexible slug (l. Tenellus)); the genus cone (Lymnaea); milax (minor slug family) (black minor slug (m. Gagates), edge minor slug (m. Marginalis), major minor slug (m sowerbyi)); oncomelania (Opeas); the genus conch (Pomacea) (ampullaria gigas (p.canaticum)); vanilla snail (Vallonia) and Zanitoides.
The active ingredients according to the invention can be used to control, i.e. contain or destroy, pests of the type described above, which are present in particular on plants, especially on plants and ornamental plants which are useful in agriculture, in horticulture and in forestry, or on organs of these plants, such as fruits, flowers, leaves, stems, tubers or roots, and in some cases plant organs which form even at a later point in time remain protected against these pests.
In particular, suitable target crops are cereals, such as wheat, barley, rye, oats, rice, maize or sorghum; beet, such as sugar beet or fodder beet; fruits, such as pomes, stone fruits or stone-less fruits, 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; oil crops, such as rape, mustard, poppy, olives, sunflowers, coconuts, castor beans, cocoa beans or groundnuts; melon crops, such as pumpkin, cucumber or melon; fiber plants, such as cotton, flax, hemp or jute; citrus fruits, such as orange, lemon, grapefruit or tangerine; vegetables, such as spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes or bell peppers; lauraceae, such as avocado, cinnamon or camphor; and also tobacco, nuts, coffee, eggplant, sugar cane, tea, pepper, grape vine, hops, plantain, and latex plants.
The compositions and/or methods of the present invention may also be used on any ornamental and/or vegetable crop, including flowers, shrubs, broad-leaved trees and evergreens.
For example, the invention may be used for any of the following ornamental plant species: agastache species, pseudoptera species (Alonsoa spp.), silver lotus species, south africa (Anisodontea capsenisis), chamomile species, chrysosporium species, aster species, begonia species (e.g., begonia, b. Tub reux)), phyllanthus species, yangher species (brachyosome spp.), brassica species (ornamental plant), cattail species, capsicum, vinca, cannabis species, cornflower species, chrysanthemum species, melon species (silver stevia (c. Maritimum)), chrysanthemum species, rhodiola (Crassula coccinea), red calyx flowers (Cuphea ignea), dahlia species, cudweed species, nettle, peonies, balloonflower species (gordonia) fructus forsythiae species, herba Pogostemonis species, herba Erodii murine Aspergillus (Geranium gnaphalium), herba Geranii species, flos Gomphrenae, geranium species, semen Brassicae Junceae species, helianthus species, hibiscus species, and herba Pogostemonis hydrangea species, henbane species (impatiens balsamina), acalypha species (irestines spp.), glabrous species, lantana camara, marshmallow, marjoram, and so forth lion, lily, pine, gourmet, spearmint, longicorn, marigold, carnation (carnation), canna, oxalis, bellflower, pelargonium (pelargonium scum, pelargonium elegans), viola (pansy), pansy (pansy), the plant species may be selected from the group consisting of petunia species, oleander species, bergamot species (plectranthus spp.), poinsettia species, reptile species (petunia, reptile), primula species, buttercup species, azalea species, rose species (rose), flaveria species, african cordierite species, sage species, echinacea (Scaevola aemia), mottlea flowers (Schizanthus wisetonensis), sedum species, solanum species, su Feini petunia species (Surfinia spp.), tagetes species, nicotiana species, verbena species, zinnia species, and other flower pot plants.
For example, the invention may be used with any of the following vegetable species: allium species (garlic, onion, a. Oschaninii, leek, allium sativum, allium fistulosum), fennel, celery (Apium graveolens), asparagus, beet (Beta vulgares), brassica species (cabbage, chinese cabbage, turnip), capsicum, chickpea, chicory (chicory ), watermelon, cucumis species (cucumber, melon), cucurbita species (pumpkin, squash), cynara species (cynara spp.) (artichoke, spiny), wild carrot, fennel, hypericum species, lettuce, tomato species (tomato, cherry tomato), mint species, basil, parsley, phaseolus species (beans, string beans), pea, radish, rheum officinale, rosemary species, sage species, black salon (Scorzonera hispanica), eggplant, spinach, neo species (vali et al, v.ocera).
Preferred ornamental species include African violet, begonia, dahlia, dadingcha, sparassis, verbena, rosa, kalanchoe, yifuchsin, aster, cornflower, tamarinus, taverum, cuphinia, america, nerium, flabella, crassularia, pelargonium, viola, impatientis, geranium, july, ranunculus, sage, salvia, rosmarinus, salvia, st. Johnswort, peppermint, sweet pepper (sweet peppers), tomato, and cucumber.
These active ingredients according to the invention are particularly suitable for controlling hyacinth bean aphids, cucumber leaf beetles, tobacco budworms, peach aphids, plutella xylostellas and sea ash wing noctuid on cotton, vegetable, maize, rice and soybean crops. These active ingredients according to the invention are furthermore particularly suitable for controlling cabbage loopers (preferably on vegetables), codling moths (preferably on apples), leafhoppers (preferably in vegetables, vineyards), potato leaf beetles (preferably on potatoes) and striped rice borers (preferably on rice).
Compounds having formula I are particularly suitable for control:
pests of the order hemiptera, for example one or more of the following species: bemisia tabaci (Bemisia tabaci), bean aphid, peach aphid, cereal Gu Yiguan aphid (Rhopalosiphum Padi), brown rice lice (Nilaparvata lugens), and hero's plant bug (euschistmus her) (preferably on vegetables, soybeans, and sugar cane);
pests of the order lepidoptera, for example one or more of the following species: spodoptera littoralis, spodoptera frugiperda (Spodoptera frugiperda), plutella xylostella, cnaphalocrocis medinalis (Cnaphalocrocis medinalis), codling moth, soybean looper (Chrysodeixis includes), chilo suppressalis, corn borer (Elasmopalpus lignosellus), soybean spodoptera frugiperda (Pseudoplusia includens), and tomato leaf miner (preferably on vegetables and corn);
Pests of the order thysanoptera, such as thrips, for example one or more of thrips tabaci and thistle (preferably on vegetables); and
soil pests (such as coleoptera), for example the species cucurbita pepo, the species click beetle, and potato beetles (preferably on vegetables and corn).
The term "crop" is to be understood as also including crop plants which have been so transformed by the use of recombinant DNA technology that they are capable of synthesizing one or more selectively acting toxins, such as are known, for example, from toxin-producing bacteria, especially those of the genus bacillus.
Toxins that can be expressed by such transgenic plants include, for example, insecticidal proteins, such as those from bacillus cereus or bacillus thuringiensis; or insecticidal proteins from bacillus thuringiensis, such as delta-endotoxins, e.g., cry1Ab, cry1Ac, cry1F, cry Fa2, cry2Ab, cry3A, cry Bb1 or Cry9C, or vegetative insecticidal proteins (Vip), e.g., vip1, vip2, vip3 or Vip3A; or insecticidal proteins of bacterial plant nematodes, for example, photorhabdus species (Photorhabdus spp.) or Xenorhabdus species (Xenorhabdus spp.), such as Xenorhabdus (Photorhabdus luminescens), xenorhabdus nematophilus (Xenorhabdus nematophilus); toxins produced by animals, such as scorpions, spider toxins, bee toxins, and other insect-specific neurotoxins; toxins produced by fungi, such as streptomycin, lectins (lecins), such as pea lectin, barley lectin or vanishing lotus lectin; lectin (agglutinin); protease inhibitors such as trypsin inhibitor, silk protease inhibitor, patatin, cystatin, papain inhibitor; ribosome Inactivating Proteins (RIPs) such as ricin, maize-RIP, abrin, luffa seed toxin, saporin or curcin; steroid metabolizing enzymes such as 3-hydroxysteroid oxidase, ecdysteroid-UDP-glycosyl-transferase, cholesterol oxidase, ecdysone inhibitor, HMG-COA-reductase, ion channel blockers such as sodium or calcium channel blockers, juvenile hormone esterase, diuretic hormone receptor, stilbene synthase, bibenzyl synthase, chitinase and glucanase.
In the context of the present invention, delta-endotoxins, such as Cry1Ab, cry1Ac, cry1F, cry Fa2, cry2Ab, cry3A, cry3Bb1 or Cry9C, or vegetative insecticidal proteins (Vip), such as Vip1, vip2, vip3 or Vip3A, are understood to obviously also include mixed toxins, truncated toxins and modified toxins. Hybrid toxins are recombinantly produced by a new combination of different domains of those proteins (see, e.g., WO 02/15701). Truncated toxins, such as truncated Cry1 abs, are known. In the case of modified toxins, one or more amino acids of the naturally occurring toxin are replaced. In such amino acid substitutions, it is preferred to insert non-naturally occurring protease recognition sequences into the toxin, such as, for example, in the case of Cry3A055, a cathepsin-G-recognition sequence into the Cry3A toxin (see WO 03/018810).
Examples of such toxins or transgenic plants capable of synthesizing such toxins are disclosed, for example, in EP-A-0 374 753, WO 93/07278, WO 95/34656, EP-A-0 427 529, EP-A-451 878 and WO 03/052073.
Methods for preparing such transgenic plants are generally known to the person skilled in the art and are described, for example, in the publications mentioned above. CryI-type deoxyribonucleic acids and their preparation are known, for example, from WO 95/34656, EP-A-0 367 474, EP-A-0 401 979 and WO 90/13651.
Toxins included in transgenic plants render the plants tolerant to harmful insects. Such insects may be present in any insect taxa, but are particularly common in beetles (coleoptera), diptera (diptera), and moths (lepidoptera).
Transgenic plants comprising one or more genes encoding insecticide resistance and expressing one or more toxins are known and some of them are commercially available. Examples of such plants are:(maize variety, expressing Cry1Ab toxin); YIELdGard-> (maize variety, expressing Cry3Bb1 toxin); YIELdGard(maize variety, expressing Cry1Ab and Cry3Bb1 toxins); />(maize variety, expressing Cry9C toxin); herculex->(maize variety, expressing Cry1Fa2 toxin and obtaining the enzyme phosphinothricin N-acetyltransferase (PAT) that is salt-tolerant to the herbicide glufosinate); nuCOTN->(cotton variety, expressing Cry1Ac toxin); bollgard->(cotton variety, expressing Cry1Ac toxin); bollgard->(cotton varieties expressing Cry1Ac and Cry2Ab toxins);(cotton variety, expressing Vip3A and Cry1Ab toxins); /> (potato variety, expressing Cry3A toxin); />GT Advantage (GA 21 glyphosate resistance trait),CB Advantage (Bt 11 Corn Borer (CB) trait) >
Further examples of such transgenic crops are:
bt11 maize from the seed company of Fangzha (Syngenta Seeds SAS), path Huo Bite (Chemin de l' Hobit) 27, F-31 st. Su Weier (St. Sauveur), france accession number C/FR/96/05/10. Genetically modified maize is rendered resistant to attack by european corn borer (corn borer and cnaphalocrocis medinalis) by transgenic expression of truncated Cry1Ab toxins. Bt11 maize also transgenically expresses PAT enzyme to obtain tolerance to the herbicide glufosinate ammonium.
Bt176 corn from seed of Fangzha, huo Bite, line 27, F-31 790 san Su Weier, france accession number C/FR/96/05/10. Genetically modified maize, genetically expressed as a Cry1Ab toxin, is resistant to attack by european corn borers (corn borers and cnaphalocrocis medinalis). Bt176 maize also transgenically expresses the enzyme PAT to obtain tolerance to the herbicide glufosinate ammonium.
MIR604 corn from seed of Fangda, huo Bite, line 27, F-31 790, sheng Su Weier, france, accession number C/FR/96/05/10. Corn that has been rendered insect-resistant by transgenic expression of the modified Cry3A toxin. The toxin is Cry3A055 modified by insertion of a cathepsin-G-protease recognition sequence. The preparation of such transgenic maize plants is described in WO 03/018810.
MON 863 corn from Monsanto Europe S.A.), 270-272 Teflon (Avenue DE Tervuren), B-1150 Brussels, belgium, accession number C/DE/02/9.MON 863 expresses a Cry3Bb1 toxin and is resistant to certain coleopteran insects.
IPC 531 cotton from Mengshan European company, 270-272 Teflon, B-1150 Brussels, belgium, accession number C/ES/96/02.
6.1507 maize, from pioneer overseas company (Pioneer Overseas Corporation), tedelsco, avenue Tedesco, 7B-1160 Brussels, belgium, accession number C/NL/00/10. Genetically modified maize, expressing the protein Cry1F to obtain resistance to certain lepidopteran insects, and PAT protein to obtain tolerance to herbicide grass Dingan.
NK603×MON 810 maize from Mengshan European company 270-272 Teflon, B-1150 Brussels, belgium under accession number C/GB/02/M3/03. By crossing the genetically modified varieties NK603 and MON 810, it is made up of a conventionally bred hybrid maize variety. NK603 xMON 810 maize transgenically expresses the protein CP4 EPSPS obtained from Agrobacterium strain CP4, rendering it herbicide resistant (containing glyphosate) and also Cry1Ab toxins obtained from Bacillus thuringiensis subspecies kurstaki, render them resistant to certain lepidopteran insects, including European corn borers.
Transgenic crops of insect-resistant plants are also described in BATS (biosafety and sustainable development center (Zentrum f u r Biosicherheit und Nachhaltigkeit), BATS center (Zentrum BATS), classification Cui She (Clarastrasse) 13, basel (Basel) 4058, switzerland) report 2003%http://bats.ch) Is a kind of medium.
The term "crop" is understood to also include crop plants which have been transformed in such a way by using recombinant DNA techniques that they are capable of synthesizing selectively acting antipathogenic substances, such as, for example, so-called "disease-associated proteins" (PRP, 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 of producing such transgenic plants are generally known to those skilled in the art and are described, for example, in the publications mentioned above.
Crops can also be modified to increase resistance to fungal (e.g., fusarium, anthracnose, or phytophthora), bacterial (e.g., pseudomonas), or viral (e.g., potexvirus, tomato spotted wilt virus, cucumber mosaic virus) pathogens.
Crops also include those having increased resistance to nematodes (e.g., heterodera glycines).
Crops with tolerance to abiotic stress include those with increased tolerance to drought, high salt, high temperature, cold, frost or light radiation, for example by expression of NF-YB or other proteins known in the art.
The anti-pathogenic substances that can be expressed by such transgenic plants include, for example, ion channel blockers, such as blockers of sodium and calcium channels, e.g., viral KP1, KP4 or KP6 toxins; stilbene synthase; bibenzyl synthase; chitinase; glucanase; so-called "disease process related proteins" (PRP; see e.g.EP-A-0 392 225); an anti-pathogenic substance produced by a microorganism, such as a peptide antibiotic or a heterocyclic antibiotic (see, e.g., WO 95/33818) or a protein or polypeptide factor involved in plant pathogen defense (so-called "plant disease resistance gene", as described in WO 03/000906).
Further areas of use of the compositions according to the invention are the protection of stored articles and storage compartments and of raw materials, such as wood, textiles, floors or buildings, and also in the hygiene sector, in particular the protection of humans, domestic animals and productive livestock from pests of the type mentioned.
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 controlling parasites in or on an animal. The invention further provides a compound of the first aspect for controlling ectoparasites in animals. The present invention further provides a compound of the first aspect for use in the prevention and/or treatment of diseases transmitted by ectoparasites.
The present invention provides the use of a compound of the first aspect for the manufacture of a medicament for controlling parasites in or on an animal. The invention further provides the use of a compound of the first aspect for the manufacture of a medicament for controlling ectoparasites in animals. The invention further provides the use of a compound of the first aspect for the manufacture of a medicament for the prevention and/or treatment of diseases transmitted by ectoparasites.
The present invention provides the use of a compound of the first aspect for controlling parasites in or on an animal. The invention further provides the use of a compound of the first aspect for controlling ectoparasites in animals.
The term "control" when used in the context of parasites in or on animals means to reduce the number of pests or parasites, eliminate pests or parasites and/or prevent further pest or parasite infestation.
The term "treating" when used in the context of parasites in or on an animal is meant to inhibit, slow, stop or reverse the progression or severity of an existing symptom or disease.
The term "preventing" when used in the context of parasites in or on animals refers to avoiding developing symptoms or diseases in the animal.
The term "animal" when used in the context of parasites in or on animals may refer to mammals and non-mammals, such as birds or fish. In the case of a mammal, it may be a human or non-human mammal. Non-human mammals include, but are not limited to, livestock animals and pets. Livestock animals include, but are not limited to, cattle, camels, pigs, sheep, goats, and horses. Pets include, but are not limited to, dogs, cats, and rabbits.
A "parasite" is a pest that lives in or on the body of a host animal and benefits by harvesting nutrients at the expense of the host animal. An "endoparasite" is a parasite that lives within the body of a host animal. An "ectoparasite" is a parasite that lives on the surface of a host animal. Ectoparasites include, but are not limited to ticks, insects, and crustaceans (e.g., sea lice). The subclasses ticks (or acarina) include ticks and mites. Ticks include, but are not limited to, members of the following genera: rhipicephalus (rhipicephalus), such as rhipicephalus (Rhipicaphalus microplus) (rhipicephalus (Boophilus microplus)) and rhipicephalus hemangiocarpus (Rhipicephalus sanguineus); amblyomra; leather tick (Dermacentor); haemaphysalis (Haemaphysalis); glehnia (Hyalomma); hard ticks (Ixodes); rhipicephalus (Rhipicer); cattle ticks (Margaropus); the genus Alnus (Argas); otobius (Otobius); the genus tick (Ornithiodoros). Mites include, but are not limited to, members of the following genera: dermatophagoides, such as itch mites of the cow; itch mites such as sheep itch mites; the genus agaricus; genus dermatophagoides; such as dermatophagoides pteronyssinus; avian tetranychus (Ortnithonyssus); demodex, such as Demodex canis; scabies, such as human scabies; the genus sore mite. Insects include, but are not limited to, members of the following objectives: flea, diptera, pubic, lepidoptera, coleoptera, and homoptera. Members of the order of the flea include, but are not limited to, chlamydia felis and Chlamydia canis (Ctenocephatides canis). Members of the diptera order include, but are not limited to, fly species; skin flies, such as horse flies and sheep flies; biting flies (flies); tabanus species, such as Tabanus species and Tabunus species; black horn flies, such as bot flies; stings genus (Stomoxys); the genus green fly; midges; and (3) mosquitoes. Members of the class of pubescens include, but are not limited to, sucking lice and chewing lice (ovicola lice), such as, for example, wool lice (Bovicola Ovis) and cattle feathers.
The term "effective amount" when used in the context of parasites in or on an animal means the amount or dose of a compound of the invention or a salt thereof which, when administered to the animal in a single dose or multiple doses, provides the desired effect in or on the animal. The effective amount can be readily determined by the attending diagnostician (as one skilled in the art) by the use of known techniques and by observing results obtained under analogous circumstances. In determining an effective amount, the attending diagnostician considers a number of factors, including, but not limited to: species of mammal; its size, age and general health; the parasite and the degree of infestation to be controlled; the particular disease or condition involved; the extent or severity of the disease or condition; individual response; a specific compound to be administered; a mode of administration; the bioavailability characteristics of the formulation; the selected dosage regimen; concomitant use of a drug; and other related situations.
The compounds of the invention may be administered to an animal by any route having the desired effect, including but not limited to topical, oral, parenteral and subcutaneous. Topical administration is preferred. Formulations suitable for topical administration include, for example, solutions, emulsions and suspensions, and may take the form of pouring, dispensing, spraying, spray bar (spray pattern) or dipping. In the alternative, the compounds of the invention may be administered via an ear tag or collar.
Salt forms of the compounds of the 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, e.g., gould, P.L. "Salt selection for basic drugs [ salt selection of base drug ]", international Journal of Pharmaceutics [ J.International pharmacy ],33:201-217 (1986); bastin, R.J. et al, "Salt Selection and Optimization Procedures for Pharmaceutical New Chemical Entities [ salt selection and optimization procedure for New pharmaceutical chemical entity ]", organic Process Research and Development [ organic Process research and development ],4:427-435 (2000); and Berge, S.M. et al, "Pharmaceutical Salts [ pharmaceutically acceptable salts ]", journal of Pharmaceutical Sciences [ journal of pharmaceutical science ],66:1-19, (1977). Those skilled in the art of synthesis will appreciate that the compounds of the present invention are readily converted to salts and can be isolated as salts (e.g., hydrochloride salts) using techniques and conditions well known to those of ordinary skill in the art. Furthermore, those skilled in the art of synthesis will appreciate that the compounds of the present invention are readily converted to the corresponding free base and can be isolated as the corresponding free base from the corresponding salt.
The invention also provides methods for controlling pests (such as mosquitoes and other disease vectors; see also http:// www.who.int/malaria/vector_controls/irs/en /). In one embodiment, the method for controlling pests includes applying the composition of the invention to the target pests, their locus or surface or substrate by brushing, rolling, spraying, coating or dipping. By way of example, IRS (indoor hold-up spray) application of a surface (such as a wall, ceiling or floor surface) is contemplated by the method of the present invention. In another embodiment, it is contemplated that such compositions are applied to substrates such as nonwoven or fabric materials in the form of netting, coverings, bedding, curtains, and tents (or may be used in the manufacture of such articles).
In one embodiment, a method for controlling such pests comprises applying a pesticidally effective amount of the composition of the invention to the target pests, their locus or surface or substrate, so as to provide effective residual pesticidal activity on the surface or substrate. Such application may be by brushing, rolling, spraying, coating or dipping the pesticidal composition of the present invention. By way of example, IRS application to a surface (e.g., a wall, ceiling or floor surface) is contemplated by the methods of the present invention so as to provide effective residual pesticidal activity on the surface. In another embodiment, application of such compositions is contemplated for residual control of pests on substrates such as textile materials in the form of netting, coverings, bedding, curtains, and tents (or may be used in the manufacture of such articles).
The substrate to be treated (including nonwoven, fabric or netting) may be made of natural fibers such as cotton, raffia leaf fibers, jute, flax, sisal, hemp or wool, or synthetic fibers such as polyamides, polyesters, polypropylenes, polyacrylonitriles and the like. Polyesters are particularly suitable. Methods of textile treatment are known, for example WO 2008/151984, WO 2003/034823, US 5631072, WO 2005/64072, WO 2006/128870, EP 1724392, WO 2005113886 or WO 2007/090739.
Further areas of use of the composition according to the invention are in the field of tree injection/trunk treatment for all ornamental trees, as well as all kinds of fruit trees and nut trees.
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 order coleoptera as mentioned above, in particular the woodworms listed in tables a and B below:
table 1. Examples of extraneous woodworms of economic importance.
Table 2. Examples of local woodworms of economic importance.
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The invention can also be used to control any insect pest that may be present in turf grass including, for example, beetles, caterpillars, fire ants, ground pearls (ground pearls), armyworms, hygrophilas, mites, mole cricket, scale insects, mealy bugs, ticks, cicada, southern wheat bugs and grubs. The present invention can be used to control insect pests, including eggs, larvae, nymphs, and adults, at various stages of their life cycle.
In particular, the invention may be used to control insect pests fed with roots of turf grass, including grubs (such as round head turtles (cyclopia spp.) (e.g., labeled turtles, c. Lurida), rhizomotgus species (e.g., european turtles, european cut root turtles (r. Majalis)), cotinus species (Cotinus spp.) (e.g., green june beetles (Green June beetle), green june beetles (c. Nita)), arctic turtles (Popillia spp.) (e.g., japanese beetles, japanese arc turtles (p. Java)), gill angle turtles (phylop spp.) (e.g., five month/six months beetles), metal species (e.g., turf turtles (Black turfgrass ataenius), black hair turtles (mailera) species (e.g., asia 3), garden beetles (bead 3), mole cricket (orange hair beetles) species (yellow, yellow haircut beetles) species (35, yellow mosquito species (yellow mosquito) and yellow mosquito (yellow mosquito) species, yellow mosquito (top) and yellow mosquito (yellow mosquito) species).
The invention can also be used to control insect pests of turf grass in thatch houses, including armyworms such as fall armyworm (fall armyworm) spodoptera frugiperda (Spodoptera frugiperda), and the common armyworm (Pseudaletia unipuncta), rootworm, trunk worms (cryptoporus species (sphagnus spp.), such as s.venatus verstus and long-beak elephant of pasture (s.parvulus)), meadow moth (such as meadow moth species (Crambus spp.), and tropical meadow moth, herpetogramma phaeopteralis).
The invention can also be used to control insect pests in turf grass living on the ground and feeding turf grass leaves, including wheat bugs such as southern wheat bugs, southern lygus (Blissus insularis), bermuda mites (Bermudagrass mite) (Eriophyes cynodoniensis), meadow (Antonina graminis), swamp hoppers (Propsapia bicincta), leafhoppers, rootworm (nocturnal), and wheat binary aphids.
The invention can also be used to control other pests in turf grass, such as exotic solenopsis invicta (Solenopsis invicta) that creates a formicary in the turf.
In the hygiene sector, the compositions according to the invention are effective against ectoparasites such as hard ticks, soft ticks, scabies, autumn mites, flies (biting and licking), parasitic fly larvae, lice, hair lice, bird lice and fleas.
Examples of such parasites are:
nits order: the genus psyllium, the genus nit (lineginaphus spp.), the genus pediculus, the genus pubescent (phthirus spp.), the genus pediculus.
Food order: hairiness species, shortfeather species, duck species, cattle species, werneckiella species, lepikentron species, beast species, pubescent species (Felicola spp.) species.
Diptera and longicotina (Nematomyces) and Brevibacterium (Brachymyces), such as Aedes species (Aedes spp.), analae species, culex spp.), gnat species (Simian spp.), etsetum spp.), eugnat species (Eusamum spp.), phlebopus species (Phlebotomus spp.), lutzomyc spp, culicades spp.), tabanus species (Chrysops spp.), tabanus species (Hybomitra spp.), huang Meng species (Atylotus spp.), tabanus species (Haemota spp.), philippia species, melissa spp, musca spp, and Hyriopsis spp. The plant species may be selected from the group consisting of a housefly species, a black horn species (haemagglia spp.), a mozzia species (Morellia spp.), a toilet species (Fannia spp.), a glossa spp.), a liriomyza species (caliphos spp.), a Lucilia spp, a chrysomya species (Chrysomyia spp.), a dirty fly species (wohlfahria spp.), a numbing species (Sarcophaga spp.), a rabies spp.), a mythica spp, a dermatophagoides spp (Hypoderma spp.), a gaster spp.), a pedicellus spp, a capricoidea spp.
The order of the fleas (Siphonapterida), for example, the genus flea (Pulex spp.), the genus flea, the genus chebya (xenopsyla spp.), the genus flea.
Heteroptera (Heteropterida), such as, for example, a bed bug species, a trypanosoma species, a red stinkbug species, a trypanosoma species (panstrongyles spp.).
Blattaria (blattaria), such as blattaria orientalis (Blatta orientalis), periplaneta americana (Periplaneta americana), german cockroach (blattelagermannia), and blattaria species (Supella spp.) of Xia Baila.
Acarina (Acaria) and Bactrocera (Meta-stingmata) and Strophaga (Meema-stingmata) such as, for example, the species of Ornithina (Argas spp.), the species of Bluntouche (Ornithovorus spp.), the species of Auricularia (Otobius spp.), the species of hard tick (Ixodes spp.), the species of Blumeria (Amblyomma spp.), the species of Bopyris (Boophulus spp.), the species of Derman (Dermacor spp.), the species of Rhemophilus (Haemophilus spp.), the species of Hyaloma (Hyaloma spp.), the species of Rhipicephalus (Rhipophagus spp.), the species of Dermatophagus (Dermatophagus spp.), the species of Rhipicephalus spp. And the species of Vaccinum spp.
The order axomedes (Actinedida) (Prostigmata) and the order anatida (anamata), such as the species of the genus Aphanus (Acarapis spp.), the species of the genus Acarina (Cheylella spp.), the species of the genus Acarina (Ornithecyleta spp.), the species of the genus Myrobia (Myobasphp.), the species of the genus Pythagoreae (Psorergates spp.), the species of Demodex spp, the species of the genus Acalycemia (Trogrip spp.), the species of the genus Yak (Litrophos spp.), the species of the genus Acarina (Acarina spp.), the species of the genus Tyrophagus (Tyrochanus spp), the species of the genus Trichophytosis (Caloglyphiphus spp), the species of the species under the neck (Hypodects spp.), the species of the genus Pterosphaerella (Pterosphaerosphp), the species of the genus Demodex spp (Psorophylus spp), the species of the genus Demodex, the species of the genus Demodex (Cyclopentas spp), the species of the genus Cyclopyra (Cyclopentas spp), the species of the genus Cyclopentades (Cytophagus spp), the species of the genus Cyclopentanus, the species of the genus Cytophagus (Cytophagus spp).
The compositions according to the invention are also suitable for protecting materials from insect infestation in the case of, for example, wood, textiles, plastics, adhesives, glues, lacquers, papers and cards, leather, floors and buildings.
The composition according to the invention can be used, for example, against the following pests: beetles, such as North America beetles, longhornbeetles, furniture beetles, red Mao Qie beetles, comb beetles, dendrobium pertinex, pine beetles, priobium carpini, brown beetles, african beetles, southern beetles, oak beetles, thorn beetles, scale Mao Fendu, wood bark beetle species, coffee beetles, oak beetles, brown heteroptera beetles, double thorn beetles species, and bamboo beetles; and also membranous species such as blue black wasps, hornets, taiwaneses and Urocerus augur; and termites such as European wood termite (Kalotermes flavicollis), ma-head sandrock termite, indian wood termite, yellow chest termite, sang Tesan termite, european termite, australian termite, nevada termite and Home termite; and moths, such as tuna.
The compounds having the formulae I and I' a or salts thereof are particularly suitable for controlling one or more pests selected from the following families: the plant species may be selected from the group consisting of nyctaceae, plutellaceae, phyllotoferae, thrips, stinkbugidae, euphoria, delphaidae, aphididae, nyctaceae, meadow moth, root knot nematode and heteroderaceae. In a preferred embodiment of each aspect, compound TX (wherein the abbreviation "TX" means "one compound selected from the group consisting of the compounds defined in tables a-1 to a-243, tables B-1 to B-81, tables X and P, preferably the compounds defined in tables X and P") controls one or more pests selected from the following families: the plant species may be selected from the group consisting of nyctaceae, plutellaceae, phyllotoferae, thrips, stinkbugidae, euphoria, delphaidae, aphididae, nyctaceae, meadow moth, root knot nematode and heteroderaceae.
The compounds having the formulae I and I' a or salts thereof are particularly suitable for controlling one or more pests selected from the following genera: the species Spodoptera, plutella, florida, thrips, apostigma, cydia, brown rice, aphis, sinonotus, leptospira, and Graminea. In a preferred embodiment of each aspect, compound TX (wherein the abbreviation "TX" means "one compound selected from the compounds defined in table X and table P") controls one or more pests selected from the following genera: the species Spodoptera, plutella, florida, thrips, apostigma, cydia, brown rice, aphis, sinonotus, leptospira, and Graminea.
The compounds having the formulae I and I' a or salts thereof are particularly suitable for controlling one or more of the following: spodoptera littoralis, plutella xylostella, frankliniella occidentalis, thrips tabaci, heroid, codling moth, brown rice lice, myzus persicae, soybean geometrid, bean aphid, cucumber leaf beetle, grass Gu Yiguan aphid, and chilo suppressalis.
In a preferred embodiment of each aspect, compound TX (wherein the abbreviation "TX" means "selected from the group consisting of the compounds defined in tables a-1 to a-243, tables B-1 to B-81, table X and table P, preferably one compound selected from table X and table P") controls one or more of the following: spodoptera littoralis, plutella xylostella, frankliniella occidentalis, thrips tabaci, hero lygus, codling moth, brown rice lice, myzus persicae, soybean geometrid, bean aphid, cucumber leaf beetle, cereal Gu Yiguan aphid, and chilo suppressalis, such as spodoptera littoralis+tx, plutella xylostella+tx; frankliniella occidentalis+tx, thrips tabaci+tx, stinkbug+tx, codling moth+tx, brown rice lice+tx, myzus persicae+tx, soybean inchworm+tx, soybean aphid+tx, cucumber leaf beetle+tx, grass Gu Yiguan aphid+tx, and chilo suppressalis+tx.
In embodiments of each aspect, one compound from tables a-1 to a-243, tables B-1 to B-81, tables X and P, preferably from tables X and P, is suitable for controlling spodoptera littoralis, plutella xylostella, frankliniella occidentalis, thrips tabaci, hero plant bug, codling moth, brown rice lice, peach aphid, soybean looper, bean aphid, cucumber leaf beetle, rice Gu Yiguan aphid, and striped rice borer on cotton, vegetable, corn, cereal, rice, and soybean crops.
In embodiments, one compound from tables a-1 to a-243, tables B-1 to B-81, table X and table P, preferably from table X and table P, is suitable for controlling cabbage loopers (Mamestra), codling moth (preferably on apples), leafhoppers (Empoasca), preferably in vegetables, vineyards, potato beetles (Leptinotarsa), preferably on potatoes, and striped rice borers, preferably on rice.
The compounds according to the invention may have any number of benefits, including in particular advantageous levels of biological activity towards protecting plants against insects or superior properties for use as agrochemical active ingredients (e.g. higher biological activity, advantageous activity profile, increased safety (against non-target organisms (such as fish, birds and bees) above and below ground), improved physico-chemical properties, or increased biodegradability). In particular, it has been unexpectedly found that certain compounds having formula I can exhibit advantageous safety against non-target arthropods, particularly pollinators (such as bees, solitary bees and bumblebees). Most particularly, it is relative to italian bees (Apis mellifera).
The compounds according to the invention can be used as pesticides in unmodified form, but they are generally formulated into compositions in a variety of ways using formulation aids such as carriers, solvents and surface-active substances. These formulations may be in different physical forms, for example, in the following forms: dusting powders, gels, wettable powders, water-dispersible granules, water-dispersible tablets, effervescent compressed tablets, emulsifiable concentrates, microemulsifyable concentrates, oil-in-water emulsions, flowable oils, aqueous dispersions, oily dispersions, suspoemulsions, capsule suspensions, emulsifiable granules, soluble liquids, water-soluble concentrates (with water or water-miscible organic solvents as a carrier), impregnated polymeric films or in other forms known, for example, from Manual on Development and Use of FAO and WHO Specifications for Pesticides [ handbook of development and use of FAO and WHO standards for pesticides ], united nations, version 1, second revision (2010). Such formulations may be used directly or may be diluted before use for reuse. Dilution may be performed with, for example, water, liquid fertilizer, micronutrients, biological organisms, oil or solvents.
These formulations can be prepared, for example, by mixing the active ingredient with formulation auxiliaries in order to obtain the compositions in the form of finely divided solids, granules, solutions, dispersions or emulsions. These active ingredients may 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.
These active ingredients may also be contained in very fine microcapsules. The microcapsules contain the active ingredient in a porous carrier. This allows the active ingredient to be released (e.g., slowly released) into the environment in controlled amounts. The microcapsules typically have a diameter of from 0.1 to 500 microns. They contain the active ingredient in an amount of from about 25% to 95% by weight of the capsule. These active ingredients may be in the form of an integral solid, in the form of fine particles in a solid or liquid dispersion, or in the form of a suitable solution. The encapsulated film may comprise, for example, natural or synthetic rubber, cellulose, styrene/butadiene copolymer, polyacrylonitrile, polyacrylate, polyester, polyamide, polyurea, polyurethane or chemically modified polymer, or other polymers known to those skilled in the art. Alternatively, very fine microcapsules may be formed in which the active ingredient is contained in the form of finely divided particles in a solid matrix of the base substance, but these microcapsules are not themselves encapsulated.
Formulation auxiliaries suitable for preparing the compositions according to the invention are known per se. As the liquid carrier, use can be made of: water, toluene, xylene, petroleum ether, vegetable oil, acetone, methyl ethyl ketone, cyclohexanone, anhydride, acetonitrile, acetophenone, amyl acetate, 2-butanone, butylene carbonate, chlorobenzene, cyclohexane, cyclohexanol, alkyl acetate, diacetone alcohol, 1, 2-dichloropropane, diethanolamine, p-diethylbenzene, diethylene glycol rosinate, diethylene glycol butyl ether, diethylene glycol ethyl ether, diethylene glycol methyl ether, N, N-dimethylformamide, dimethyl sulfoxide, 1, 4-dioxane, dipropylene glycol methyl ether, dipropylene glycol dibenzoate, dipropylene glycol, alkylpyrrolidones, ethyl acetate, 2-ethylhexanol, ethylene carbonate, 1-trichloroethane, 2-heptanone, alpha-pinene, d-limonene, ethyl lactate, ethylene glycol butyl ether, ethylene glycol methyl ether, gamma-butyrolactone, glycerol acetate, glycerol diacetate, glycerol triacetate, hexadecane, hexylene glycol, isoamyl acetate, isobornyl acetate, isooctane, isophorone, cumene, isopropyl alcohol isopropyl myristate, lactic acid, laurylamine, mesityl oxide, methoxypropanol, methyl isoamyl ketone, methyl isobutyl ketone, methyl laurate, methyl octanoate, methyl oleate, methylene chloride, m-xylene, N-hexane, N-octylamine, stearic acid, octylamine acetate, oleic acid, oleylamine, o-xylene, phenol, polyethylene glycol, propionic acid, propyl lactate, propylene carbonate, propylene glycol methyl ether, p-xylene, toluene, triethyl phosphate, triethylene glycol, xylene sulfonic acid, paraffin, mineral oil, trichloroethylene, perchloroethylene, ethyl acetate, amyl acetate, butyl acetate, propylene glycol methyl ether, diethylene glycol methyl ether, methanol, ethanol, isopropanol, and higher molecular weight alcohols such as amyl alcohol, tetrahydrofuryl alcohol, hexyl alcohol, octyl alcohol, ethylene glycol, propylene glycol, glycerol, N-methyl-2-pyrrolidone, and the like.
Suitable solid carriers are, for example, talc, titanium dioxide, pyrophyllite clay, silica, attapulgite clay, diatomaceous earth, limestone, calcium carbonate, bentonite, calcium montmorillonite, cotton seed hulls, wheat flour, soybean flour, pumice, wood flour, ground walnut hulls, lignin and the like.
Many surface-active substances can be advantageously used in both solid and liquid formulations, especially those formulations which can be diluted by a carrier before use. The surface-active substances may be anionic, cationic, nonionic or polymeric and they may be used 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 dodecyl sulfate; salts of alkylaryl sulfonates such as calcium dodecylbenzenesulfonate; alkylphenol/alkylene oxide addition products such as ethoxylated nonylphenols; alcohol/alkylene oxide addition products, such as ethoxylated tridecyl alcohol; soaps, such as sodium stearate; salts of alkyl naphthalene sulfonates such as sodium dibutyl naphthalene sulfonate; salts of dialkyl sulfosuccinates, 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 di-alkyl phosphates; and also other substances, such as described in: mcCutcheon's Detergents and Emulsifiers Annual [ Mascin cleaner and emulsifier yearbook ], MC Publishing company (MC Publishing Corp.), richwood, N.J. (Ridgewood New Jersey) (1981).
Additional adjuvants that may be used in the pesticide formulation include crystallization inhibitors, viscosity modifiers, suspending agents, dyes, antioxidants, foaming agents, light absorbers, mixing aids, defoamers, complexing agents, substances and buffers that neutralize or alter the pH, corrosion inhibitors, fragrances, wetting agents, absorption enhancers, micronutrients, plasticizers, glidants, lubricants, dispersants, thickeners, anti-freezing agents, microbiocides, and liquid and solid fertilizers.
The composition according to the invention may comprise additives comprising oils of vegetable 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 may be added to the spray tank at the desired concentration after the spray mixture has been prepared. Preferred oil additives include mineral oilsOr oils of vegetable origin, such as rapeseed oil, olive oil or sunflower oil; emulsified vegetable oil; alkyl esters of oils of vegetable origin, such as methyl derivatives; or oils of animal origin, such as fish oil or tallow. Preferred oil additives include C 8 -C 22 Alkyl esters of fatty acids, especially C 12 -C 18 Methyl derivatives of fatty acids, such as methyl esters of lauric acid, palmitic acid and oleic acid (methyl laurate, methyl palmitate and methyl oleate, respectively). Many oil derivatives are known from Compendium of Herbicide Adjuvants [ herbicide adjuvant outline ]]Edition 10, university of south illinois, 2010.
These inventive compositions generally comprise from 0.1 to 99% by weight, in particular from 0.1 to 95% by weight, of the inventive compound and from 1 to 99.9% by weight of a formulation aid, preferably comprising from 0 to 25% by weight of a surface-active substance. Whereas commercial products may preferably be formulated as concentrates, the end user will typically use a diluted formulation.
The application rate varies within a wide range and depends on the nature of the soil, the application method, the crop plant, the pest to be controlled, the prevailing climatic conditions, and other factors dictated by the application method, the application time and the target crop. Generally, the compounds may be applied at a rate of from 1l/ha to 2000l/ha, especially from 10l/ha to 1000 l/ha.
Preferred formulations may have the following composition (in weight%):
Emulsifiable concentrate：
Active ingredients: 1% to 95%, preferably 60% to 90%
And (2) a surfactant: 1% to 30%, preferably 5% to 20%
A liquid carrier: 1% to 80%, preferably 1% to 35%
Dust powder：
Active ingredients: 0.1% to 10%, preferably 0.1% to 5%
Solid carrier: 99.9% to 90%, preferably 99.9% to 99%
Suspension concentrate:
active ingredients: 5% to 75%, preferably 10% to 50%
Water: 94% to 24%, preferably 88% to 30%
And (2) a surfactant: 1% to 40%, preferably 2% to 30%
Wettable powder：
Active ingredients: 0.5% to 90%, preferably 1% to 80%
And (2) a surfactant: 0.5% to 20%, preferably 1% to 15%
Solid carrier: 5% to 95%, preferably 15% to 90%
The granule comprises the following components:
active ingredients: 0.1% to 30%, preferably 0.1% to 15%
Solid carrier: 99.5% to 70%, preferably 97% to 85%
The following examples further illustrate (but do not limit) the invention.
The combination is thoroughly mixed with these adjuvants and the mixture is thoroughly ground in a suitable mill, whereby a wettable powder is obtained which can be diluted with water to give a suspension of the desired concentration.
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 clay 65％ 40％ -
Talc - 20％
The combination is thoroughly mixed with the adjuvants and the mixture is thoroughly ground in a suitable grinder, so that a powder is obtained which can be used directly for seed treatment.
Emulsifiable concentrate
Active ingredient 10％
Octyl phenol polyglycol ether (4-5 mol of ethylene oxide) 3％
Dodecyl benzene sulfonic acid calcium salt 3％
Castor oil polyglycol ether (35 mol of ethylene oxide) 4％
Cyclohexanone 30％
Xylene mixture 50％
Emulsions with any desired dilution that can be used in plant protection can be obtained from such concentrates by dilution with water.
Dust powder a) b) c)
Active ingredient 5％ 6％ 4％
Talc 95％ - -
Kaolin clay - 94％ -
Mineral filler - - 96％
A ready-to-use dust powder is obtained by mixing the combination with a carrier and grinding the mixture in a suitable grinder. Such powders may also be used for dry dressing of seeds.
The combination is mixed and ground with these adjuvants and the mixture is moistened with water.
The mixture is extruded and then dried in an air stream.
Coated granules
Active ingredient 8％
Polyethylene glycol (molecular weight 200) 3％
Kaolin clay 89％
This finely ground combination is applied uniformly in a mixer to kaolin wet with polyethylene glycol. In this way dust-free coated granules are obtained.
Suspension concentrate
Active ingredient 40％
Propylene glycol 10％
Nonylphenol polyethylene glycol ether (15 mol of ethylene oxide) 6％
Sodium lignin sulfonate 10％
Carboxymethyl cellulose 1％
Silicone oils (in the form of a 75% emulsion in water) 1％
Water and its preparation method 32％
The finely ground combination is intimately mixed with the adjuvants to give a suspension concentrate from which any desired dilution of the suspension can be obtained by dilution with water. Using such dilutions, living plants can be treated together with plant propagation material and protected against microbial infestation by spraying, watering or dipping.
Flowable concentrate for seed treatment
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The finely ground combination is intimately mixed with the adjuvants to give a suspension concentrate from which any desired dilution of the suspension can be obtained by dilution with water. Using such dilutions, living plants can be treated together with plant propagation material and protected against microbial infestation by spraying, watering or dipping.
Sustained release capsule suspension
28 parts of the combination are mixed with 2 parts of aromatic solvent and 7 parts of toluene diisocyanate/polymethylene-polyphenyl isocyanate-mixture (8:1). This mixture was emulsified in a mixture of 1.2 parts of polyvinyl alcohol, 0.05 parts of defoamer and 51.6 parts of water until the desired particle size was reached. To this emulsion was added 2.8 parts of a 1, 6-hexamethylenediamine mixture in 5.3 parts of water. The mixture was stirred until the polymerization was completed. The capsule suspension obtained is stabilized by adding 0.25 parts of thickener and 3 parts of dispersant. The capsule suspension formulation contains 28% active ingredient. The diameter of the media capsule is 8-15 microns. The resulting formulation is applied to the seeds as an aqueous suspension suitable for use in the device for this purpose.
Formulation types include Emulsion Concentrates (EC), suspension Concentrates (SC), suspoemulsions (SE), capsule Suspensions (CS), water dispersible granules (WG), emulsifiable Granules (EG), emulsions, water-in-oil Emulsions (EO), oil-in-water Emulsions (EW), microemulsions (ME), oil Dispersions (OD), oil suspensions (OF), oil-soluble solutions (OL), soluble concentrates (SL), ultra-low volume Suspensions (SU), ultra-low volume solutions (UL), parent drugs (TK), dispersible Concentrates (DC), wettable Powders (WP), soluble Granules (SG) or any technically feasible formulation in combination with agriculturally acceptable adjuvants.
Preparation example:
the following examples further illustrate (but do not limit) the invention. Those skilled in the art will readily recognize from such procedures appropriate variations regarding reactants and regarding reaction conditions and techniques.
Throughout this specification, temperature is given in degrees celsius (°c). The following abbreviations are used: s = single peak; br s = broad unimodal; d = double peak; brd = broad doublet; dd = double doublet; dt = double triplet; t=triplet, tt=triplet, q=quartet, quin=quintet, sept=heptad; m=multiple peaks.
The LC/MS apparatus and method are:
method 1:
spectra were recorded on a mass spectrometer (SQD, SQDII single quadrupole mass spectrometer) from Waters, equipped with electrospray sources (polarity: positive and negative ions, capillary: 3.00kV, cone range: 41V, extractor: 2.00V, source temperature: 150 ℃, desolvation temperature: 500 ℃, cone gas flow: 50l/h, desolvation gas flow: 1000l/h; mass range: 110 to 800 Da) and Acquity UPLC from Waters: binary pumps, heated column chambers, diode array detectors, and ELSD detectors. Column: waters UPLC HSS T3,1.8 μm, 30X 2.1mm, temperature: PDA wavelength range (nm) at 40 ℃): 200 to 400, solvent gradient: a=water+5% acetonitrile+0.1% HCOOH, b=acetonitrile+0.05% HCOOH; gradient: 10% -100% B, within 1.3 min; the flow rate (ml/min) was 0.6.
Method 2:
spectra were recorded on a mass spectrometer from Waters company (SQD, SQDII single quadrupole mass spectrometer) equipped with electrospray sources (polarity: positive and negative ions, capillary: 3.00kV, cone aperture range: 30V, extractor: 2.00V, source temperature: 150 ℃, desolvation temperature: 350 ℃, cone aperture gas flow: 50l/h, desolvation gas flow: 650l/h; mass range: 100 to 900 Da) and acquisition UPLC from Waters company: binary pumps, heated column chambers, diode array detectors, and ELSD detectors. Column: waters UPLC HSS T3,1.8 μm, 30X 2.1mm, temperature: 60 ℃, DAD wavelength range (nm): 210 to 500, solvent gradient: a=water+5% meoh+0.05% HCOOH, b=acetonitrile+0.05% HCOOH; gradient: 10% -100% B, within 1.2 min; the flow rate (ml/min) was 0.85.
Method 3:
spectra were recorded on an ACQUITY mass spectrometer (SQD or SQDII single quadrupole mass spectrometer) from Waters, equipped with an electrospray source (polarity: positive or negative ions, capillary: 3.0kV, cone: 30V, extractor: 3.00V, source temperature: 150 ℃, desolvation temperature: 400 ℃, cone gas flow: 60L/hr, desolvation gas flow: 700L/hr, mass range: 140Da to 800 Da), and an ACQUITY UPLC (with solvent degasser, binary pump, heated column chamber, and diode array detector) from Waters. Column: waters UPLC HSS T3,1.8 μm, 30X 2.1mm, temperature: 60 ℃, 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, within 2.5 min; the flow rate (ml/min) was 0.75.
Method 4:
spectra were recorded on a 6410 triple quadrupole mass spectrometer (Agilent 1200 series HPLC) from Agilent technologies (Agilent Technologies) equipped with an electrospray source (polarity: positive and negative polarity transitions, scan type: MS2 scan, capillary (kV): 4.00, fragmentation voltage (V): 100.00, gas temperature (DEG C): 350, gas flow (L/min): 11, nebulizer gas (psi): 45, mass range: 110 to 1000Da, DAD wavelength range: 210 to 400 nm). Column: KINETEX EVO C18, column length: 50mm, column inner diameter: 4.6mm, particle size: 2.6 mu, column oven temperature: 40 ℃, optimized chromatographic parameters: gradient conditions: solvent a: water containing 0.1% formic acid: acetonitrile: 95:5v/v; solvent B: acetonitrile containing 0.1% formic acid; gradient: 10% -100% B, within 2.5 min; the flow rate (ml/min) was 1.8.
Method 5:
spectra were recorded on a mass spectrometer (QDA single quadrupole mass spectrometer) from waters company (Waters Corporations) equipped with electrospray sources (polarity: positive and negative ions, detector gain 1, sample temperature: 500 ℃, cone voltage: 10v, esi capillary positive voltage 0.8-negative voltage 0.8, sampling frequency 5Hz, mass range 100 to 850 Da)
Source temperature: desolvation temperature at 120 ℃): 600 ℃, taper hole gas flow: 150l/h, desolvation gas flow: 1000 l/h) and UPC2 from Waters: binary solvent manager, heated column chamber, sample manager, isocratic solvent manager, convergence manager (convergence manager), diode array detector, DAD wavelength range (nm): 200 to 500, back pressure 1800psi. Column: daicel SFCIC,3 μm,0.3 cm. Times.10 cm, temperature: 40 ℃, running time: 4.8min; flow (ml/min) 2.0; solvent: a=co 2 B=methanol+0.1% NH 4 OH (at H) 2 30% in O); gradient: 15% B isocratic lasted 4.8min, then 100% A.
Method 6:
spectra were recorded on a mass spectrometer from Waters company (QDA single quadrupole mass spectrometer) equipped with electrospray sources (polarity: positive and negative ions, detector gain 1, probe temperature: 350 ℃, cone voltage: 10V, ESI capillary positive voltage 0.8-negative voltage 0.8, sampling frequency 5Hz, mass range: 100 to 850Da
Source temperature: desolvation temperature at 120 ℃): 600 ℃, taper hole gas flow: 150l/h, desolvation gas flow: 1000 l/h) and UPC2 from Waters: binary solvent manager, heated column chamber, sample manager, isocratic solvent manager, convergence manager (convergence manager), diode array detector, DAD wavelength range (nm): 200 to 500, back pressure 1800psi. Column: waters Torus TM 1-AA column, 1.7 μm,3 mm. Times.100 mm, temperature: 40 ℃, running time: 4.8min; flow (ml/min) 2.0; solvent: a=co 2 B=methanol; gradient: 5% B isocratic lasted 4.8min.
Example P1:1- [2, 4-bis (trifluoromethyl) phenyl ]]-3- [1- (2-pyrimidin-2-yl-1, 2, 4-triazol-3-yl) ethyl Base group]Preparation of urea (P1)
Step A: preparation of 2- (2, 2-trifluoroethylamino) -5- (trifluoromethyl) benzonitrile (I-1)
2-neck RBF equipped with a nitrogen inlet and condenser was charged with 1- (2-pyrimidin-2-yl-1, 2, 4-triazol-3-yl) ethylammonium in acetonitrile (20 mL/g) at room temperature; 2, 2-trifluoroacetate salt (1.5 g,4.93 mmol) followed by triethylamine (12.32 mmol,1.26 g). Phenyl chloroformate (7.39 mmol,1.21 g) was further slowly added. The reaction was heated and stirred at 80 ℃ under nitrogen atmosphere for 2 hours. The reaction mixture was cooled to room temperature, quenched with water and extracted twice with ethyl acetate. The combined organic layers were washed with brine, dried over anhydrous sodium sulfate and concentrated under reduced pressure to give a brown gum-like material (1.96 g, crude). The crude product was purified by silica gel column chromatography (using 50% ethyl acetate in cyclohexane) and concentrated under reduced pressure to give phenyl N- [1- (2-pyrimidin-2-yl-1, 2, 4-triazol-3-yl) ethyl ] carbamate (I-1, 1.15 g) as a white solid.
LC-MS (method 1): retention time 0.93min, m/z 311.50[ M+H ]] +
1 H NMR (400 MHz, chloroform-d) delta ppm 8.84-8.92 (m, 2H) 7.99-8.12 (m, 1H) 7.30-7.41 (m, 3H) 7.10 (d, J=7.83 Hz, 1H) 6.96-7.21 (m, 2H) 6.33 (br d, J=8.56 Hz, 1H) 6.09-6.19 (m, 1H) 1.63-1.72 (m, 3H)
And (B) step (B): 1- [2, 4-bis (trifluoromethyl) phenyl ]]-3- [1- (2-pyrimidin-2-yl-1, 2, 4-triazol-3-yl) ethyl Base group]Preparation of urea (P1)
A clean dry 25mL RBF was charged with triethylamine (20 mL/g,28.7 mmol) at room temperatureN- [1- (2-pyrimidin-2-yl-1, 2, 4-triazol-3-yl) ethyl group]Phenyl carbamate (0.2 g, 0.640 mmol) and 2, 4-bis (trifluoromethyl) aniline (3.223 mmol,0.761 g). The reaction mass was then heated and stirred at 120 ℃ for 2h. The reaction was cooled to room temperature, a solid precipitated, diluted with pentane and filtered through a buchner funnel to give a crude product which was purified by using a C18 column and acetonitrile and water as eluent. The desired compound was found to be 25% MeCN: H 2 O elution and lyophilization to give 1- [2, 4-bis (trifluoromethyl) phenyl ] as a white solid]-3- [1- (2-pyrimidin-2-yl-1, 2, 4-triazol-3-yl) ethyl group]Urea (180 mg).
LC-MS (method 1): retention time 1.03min, m/z 446.4[ M+H ]] +
1 H NMR(400MHz,DMSO-d6)δppm 9.03(d,2H)8.19-8.28(m,3H)8.03-8.19(m,1H)7.85-7.92(m,2H)7.67(t,1H)5.81(t,1H)1.54(d,3H)
M.P.：189℃-191℃
Alternatively, 1- [2, 4-bis (trifluoromethyl) phenyl ] -3- [1- (2-pyrimidin-2-yl-1, 2, 4-triazol-3-yl) ethyl ] -urea (P1) can be prepared according to the following procedure:
To a solution of triphosgene (0.026 g,0.09 mmol) in ethyl acetate (2 mL) at 0deg.C was added 2, 4-bis (trifluoromethyl) aniline (0.05 g,0.22 mmol) and triethylamine (0.06 g,0.55 mmol). The resulting suspension was stirred at 0 ℃ for 45min and then 1- (2-pyrimidin-2-yl-1, 2, 4-triazol-3-yl) ethylammonium was added; a solution of 2, 2-trifluoroacetate salt (0.07 g,0.22 mmol) and triethylamine (0.05 g,0.45 mmol) in ethyl acetate (1 mL). The resulting mixture was gradually warmed to room temperature and stirred at this temperature for 18h. The reaction mixture was partitioned between water and ethyl acetate. The organic layer was purified by Na 2 SO 4 Dried, filtered and concentrated under reduced pressure. The residue was purified as described in example P1, step B to give 1- [2, 4-bis (trifluoromethyl) phenyl ] as a white solid]-3- [1- (2-pyrimidin-2-yl-1, 2, 4-triazol-3-yl) ethyl group]Urea.
Example P2:1- [3, 5-bis (trifluoromethyl) phenyl ]]-3- [1- (2-pyrimidin-2-yl-1, 2, 4-triazol-3-yl) ethyl Base group]Urea (P2)
1- (2-pyrimidin-2-yl-1, 2, 4-triazol-3-yl) ethylamine (200 mg,1.05 mmol) was dissolved in tetrahydrofuran (3.5 mL/mmol) under nitrogen at room temperature, then 1-isocyanato-3, 5-bis (trifluoromethyl) benzene (1 eq, 1.05 mmol) was slowly added followed by N, N-diethyl ethylamine (1 eq, 1.0515 mmol) and stirred at room temperature for 16h. The reaction mixture was diluted with water/brine and EtOAc. The aqueous layer was extracted twice with EtOAc. The combined organic layers were washed twice with water. The organic layer was dried, filtered and evaporated to give 1- [3, 5-bis (trifluoromethyl) phenyl ] -3- [1- (2-pyrimidin-2-yl-1, 2, 4-triazol-3-yl) ethyl ] urea (250 mg, 53%) as an off-white solid.
LC-MS (method 1): retention time 0.99min, m/z 446.15[ M+H ]] +
1 H NMR(400MHz,DMSO-d6)δppm 9.33(s,1H)9.02(d,2H)8.20(s,1H)7.98(s,2H)7.67(t,1H)7.56(s,1H)7.22(d,1H)5.82(s,1H)1.52(d,3H)
M.P.：124℃-127℃
Example P3:1- [3, 5-bis (trifluoromethyl) phenyl ]]-3- [1- (2-pyrimidin-2-yl-1, 2, 4-triazol-3-yl) ethyl Base group]Thiourea (P3)
1- (2-pyrimidin-2-yl-1, 2, 4-triazol-3-yl) ethylamine (100 mg,0.525 mmol) was dissolved in tetrahydrofuran (3.5 mL/mmol) under argon at room temperature, then 1-isothiocyanato-3, 5-bis (trifluoromethyl) benzene (1 eq, 0.525 mmol) was slowly added followed by N, N-diethylamine (1 eq, 0.525 mmol) and stirred at room temperature for 15h. The reaction mixture was diluted with water/brine. The aqueous layer was extracted twice with EtOAc. The combined organic layers were washed twice with water. The organic layer was dried, filtered and evaporated to give 1- [3, 5-bis (trifluoromethyl) phenyl ] -3- [1- (2-pyrimidin-2-yl-1, 2, 4-triazol-3-yl) ethyl ] thiourea as an off-white solid (177 mg, 72%).
LC-MS (method 1): retention time 1.02min, m/z 460.16[ M-H ]] +
1 H NMR(400MHz,DMSO-d6)δppm 10.15(br s,1H)9.03(d,2H)8.84-8.98(m,1H)8.21(d,3H)7.74(s,1H)7.66(t,1H)6.33(br d,1H)1.62(d,3H)
Example P103:1- [ 4-chloro-6- (trifluoromethyl) -3-pyridinyl]3- [ (1S) -1- (2-pyrimidin-2-yl-1, 2, 4-) Triazol-3-yl) ethyl]Urea (P103)
To a solution of triphosgene (0.151 g,0.509mmol,0.5 eq.) in acetonitrile (5 mL) cooled at 0℃under argon was added 4-chloro-6- (trifluoromethyl) pyridin-3-amine (0.20 g,1.017mmol,1.0 eq.) and triethylamine (0.356 mL,2.54mmol,2.5 eq.) in acetonitrile (5 mL). The reaction was stirred at 0℃for 45 min. Then [ (1S) -1- (2-pyrimidin-2-yl-1, 2, 4-triazol-3-yl) ethyl ] ammonium at 0 ℃; a solution of 2, 2-trifluoroacetate salt (0.309 g,1.017mmol,1.0 eq.) and triethylamine (0.356 mL,2.54mmol,2.5 eq.) in acetonitrile (5 mL) was added to the reaction mixture and the solution was stirred at room temperature overnight. The reaction was quenched with water and the aqueous layer was extracted with ethyl acetate. The combined organic layers were washed with water, dried over sodium sulfate, filtered and concentrated under reduced pressure. The crude product was precipitated in diisopropyl ether and the resulting off-white solid was filtered and washed three times with diisopropyl ether to give the desired compound 1- [ 4-chloro-6- (trifluoromethyl) -3-pyridinyl ] -3- [ (1S) -1- (2-pyrimidin-2-yl-1, 2, 4-triazol-3-yl) ethyl ] urea as an off-white solid.
LC-MS (method 2): retention time 0.82min, m/z 413[ M+H ] + ]。
1 H NMR (400 MHz, chloroform-d) delta ppm 9.54 (s, 1H) 8.96 (d, j=4.72 hz, 2H) 8.18 (s, 1H) 8.08 (br d, j=9.08 hz, 1H) 7.42-7.49 (m, 3H) 6.30-6.38 (m, 1H) 1.15 (d, j=6.18 hz, 3H).
19 F NMR (377 MHz, chloroform-d) delta ppm-67.51 (s, 3F).
M.P.：191℃-193℃
Example P47:(2S) -2- [ [2, 4-dichloro-5- (1, 2-tetrafluoroethoxy) phenyl]Carbamoyl amino groups] Preparation of methyl propionate (P134)
Step A: preparation of 1, 5-dichloro-2-nitro-4- (1, 2-tetrafluoroethoxy) benzene (I-2)
To a solution of 2, 4-dichloro-5-nitrophenol (5.0 g,24mmol,1.0 eq.) in N, N-dimethylformamide (50 mL) was added potassium carbonate (11.0 g,82mmol,3.5 eq.) in portions under argon. The reaction mixture was heated to 70 ℃ and stirred at that temperature overnight. The solution was quenched with water and the aqueous layer was extracted twice with ethyl acetate. The combined organic layers were washed with water, dried over sodium sulfate, filtered and concentrated under reduced pressure. The crude product was purified by flash chromatography (ethyl acetate in cyclohexane) to give the desired compound 1, 5-dichloro-2-nitro-4- (1, 2-tetrafluoroethoxy) benzene as an orange oil.
LC-MS (method 2): the retention time was 1.22min.
1 H NMR (400 MHz, chloroform-d) delta ppm 7.98 (s, 1H) 7.75 (s, 1H) 5.88-6.19 (m, 1H)
19 F NMR (377 MHz, chloroform-d) delta ppm-88.09 (s, 1F) -136.49 (s, 1F)And (B) step (B): 2, 4-dichloro-5- Preparation of (1, 2-tetrafluoroethoxy) aniline (I-3)
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To a solution of 1, 5-dichloro-2-nitro-4- (1, 2-tetrafluoroethoxy) benzene (1.53 g,4.97mmol,1.0 eq.) in methanol (20 mL) was added palladium (0.265 g, 0.247 mmol,0.05 eq.) under argon. The reaction mixture was left under a hydrogen atmosphere (3 bar) at room temperature for 2 hours. The mixture was then diluted with methanol and filtered through a Hyflo pad under argon. The filtrate was concentrated under reduced pressure and the crude product was purified by flash chromatography (ethyl acetate in cyclohexane) to give the desired compound 2, 4-dichloro-5- (1, 2-tetrafluoroethoxy) aniline as a yellow oil.
LC-MS (method 2): retention time 1.06min, m/z 278[ M+H ] + ]。
1 H NMR (400 MHz, chloroform-d) delta ppm 7.36 (s, 1H) 6.77-6.80 (m, 1H) 5.81-6.12 (m, 1H) 4.18 (br d, J=8.72 Hz, 2H).
19 F NMR (377 MHz, chloroform-d) delta ppm-88.33 (s, 2F) -136.53 (s, 2F).
Step C: (2S) -2- [ [2, 4-dichloro-5- (1, 2-tetrafluoroethoxy) phenyl]Carbamoyl amino groups]Polypropylene (C) Preparation of methyl ester (I-4)
To a solution of triphosgene (0.133 g,0.45mmol,0.5 eq.) in acetonitrile (4 mL) cooled at 0℃under argon was added 2, 4-dichloro-5- (1, 2-tetrafluoroethoxy) aniline (0.25 g,0.899mmol,1.0 eq.) and triethylamine (0.313 mL,2.25mmol,2.5 eq.) in acetonitrile (2 mL). The reaction was stirred at 0℃for 45 min. Then [ (1S) -2-methoxy-1-methyl-2-oxo-ethyl ] ammonium at 0 ℃; a solution of chloride (0.126 g,0.90mmol,1.0 eq.) and triethylamine (0.314 mL,2.25mmol,2.5 eq.) in acetonitrile (3 mL) was added to the reaction mixture and the solution was stirred at room temperature overnight. The reaction was quenched with water and the aqueous layer was extracted with ethyl acetate. The combined organic layers were washed with water, dried over sodium sulfate, filtered and concentrated under reduced pressure. The crude product was purified by flash chromatography (ethyl acetate in cyclohexane) to give the desired compound (2S) -2- [ [2, 4-dichloro-5- (1, 2-tetrafluoroethoxy) phenyl ] carbamoyl amino ] propionic acid methyl ester as a white solid.
LC-MS (method 2): retention time 1.04min, m/z 407[ M+H ] + ]。
1 H NMR (400 MHz, chloroform-d) delta ppm 8.38 (s, 1H) 7.42 (s, 1H) 6.96 (s, 1H) 5.82-6.11 (m, 1H) 5.74 (br d, j=7.63 hz, 1H) 4.61 (quin, j=7.27 hz, 1H) 3.83 (s, 3H) 1.49 (d, j=7.27 hz, 3H).
19 F NMR (377 MHz, chloroform-d) delta ppm-88.32 (s, 2F) -136.56 (s, 2F).
Step D: (2S) -2- [3- [2, 4-dichloro-5- (1, 2-tetrafluoroethoxy) phenyl]2-oxo-imidazolidine 1-yl group]Preparation of methyl propionate (I-5)
To a solution of methyl (2S) -2- [ [2, 4-dichloro-5- (1, 2-tetrafluoroethoxy) phenyl ] carbamoylamino ] propanoate (0.100 g,0.246mmol,1.0 eq.) and 1, 2-dibromoethane (0.064 mL,0.737mmol,3.0 eq.) in tetrahydrofuran (1.23 mL) was slowly added sodium hydride (60 mass%, 0.025g,0.614mmol,2.5 eq.) at 0deg.C. The reaction was stirred at 0 ℃ for 20 minutes and then warmed to room temperature. The reaction was quenched with water and the aqueous layer was extracted twice with ethyl acetate. The combined organic layers were washed with water, dried over sodium sulfate, filtered and concentrated under reduced pressure. The crude product was purified by flash chromatography (ethyl acetate/ethanol in cyclohexane (3:1)) to give the desired compound (2S) -2- [3- [2, 4-dichloro-5- (1, 2-tetrafluoroethoxy) phenyl ] -2-oxo-imidazolidin-1-yl ] propionic acid methyl ester as a beige solid.
LC-MS (method 2): retention time 1.05min, m/z 433[ M+H ] + ]。
Step E: (2S) -2- [3- [2, 4-dichloro-5- (1, 2-tetrafluoroethoxy) phenyl]2-oxo-imidazolidine 1-yl group]Preparation of propionamide (I-6)
A solution of methyl (2S) -2- [3- [2, 4-dichloro-5- (1, 2-tetrafluoroethoxy) phenyl ] -2-oxo-imidazolidin-1-yl ] propionate (0.102 g,0.235mmol,1.0 eq.) in ammonia (7M in methanol, 0.47mL,3.3mmol,14 eq.) was heated overnight in microwaves at 50 ℃. The reaction was concentrated under reduced pressure to give the desired compound (2S) -2- [3- [2, 4-dichloro-5- (1, 2-tetrafluoroethoxy) phenyl ] -2-oxo-imidazolidin-1-yl ] acrylamide as an off-white solid.
LC-MS (method 2): retention time 0.91min, m/z 418[ M+H ] + ]。
Example P47:(2S) -2- [ [2, 4-dichloro-5- (1, 2-tetrafluoroethoxy) phenyl]Carbamoyl amino groups] Preparation of methyl propionate (P134)
To a solution of (2S) -2- [3- [2, 4-dichloro-5- (1, 2-tetrafluoroethoxy) phenyl ] -2-oxo-imidazolidin-1-yl ] acrylamide (prepared as described in example 3, step B) (0.103 g,0.246mmol,1.0 eq.) in dichloromethane (2.46 mL) was added N, N-dimethylformamide dimethyl acetal (0.066 mL,0.493mmol,2.0 eq.) under argon. The reaction mixture was stirred at 50 ℃ for 30 minutes and then concentrated under reduced pressure. The residue was dissolved in dioxane (1 mL) and pyrimidin-2-yl hydrazine (0.054 g,0.495mmol,2.0 eq.) and acetic acid (0.618 mL,10.8mmol,43.6 eq.) were added to the solution. The reaction mixture was stirred at 80℃for 1 hour. The reaction mixture was quenched with sodium bicarbonate. The aqueous layer was extracted twice with ethyl acetate, and the combined organic layers were washed twice with water, dried over sodium sulfate, filtered and concentrated under reduced pressure. The crude product was purified by flash chromatography (ethyl acetate in cyclohexane) to give the desired compound 1- [2, 4-dichloro-5- (1, 2-tetrafluoroethoxy) phenyl ] -3- [ (1S) -1- (2-pyrimidin-2-yl-1, 2, 4-triazol-3-yl) ethyl ] imidazolidin-2-one as a white solid.
LC-MS (method 1): retention time 0.98min, m/z 520[ M+H ] + ]。
1 H NMR (400 MHz, chloroform-d) delta ppm 8.48-8.58 (m, 2H) 7.89-7.98 (m, 1H) 7.55-7.61 (m, 1H) 6.84-6.92 (m, 1H) 5.83-6.18 (m, 2H) 3.46-3.55 (m, 1H) 1.89-1.99 (m, 3H) 1.54-1.57 (m, 3H) 1.20-1.27 (m, 1H)
M.P.：207℃-209℃。
Table P: examples of compounds having formula I:
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table Q-examples of intermediates:
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by adding further insecticidal, acaricidal and/or fungicidal active ingredients, the activity of the composition according to the invention can be considerably broadened and adapted to the prevailing circumstances. Mixtures of the compounds of the formula I with other insecticidal, acaricidal and/or fungicidal active ingredients can also have further surprising advantages which can also be described in a broader sense as synergistic activity. For example, better tolerance of plants, reduced phytotoxicity, better behaviour of insects can be controlled at their different developmental stages, or during their production (e.g. during grinding or mixing, during their storage or during their use).
Here, the active ingredients appropriately added are, for example, representative of the following classes of active ingredients: organophosphorus compounds, nitrophenol derivatives, thiourea, juvenile hormone, formamidine, benzophenone derivatives, ureas, pyrrole derivatives, carbamates, pyrethroids, chlorinated hydrocarbons, acylureas, pyridylmethyleneamino derivatives, macrolides, neonicotinoids, and bacillus thuringiensis preparations.
The following mixture of compounds of formula I with active substances is preferred (the abbreviation "TX" means "one compound selected from the group consisting of the compounds defined in tables a-1 to a-243, tables B-1 to B-81, tables X and P, preferably the compounds defined in tables X and P"):
an adjuvant selected from the group consisting of: petroleum (alias) (628) +tx;
an insect control active selected from abamectin+tx, methoquinone+tx, acetamiprid+tx, acetylchlorfenapyr+tx, bifenthrin+ TX, acynonapyr +tx, bifenthrin+tx, alfuna+tx, cotton bollwire+tx, allethrin+tx, alpha-cypermethrin+tx, fenpropathrin+tx, sulfamate+tx, methomyl+tx, azocyclotin+tx, sulfenuron+tx, bennett+ TX, benzpyrimoxan +tx, beta-flucythrin+tx, beta-cypermethrin+tx, bifenthrin+tx, lenacil+tx, bioallethrin+tx, S-bioallethrin+tx, bifenthrin+tx, ditrifluorourea+tx, bronilide+tx, bromaron+ethyl+tx, buproflumin+tx, sulfenuron+tx, carboxin+tx, furin+tx,: 1632218-00-8+TX, CAS number: 1808115-49-2+TX, CAS number: 2032403-97-5+TX, CAS number: 2044701-44-0+TX, CAS number: 2128706-05-6+TX, CAS number: 2095470-94-1+TX, CAS number: 2377084-09-6+TX, CAS number: 1445683-71-5+TX, CAS number: 2408220-94-8+TX, CAS number: 2408220-91-5+TX, CAS number: 1365070-72-9+TX, CAS number: 2171099-09-3+TX, CAS number: 2396747-83-2+TX, CAS number: 2133042-31-4+TX, CAS number: 2133042-44-9+TX, CAS number: 1445684-82-1+TX, CAS number: 1445684-82-1+TX, CAS number: 1922957-45-6+TX, CAS number: 1922957-46-7+TX, CAS number: 1922957-47-8+TX, CAS number: 1922957-48-9+TX, CAS number: 2415706-16-8+TX, CAS number: 1594624-87-9+TX, CAS number: 1594637-65-6+TX, CAS number: 1594626-19-3+TX, CAS number: 1990457-52-7+TX, CAS number: 1990457-55-0+TX, CAS number: 1990457-57-2+TX, CAS number: 1990457-77-6+TX, CAS number: 1990457-66-3+TX, CAS number: 1990457-85-6+TX, CAS number: 2220132-55-6+TX, CAS number: 1255091-74-7+TX, chlorantraniliprole+TX, chlordane+TX, chlorantraniliprole+TX, propathrin+TX, chromafenozide+TX, clenpyralin+TX, carboline (clomethocarb) +TX, clothianidin+TX, 2-chlorophenyl N-methyl carbamate (CPMC) +TX, benzonitrile phosphorus+TX, cyantraniliprole+TX, cyclobrimonide + TX, cyclobutrifluram +tx, pyrethroid+tx, cycloxaprid+tx, cytebufenpyrad+tx, etoxazole+tx, cyflumetofen+tx, cyhalothrin+tx, cyhalodiamide (cyhalodiamide) +tx, cyhalothrin+tx, cypermethrin+tx, fencythrin+ TX, cyproflanilide +tx, cyromazine+tx, deltamethrin+tx, flufenuron+tx, chlorimphos+tx, dibromophosphorus (dibromim) + TX, dicloromezotiaz +tx, flufenzine+tx, difluben+ TX, dimpropyridaz +tx, divalidin+tx, diuron+tx, dinotebufenpyrad+tx, cymophos+tx, emamectin (or emamectin) +tx, dextromethrin+tx, epsilon-momfluthrin+tx, epsilon-methofipronil+tx, fenphos+fenphos+tx, ethylfenphos+tx, ethiprole+tx, ethylfenpyrad+tx; etoxazole+tx, valinate+tx, fenazaquin+tx, penflufen+ TX, fenmezoditiaz +tx, fenitrothion+tx, fenobucarb+tx, benfuracarb+tx, fenoxycarb+tx, fenpropathrin+tx, fenpyrad+tx, fenphos+tx, beclomethasone+tx, she Sailing +tx, fenvalerate+tx, fipronil+tx, flumetoquinone (fimetoquin) +tx, flonicamid+tx, azoxystrobin+ TX, fluazaindolizine +tx, pyrifturon+tx, flubendiamide+tx, flufenpyrad+ TX, fluchlordiniliprole + TX, flucitrinate +tx, flufenuron+tx, fluthiamethoxam+tx, azoxystrobin+tx, trifluramide+tx, fipronil+tx, fluhexafipronil+tx, flufenthrin+tx, fluflufluflubendiamide+ TX, flupentiofenox +tx, fluflubendiamide+tx, flubendiamide+tx, fluvalinate+ Lei Lana +fluvalinate+tx Cyfluthrin + TX, fluxametamide + TX, fosthiazate + TX, gamma-cyfluthrin + TX, gossyplure TM +TX, tebufenpyrad+TX, chlorfenozide+TX, fenacet (halfenprox) + TX, heptafluthrin +TX, thiamethoxam+TX, triadimefon+TX, imidazophos (imacyfos) +TX, imidacloprid+TX, imazafen+ TX, indazapyroxamet +TX, indoxacarb+TX, methyl iodide+TX, iprodione+ TX, isocycloseram +TX, isoxadifon+TX, ivermectin+TX, kappa-bifenthrin+TX, kappa-tefluthrin+TX, lambda-cyhalothrin+TX, leptoside+TX, lotilant+TX, lufenuron+TX, metaflumizone+TX, metalaxyl+TX, carbofuran+TX, methoprene+TX, methomyl+TX, methoprene+TXThe composition comprises a compound selected from the group consisting of a fungus + TX, momfluorothrin + TX, a methoprene + TX, nicofluprole + TX, nitenpyram + TX, omethoate + TX, carboline + TX, oxazosulfyl + TX, parathion-ethyl + TX, permethrin + TX, phenothrin + TX, phosphocarb + TX, piperonyl butoxide + TX, pirimicarb + TX, pyrimidephos-ethyl + TX, pyrimidephos-methyl + TX, polyhedrosis virus + TX, propathrin + TX, profenofos + TX, propathrin + TX, propafenox + TX, fenpropidin + TX, prafluben (profenox) TX, pyfluben-methyl + TX, pyraffinol + TX, pyridalyl + TX, pyriproxyfen + TX, fluben (pyrifluben) and flubenazolin + fluben-methyl + fluben-ethyl; pyrazolidinium+TX, pyriproxyfen+TX, benfurin+TX, sartaner+TX, selamectin+TX, silafluofen+TX, spinetoram+TX, spinosad+TX, spirodiclofen+TX, spiromesifen+ TX, spiropidion +TX, spirotetramat+ TX, spidoxamat +TX, dinotefuran+TX, tebufenpyrad+TX, tetrafipronate+TX, dithiophos+TX, tetrachlorethamide+TX, tetramethrin+TX, tetrachlorethrin+TX, flucyamide+TX, theta-chlorocyanogen+TX, thiacloprid+TX, thiamethoxam+TX, thiocyclam+TX, thiodicarb+TX, fenbufenpyrad+TX, methiphos+TX, monosultap+TX, tetrachlorethamide+TX, TX, tioxazafen +lanin+TX Tolfenpyrad+tx, toxafen+tx, tetrabromothrin+tx, tebufenpyrad+tx, triazophos+tx, trichlorfon+tx, toxic soil phosphorus+tx, trichlorfon+tx, trifluoracel (triflumezopyrilm) + TX, tyclopyrazoflor +tx, zeta-cypermethrin+tx, seaweed extract and fermentation products derived from sugar acyl +tx, seaweed extract and fermentation products derived from sugar acyl (comprising urea+tx, amino acids +tx, potassium and molybdenum and EDTA chelated manganese) +tx, seaweed extract and fermentation plant products (comprising phytohormone +tx, vitamin +tx, EDTA chelated copper +tx, zinc +tx, and iron +tx), azadirachtin +tx, bacillus catum (Bacillus mail) +tx, bacillus (Bacillus chitinosporus) AQ746 (rl symbol B-21) +bacillus+618, bacillus sp Bacillus kurther (Bacillus kurstaki) +TX, bacillus mycoides AQ726 (NRRL accession number B-21664) +TX, bacillus pumilus (NRRL accession number B-30087) +TX, bacillus pumilus AQ717 (NRRL accession number B-21662) +TX, bacillus species AQ178 (ATCC accession number 53522) +TX, bacillus species AQ175 (ATCC accession number 55608) +TX, bacillus species AQ177 (ATCC accession number 55609) +TX, unspecified Bacillus subtilis+TX, bacillus subtilis AQ153 (ATCC accession number 55614) +TX, bacillus subtilis AQ30002 (NRRL accession number B-50421) +TX, bacillus subtilis AQ30004 (NRRL accession number B-50455) +TX, bacillus subtilis AQ713 (NRRL accession number 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 kulark subspecies (subspecies. Kurstaki) BMP 123+tx, beauveria bassiana+tx, D-limonene+tx, granulosis virus+tx, kang Zhuangsu (Harpin) +tx, cotton bollworm nuclear polyhedrosis virus+tx, noctilus nuclear polyhedrosis virus+tx, smoke bud noctilus nuclear polyhedrosis virus+tx, australis cotton bollworm nuclear polyhedrosis virus+tx, metarhizium species+tx, muscor al620 (NRRL accession No. 30547) +tx, muscodor roseus A-5 (NRRL accession No. 3055048) +tx), the neem-based products +tx, paecilomyces fumosoroseus +tx, paecilomyces lilacinus +tx, paenibacillus pseudosewampee +tx, pasteurella puncture +tx, pasteurella mycobacteria +tx, cord Lei Bashi bacillus (Pasteuria thornei) +tx, pasteurella +tx, p-cymene +tx, plutella xylostella granulosis virus +tx, plutella xylostella nuclear polyhedrosis virus +tx, polyhedra virus +tx, pyrethrum +tx, QRD 420 (terpenoid blend) +tx, QRD 452 (terpenoid blend) +tx, QRD 460 (terpenoid blend) +tx, quillaja +tx, rhodococcus globosus AQ719 (NRRL accession number B-21663) +tx, spodoptera nuclear polyhedrosis virus +tx, fresh streptomyces (NRRL accession number 30232) +tx, streptomyces species (NRRL accession number B-30145) +tx, terpenoid blend +tx, and verticillium +tx;
An algicide selected from the group consisting of: baishazin (bethoxazin) [ CCN ] +tx, copper dioctanoate (IUPAC name) (170) +tx, copper sulfate (172) +tx, cybutryne [ CCN ] +tx, dichloro naphthoquinone (dichlorine) (1052) +tx, dichlorophenol (232) +tx, polyacid (295) +tx, triphenyltin (Fenin) (347) +tx, slaked lime [ CCN ] +tx, sodium zincate (nabam) (566) +tx, algicidal quinone (quinine) (714) +tx, quinone amine (quininamid) (1379) +tx, cimex (730) +tx, triphenyltin acetate (IUPAC name) (347) and triphenyltin hydroxide (IUPAC name) (347) +tx;
an anthelmintic agent selected from the group consisting of: avermectin (1) +TX, krephosphite (1011) + TX, cyclobutrifluram + TX, doramectin (alias) [ CCN ] +TX, emamectin (291) +TX, emamectin benzoate (291) +TX, irinotetin (alias) [ CCN ] +TX, ivermectin (alias) [ CCN ] +TX, milbemycin oxime (alias) [ CCN ] +TX, moxidectin (alias) [ CCN ] +TX, piperazine [ CCN ] +TX, selametin (alias) [ CCN ] +TX, spinosad (737), and thiophanate (1435) +TX;
a bird killer selected from the group consisting of: aldochloroses (127) +tx, additives (1122) +tx, phoxim (346) +tx, pyridin-4-amine (IUPAC name) (23) and strychnine (745) +tx;
A bactericide selected from the group consisting of: 1-hydroxy-1H-pyridine-2-thione (IUPAC name) (1222) +TX, 4- (quinoxalin-2-ylamino) benzenesulfonamide (IUPAC name) (748) +TX, 8-hydroxyquinoline sulfate (446) +TX, bromonitro alcohol (97) +TX, copper dioctate (IUPAC name) (170) +TX, copper hydroxide (IUPAC name) (169) +TX, cresol [ CCN ] +TX, dichlorophenol (232) +TX, bipyralid (1105) +TX, doxine (1112) +TX, sodium disulfone (fenaminosf) (1144) +TX, formaldehyde (404) +TX, mercuric plus (alias) [ CCN ] +TX, kasugamycin (483) +TX, kasugamycin hydrochloride hydrate (483) +TX, bis (dimethyldithiocarbamate) nickel (PAC name) (1308) +TX, trichlorethylpyridine (nipy) (580) +TX, xin Saitong) (lymphomycin sulfate) (590, oltipraz (606), doxycycline (766) +, doxycycline (766) +sulfate (744) and streptomycin sulfate (744);
a biological agent selected from the group consisting of: the species Apostigma littoralis GV (alias) (12) +TX, agrobacterium radiobacter (alias) (13) +TX, amblyseius spp (alias) (19) +TX, apostigma apiacea NPV (alias) (28) +TX, oenoptera primordica Anagrus (Anagrus atoms) (alias) (29) +TX, apostigma brachypus (Aphelinus abdominalis) (alias) (33) +TX, apostigma gossypii parasitic wasp (Aphidius colemani) (alias) (34) +TX, aphidius gifuensis (Aphidoletes aphidimyza) (alias) (35) +TX, apostigma medica NPV (alias) (38) +TX, bacillus firmus (Bacillus firmus) (alias) (48) +TX) Bacillus sphaericus (Bacillus sphaericus Neide) (academy) (49) +TX, bacillus thuringiensis (Bacillus thuringiensis Berliner) (academy) (51) +TX, bacillus thuringiensis catfish subspecies (Bacillus thuringiensis subsp. Aizawai) (academy) (51) +TX, bacillus thuringiensis subspecies (Bacillus thuringiensis subsp. Israeli) (academy) (51) +TX, bacillus thuringiensis subspecies (Bacillus thuringiensis subsp. Japonensis) (academy) (51) +TX, bacillus thuringiensis subspecies (Bacillus thuringiensis subsp. Kurstaki) (academy) (51) +TX), bacillus thuringiensis is intended to be by the genus Methania (Bacillus thuringiensis subsp. Tenebrionis) (academic) 51) +TX, beauveria bassiana Beauveria bassiana (aliases) 53) +TX, beauveria bassiana Beauveria brongniartii (aliases) 54) +TX, fabryozoa (Chrysoperla carnea) (aliases) 151) +TX, cryptolepis mandshurica Cryptolaemus montrouzieri (aliases) 178) +TX, codling moth GV (aliases) 191 (aliases) TX, siberian from the jaw cocoon bee (Dacanula sibirica) 212 (aliases) TX, pisum sativum She Yingji small bee (Diglyphus isaea) aliases (aliases) 254) +TX, aphis pomonensis (Encarsia fortis) for the chemical name TX (293) +TX, aphis pratensis Eretmocerus eremicus) (300) +TX, novata NPV (aliases) 431 TX, heteropapilis (Heterorhabditis bacteriophora) and Lepidogyra sp H.ensii (62) +) can be placed in the blood vessel (fig. 39) +, metarhizium anisopliae (Metarhizium anisopliae var. Acridum) (academic name) (523) +TX, metarhizium anisopliae microsporoseum variety (Metarhizium anisopliae var. Aniopliae) (academic name) (523) +TX, new european pine needle (Neodiprion sertifer) NPV and new red pine needle (N.lecontei) NPV (alias) (575) +TX, cerjous species (alias) (596) +TX, paecilomyces fumosoroseus (Paecilomyces fumosoroseus) (alias) (613) +TX, small white fungus small plant mite (Phytoseiulus persimilis) (alias) (644) +TX, beet moth nuclear polyhedrosis virus (Spodoptera exigua multicapsid nuclear polyhedrosis virus) (academic name) (741) +TX, mao Wen nematode (Steinernema bibionis) (alias) (742) +TX, small leaf roller nematode (Steinernema carpocapsae) (alias) (742) +TX, night moth (742) +TX, TX) (Steinernema glaseri) (742) +TX, sharp us species (Steinernema riobrave) (7432) (742) +PYPRESTERIUM (742) +Tx, fig. 5 alias TX) +PYPRESTERIUM species (742) +STYPRUM (742) (TKyotis (742) (TXYRIUM) Western blind spider mites (Typhlodromus occidentalis) (alias) (844) and verticillium lecanii (Verticillium lecanii) (alias) (848) +tx;
A soil disinfectant selected from the group consisting of: methyl iodide (IUPAC name) (542) and methyl bromide (537) +tx;
a chemosterilant selected from the group consisting of: azophos (apholate) [ CCN ] +TX, bis (aziridine) methylaminophosphine sulfide (bisazir) (alias) [ CCN ] +TX, busulfan (alias) [ CCN ] +TX, diflubenzuron (250) +TX, dimetif (dimatif) (alias) [ CCN ] +TX, altretamine (hemel) [ CCN ] +TX, altfophos (hempa) [ CCN ] +TX, methylaldiba (metepa) [ CCN ] +TX, methylthioaldiba (methyoepa) [ CCN ] +TX, methylphospholazine (methyholate) [ CCN ] +TX, infertility (moving zid) [ CCN ] +TX, fluoroyoung urea (penfluron) (CCN ] +TX, bars (tepa) [ CCN ] +TX, thiohexamethylphosphorus (hempa) [ CCN ] +TX, thiohexamethylphosphorus (thia) [ CCN ] +TX, thioaldimine (CCN ] +alias, [ CCN ] +alias ] [ thioimine ] (thioimine ] [ CCN ];
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) -dodeca-7-en-1-yl acetate (IUPAC name) (285) +TX, (Z) -hexadec-11-en aldehyde (IUPAC name) (436) +TX, (Z) -hexadec-11-en-1-yl acetate (IUPAC name) (438) +TX, (Z) -hexadec-13-en-11-en-1-yl acetate (IUPAC name) (448) + (Z) -hexadec-7-en-1-yl acetate (IUPAC name) (782) +TX, (Z) -hexadec-13-en-10-one (IUPAC name), (Z) -tetradec-9-en-1-ol (IUPAC name) (783) +TX, (Z) -tetradec-9-en-1-yl acetate (IUPAC name) (784) +TX, (7E, 9Z) -dodeca-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-methyl octadec-1-ene (IUPAC name) (545) +TX, 4-methyl nonan-5-ol and 4-methyl nonan-5-one (IUPAC name) (544) +TX, alpha-multi-nutrient (Ten) (alias TX), western-1-yl acetate (iun) (780) +micro-N), small album (bromocrine) (flexible) and (flexible) N (flexible) can be obtained by (77) +dodecyl (flexible) and (flexible) methyl octa-5-one (iuPAC name) (167) and (flexible) methyl octa (35) TX and (4-methyl octa-5-alcohol (35) Dodecyl-8-en-1-yl acetate (IUPAC name) (286) +tx, dodecyl-9-en-1-yl acetate (IUPAC name) (287) +tx, dodecyl-8+tx, 10-dien-1-yl acetate (IUPAC name) (284) + TX, dominicalure (alias) [ CCN ] +tx, 4-methyl ethyl octoate (IUPAC name) (317) +tx, eugenol (alias) [ CCN ] +tx, southern pine bark beetle set pheromone (front) alias [ CCN ] +tx, lure hexadecyl (gospypline) (alias) (420) +tx, lure mixture (grandol) (421) +tx, lure mixture I (alias) (421) +tx, lure mixture II (alias) (421) +tx, lure mixture III (alias) (421) +tx, lure mixture IV (421) +tx, lure mixture (fan) (CCN ] +tx), lure (CCN ] +fan), lure (fan) and lure (CCN ] +fan-9-alkene-1-yl acetate (IUPAC name) (284) +) TX, lure mixture (421) +tx, lure mixture II (alias) (421) +tx), lure (alias) and lure mixture III (alias) and lure) n ] (421+tx (alias) and lure) n ] (attractive (421+tx) An attractant for killing esters (meclure) [ CCN ] +tx, megamobile acid (alias) [ CCN ] +tx, methyl eugenol (alias) (540) +tx, lure (mux) (563) +tx, octadec-2, 13-dien-1-yl acetate (IUPAC name) (588) +tx, octadec-3, 13-dien-1-yl acetate (IUPAC name) (589) +tx, he Kangbi (orfraure) (alias) [ CCN ] +tx, coconut tortoise aggregate pheromone (oriycure) (alias) (317) +tx, non-lecan (ostromone) (alias) [ CCN ] +tx, lure ring (siglure) [ CCN ] +tx, sound (TX) (736), phagostimulal (sucrose) (flexible) [ CCN ] +tx, tetradec-11-dien-1-yl acetate (IUPAC name) (589) +tx, he Kangbi (alias) (CCN ] +tx), sea cucumber (8) and sea cucumber (8) in the 6-base acetate (IUPAC) (alias) (9) +6) (alias) in the 6-sea cucumber (alias) and sea (alias) in the sea cucumber (8B) (alias) of the sea-9;
An insect repellent selected from the group consisting of: 2- (octylthio) ethanol (IUPAC name) (591) +tx, mosquito-repellent ketone (butylopyronoxy) (933) +tx, butoxy (polypropylene glycol) (936) +tx, dibutyl adipate (IUPAC name) (1046) +tx, dibutyl phthalate (1047) +tx, dibutyl succinate (IUPAC name) (1048) +tx, mosquito-repellent amine [ CCN ] +tx, mosquito-repellent (dimethyl carbate) [ CCN ] +tx, dimethyl phthalate [ CCN ] +tx, ethylhexyl glycol (1137) +tx, hexylurea [ CCN ] +tx, mequindine (methoquin-butyl) (1276) +tx, methyl neodecanoamide [ CCN ] +tx, oxamate) [ CCN ] and percalide [ CCN ] +tx;
a molluscicide selected from the group consisting of: di (tributyltin) oxide (IUPAC name) (913) +tx, bromoacetamide [ CCN ] +tx, calcium arsenate [ CCN ] +tx, triamcinolone (999) +tx, copper acetylarsenite [ CCN ] +tx, copper sulfate (172) +tx, triphenyltin (347) +tx, iron phosphate (IUPAC name) (352) +tx, metaldehyde (518) +tx, methomyl (530) +tx, niclosamide (576) +tx, niclosamide-ethanolamine (576) +tx, pentachlorophenol (623) +tx, sodium pentachlorobenzene oxide (623) +tx, thiamethomyl (tazimcarb) (1412) +tx, thiodicarb (799) +tx, tributyltin oxide (913) +tx, snail killing (trimethorph) (1454) +tx, mixed insecticidal pac (840) +tx, triphenyltin acetate (347) and triphenyltin hydroxide (IUPAC) (347) +60) +pyridine (3-35) +pyridine (73) +pyridine;
Nematicides selected from the group consisting of: AKD-3088 (compound code) +tx, 1, 2-dibromo-3-chloropropane (IUPAC/chemical abstract name) (1045) +tx, 1, 2-dichloropropane (IUPAC/chemical abstract 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 abstract name) (1065) +tx, 3- (4-chlorophenyl) -5-methyl rhodanin (IUPAC name) (980) +tx, 5-methyl-6-thio-1, 3, 5-thiadiazin-3-ylacetic acid (IUPAC name) (1286) +tx, 6-isopentenylaminopurine (TX) (210) +tx, abamectin (IUPAC name) (1063) +tx, acetylworm nitrile [ CCN ] +tx, cotton bolone (15) +tx, carbosulfan (TX), carbosulfan (62) +, AZ (62) +4-chloranin) +6, AZ (35), 3-propylsulfan (60) +, 3-thio) and (60) +6-thio) carbosulfan (IUPAC name) (35), 5) +6-thio-6-thio-1, 5-thiadiazin (IUPAC name) (1286) +tx), 5-methyl-6) +x, 6) +6-isopentenyl (TX) +tx (210) +x, 6) +6-isopropyl (TX, 6) +, chlorpyrifos (145) +TX, desmethylwire (999) + TX, cyclobutrifluram + TX, cytokinin (alias) (210) +TX, dazomet (216) +TX, DBCP (1045) +TX, DCIP (218) +TX, desmethylwire (diamidafos) (1044) +TX, desmephosphine (1051) +TX, dicarboxyphos (dicyclopos) (alias) +TX, dimethoate (262) +TX, doramectin (alias) [ CCN ] +TX, emamectin (291) +TX, emamectin benzoate (291) +TX, irinotecan (alias) [ CCN ] +TX, desmopraph (312) +TX, dibromoethane (316) +TX, benzoline phosphorus (326) +TX fenpyrad (alias) +TX, feng Suolin (1158) +TX, thiazole phosphorus (408) +TX, carbosulfan (1196) +TX, furfural (alias) [ CCN ] +TX, GY-81 (research code) (423) +TX, fashion [ CCN ] +TX, methyl iodide (IUPAC name) (542) +TX, isoamide phosphorus (isamidofos) (1230) +TX, chlorazol phosphorus (1231) +TX, ivermectin (alias) [ CCN ] +TX, kinetin (alias) (210) +TX, methyl triaphos (1258) +TX, wei (mu) potassium salt (alias) (519) +TX, wei (519 mu sodium salt (519) +TX), bromomethane (537) +tx, methyl isothiocyanate (543) +tx, milbexime (alias) [ CCN ] +tx, moxidectin (alias) [ CCN ] +tx, verrucosa (Myrothecium verrucaria) composition (alias) (565) +tx, NC-184 (compound code) +tx, carboline (602) +tx, tolfenphos (636) +tx, phospham (639) +tx, carboline [ CCN ] +tx, carboline (alias) +tx, selametin (alias) [ CCN ] +tx, spinosad (737) +tx, tertbutyback (alias) +tx, tertbutylphos (773) +tx, tetrachlorethiophene (IUPAC/chemical abstract name) (1422) +tx, thiafenox (TX) +tx, cordos (1434) +tx, triazophos (820) +tx, triazuron (triazuron) (TX) +xylenol ] (CCN) +tx, xylenol [ CCN ] +tx, yu 2+fluben (alias) and (5335-35+fluben (alias) fipron (alias) and [ code ] +fipronil (alias ];
A nitrification inhibitor selected from the group consisting of: potassium ethylxanthate [ CCN ] and chloropyridine (580) +tx;
a plant activator selected from the group consisting of: ala acid benzene (acibenzolar) (6) +TX, ala acid benzene-S-methyl (6) +TX, thiabendazole (658) and giant knotweed (Reynoutria sachalinensis) extract (alias) (720) +TX;
rodenticide consisting of the group of: 2-isovalerylindan-1, 3-dione (IUPAC name) (1246) +TX, 4- (quinoxalin-2-ylamino) benzenesulfonamide (IUPAC name) (748) +TX, alpha-chlorohydrin [ CCN ] +TX, aluminum phosphide (640) +TX, anto (880) +TX, arsenic trioxide (882) +TX, barium carbonate (891) +TX, bismurine urea (912) +TX, bromomurine (89) +TX, bromodiuron (including alpha-bromodiuron) +TX, bromomurine amine (92) +TX, calcium cyanide (444) +TX, chloroaldehyde sugar (127) +TX, chloromurine ketone (140) +TX, cholecalciferol (alias) (850) +TX) clomazone (1004) +TX, clomazone (1005) +TX, deratization naphthalene (175) +TX, deratization pyrimidine (1009) +TX, muodex (246) +TX, thiabendazole (249) +TX, diphacinone (273) +TX, calcified alcohol (301) +TX, fluoromous (357) +TX, fluoroacetamide (379) +TX, fluoromous pyridine (1183) +TX, fluoromous pyridine hydrochloride (1183) +TX, gamma-HCH (430) +TX, hydrogen cyanide (444) +TX, methyl iodide (IUPAC name) (542) +TX, lindan (430) +TX, magnesium phosphide (IUPAC name) (640) +TX, methyl bromide (537) +tx, mouse telnet (1318) +tx, mouse phosphorus (1336) +tx, phosphine (IUPAC name) (640) +tx, phosphorus [ CCN ] +tx, raticide (1341) +tx, potassium arsenite [ CCN ] +tx, mouse killer (1371) +tx, chives glucoside (1390) +tx, sodium arsenite [ CCN ] +tx, sodium cyanide (444) +tx, sodium fluoroacetate (735) +tx, strychnine (745) +tx, thallium sulfate [ CCN ] +tx, mouse killer (851), and zinc phosphide (640) +tx;
A potentiator selected from the group consisting of: 2- (2-butoxyethoxy) ethyl piperonate (IUPAC name) (934) +tx, 5- (1, 3-benzodioxol-5-yl) -3-hexylcyclohex-2-enone (IUPAC name) (903) +tx, farnesol (alias) with nerolidol (324) +tx, MB-599 (research code) (498) +tx, MGK 264 (research code) (296) +tx, synergistic ether (piperonyl butoxide) (649) +tx, synergistic aldehyde (piportal) (1343) +tx, synergistic ester (propyl iscomer) (1358) +tx, S421 (research code) (724) +tx, synergistic powder (sesamex) (1393) +tx, sesamin (sesamolin) (1394), and sulfoxide (1406) +tx;
an animal repellent consisting of the group of substances consisting of: anthraquinone (32) +tx, chloral candy (127) +tx, copper naphthenate [ CCN ] +tx, copper (171) +tx, diazinon (227) +tx, dicyclopentadiene (chemical name) (1069) +tx, bispentalene (chemical name) (422) +tx, bisguanosine acetate (422) +tx, methomyl (530) +tx, pyridin-4-amine (IUPAC name) (23) +tx, zeram (804) +tx, methocarb (trimethacarb) (840) +tx, zinc naphthenate [ CCN ] and fomesan (856) +tx;
a virucide selected from the group consisting of: garment Ma Ning (alias) [ CCN ] and ribavirin (alias) [ CCN ] +tx;
A wound protectant selected from the group consisting of: mercuric oxide (512) +tx, xin Saitong (octilinone) (590) and thiophanate methyl (802) +tx;
the bioactive substance is a bioactive substance that, selected from 1, 1-bis (4-chlorophenyl) -2-ethoxyethanol +TX, 2, 4-dichlorophenyl benzenesulfonate +TX, 2-fluoro-N-methyl-N-1-naphthylacetamide +TX, 4-chlorophenyl sulfone +TX, acetylfipronil +TX aldicarb+TX, racetrack+TX, methophos+TX, amine phosphorus+TX, amine hydrogen oxalate phosphorus+TX, amitraz+TX, mite+TX, arsenic trioxide+TX, azobenzene+TX, azophosphorus+TX, benomyl+TX, amine hydrogen oxalate phosphorus+TX, amitraz+TX, amine hydrogen oxalate phosphorus+TX, amine hydrogen peroxide Benno Sha Lin (benoxafos) +TX, benzyl benzoate+TX, bixafen+TX, bromethrin+TX, bromthiophos+TX, bromethrin+TX, buprofezin+TX, carboline+TX, butylpyridaben+TX, calcium polysulfide+TX, octachlorocamphene+TX, chlorcarboline+TX, trithion+TX, fenpicrine+TX, fenpicrin+TX, chlorpyrifos+TX, chlorpyrifos hydrochloride+TX, acaricidal+TX, dichlormite+TX, ethylacaricidal+TX, acaricidal (chlormeform) +TX, chlormeurea+TX, propylacaricidal+TX, acaricidal+TX, fenphos+TX, fenvalerate I+TX, fenvalerate II+TX, fenvalerate+TX, clomiphos+TX, baphos+TX, thiazalin+TX, fructophos+TX, DCPM+TX, DDT+TX, trifluophos+TX, trifluophos-O+TX, trifluophos-S+TX, inner phosphorus-methyl+TX, inner phosphorus-O+TX, inner phosphorus-S+TX, inner phosphorus-S-methyl+TX, sulfophosphorus (methyl-S-methyl) +TX, inner phosphorus+TX, dichlorvos+TX, dichlorphos+TX, dite+TX, dithium+TX, trifluophos+TX, fluben+TX; dermatophagoides (dinex-dicylexine) +TX, dermatophagoides-4+TX, dermatophagoides-6+TX, dermatophagoides-TX, nitropenyl+TX, nitrooctyl acaricide+TX, nitrobutyl+TX, dephos+TX, sulfodiphenyl+TX, alcohol-stopping sulfur+TX, DNOC+TX, phenoxypropargite (dofenapyn) +TX, doraglutin+TX, duropectin+TX, durophos+TX, irinotetin+TX, yilufenphos+TX, difenphos+TX bupirimate+tx, fenbuconazole+tx, fenbutatin oxide+tx, benfuracarb+tx, fenpyrad+tx, fenpyroximate+tx, fenpyraclostrobin+tx, fenbuconazole+tx, flunifanil (fenrifanil) +tx, flucyclox+tx, flucycloxuron+tx, varroa+tx, flucycloxaprid+tx, FMC 1137+tx, valicamidine+tx, valicamidine hydrochloride+tx, carboxin (formarate) +tx, gamma-hch+tx, levalidine+tx, benzyl mite ether+tx, cetyl cyclopropanecarboxylate+tx, hydrohead thiophosphorus+tx, jasmine i+tx, jasmine ii+tx, iodipin+tx, lindane+tx, propargin+tx, aphphos+tx, dithiine+tx, methylthiophen+tx, chlorfenphos+tx, methyl bromide+tx, speed mecarb+tx, from carbofuran+tx, milbexime+tx, propylamine fluoro+tx, monocrotophos+tx, cyclopentadienyl+tx, moxidectin+tx, dibromophosphorus (naled) +tx, 4-chloro-2- (2-chloro-2-methyl-propyl) -5- [ (6-iodo-3-pyridinyl) methoxy ]pyridazin-3-one+TX, fluoroformin+TX, nikkomycin+TX, pentacarbofuran+TX, pentacarbofuran 1:1 zinc chloride complex+TX, omethoate+TX, isosulfone phosphorus+TX, sulfone phosphorus+TX, pp' -DDT+TX, parathion+TX, permethrin+TX, fenphos+TX, fuphos+TX, thiocyclophosphorus+TX, phospham+TX, turpentine chloride (polychloroeteres) +TX, acaricide (polynaphins) +TX, prochloraz+TX, tick carbofuran+TX, propoxur+TX, ethidium+TX, hydrophoshan+TX, pyrethrin+TX, pyrethrin II+TX, pyrethrin+TX, pyridazinethion+TX, azophos+TX, quinalphos+TX, quinalphos (quinalphos) +TX, R-1492+TX, glycilphos+TX, rotenone+TX, octamethyl+TX, captan+TX, selacin+TX, su Liu phosphorus+TX, SSI-121+TX, shu Feilun +TX, flubendiamide+TX, thiotepa+TX, sulfur+TX, flubenzine+TX, tau-flufenpropathrin+TX, TEPP+TX, terbucarb+TX, tetrachlorethamine+TX, miticidal+TX, thiafenox+TX, indoxacarb+TX, jicarb+TX, jiuwei+TX, methyiphos+TX, cyphos+TX, flufenphos+TX, triazu+TX, triazamate (triazamate) triclopyr+tx, trialumin+tx, aphididol+tx, tolfenpyr (vaniliprole) +tx, baishazin (bethoxazin) +tx, copper dioctate+tx, copper sulfate+tx, cybutryne+tx, dichloro naphthoquinone+tx, bischlorophenol+tx, skim acid+tx, triphenyltin+tx, slaked lime+tx, zineb+tx, algin+tx, quinodown+tx, simazine+tx, triphenyltin acetate+tx, triphenyltin hydroxide+tx, livestock phosphorus+tx, piperazine+tx, thiophan+tx, chloral sugar+tx, doubly thiophos+tx, pyridin-4-amine+tx, strychnine+tx, 1-hydroxy-1H-pyridin-2-thione+tx, 4- (quinolin-2-ylamino) benzenesulfonamide+tx, 8-hydroxyquinoline sulfate+tx, bromohydrin+tx, copper+tx, cresol+tx, bipyramid+tx, polydatin+tx, disodium+tx, formaldehyde+tx, mercuric+tx, kasugamycin+tx, kasugamycin hydrochloride hydrate+tx, nickel bis (dimethyldithiocarbamate) +tx, trichloromethylpyridine+tx, xin Saitong +tx, oxolinic acid+tx, terramycin+tx, potassium hydroxyquinoline sulfate+tx, thiabendazole+tx, streptomycin+tx, streptomycin sesquisulfate+tx, phyllostachys-phthalein+tx, thimerosal+tx brown moths GV+TX, agrobacterium radiobacter+TX, amblyseius species (Amblyseius spp.) +TX, apium graveolens NPV+TX, oenothera biennis (Anagrus atomus) yellow moths (Anagrus atomus) +TX, aphidius aphycus (Aphelinus abdominalis) +TX, aphidius gossypii parasitic bees (Aphidius colemani) +TX, aphidius gifuensis (Aphidoletes aphidimyza) +TX, aphidius albopictus NPV+TX, bacillus sphaericus (Bacillus sphaericus Neide) +TX, beauveria brucei (Beauveria brongniartii) +TX, phaeda munta (Chrysoperla carnea) +TX, cryptomeria montosa (Cryptolaemus montrouzieri) +T X, codling moth GV+TX, siberian off-board cocoon bee (Dacnussa sibirica) +TX, pisum sativum potential She Yingji wasp (Diglyphus isaea) +TX, aphis citrifolia (Encarsia for mosa) +TX, aphis citrifolia (Eretmocerus eremicus) +TX, heterodera avenae (Heterorhabditis bacteriophora) and heterodera avenae (H.megdis) +TX, ladybug (Hippodamia convergens) +TX, orange powder scale parasitic wasp (Leptomastix dactylopii) +TX, lygus lucorum (Macrolophus caliginosus) +TX, cabbage looper NPV+TX, huang Kuobing jumping wasp (Metaphycus helvolus) +TX, yellow green muscardine (Metarhizium anisopliae vacridum) +TX, tortoise green muscardine small spore variety (Metarhizium anisopliae var. Aniopsis) +TX, european new pine needle (Neodiprion sertifer) V and red pine needle new leaf (N.tei+NPV) the plant species of the genus orius +tx, paecilomyces fumosoroseus (Paecilomyces fumosoroseus) +tx, phytoseiulus wisdom (Phytoseiulus persimilis) +tx, mao Wen nematodes (Steinernema bibionis) +tx, strongylos-worm (Steinernema carpocapsae) +tx, night moths +tx, grignard nematodes (Steinernema glaseri) +tx, rubis-worm (Steinernema riobrave) +tx, steinernema riobravis +tx, mole cricket-worm (Steinernema scapterisci) +tx, strongylos-worm species (stenernema spp.) +tx, trichogramma species +tx, cygnus wegianus (Typhlodromus occidentalis) +tx, verticillium lecanii (Verticillium lecanii) +tx, azolphoszine (apholate) +tx, bis (aziridine) methylaminophosphine sulfide (bisazi) +tx, busulfan+tx, dimatif (dimatif) +tx, hexamethylmelamine (hemel) +tx, hexamethylphosphoric (hempa) +tx, methylnasal discharge bar (metepa) +tx, methylthionasal discharge bar (methyoepa) +tx, methylphosphinazine (methyl apholate) +tx, infertility (morzid) +tx, fluprolyl (penfluron) +tx, nasal discharge bar (opa) +tx, thiohexamethylphosphoric (thiohempa) +tx, thionasal discharge bar+tx, tritamine+tx, urethanimine+tx, (E) -dec-5-en-1-ylacetate and (E) -dec-5-en-1-ol+tx, (E) -tridec-4-en-1-ylacetate+tx, (E) -dec-2-en-4-ol+tx, (E, Z) -tetradec-4, 10-dien-1-acetate, (Z) -hexadec-7-1-yl acetate, (Z) -hexadec-11-en-1-yl acetate, (Z) -hexadecen-11-yl acetate -7-en-1-al +tx, (Z) -tetradec-9-en-1-ol +tx, (Z) -tetradec-9-en-1-yl acetate +tx, (7 e, 9Z) -dodeca-7, 9-dien-1-yl acetate +tx, (9Z, 11 e) -tetradec-9, 11-dien-1-yl acetate +tx, (9Z, 12 e) -tetradec-9, 12-dien-1-yl acetate +tx, 14-methyl octadec-1-en +tx, 4-methyl non-5-ol and 4-methyl non-5-one +tx, alpha-multislot +tx, western pine bark aggregate pheromone +tx, dodecadienol (codlemore) +tx, obtainable (codlemone) +tx lure (cure) +TX, epoxynonadecane+TX, dodeca-8-en-1-yl acetate+TX, dodeca-9-en-1-yl acetate+TX, dodeca-8+TX, 10-dien-1-yl acetate+ TX, dominicalure +TX, 4-methyl ethyl octoate+TX, eugenol+TX, southern pine bark beetle aggregate pheromone (front paint) +TX, lure mixture (grand paint) +TX, lure mixture I+TX, lure mixture II+TX, lure mixture III+TX, lure mixture IV+TX, lure (hexapaint) +TX, bark beetle dienol (ipsdienol) +TX, the preparation method comprises the steps of (1) performing a chemical reaction on a small kipedia enol (ipsenol) +TX, a chafer sex attractant (japoniure) +TX, trimethyldioxacyclononane (linetin) +TX, liture+TX, a noctuid sex attractant (looplus) +TX, a trapping ester (medure) +TX, a megajig acid+TX, a trap ether (methyl eugenol) +TX, a trap alkene (mu scale) +TX, octadeca-2, 13-diene-1-yl acetate+TX, octadeca-3, 13-diene-1-yl acetate+TX He Kangbi (orfraure) +TX, cocois Rhinocerotis, testudinis, non-Lekon (ostrimone) +TX, lure ring (siglure) +TX, sordidin+TX, edible fungus methyl lure alcohol (sulcatol) +TX, tetradec-11-en-1-yl acetate+TX, mediterranean fly attractant (trimedlure) +TX, mediterranean fly attractant A+TX, and Mediterranean fly attractant B 1 +TX, mediterranean fruit fly attractant B 2 +TX, drosophila attractant C+TX, trunk-call+TX, 2- (octylthio) ethanol+TX, mosquito-repellent ketone (butylopyronoxy) +TX, butoxy (polypropylene glycol) +TX, dibutyl adipate+TX, dibutyl phthalate+TX, dibutyl succinate+TX, mosquito-repellent amine+TX, mosquito-repellent (dimethyl carbate) +TX, dimethyl phthalate+TX, ethyl hexanediol+TX, hexamide (hexamide) +TX, mequintin (methoquin-butyl) +TX, methyl neodecanoamide (methylneodecanamide) +TX, oxamate) +TX, pie-calidine (picatidine)) +TX, 1-dichloro-1-nitroethane+TX, 1-dichloro-2, 2-bis (4-ethylphenyl) ethane+TX, 1, 2-dichloropropane and 1, 3-dichloropropene+TX, 1-bromo-2-chloroethane+TX, 2-trichloro-1- (3, 4-dichlorophenyl) ethyl acetate+TX, 2-dichloroethylene 2-ethylsulfinyl ethyl methyl phosphate+TX, 2- (1, 3-dithio-2-yl) phenyldimethylcarbamate+TX, 2- (2-butoxyethoxy) ethylthiocyanate+TX, 2- (4, 5-dimethyl-1, 3-dioxolan-2-yl) phenylmethylcarbamate+TX, 2- (4-chloro-3, 5-xylyloxy) ethanol+TX, 2-chlorovinyl diethyl phosphate+TX, 2-imidazolidinone+TX, 2-isovaleryl-1, 3-dimethyl-2-alkynyl methyl carbamate+TX, 2-dimethyl-2-propargyl 2-methyl carbamate (2-methyl-3-propargyl) 2-methyl carbamate+TX, 2- (4, 5-dimethyl-1, 3-dioxolan-2-yl) phenylmethyl carbamate+TX, 2- (4-dimethyl-1, 3-dimethyioxy) phenylcarbamate+TX, 2-methyl carbamate+TX, 5, 5-dimethyl-3-oxocyclohex-1-enyl dimethylcarbamate+TX, acephate+TX, acrylonitrile+TX, airy-side agent+TX, alomicin+TX, carbofuran+TX, alpha-ecdysone+TX, aluminum phosphide+TX, methomyl+TX, neonicotin+TX, ethylmethidathion (ath) +TX, picoline+TX, bacillus thuringiensis delta-endotoxin+TX, barium hexafluorosilicate+TX, barium polysulfide+TX, fumigating pyrethrin+TX, bayer 22/190+TX, bayer 22408+TX, beta-cyhalothrin+TX, pencycurthrin (bioethotetrain) +TX, biochlorethrin+TX, bis (2-chloroethyl) ether+TX, borax+TX, bromophenaphos+TX, bromo-DDT+TX, methoprene+TX carbofuran+tx, tertiaryphos (bustathiofos) +tx, butylphosphorus+tx, calcium arsenate+tx, calcium cyanide+tx, carbon disulfide+tx, carbon tetrachloride+tx, bardane hydrochloride+tx, sivadine (cevadine) +tx, borneol+tx, chlordane+tx, decachloroketone+tx, chloroform+tx, chloropicrin+tx, chlorpyrifos+tx, chlorpyrifos (chlorpyrizophos) +tx, cis-bifenthrin (cis-resmethrin) +tx, cis-bifenthrin (cismithrin) +tx, fenpropathrin (clochettrin) (alias) +tx, copper acetylarsenite+tx, copper arsenate+tx, copper oleate+tx, benazel+tx, fenitron+tx, cyclochrysanthemate+tx, fenphos+tx, d-chrysanthemate+tx, d-chrysanthemate+chrysanthemate Daep+tx, daon+tx, demethylation Carbofuran (carbofuran) +TX, desmethyl (diamidafos) +TX, isochlorophosphorus+TX, desmphosphorus+TX, dicresyl+TX, dicycloprid+TX, di-reagent+TX, diethyl 5-methylpyrazol-3-yl phosphate+TX, asthma (dior) +TX, tetrafluoromethyl ether pyrethrin+TX, dimchip+TX, permethrin+TX, methyl toxalate+TX, difly carb+TX, propofol+TX, pentanitrophenol+TX, dinotefuran+TX, benflumetol+TX, benflumorph+TX, thiopyran phosphorus+TX, DSP+TX, ecdysterone+TX, EI 1642+TX, EMPC+TX, EPBP+TX, etahos+TX, ethionine+TX, ethyl formate+TX, dibromoethane+TX, dichloroethane+TX, ethylene oxide+TX, EXD+TX, piroman+TX, ethylbenzene-wire+TX, fenitrothion+TX, oxamide (fenoxacrim) +TX, cyhalothrin+TX, fenitrothion+TX, ethylthiophos+TX, fluclobisfenuron (fluofuron) +TX, fenitrothion+TX phosphorus arsenic ester (TX), butyl ring sulfur phosphorus (TX), furbenfuracarb (TX), anti-insect chrysanthemum (TX), biguanide octyl salt (TX), biguanide octyl acetate (TX), sodium Tetrathiocarbonate (TX), benzyl fenprox (halfenprox) +TX, HCH (TX), HEOD (TX), heptachloride (TX) Sulfothioate+TX, HHTN+TX, hydrogen cyanide+TX, quinolinyl+TX, IPSP+TX, chlorazol-P+TX, carbochlor+TX, isoeudipyr+TX, iso Liu Lin +TX, transplanting agent+TX, isoprothiolane+TX, oxazalin+TX, juvenile hormone I+TX, juvenile hormone II+TX, juvenile hormone III+TX, chlorpentan+TX, eneyne+TX, lead arsenate+TX, bromophenyl phosphorus+TX, acetamiprid+TX, thiazolium+TX, m-isopropylphenyl methyl carbamate+TX, chlorpyrifos+TX, magnesium phosphide+TX, azido+TX, methylparaben+TX, aphethion+TX, mercurous chloride+TX, methylsulfonylphosphine+TX, carb+TX, carb-mu potassium salt+TX, carb-mu sodium salt+TX, methylsulfonyl fluoride+TX, butenin+TX, methopren+TX, methothrin+TX, methox D+TX, methyl isothiocyanate+TX, methyl chloroform+TX, dichloromethane+TX, oxadone+TX, imazalin+TX, nepenthion+TX, naphthalene+TX, NC-170+TX, nicotine+TX, nitrothiazine+TX, primordial nicotine+TX, O-5-dichloro-4-iodophenyl O-ethyl thiophosphonate+TX, O, O-diethyl O-4-methyl-2-oxo-2H-benzopyran-7-yl thiophosphonate+TX, O, O, O-diethyl O-6-methyl-2-pyrimidine-4-yl thiophosphate+TX, O, p-dimethyl-4-propyl-thiophosphate+p-phenyl, O, O '-thio-4-methyl-p-thiophosphate+TX, O, p-butyl p-phenyl, O, p-thio-methyl-4-methyl-ethyl thiophosphonate+TX, O, O' -methyl-2-ethyl thiophosphate+TX TX, pentachlorophenyl laurate+TX, PH 60-38+TX, fenphos+TX, parachlorothio+TX, phosphine+TX, methyl octylthio+TX, methamidothion+TX, polychlorinated dicyclopentadiene isomer+TX, arsenite+TX, potassium thiocyanate+TX, precocin I+TX, precocin II+TX, precocin III+TX, amidephosphine+TX, profenothrin+TX, fipronil+TX, propylthio-phosphorus+TX, piroxicam+TX, antichlorethamine+TX, kudo extract (quassia) +TX, quinalphos-methyl+TX, fluanin+TX, iosalazine+TX, benzofuranone+TX, thienyl TX, rypsin+TX, rimorin+TX, sabachela+TX, octamethiphos+TX, cretinin+TX, SI-0009+TX, thiazide+sodium, sodium cyanide+sodium chloride+sodium fluoride, sodium fluoride+sodium fluoride, sodium fluoride+sodium fluoride, sodium selenate+TX, sodium thiocyanate+TX, sulfometuron (sulfofuron) +TX, sulfometuron sodium salt (sulfofuron-sodium) +TX, sulfuryl fluoride+TX, thioprop+TX, tar+TX, thiamethoxam+TX, TDE+TX, butylpyrimidyl phosphate+TX, dithiophosphate+TX, cycloprothrin+TX, tetrachloroethane+TX, thiacloprid+TX, thiocyclam+TX, cycloxapride+TX, triad+TX, monosultap+TX, tetrabromothrin+TX, antichlorethrin+TX, triazamate+TX, trichlorethamate-3 (trichlorethamethos-3) +TX, toxaphos+TX, triadimefon+TX, triflumon (tolpro+TX), chlorpyrifos+TX, methoprene+TX, triad+TX, veratrine+tx, xmc+ TX, zetamethrin +tx, zinc phosphide+tx, tolfenpyrad+tx, halothrin+tx, tetrafluorotetramethrin+tx, bis (tributyltin) oxide+tx, bromoacetamide+tx, ferric phosphate+tx, niclosamide-ethanolamine+tx, tributyltin oxide+tx, pyrimorph+tx, snail+tx, 1, 2-dibromo-3-chloropropane+tx, 1, 3-dichloropropene+tx, 3, 4-dichlorotetrahydrothiophene 1, 1-dioxide+tx, 3- (4-chlorophenyl) -5-methylrhodamine+tx 5-methyl-6-thioxo-1, 3, 5-thiadiazin-3-ylacetic acid +TX, 6-isopentenylaminopurine + TX, anisiflupurin +TX, benzothiadiazine +TX, cytokinin +TX, DCIP +TX, furfuraldehyde +TX, isoamidophosphorus +TX, kinetin +TX, verrucosa composition +TX, tetrachlorothiophene +TX, xylenol +TX, zeatin +TX, ethylxanthate +TX, alac benzene-S-methyl +TX, giant knotweed (Reynoutriea sa) chaminesis) extract +tx, α -chlorohydrin +tx, antoin +tx, barium carbonate +tx, bismurine urea +tx, bromomuolone +tx, bromodiuron +tx, bromomurinamine +tx, chloromurinone +tx, cholecalciferol +tx, chlorowarfarin +tx, kemized +tx, mousetrap +tx, mucedin +tx, thiabendazole +tx, diuron +tx, calcific alcohol +tx, fluoromurinin +tx, fluoroacetamide +tx, fluorozidine +tx, fluoroziridine hydrochloride +tx, mousetrap +tx, phosphorus +tx, murinone +tx, mousetrap +tx, sodium fluoroacetate +tx, thallium sulfate +tx, warfarin +tx, 2- (-2-butoxyethoxy) ethyl acetate +tx, 5- (1, 3-benzodioxol-5-yl) -3-hexyl-cyclohexenone +264, methyl, falcine +tx, and falcine +tx, + (MGK), synergistic ether+tx, synergistic aldehyde+tx, synergistic ester (propylisomer) +tx, s421+tx, synergistic powder+tx, sesamin (sesamolin) +tx, sulfoxide+tx, anthraquinone+tx, copper naphthenate+tx, copper king+tx, dicyclopentadiene+tx, sialon+tx, zinc naphthenate+tx, ziram+tx, clothing Ma Ning +tx, ribavirin+tx, chloroindole hydrazide (chloroindole azide) +tx, mercuric oxide+tx, thiophanate methyl+tx, azaconazole+tx, bitertanol+tx, furfuryl+tx, cyproconazole+tx, difenoconazole+tx, diniconazole+tx, epoxiconazole+tx, nitrile benzoxazole+tx, fluquinconazole+tx, flusilazole+tx, flutriazole+tx, fluquine+tx, furazamine+tx, hexaconazole+tx, imazalil+tx, imibenconazole+tx, ipconazole+tx, metconazole+tx, myclobutanil+tx, paclobutrazol+tx, fenoxanil+tx, penconazole+tx, prothioconazole+tx, pyripyroxime (pyrifenox) +tx, prochloraz+tx, propiconazole+tx, pyribenzoxazole+tx, simeconazole (simeconazole) +tx, tebuconazole+tx, fluoroether+tx, triazolone+tx, triadimenol+tx, fluxazole+tx, sterilizing azole+tx, pyrimidol+tx, chloropyrimidol+tx, bupirimate+tx, methiodine (dimethirimol) +tx, ethirimol+tx, dodine+tx, propidium+tx, fenpiclonil+tx, spiroxamine+tx, pyrimethanil+tx; fenpiclonil+tx, fludioxonil+tx, benalaxyl (benalaxyl) +tx, furalaxyl (furalaxyl) +tx, metalaxyl+tx, R-metalaxyl+tx; furamide+tx; oxadixyl (oxadixyl) +TX, carbendazim+TX, Prochloraz (debacarb) +TX, fuberine+TX, thiabendazole+TX, ethiprole (chlorazolinate) +TX, sclerotinia (dichlorizoline) +TX, methicillin (myclobulin) +TX, procymidone) +TX, vinylsclerotinia (vinclozoline) +TX, boscalid (boscalid) +TX, carboxin+TX, furamide+TX, fluoroamide (flutolanil) +TX, methoxam+TX, methide+TX carboxin+tx, penthiopyrad+tx, thifluzamide+tx, docusamine+tx, biguanide octylamine+tx, azoxystrobin+tx, kresoxim-methyl+tx, enoxim-methyl (enestrobulin) +tx, enoxim-methyl+tx, flufenpyroxim-methyl+tx, fluoxastrobin+tx, kresoxim-methyl+tx, trifloxystrobin+tx, oxime kresoxim-methyl+tx, picoxystrobin+tx pyraclostrobin+tx, ferbam+tx, mancozeb+tx, metiram+tx, zineb+tx, diroller+tx, captan+tx, furazolidone+tx, folpet+tx, dimoxystrobin+tx, poldoc+tx, copper oxide+tx, mancozeb+tx, quinolinium+tx, phthalazoxystrobin+tx, kewen+tx, iprobenfos+tx, clocophos+tx, methyl-ricketamine+tx, diroller+tx, benthiavalicarb+tx, chlorothalonil (blicidin-S) +tx, triclopyr+tx, cyfluanide+ TX, cyclobutrifluram +tx, dicyclanil+tx, pyridalyne (dicyclanil) +, pyridalyne (diazirine), and chlororam (clomazone) Diethofencarb (diethofencarb) +TX, dimethomorph+TX, flumorph+TX, dithianon (dithianon) +TX, ethaboxam (ethaboxam) +TX, hymexazol (ethidiazole) +TX, famoxadone+TX, fenamidone (fenamidone) +TX, fenoxanil) +TX, azomethizone (ferimzone) +TX, fluazinam (fluazinam) + TX, flumetylsulforim + TX, flupyraclostrobin (fluopimide) + TX, fluoxytioconazole + TX, sulfenamide (fluvulfamide) +TX, fluazolamide+TX, cycloxamide+TX aluminum triethylphosphonate (fosetyl-aluminum) +TX, hymexazol) +TX, propineb+TX, triamcinolone (cyazofamid) +TX, thiodicarb (methasulfocarb) +TX, metrafenone+TX, pencycuron (pencycuron) +TX, phthalide+TX, polyoxin (polyoxin) +TX, propamocarb (propamocarb) +TX, piroxicam+TX, iodoquinazin (proquinazin) +TX, fluquintozene (pyroquin) +TX, piroxicam+TX, quinoxyfen+TX, pentachloronitrobenzene+TX, thiabendazole+TX Amide+tx, imidazoxide (triazoxide) +tx, tricyclazole+tx, oxazine+tx, validamycin+tx, valamine+tx, zoxamide (zoxamide) +tx, mandipropamid+tx, fluorophenylamine (flubeneteram) +tx, isopyrazam+tx, fluxazol cycloxamine (sedaxane) +tx, benzovindiflupyr+tx, fluxazoxamide+tx, 3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid (3 ',4',5' -trifluoro-dibenzo-2-yl) -amide+ TX, isoflucypram +tx, isothiamine+ TX, dipymetitrone +tx, 6-ethyl-5, 7-dioxo-pyrrolo [4,5 ]][1,4]Dithiino [1,2-c ]]Isothiazole-3-carbonitrile +TX, 2- (difluoromethyl) -N- [ 3-ethyl-1, 1-dimethyl-indan-4-yl]Pyridine-3-carboxamide +tx, 4- (2, 6-difluorophenyl) -6-methyl-5-phenyl-pyridazine-3-carbonitrile +tx, (R) -3- (difluoromethyl) -1-methyl-N- [1, 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, azoxystrobin (jiaxigjunzhi) + TX, lvbenmixianan + TX, dichlobentiazox +tx, mandesbinin +tx, 3- (4, 4-difluoro-3, 4-dihydro-3, 3-dimethylisoquinolin-1-yl) quinolone +tx, 2- [ 2-fluoro-6- [ (8-fluoro-2-methyl-3-quinolinyl) oxy ]Phenyl group]propan-2-ol+TX, thiapiprazole (oxathiapiprolin) +TX, N- [6- [ [ [ (1-methyltetrazol-5-yl) -phenyl-methylene]Amino group]Oxymethyl group]-2-pyridyl group]Tert-butyl carbamate + TX, pyraziflumid + TX, inpyrfluxam + TX, trolprocarb +TX, haloxyfop-butyl + 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-carboxamide +tx, N' - [4- (4, 5-dichlorothiazol-2-yl) oxy-2, 5-dimethyl-phenyl]-N-ethyl-N-methyl-formamidine +TX, [2- [3- [2- [1- [2- [3, 5-bis (difluoromethyl) pyrazol-1-yl ]]Acetyl group]-4-piperidinyl]Thiazol-4-yl]-4, 5-dihydro-isoxazol-5-yl]-3-chloro-phenyl]Methanesulfonate +TX, N- [6- [ [ (Z) - [ (1-methyltetrazol-5-yl) -phenyl-methylene]Amino group]Oxymethyl group]-2-pyridyl group]But-3-ynyl carbamate + TX, N- [ [5- [4- (2, 4-dimethylphenyl) triazol-2-yl ]]-2-methyl-phenyl]Methyl group]Carbamic acid methyl ester +TX, 3-chloro-6-methyl-5-phenyl group-4- (2, 4, 6-trifluorophenyl) pyridazin + TX, pyridachlometyl +TX, 3- (difluoromethyl) -1-methyl-N- [1, 3-trimethylindan-4-yl]Pyrazole-4-carboxamide +TX and 1- [2- [ [1- (4-chlorophenyl) pyrazol-3-yl ] ]Oxymethyl group]-3-methyl-phenyl]-4-methyl-tetrazol-5-one+tx, 1-methyl-4- [ 3-methyl-2- [ [ 2-methyl-4- (3, 4, 5-trimethylpyrazol-1-yl) phenoxy ]]Methyl group]Phenyl group]Tetrazol-5-one + TX, aminopyrifen +TX, azoxystrobin +TX, indazole-sulbactam +TX, fluxapyroxad +TX, (Z, 2E) -5- [1- (4-chlorophenyl) pyrazol-3-yl]oxy-2-methoxyimino-N, 3-dimethyl-pent-3-enamine + TX, florylpicoxamid +TX, topiramate (fenpicoxamid) + TX, metarylpicoxamid + TX, tebufloquin + TX, ipflufenoquin + TX, quinofumelin +TX, ipratropium +TX, N- [2, 4-dichloro-phenoxy]Phenyl group]-3- (difluoromethyl) -1-methyl-pyrazole-4-carboxamide +tx, N- [2- [ 2-chloro-4- (trifluoromethyl) phenoxy ]]Phenyl group]-3- (difluoromethyl) -1-methyl-pyrazole-4-carboxamide +tx, benzothiostrobin +tx, cyanophenyl +tx, 5-amino-1, 3, 4-thiadiazole-2-thiol zinc salt (2:1) +tx, fluopyram + TX, flufenoxadiazam +tx, fluothiazolazetidine +tx, fluoroether carboxamide + TX, pyrapropoyne +tx, piprazole (picartrazox) +tx, 2- (difluoromethyl) -N- (3-ethyl-1, 1-dimethyl-indan-4-yl) pyridine-3-carboxamide +tx, 2- (difluoromethyl) -N- ((3R) -1, 3-trimethylindan-4-yl) pyridine-3-carboxamide +tx, 4- [ [6- [2- (2, 4-difluorophenyl) -1, 1-difluoro-2-hydroxy-3- (1, 2, 4-triazol-1-yl) propyl ]-3-pyridyl]Oxy group]Benzonitrile + TX, metyltetraprole +TX, 2- (difluoromethyl) -N- ((3R) -1, 3-trimethylindan-4-yl) pyridine-3-carboxamide +TX, alpha- (1, 1-dimethylethyl) -alpha- [4'- (trifluoromethoxy) [1,1' -diphenyl]-4-yl]-5-pyrimidinemethanol+ TX, fluoxapiprolin +TX, enestrobin (enoxaprop) TX, 4- [ [6- [2- (2, 4-difluorophenyl) -1, 1-difluoro-2-hydroxy-3- (1, 2, 4-triazol-1-yl) propyl ]]-3-pyridyl]Oxy group]Benzonitrile +TX, 4- [ [6- [2- (2, 4-difluorophenyl) -1, 1-difluoro-2-hydroxy-3- (5-sulfanyl-1, 2, 4-triazol-1-yl) propyl ]]-3-pyridyl]Oxy group]Benzonitrile +TX, 4- [ [6- [2- (2, 4-difluorophenyl) -1, 1-difluoro-2-hydroxy-3- (5-thio-4H-1, 2, 4-triazol-1-yl) propyl ]]-3-pyridyl]Oxy group]benzonitrile+TX, trinexapac-ethyl+TX, coumoxystrobin+TX, mesogenic agent+TX, thiabendazole+TX, thiazole zinc+ TX, amectotractin +TX, iprodione+ TX, seboctylamine +TX, N' - [ 5-bromo-2-methyl-6- [ (1S) -1-methyl-2-propoxy-ethoxy ]]-3-pyridyl]-N-ethyl-N-methyl-formamidine +tx, N' - [ 5-bromo-2-methyl-6- [ (1R) -1-methyl-2-propoxy-ethoxy ]]-3-pyridyl]-N-ethyl-N-methyl-formamidine +tx, N' - [ 5-bromo-2-methyl-6- (1-methyl-2-propoxy-ethoxy) -3-pyridinyl ]-N-ethyl-N-methyl-formamidine +tx, N' - [ 5-chloro-2-methyl-6- (1-methyl-2-propoxy-ethoxy) -3-pyridinyl]-N-ethyl-N-methyl-formamidine +tx, N' - [ 5-bromo-2-methyl-6- (1-methyl-2-propoxy-ethoxy) -3-pyridinyl]-N-isopropyl-N-methyl-formamidine+tx (these compounds may be prepared by the methods described in WO 2015/155075); n' - [ 5-bromo-2-methyl-6- (2-propoxypropoxy) -3-pyridinyl]-N-ethyl-N-methyl-formamidine+tx (this compound can be prepared by the method described in IPCOM 000249876D); N-isopropyl-N' - [ 5-methoxy-2-methyl-4- (2, 2-trifluoro-1-hydroxy-1-phenyl-ethyl) phenyl]-N-methyl-formamidine +tx, N' - [4- (1-cyclopropyl-2, 2-trifluoro-1-hydroxy-ethyl) -5-methoxy-2-methyl-phenyl ]]-N-isopropyl-N-methyl-formamidine+tx (these compounds may be prepared by the methods described in WO 2018/228896); N-ethyl-N' - [ 5-methoxy-2-methyl-4- [ (2-trifluoromethyl) oxetan-2-yl ]]Phenyl group]-N-methyl-formamidine+tx, N-ethyl-N' - [ 5-methoxy-2-methyl-4- [ (2-trifluoromethyl) tetrahydrofuran-2-yl]Phenyl group]-N-methyl-formamidine+tx (these compounds can be prepared by the methods described in WO 2019/110427); n- [ (1R) -1-benzyl-3-chloro-1-methyl-but-3-enyl ]-8-fluoro-quinoline-3-carboxamide +TX, N- [ (1S) -1-benzyl-3-chloro-1-methyl-but-3-enyl]-8-fluoro-quinoline-3-carboxamide +TX, N- [ (1R) -1-benzyl-3, 3-trifluoro-1-methyl-propyl]-8-fluoro-quinoline-3-carboxamide +TX, N- [ (1S) -1-benzyl-3, 3-trifluoro-1-methyl-propyl]-8-fluoro-quinoline-3-carboxamide +TX, N- [ (1R) -1-benzyl-1, 3-dimethyl-butyl]-7, 8-difluoro-quinoline-3-carboxamide +tx, N- [ (1S) -1-benzyl-1, 3-dimethyl-butyl]-7, 8-difluoro-quinoline-3-carboxamide +TX, 8-fluoro-N- [ (1R) -1- [ (3-fluorophenyl) methyl]-1, 3-dimethyl-butyl]Quinoline-3-carboxamide +TX, 8-fluoro-N- [ (1S) -1- [ (3-fluorophenyl) methyl]-1, 3-dimethyl-butyl]Quinoline-3-carboxamide + TX, N- [ (1R) -1-benzyl-1, 3-dimethyl-butyl]-8-fluoro-quinoline-3-carboxamide +TX, N- [ (1S) -1-benzyl-1, 3-dimethyl-butyl]8-fluoro-quinoline-3-carboxamide +tx, N- ((1R) -1-benzyl-3-chloro-1-methyl-but-3-enyl) -8-fluoro-quinoline-3-carboxamide +tx, N- ((1S) -1-benzyl-3-chloro-1-methyl-but-3-enyl) -8-fluoro-quinoline-3-carboxamide +tx (these compounds may be prepared by the methods described in WO 2017/153380); 1- (6, 7-dimethylpyrazolo [1, 5-a)]Pyridin-3-yl) -4, 5-trifluoro-3, 3-dimethyl-isoquinoline +tx, 1- (6, 7-dimethylpyrazolo [1,5-a ] ]Pyridin-3-yl) -4, 6-trifluoro-3, 3-dimethyl-isoquinoline +tx, 4-difluoro-3, 3-dimethyl-1- (6-methylpyrazolo [1, 5-a)]Pyridin-3-yl) isoquinoline +TX, 4-difluoro-3, 3-dimethyl-1- (7-methylpyrazolo [1, 5-a)]Pyridin-3-yl) isoquinoline +TX, 1- (6-chloro-7-methyl-pyrazolo [1,5-a ]]Pyridin-3-yl) -4, 4-difluoro-3, 3-dimethyl-isoquinoline + TX (these compounds may be prepared by the methods described in WO 2017/025510); 1- (4, 5-dimethylbenzimidazol-1-yl) -4, 5-trifluoro-3, 3-dimethyl-isoquinoline + TX, 1- (4, 5-dimethylbenzimidazol-1-yl) -4, 4-difluoro-3, 3-dimethyl-isoquinoline + TX, 6-chloro-4, 4-difluoro-3, 3-dimethyl-1- (4-methylbenzimidazol-1-yl) isoquinoline + TX, 4-difluoro-1- (5-fluoro-4-methyl-benzoimidazol-1-yl) -3, 3-dimethyl-isoquinoline + TX, 3- (4, 4-difluoro-3, 3-dimethyl-1-isoquinolyl) -7, 8-dihydro-6H-cyclopenta [ e ]]benzimidazole+TX (these compounds may be prepared by the methods described in WO 2016/156085); N-methoxy-N- [ [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl]Phenyl group]Methyl group]Cyclopropanecarboxamide +tx, N, 2-dimethoxy-N- [ [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ]]Phenyl group]Methyl group]Propionamide+tx, N-ethyl-2-methyl-N- [ [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ] ]Phenyl group]Methyl group]Propionamide+tx, 1-methoxy-3-methyl-1- [ [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ]]Phenyl group]Methyl group]Urea+tx, 1, 3-dimethoxy-1- [ [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ]]Phenyl group]Methyl group]Urea+tx, 3-ethyl-1-methoxy-1- [ [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ]]Phenyl group]Methyl group]Urea+tx, N- [ [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ]]Phenyl group]Methyl group]Propionamide+tx, 4-dimethyl-2- [ [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ]]Phenyl group]Methyl group]Isoxazolidin-3-one+tx, 5-dimethyl-2- [ [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ]]Phenyl group]Methyl group]Isoxazolidin-3-one+tx, 1- [ [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ]]Phenyl group]Methyl group]Pyrazole-4-carboxylic acid ethyl ester +TX, N-dimethyl-1- [ [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ]]Phenyl group]Methyl group]-1,2, 4-triazol-3-amine+tx. The compounds in this paragraph can be prepared by the methods described in WO 2017/055473, WO 2017/055469, WO 2017/093348 and WO 2017/118689; 2- [6- (4-chlorophenoxy) -2- (trifluoromethyl) -3-pyridyl]-1- (1, 2, 4-triazol-1-yl) propan-2-ol+tx (this compound may be prepared by the method described in WO 2017/029179); 2- [6- (4-bromophenoxy) -2- (trifluoromethyl) -3-pyridinyl ]-1- (1, 2, 4-triazol-1-yl) propan-2-ol+tx (this compound may be prepared by the method described in WO 2017/029179); 3- [2- (1-chlorocyclopropyl) -3- (2-fluorophenyl) -2-hydroxy-propyl]Imidazole-4-carbonitrile + TX (this compound may be prepared by the 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 may be prepared by the method described in WO 2016/156290); 2-amino-6-methyl-pyridine-3-carboxylic acid (4-phenoxyphenyl) methyl ester+tx (this compound may be prepared by the method described in WO 2014/006945); 2, 6-dimethyl-1H, 5H- [1,4 ]]Dithiino [2,3-c:5,6-c ]']Bipyrrole-1, 3,5,7 (2 h,6 h) -tetraone + TX (this compound may be prepared by the method described in WO 2011/138281); n-methyl-4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl]Thiobenzamide+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 may be prepared by the method described in WO 2018/153707); n' - (2-chloro-5-methyl-4-phenoxy-phenyl) -N-ethyl-N-methyl-formamidine+tx; n' - [ 2-chloro-4- (2-fluorophenoxy) -5-methyl-phenyl ] ]-N-ethyl-N-methyl-formamidine+tx (this compound may be prepared by the process described in WO 2016/202742); 2- (difluoromethyl) -N- [ (3S) -3-ethyl-1, 1-dimethyl-indan-4-yl]Pyridine-3-carboxamide + TX (this compound can be prepared by the method described in WO 2014/095675); (5-methyl-2-pyridinyl) - [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ]]Phenyl group]Methanone +tx, (3-methylisoxazol-5-yl) - [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ]]Phenyl group]Methanone+tx (these compounds may be prepared by the methods described in WO 2017/220485); 2-oxo-N-propyl-2- [4- [5 ](trifluoromethyl) -1,2, 4-oxadiazol-3-yl]Phenyl group]Acetamide+tx (this compound may be prepared by the method described in WO 2018/065414); 1- [ [5- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl]-2-thienyl]Methyl group]Pyrazole-4-carboxylic acid ethyl ester+tx (this compound can be prepared by the method described in WO 2018/158365); 2, 2-difluoro-N-methyl-2- [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl]Phenyl group]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 and N- [ N-methoxy-C-methyl-carboximide]-4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl]Benzamide + TX (these compounds may be prepared by the methods described in WO 2018/202428);
a microbial agent comprising: acinetobacter reuteri+TX, acremonium+TX, cephalosporium+TX+TX, acremonium diospyri +TX, acremonium obclavatum +TX, and Philippine moth granulosis virus (AdoxGV)+TX, agrobacterium radiobacter strain K84->+TX, alternaria cassia +TX, alternaria destructor (Alternaria destruens)/(N.destructor)>+TX, powdery mildew parasitic spore->+TX, aspergillus flavus AF 36->+TX, aspergillus flavus NRRL 21882 +.>+TX, aspergillus species+TX, aureobasidium pullulans+TX, azospirillum+TX, (-A.sub.)>+TX、TAZO/>) +TX, azotobacter+TX, azotobacter chroococcus (Azotobacter chroocuccum)/(N.fuscosum)>+TX, azotobacter aschersonia (Bionatural Blooming->) +TX, bacillus amyloliquefaciens+TX, bacillus cereus+TX, bacillus chitin-eroding strain (Bacillus chitinosporus strain) CM-1+TX, bacillus chitin-eroding strain (Bacillus chitinosporus strain) AQ746+TX, bacillus licheniformis strain HB-2 (Biostart) TM />) +TX, bacillus licheniformis strain 3086 (+.>+TX、Green/>) +TX, bacillus circulans+TX, bacillus firmus (++ >+TX、BioNem-/>+TX、/>) +TX, bacillus firmus strain I-1582+TX, bacillus macerans+TX, bacillus dead sea (Bacillus marismortui) +TX, bacillus megaterium+TX, bacillus mycoides strain AQ726+TX, bacillus masti (Milky Spore depicting)>) +TX, bacillus pumilus species+TX, bacillus pumilus strain GB34 (YIeld +.>) +TX, bacillus pumilus strain AQ717+TX, bacillus pumilus strain QST 2808 (-)>+TX、Ballad/>) +TX, bacillus sphaericus (Bacillus spahericus)/(T.sp.)>+TX, bacillus species+TX, bacillus strain AQ175+TX, bacillus strain AQ177+TX, bacillus strain AQ178+TX, bacillus strain QST 713-+TX、/>+TX、/>) +TX, bacillus subtilis strain QST 714+TX, bacillus subtilis strain AQ153+TX, bacillus subtilis strain AQ743+TX, bacillus subtilis strain QST3002+TX, bacillus subtilis strain QST3004+TX, bacillus amyloliquefaciens variant strain FZB24 ]+TX、/>) +TX, bacillus thuringiensis Cry 2Ae+TX, bacillus thuringiensis Cry1Ab+TX, bacillus thuringiensis catze (Bacillus thuringiensis aizawai) GC 91->+TX, bacillus thuringiensis israel (Bacillus thuringiensis israelensis) (-A.sub.f.)>+TX、+TX、/>) +TX, bacillus thuringiensis Coulter (Bacillus thuringiensis kurstaki) (-A.sub.f.) >+TX、/>+TX、/>+TX、+TX、Scutella/>+TX、Turilav/>+TX、/>+TX、Dipel/>+TX、/>+TX、/>) +TX, bacillus thuringiensis Coulter BMP 123 +.>+TX, bacillus thuringiensis Coulter HD-1 (Bioprotection-/I)>) +TX, bacillus thuringiensis strain BD#32+TX, bacillus thuringiensis strain AQ52+TX, bacillus thuringiensis catze variety (Bacillus thuringiensis var. Aizawai) ("A)>+TX、/>) +TX, bacterial species (bacterial spp.) (-A.sub.f.)>+TX、/>+TX、/>) +TX, clavipacter michiganensis phage->+TX、/>+TX, beauveria bassiana (Beauveria bassiana) (-A. Sphaericus)>+TX、Brocaril/>) +TX, beauveria bassiana GHA (Mycotrol +.>+TX、Mycotrol/>+TX、/>) +TX, beauveria bassiana (Beauveria brongniartii) (-A.brucei)>+TX、Schweizer/>+TX、/>) +TX, beauveria spp. + TX, botrytis cinerea) +TX, soybean slow-growing rhizobia (Bradyrhizobium japonicum)/(Botrytis cinerea)>+TX, bacillus pumilus (Brevibacillus brevis) +TX, bacillus thuringiensis, walking-aid (Bacillus thuringiensis tenebrionis)/(P.sp)>+TX, btBooster+TX, burkholderia cepacia (Burkholderia cepacia) (-A.cepacia)>+TX、/>+TX、Blue/>) +TX, burkholderia (Burkholderia gladii) +TX, burkholderia gladioli (Burkholderia gladioli) +TX, burkholderia species (Burkholderia spp.) +TX, canada fungus (Canadian thistle fungus) (CBH Canadian) >) +TX, candida casei (Candida butyl) +TX, candida famata) +TX, candida frame+TX, candida glabrata) +TX, candida Jijohnsonensis (Candida guilliermondii) +TX, candida kochia (Candida melibiosica) +TX, candida olive (Candida oleophila) strain O+TX, candida parapsilosis (Candida parapsilosis) +TX, candida membrana (Candida pelliculosa) +TX, rhodotorula iron (Candida pulcherrima) +TX, candida ruit (Candida reukaufii) +TX, and Candida zizaniae ((G)>+TX、/>) +TX, candida sake (Candida sake) +TX, candida spp.+ -. TX, candida tenuis) +TX, celiriopsis dessicata (Cedecea dravisae) +TX, cedrus flavigena (Cellulomonas flavigena) +TX, and spiral shell (Chaetomium cochliodes)+TX, chaetomium globosum (Chaetomium globosum)/(N.globosum)>+TX, purple bacillus (Chromobacterium subtsugae) iron-yew strain PRAA4-1T ∈>+TX, cladosporium (Cladosporium c)ladosporides) +TX, cladosporium (Cladosporium oxysporum) +TX, cladosporium viridis (Cladosporium chlorocephalum) +TX, cladosporium spp.) +TX, cladosporium superfine (Cladosporium tenuissimum) +TX, scopularium roseum (Clonostachys rosea) +TX, anthrax aculeatus (Colletotrichum acutatum) +TX, coniothyrium minitans (Coniothyrium minitans) (Cotans +)>) +TX, coniothyrium spp, +TX, cryptococcus albus (Cryptococcus albidus)/(I/O)>+TX, cryptococcus terranei (Cryptococcus humicola) +TX, cryptococcus infirmitis-miniatus+TX, cryptococcus laurentii (Cryptococcus laurentii) +TX, malus pumila particle virus (Cryptophlebia leucotreta granulovirus)/(35)>+TX, cupriavidus campinensis +TX, codling moth granulovirus (Cydia pomonella granulovirus)/(Texil)>+TX, codling moth granulosis virus (+.>+TX、Madex/>+TX、Madex Max//>)+TX、Cylindrobasidium laeve+TX, cladosporium(Cylindrocaladium) +TX, debaryomyces hansenii (Debaryomyces hansenii) +TX, drechslera hawaiinensis +TX, enterobacter cloacae (Enterobacter cloacae) +TX, enterobacteriaceae (Enterobacteriaceae) +TX, and Aureobasidium (Entomophtora virulenta)>+TX, epicoccum nigrum) +TX, epicoccum nigrum Epicoccum purpurascens) +TX, epicoccum species+TX, filobasidium floriforme +TX, fusarium anatase+TX, fusarium oxysporum+TX, fusarium oxysporum @/Biofox />) +TX, fusarium+TX, fusarium species+TX, geotrichum candidum (Galactomyces geotrichum) +TX, scopulariopsis tenuis (Gliocladium catenulatum) +TX、/>) +TX, gliocladium roseum (Gliocladium roseum) +TX, gliocladium species +.>+TX, scolopendra viridis->+TX, granulosis virus->+TX, halophilus (Halobacillus halophilus) +TX, halophilus (Halobacillus litoralis) +TX, halophilus (Halobacillus trueperi) +TX, halophilus species +TX, halophilus (Halomonas subglaciescola) +TX, vibrio polytropus (Halovibrio variabilis) +TX, grape juiceHansenula polymorpha+TX, cotton bollworm nuclear polyhedrosis virus ++>+TX, heliothis sitophila nuclear polyhedrosis virus ++>+TX, isoflavone-formononetin->+TX, klebsiella lemon+TX, klebsiella species+TX, dactylicapnos (Lagenidium giganteum)/(Tx)>+TX, lecanicillium longiforme (Lecanicillium longisporum)>+TX, gecko scabies (Lecanicillium muscarium)>+TX, lymantria dispar nuclear polyhedrosis virus ++>+TX, haemophilus+TX, grignard Mei Lajun (Meira geulakonigii) +TX, metarhizium anisopliae +.>+TX, metarhizium anisopliae (Destruxin->)+TX、Metschnikowia fruticola/>+TX, mei Ji Yeast (Metschnikowia pulcherrima) +TX, microdochium dimerum +.>+TX, micromonospora coelicolor (Micromonospora coerulea) +TX, microsphaeropsis ochracea +TX, malodorous white fungus (Muscor albus) 620- >+TX, muscor roseus strain A3-5+TX, mycorrhiza species (mycorrizae spp.) (. About.>+TX、Root />) +TX, veratri-Veratri strain AARC-0255->+TX、BROS/>+TX, ophiostoma piliferum Strain D97+TX, paecilomyces farinosa (Paecilomyces farinosus) +TX, paecilomyces fumosoroseus+TX、/>) +TX, paecilomyces lilacinus (Paecilomyces lilacinus) (Biostat)) +TX, paecilomyces lilacinus strain 251 (MeloCon +.>) +TX, paenibacillus polymyxa+TX, pantoea agglomerans (Blight Band +)>) +TX, pantoea spGenus +TX, barnyces species +.>+TX, paecilomyces toenavatus (Pasteuria nishizawae) +TX, penicillium chrysogenum+TX, penicillium beijerinum (Penicillium billai) (. About.>+TX、/>) +TX, penicillium breve+TX, penicillium freudenreichii+TX, penicillium griseofulvum+TX, penicillium purpurogenum+TX, penicillium species+TX, pure green Kenymia+TX, phanerochaete (Phlebiopsis gigantean)+ TX, phosphate-solubilizing bacteria->+TX, cryptophan+TX, phytophthora palmi+TX, pichia anomala+TX, pichia guilliermondii (Pichia guilermondii) +TX, pichia membranaefaciens+TX, pichia unguicalis+TX, pichia stipitis+TX, pseudomonas aeruginosa+TX, pseudomonas aureofaciens (Pseudomonas aureofasciens) (Spot-Less)>) +TX, pseudomonas cepacia+TX, pseudomonas aeruginosa +. >+TX, pseudomonas rugosa (Pseudomonas corrugate) +TX, pseudomonas fluorescens strain A506 (Blight Band +)>) +TX, pseudomonas putida+TX, pseudomonas reactans +TX, pseudomonasSpecies +TX, pseudomonas syringae->+TX, pseudomonas aeruginosa+TX, pseudomonas fluorescens+TX, pseudozyma flocculosa strain PF-A22 UL (Sponodex +)>) +TX, puccinia longitus (Puccinia canaliculata) +TX, puccinia thlaspeos (Wood +.>) +TX, pythium side (Pythium oligandrum) +TX, pythium oligandrum (++>+TX、/>) +TX, pythium reesei +TX, rahnella aquatica (Rhanella aquatilis) +TX, rahnella species (Rhanella spp.) +TX, rhizobium (Rhizobia) (. Sub.f.)>+TX、/>) +TX, rhizoctonia (Rhizoctonia) +TX, rhodococcus globosus (Rhodococcus globerulus) AQ719+TX, rhodosporidium bicolor (Rhodosporidium diobovatum) +TX, rhodosporidium toruloides (Rhodosporidium toruloides) +TX, rhodotorula species (Rhodotorula spp.) +TX, rhodotorula glutinosa (Rhodotorula glutinis) +TX, rhodotorula graminearum (Rhodotorula graminis) +TX, rhodotorula mucilaginosa (Rhodotorula mucilagnosa) +TX, rhodotorula rubra (Rhodotorula rubra) +TX, saccharomyces cerevisiae (Saccharomyces cerevisiae) +TX, rhodococcus rhodochrous (Salinococcus roseus) +TX, sclerotinia sclerotiorum (Sclerotinia minor) +TX, sclerotinia sclerotiorum) />+TX, acremonium species (Scytalidium spp.) +TX, scytalidium uredinicola +TX, spodoptera exigua nuclear polyhedrosis virus (Spodoptera exigua nuclear polyhedrosis virus) (. About.>+TX、/>) +TX, serratia marcescens (Serratia marcescens) +TX, serratia praecox (Serratia plymuthica) +TX, serratia species (Serratia spp.) +TX, chaetomium faecalis (Sordaria fimicola) +TX, spodoptera frugiperda nuclear polyhedrosis virus (Spodoptera littoralis nucleopolyhedrovirus) at right angles>+TX, rhodosporidium erythropolis (Sporobolomyces roseus) +TX, stenotrophomonas maltophilia (Stenotrophomonas maltophilia) +TX, streptomyces hygroscopicus (Streptomyces ahygroscopicus) +TX, bai Qiulian mould (Streptomyces albaduncus) +TX, streptomyces defoliatus (Streptomyces exfoliates) +TX, streptomyces flavus (Streptomyces galbus) +TX, streptomyces griseus (Streptomyces griseoplanus) +TX, streptomyces griseus (Streptomyces griseoviridis)+TX, streptomyces lydicus (Streptomyces lydicus)/(S.lydicus)>+TX, streptomyces lydicus WYEC-108->+TX, streptomyces violaceus (Streptomyces violaceus) +TX, iron Ai Jiaomu (Tilletiopsis minor) +TX, iron Ai Jiaomu species (Tilletiopsis spp.) +TX, trichoderma asperellum (Trichoderma asperellum) (T34 depictinga combination of two or more species) >) +TX, trichoderma (Trichoderma gamsii)+TX, trichoderma atroviride (Trichoderma atroviride)/(S.atroviride)>+TX, trichoderma hook (Trichoderma hamatum) TH 382+TX, trichoderma harzianum (Trichoderma harzianum rifai)+TX, trichoderma harzianum (Trichoderma harzianum) T-22 (Trianum->+TX、PlantShield/>+TX、/>+TX、/>) +TX, trichoderma harzianum (Trichoderma harzianum) T-39->+TX, trichoderma atroviride (Trichoderma inhamatum) +TX, trichoderma koningii (Trichoderma koningii) +TX, trichoderma spp. Species (Trichoderma spp.) LC 52 +.>+TX, trichoderma lignin (Trichoderma lignorum) +TX, trichoderma longibrachiatum (Trichoderma longibrachiatum) +TX, trichoderma polyspora (Trichoderma polysporum) (Binab +)>) +TX, taxus chinensisTrichoderma (Trichoderma taxi) +TX, trichoderma viride (Trichoderma virens) +TX, trichoderma viride (originally called as Scopulariopsis viride (Gliocladium virens) GL-21)/(Trichoderma viride)>+TX, trichoderma viride (Trichoderma viride) +TX, trichoderma viride strain ICC 080 +.>+TX, trichosporon species (Trichosporon spp.) +TX, trichosporon species (Trichotheca spp.) +TX, monascus roseus (Trichothecium roseum) +TX, typhula phacorrhiza strain 94670+TX, typhula phacorrhiza strain 94671+TX, alternaria nigra (Ulocladium atrum) +TX, alternaria schradfimbriae (Ulocladium oudemansii) and/or Alternaria farina >+TX, maize melanogaster (Ustilago maydis) +TX, various bacteria and micronutrient supplementation (Natural->) +TX, various fungi (Millennium +.>) +TX, verticillium chlamydosporium (Verticillium chlamydosporium) +TX, verticillium lecanii (Verticillium lecanii) (-)>+TX、/>)+TX、Vip3Aa20/>+TX, cladosporium decubitus (Virgibaclillus marismortui) +TX, xanthomonas campestris pv.Poae +.>+TX, B.buriei+TX, B.nematophilus;
a plant extract comprising: pine tree oil+TX, azadirachtin (Plasma Neem +.>+TX、+TX、/>+TX、/>+TX, plant IGR (>+TX、) +TX, canola oil (Lilly Miller +.>) +TX, chenopodium ambrosioides (Chenopodium ambrosioides near ambrosioides)/(S)>+TX, chrysanthemum extract->+TX, neem oil extract +.>+TX, labiatae essential oil +.>+TX, clove-rosemary-peppermint and thyme oil extracts (Garden extract +.>) +TX, betaine->+TX, garlic+TX, lemon grass oil +.>+TX, neem oil+TX, catmint (Nepeta cataria) (catmint oil) +TX, nepeta catina+TX, nicotine+TX, oregano oil +.>+TX, pedaliaceae (Pedaliaceae) oil +.>+TX, pyrethrum+TX, quillaja (Quillaja saponaria)+TX, giant knotweed (Reynoutria sachalinensis) (-A.sub.L.)>+TX、/>) +TX, rotenone (Eco->) +TX, rutaceae (Rutaceae) plant extract ++ >+TX, soybean oil (Ortho->) +TX, tea tree oil (Timorex->) +TX, thyme oil+TX, +.>MMF+TX、/>+TX, rosemary-sesame-peppermint-thyme and cinnamon extract mixture (EF +.>) +TX, clove-rosemary and peppermint extract mixtures (EF +.>) +TX, clove-peppermint-garlic oil and peppermint mixture (oil>) +TX, kaolin->Storage dextran of +TX and brown algae
A pheromone, comprising: black spot firefly pheromone (3M Sprayable Blackheaded Fireworm)) +TX, codling moth pheromone (Paramount dispenser- (CM)/Isomate +.>) +TX, grape leaf roller pheromone (3 MMEC-GBM Sprayable +.>) +TX, leaf roller pheromone (3M MEC-LR Sprayable +.>) +TX, housefly pheromone (Musca) Snip7 Fly->+TX、Starbar Premium Fly/>) +TX, pear borer pheromone (3M oriental fruit moth sprayable +)>) +TX, peach wing moth (Peachtree Borer) pheromone +.>+TX, tomato Pinworm (Tomato Pinworld) pheromone (3M Sprayable +.>) +TX, netostat powder (extract from palm tree) (Exosex +.>) +tx, (e+tx, z+tx, Z) -3+tx,8+tx,11 tetradecatrienacetate+tx, (z+tx, E) -7+tx,11+tx, 13-hexadecatrienal+tx, (e+tx, Z) -7+tx, 9-dodecen-1-ylacetate+tx, 2-methyl-1-butanol+tx, calcium acetate+tx, and the like >+TX、/>+TX、/>+tx, lavender senecide (Lavandulyl senecioate);
macrobiological agent (macrobiological), comprising: short-range aphidius+TX, aphis aphis (Aphis ervi)+TX, acerophagus papaya +TX, ladybug distichondarium+TX, two star ladybug->+TX, two star ladybug->+TX, boschniakia rossica (Ageniaspis citricola) +TX, chaetoceros polyporus Boschniakia rossica+TX, amblyseius andersoni (Amblyseius andersoni) (-A. Fragrans)>+TX、/>) +TX, amblyseius californicus (Amblyseius californicus) (-A. Californicus)>+TX、/>) +TX, amblyseius cucumeris (>+TX、Bugline/>) +TX, amblyseius pseudoamblyseius->+TX, amblyseius spinosus (Bugline)+TX、Swirskii-/>) +TX, amblyseius oldhamii->+TX, bemisia tabaci fine bee (Amitus hesperidum) +TX, yuancherokee wing small bee (Anagrus atomus) +TX, dark abdomen long cable jumping small bee (Anagyrus fusciventris) +TX, kama long cable jumping small bee (Anagrus kamali) +TX, anagrus loecki+TX, pink long cable jumping small bee (Anagyrus pseudococci)>+TX, ericerus pela flat angle flea (Anicetus benefices) +TX, kidney bee (Anisopteromalus calandrae) +TX, dioscorea lindera (Anthocoris nemoralis)/(Tencer)>+TX, short-range Aphis cerana (>+TX、/>) +TX, aphis bre (Aphelinus asychis) +TX, aphis gossypii parasitic wasp (Aphidius colemani)/(X)>+TX, aphidius gifuensis George +.>+TX, aphidius gifuensis George+TX, aphidius gifuensis George +. >+TX, aphid eating goiter->+TX, aphid eating goiter->+TX, linnan Huang Yaxiao bee+TX, inbus Huang Yaxiao bee+TX, ha's long tail rodent bee (Aprostocetus hagenowii) +TX, ant's Crypthecodinium (Atheta coriaria) ->+TX, bumblebee species+TX, european bumblebee (Natupol)) +TX, european bumblebee (>+TX、/>) +TX, cephalonomia stephanoderis +TX, ladybug (Chilocorus nigritus) +TX, common green lacewing (Chrysoperla carnea)/(Peronotus obliquus)>+TX, common green lacewing->+TX, red-blood sand fly (Chrysoperla rufilabris) +TX, cirrospilus ingenuus +TX, tetrapanum melitense (Cirrospilus quadristriatus) +TX, bai Xingju rodent bee (Citrostichus phyllocnistoides) +TX, closterocerus chamaeleon + TX, closterocerus species+TX, coccidoxenoides perminutus+TX, porphyra tenera (Coccophagus cowperi) +TX, leidesia polycarpa (Coccophagus lycimnia) +TX, trichinella inferens (Huang Zupan) Trichinella inferens+TX, trichinella plutella+TX, cryptophanus mansoni (, meng's Cryptophanus japonicus)>+TX、) +TX, japanese Fangjia+TX, siberian ionCoptis chinensis+TX, siberia off-jaw Coptis chinensis+TX, pisum sativum (peas) potential She Yingji Apis cerana Fabricius->+TX, heilonggonella minutissima (Delphastus catalinae)/(N.sub.X)>+tx, delphastus pusillus +tx, diachasmimorpha krausii +tx, longtail fly cocoons+tx, diaparsis jucunda +tx, euonymus Alnus (Diaphorencyrtus aligarhensis) +tx, pisum sativum She Yingji calfset+tx, pisum sativum She Yingji calfset ( >+TX、/>) +TX, siberian off-jaw cocoon bee (>+TX、/>) +TX, tolyzus species+TX, lepium pythium and TX, and Aphis lividae (Encarsia->+TX、/>+TX、) +TX, aphis serovara (Eretmocerus eremicus)/(Temminck)>+TX, golden aphidis (E)ncarsia guadeloupae) +TX, engis maritima (Encarsia haitiensis) +TX, and Aphis grazing+TX, eretmoceris siphonini +TX, california myzus (Eretmocerus californicus) +TX, myzus persicae (Eretmocerus eremicus) (-A. Californica)>+TX、Eretline/>) +TX, aphis serovara (Eretmocerus eremicus)/(Temminck)>+TX, hai's oar horn aphidius+TX, mongolian oar horn aphidius (>+TX、Eretline/>) +TX, eretmocerus siphonini +TX, aleurites tetranychus (Exochomus quadripustulatus) +TX, mite goiter (Feltiella acarisuga)+TX, mite goiter->+TX, apriona domestica+TX, fopius ceratitivorus +TX, formononetin (Wirless->) +TX, thin waist thrips ++>+TX, western spider mites (Galendromus occidentalis) +TX, lei's angular head (Goniozus legeri) +TX, maifanitumCocoon bee +TX, holothuria sinensis->+TX, heterodera species (Lawn) +TX, heterodera mobilis (NemaShield +.>+TX、/>+TX、+TX、/>+TX、/>+TX、/>+TX、+TX、/>) +TX, heterodera grandis (Heterorhabditis megidis) (Nemasys +. >+TX、BioNem />+TX、Exhibitline />+TX、Larvanem-/>) +TX, aleurites maculata (Hippodamia convergens) +TX, panicum acutangulus (Hypoaspis aculeifer)+TX、/>) +TX, dermatophagoides pteronyssinus (Hypoaspis mils) (Hypoline +.>+TX、/>) +TX, black branch tarsometatarsal+TX, lecanoideus floccissimus +TX, lemophagus errabundus +TX, tri-color Liuzhuzhu wasp (Leptomastidea abnormis) +TX, orange powder scale insect parasitic wasp (Leptomastix dactylopii)/(A)>+TX, long angle Bolus (Leptomastix epona) +TX, lindorus lophanthae +TX, lipolexis oregmae +TX, and Leptophaea armigera +.>+TX, aphidius pedunculata+TX, aphidius furgus (Macrolophus caliginosus)/(Tx)+TX、Macroline/>+TX、/>) +TX, mesoseiulus longipes +TX, yellow broad-shank wasp (Metaphycus flavus) +TX, metaphycus lounsburyi +TX, keratosis kiosks+TX, yellow flea bee (Microterys flavus) +TX, muscidifurax raptorellus and Spalangia cameroni +.>+TX, neodryinus typhlocybae +TX, new Small Calif. mite+TX, new Small cucumber mite ++TX>+TX, pseudoamblyseius (Neoseiulus fallacis) +TX, nesideocoris tenuis (++>+TX、/>) +TX, bronze black fly->+TX, dolphin (Orius insolosus) (-Dolphin)>+TX、Oriline/>) +TX, orius laevigatus (Orius laevigatus) (-jersey)>+TX、Oriline/>) +TX, orius majus (Oriline +.>) +TX, stink bug- >+TX、Pauesia juniperorum+TX, ladybug, celastrus gracilis (Pediobius foveolatus) +TX, phasmarhabditis hermaphrodita +.>+TX, phymastichus coffea +TX, phytoseius macrolobus (Phytoseiulus macropilus) +TX, phytoseius Chilean ()>+TX、Phytoline/>) +TX, leucotton->+TX, parasitic flea flies (pseudoacteon) curvatus+TX, parasitic flea flies (pseudoacteon) obtusus+TX, parasitic flea flies (pseudoacteon) tricuspis+TX, pseudaphycus maculipennis +TX, pseudleptomastix mexicana +TX, wasps with Mao Shimu lice (Psyllaephagus pilosus) +TX, homochromy short back cocoons (Psyttalia concolor) (complex) +TX, crotch cornucopia species (quadricutes spp.) +TX, rhyzobius lophanthae +TX, australian ladybug+TX, rumina decolate+TX, semielacher petiolatus +TX, wheat long tube aphid @, and the like>+TX, heterodera plutella (Nematic +)>+TX、/>+TX、BioNem />+TX、/>+TX、+TX、/>) +TX, spodoptera exigua (+.>+TX、Nemasys +TX、BioNem />+TX、/>+TX、/>+TX、+TX、Exhibitline/>+TX、/>+TX、/>) +TX, apis cerana (Steinernema kraussei) (Nemasys ]>+TX、BioNem />+TX、Exhibitline />)+TXNematoda griseus (Steinernema riobrave) (-A.griseus)>+TX、/>) +TX, gryllotalpa nematode (Steinernema scapterisci) (Nematac +.>) +TX, sphaeroides species +TX, steiner (Steinernematid) species (Guardian>) +TX, deep-spotted acarid ladybug+TX, litsea Coreana+TX, tetrastichus setifer +TX, thripobius semiluteus +TX, trichinella sinensis (Torympus sinensis) +TX, trichocephalus brassicae (Tricholine) ) +TX, cabbage looper trichogramma +.>+TX, trichogramma+TX, trichogramma minutissima+TX, corn borer trichogramma+TX, trichogramma widi (Trichogramma platneri) +TX, trichogramma minor+TX, and black spot borer (Xanthopimpla stemmator);
other biological agents, including: abscisic acid +TX,+TX, silver leaf bacteria (Chondrostereum purpureum) (Chontrol->) +TX, cephalosporium longum +.>+TX, copper octoate+TX, delta trap (Trapline +.>) +TX, erwinia amylovora (Harpin)+TX、Ni-HIBIT Gold/>) +TX, ferric phosphate->+TX, funnel trap (Trapline +.>)+TX、/>+TX、Grower’s/>+TX, high brassinolide (Homo-brissolide) +TX, iron phosphate (Lilly Miller Worry Free Ferramol Slug)&Snail />) +TX, MCP hail trap (Trapline->) +TX, parasitic insect Nannocheir sinensis (Microctonus hyperodae) +TX, mycoleptodiscus terrestris +.>+TX、+TX、/>+TX、/>+TX, pheromone Row net (thread->) +TX, potassium bicarbonate->+TX, potassium salt of fatty acid +.>+TX, potassium silicate solution+TX, potassium iodide+Potassium thiocyanate->+TX、/>+TX, spider venom+TX, microsporidian locusts (Semaspore Organic Grasshopper +.>) +TX, sticky trap (Trapline->+TX、Rebell/>) +TX and Capture (Takitrapline +)>) +TX; and
safeners such as clomazone+tx, clomazone (including clomazone-methyl) +tx, cyclopropanesulfonamide+tx, dichloropropylamine+tx, clomazone (including clomazone-ethyl) +tx, clomazone+tx, fluroxypyr+tx, clomazone+tx, bisbenzoxazole acid (including bisbenzoxazole-ethyl) +tx, mefenpyr (mefenpyr) (including mefenpyr-diethyl) + TX, metcamifen +tx, and mevalonate+tx.
References in brackets after the active ingredient, e.g. [3878-19-1]Refers to chemical abstract accession numbers. The above described mixed formulations are known. The active ingredients are contained in' The Pesticide Manual [ handbook of pesticides ]]"[ The Pesticide Manual-AWorld Compendium [ handbook of pesticides-Global overview ]]The method comprises the steps of carrying out a first treatment on the surface of the 13 th edition; editing: c.d.s.tomlin; the British Crop Protection Coimcil [ British crop protection Committee ]]]In which they are described with the entry numbers given in parentheses above for the particular compound; for example, the compound "abamectin" is described by entry number (1). In "[ CCN]"in the case of the above addition to a specific compound, said compound is included in" Compendium of Pesticide Common Names [ pesticide general outline ]]"in, it can be on the internet [ a.wood;Compendium of Pesticide Common Names,1995-2004]obtaining; for example, the compound "acetylfipronil" is described in Internet addresseshttp:// www.alanwood.net/pesticides/acetoprole.htmlIs a kind of medium.
Most active ingredients are indicated by the so-called "common name" hereinabove, the corresponding "ISO common name" or other "common name" being used in different situations. If the name is not "common name", the name species used is replaced with the name given in parentheses for the particular compound; in this case, IUPAC names, IUPAC/chemical abstract names, "chemical names", "conventional names", "compound names", or "development codes" are used, or "aliases" are used if neither one of those names nor "common names" is used. "CAS registry number" means a chemical abstract registry number.
The active ingredient mixtures of the compounds of the formula I with the abovementioned active ingredients selected from the compounds defined in tables A-1 to A-243, tables B-1 to B-81, tables X and P comprise the compounds selected from one of the compounds defined in tables A-1 to A-243, tables B-1 to B-81, tables X and P, preferably defined in tables X and P, and the active ingredients described above, preferably in a mixing ratio of from 100:1 to 1:6000, in particular from 50:1 to 1:50, more in particular in a ratio of from 20:1 to 1:20, even more in particular from 10:1 to 1:10, very in particular from 5:1 to 1:5, particularly preferred are ratios from 2:1 to 1:2, and also preferred are ratios from 4:1 to 2:1, especially at a ratio of 1:1, or 5:1, or 5:2, or 5:3, or 5:4, or 4:1, or 4:2, or 4:3, or 3:1, or 3:2, or 2:1, or 1:5, or 2:5, or 3:5, or 4:5, or 1:4, or 2:4, or 3:4, or 1:3, or 2:3, or 1:2, or 1:600, or 1:300, or 1:150, or 1:35, or 2:35, or 1:75, or 2:75, or 4:75, or 1:6000, or 1:3000, or 1:1500, or 1:350, or 2:350, or 4:350, or 1:750, or 2:750, or 4:750. Those mixing ratios are by weight.
The mixture as described above may be used in a method for controlling pests, which comprises applying a composition comprising the mixture as described above to the pest or its environment, a method for treating the human or animal body by surgery or therapy, and a diagnostic method carried out on the human or animal body.
The mixture of compounds of formula I comprising compounds selected from the group consisting of the compounds defined in tables a-1 to a-243, tables B-1 to B-81, table X and table P and one or more active ingredients as described above may be applied, for example, as follows: these single active ingredients are used in combination in a single "water-in-use" form, in a combined spray mixture (which consists of separate formulations of the single active ingredient components, such as a "tank mix"), and when applied in a sequential manner (i.e., one after another for a moderately short period of time, such as hours or days). The order of administration of the compounds of formula I with the active ingredients as described above is not critical to the practice of the invention.
The compositions according to the invention may also comprise other solid or liquid adjuvants, such as stabilizers, for example non-epoxidized or epoxidized vegetable oils (for example epoxidized coconut oil, rapeseed oil or soybean oil), defoamers (for example silicone oil), preservatives, viscosity regulators, binders and/or adhesion promoters, fertilizers or other active ingredients for achieving a particular effect, for example bactericides, fungicides, nematicides, plant activators, molluscicides or herbicides.
The compositions according to the invention are prepared in a manner known per se, in the absence of auxiliaries, for example by grinding, sieving and/or compressing the solid active ingredients; and in the presence of at least one auxiliary, for example by intimately mixing the active ingredient with one or more auxiliary and/or grinding the active ingredient with one or more auxiliary. These processes for preparing the compositions and the use of the compounds I for preparing these compositions are also subjects of the invention.
Methods of application of these compositions, i.e. methods of controlling pests of the above-mentioned type, such as spraying, atomizing, dusting, brushing, coating, broadcasting or pouring-which are selected to be suitable for the intended purpose of the prevailing circumstances-and the use of these compositions for controlling pests of the above-mentioned type are further subjects of the invention. Typical concentration ratios are between 0.1 and 1000ppm, preferably between 0.1 and 500ppm, of active ingredient. The amount applied per item is generally from 1g to 2000g of active ingredient per item, in particular from 10g/ha to 1000g/ha, preferably from 10g/ha to 600g/ha.
In the field of crop protection, the preferred application method is to apply to the foliage of these plants (foliar application), it being possible to select the frequency and rate of application to correspond to the risk of infestation by the pest in question. Alternatively, the active ingredient may reach the plants through the root system (systemic action) by impregnating the locus of these plants with a liquid composition or by introducing the active ingredient in solid form into the locus of the plants (for example into the soil, for example in the form of granules (soil application)). In the case of rice crops, such granules may be metered into flooded rice fields.
The compounds of formula I and their compositions according to the invention are also suitable for the protection of plant propagation material (e.g. seeds, like fruits, tubers or grains, or nursery plants) against the types of pests mentioned above. The propagation material may be treated with the compound prior to planting, e.g. seeds may be treated prior to sowing. Alternatively, the compound may be applied to the seed kernel (coating) by dipping the kernel into a liquid composition or by applying a layer of a solid composition. It is also possible to apply these compositions when the propagation material is planted at the application site, for example during drill seeding, to apply the compositions to seed furrows. These methods of treatment for plant propagation material and plant propagation material so treated are further subjects of the invention. Typical treatment rates will depend on the plant to be controlled and the pests/fungi and will generally be between 1 gram and 200 grams per 100kg seed, preferably between 5 grams and 150 grams per 100kg seed, such as between 10 grams and 100 grams per 100kg seed.
The term seed includes all kinds of seeds as well as plant propagules including but not limited to true seeds, seed pieces, sucking discs, grains, lepidocrocas, fruits, tubers, grains, rhizomes, cuttings, cut shoots and the like and in preferred embodiments means true seeds.
The invention also includes seeds coated or treated with or containing a compound having formula I. Although more or less of the ingredients may penetrate into the seed material depending on the method of application, the term "coating or treating and/or containing" generally means that the active ingredient is at the surface of the seed at the time of application, in most cases. When the seed product is (re) planted, it may absorb the active ingredient. In an embodiment, the present invention makes it possible to obtain plant propagation material having adhered thereto a compound having formula I. Furthermore, a composition comprising plant propagation material treated with a compound of formula I is thereby made available.
Seed treatment includes all suitable seed treatment techniques known in the art, such as seed dressing, seed coating, seed dusting, seed soaking, and seed pelleting. The seed treatment application of the compounds of formula I may be carried out by any known method, such as spraying or dusting the seeds prior to or during sowing of the seeds.
In each aspect and embodiment of the present invention, "consisting essentially of … …" and variants thereof are preferred embodiments of "comprising" and variants thereof, and "consisting of … …" and variants thereof are preferred embodiments of "consisting essentially of … …" and variants thereof.
The disclosure of the present application makes available each combination of embodiments disclosed herein.
It should be noted that the disclosure herein regarding compounds having formula I applies equally to compounds having each of formulas I x, I' a, iaa and Iab.
The compounds of the invention may differ from other similar compounds in greater efficacy and/or different pest control at low application rates, which may be achieved by one skilled in the art using experimental procedures with lower concentrations (if necessary) such as, for example, 10ppm, 5ppm, 2ppm, 1ppm or 0.2ppm, or lower application rates such as 300, 200 or 100mg AI/m 2 To confirm. Greater efficacy can be observed by increased safety (against above-and below-ground non-target organisms (such as fish, birds and bees), improved physico-chemical properties or increased biodegradability).
Biological examples:
the following examples serve to illustrate the invention. Certain compounds of the present invention may differ from known compounds in greater efficacy at low application rates, as demonstrated by one skilled in the art using the experimental procedures outlined in the examples, using lower application rates (if necessary) such as 50ppm, 24ppm, 12.5ppm, 6ppm, 3ppm, 1.5ppm, 0.8ppm, or 0.2 ppm.
Example B1: chilo suppressalis (Chilo suppresalis) (rice stem borer (restricted rice st)emborer))
24-well microtiter plates with artificial feed were treated by pipetting with aqueous test solutions prepared from 10,000 ppm DMSO stock solutions. After drying, the plates were infested with L2 stage larvae (6-8/well). After 6 days of infestation, these samples were evaluated for mortality, antifeedant effect and growth inhibition compared to untreated samples. Control of the test sample over the Chilo suppressalis was achieved when at least one of these categories (mortality, antifeedant effect and growth inhibition) was higher than the untreated sample.
The following compounds gave at least 80% control of at least one of the three categories (mortality, antifeedant effect or growth inhibition) at an application rate of 200 ppm:
P1、P4、P5、P6、P7、P9、P10、P13、P14、P15、P25、P30、P35、P43、P45、P46、P48、P50、P51、P55、P58、P70、P72、P76、P79、P103、P106、P107、P114、P116、P118、P127、P128、P129、P130、P131、P132、P133、P135、P136、P137、P138、P140、P170、P172、P173、P176、P177、P178、P181、P182、P192、P200、P202、P205、P210、P212、P214、P215、P217、P219、P220、P221、P223、P235、P236、P237、P238、P240、P241、P242、P243、P244、P245、P247、P248、P249、P250、P251、P253、P255、P256、P257、P258、P260、P261、P263、P264、P265、P270、P271、P272、P273、P274、P275、P276、P277、P278、P279、P280、P294、P295、P296、P297、P299、P300、P303、P311、P314、P316、P318、P322、P323、P328、P332、P339、P342、P343、P344、P348、P350、P351、P355、P360、P367、P370、P371、P373、P376、P378、P379、P380、P383、P385、P388、P390、P391、P393、P395、P396、P397。
example B2: cucumber strip leaf beetle (Diabrotica balteata) (corn rootworm)
Maize shoots placed on agar layers in 24 well microtiter plates were treated by spraying with an aqueous test solution prepared from a 10,000 ppm DMSO stock solution. After drying, the plates were infested with L2 stage larvae (6 to 10 per well). After 4 days of infestation, these samples were evaluated for mortality and growth inhibition compared to untreated samples.
The following compounds gave at least 80% control effect of at least one of the two categories (mortality or growth inhibition) at an application rate of 200 ppm:
P1、P4、P5、P6、P13、P14、P35、P43、P46、P48、P57、P58、P103、P114、P132、P133、P135、P136、P137、P140、P172、P176、P177、P178、P205、P214、P215、P219、P223、P236、P238、P246、P257、P258、P261、P269、P272、P276、P277、P278、P279、P280、P390。
example B3: heroid (euschistmus her) (New tropical brown stink bug)
Soybean leaves on agar in 24-well microtiter plates were sprayed with aqueous test solutions prepared from 10,000 ppm DMSO stock solutions. After drying, the leaves were infested with N2 stage nymphs. After 5 days of infestation, these samples were evaluated for mortality and growth inhibition compared to untreated samples.
The following compounds gave at least 80% control effect of at least one of the two categories (mortality or growth inhibition) at an application rate of 200 ppm:
P1、P5、P18、P46、P55、P62、P72、P103、P172、P182、P235、P246、P255、P269、P273、P277、P280、P328、P348、P390、P391、P397。
example B4: frankliniella occidentalis (frankliniella occidentalis): ingestion/contact Activity
Sunflower leaf discs were placed on agar in 24-well microtiter plates and sprayed with aqueous test solutions prepared from 10'000dmso stock solutions. After drying, leaf discs were infested with a mixed age population of flower thrips. These samples were evaluated for mortality 7 days after infestation.
The following compounds gave at least 80% mortality at an application rate of 200 ppm:
P71、P103、P142、P199、P208、P219、P235、P280。
Example B5: green peach aphid: ingestion/contact Activity
Sunflower leaf discs were placed on agar in 24-well microtiter plates and sprayed with aqueous test solutions prepared from 10,000 ppm DMSO stock solutions. After drying, leaf discs were infested with aphid populations of mixed ages. These samples were evaluated for mortality after 6 days of infestation.
The following compounds gave at least 80% mortality at an application rate of 200 ppm:
P17、P32、P46、P58、P62、P91、P103、P108、P132、P133、P135、P137、P145、P168、P172、P176、P181、P202、P204、P205、P207、P235、P244、P277、P278、P328、P348。
example B6: green peach aphid. Systemic activity
Roots of pea seedlings infested with aphid populations of mixed ages were placed directly in an aqueous test solution prepared from a 10'000dmso stock solution. After 6 days of seedlings were placed in the test solutions, these samples were evaluated for mortality.
The following compounds produced at least 80% mortality at a 24ppm test rate:
P103、P172、P235、P244、P273、P348、P397。
example B7: green peach aphid. Intrinsic Activity
Test compounds prepared from 10,000 ppm DMSO stock solutions were applied by pipette into 24 well microtiter plates and mixed with sucrose solutions. The plates were blocked with stretched Parafilm (Parafilm). A plastic template with 24 wells was placed on the plate and the infested pea seedlings were placed directly on the parafilm. The infested plate was closed with gel blotting paper and another plastic template, and then inverted. 5 days after infestation, these samples were evaluated for mortality.
The following compounds gave at least 80% control effect at an application rate of 12.5 ppm:
P1、P5、P6、P18、P30、P35、P46、P48、P55、P57、P58、P72、P79、P99、P103、P122、P127、P130、P132、P133、P135、P137、P138、P172、P176、P177、P178、P179、P181、P182、P202、P205、P210、P214、P215、P219、P221、P231、P235、P236、P238、P241、P244、P250、P257、P269、P272、P273、P274、P276、P277、P278、P280、P304、P315、P316、P328、P332、P348、P355、P360、P380、P390、P391、P397。
example B8: plutella xylostella (Plutella xylostella) (Diamond back moth)
24-well microtiter plates with artificial feed were treated by pipetting with aqueous test solutions prepared from 10,000 ppm DMSO stock solutions. After drying, the plutella eggs were pipetted through a plastic template onto gel blotting paper and the plates were blocked with it. After 8 days of infestation, these samples were evaluated for mortality and growth inhibition compared to untreated samples.
The following compounds gave at least 80% effect of at least one of the two categories (mortality or growth inhibition) at an application rate of 200 ppm:
P1、P4、P5、P6、P7、P9、P10、P11、P12、P13、P14、P25、P26、P33、P35、P43、P46、P48、P50、P51、P55、P57、P58、P70、P72、P76、P79、P103、P107、P114、P118、P127、P128、P129、P130、P132、P133、P135、P136、P137、P138、P140、P161、P170、P171、P172、P173、P175、P176、P177、P178、P182、P191、P200、P202、P203、P205、P209、P210、P211、P214、P215、P217、P219、P220、P221、P223、P228、P229、P231、P235、P236、P237、P238、P240、P241、P243、P244、P245、P247、P248、P249、P250、P251、P253、P254、P255、P256、P257、P258、P259、P260、P261、P263、P264、P265、P270、P271、P272、P273、P274、P275、P276、P277、P278、P279、P280、P288、P290、P299、P300、P304、P305、P314、P316、P351、P367、P368、P369、P376、P380、P388、P390、P395、P396、P397。
examplesB9: sea ash wing night moth (Spodoptera littoralis) (Egypt cotton leaf worm)
Cotton leaf discs were placed on agar in 24 well microtiter plates and sprayed with aqueous test solutions prepared from 10,000 ppm DMSO stock solutions. After drying, leaf discs were infested with five L1 stage larvae. After 3 days of infestation, these samples were evaluated for mortality, antifeedant effect and growth inhibition compared to untreated samples. Control of the test sample over Spodoptera frugiperda was achieved when at least one of these categories (mortality, antifeedant effect and growth inhibition) was higher than the untreated sample.
The following compounds gave at least 80% control of at least one of the three categories (mortality, antifeedant effect or growth inhibition) at an application rate of 200 ppm:
P1、P3、P4、P5、P6、P7、P11、P13、P14、P15、P18、P26、P35、P43、P46、P48、P55、P57、P58、P70、P72、P76、P79、P95、P102、P103、P114、P118、P127、P129、P130、P131、P132、P133、P135、P137、P140、P172、P173、P176、P177、P178、P182、P191、P197、P202、P203、P205、P209、P214、P215、P219、P223、P236、P237、P238、P240、P241、P242、P243、P244、P246、P247、P248、P249、P250、P251、P253、P254、P255、P256、P257、P261、P262、P263、P264、P265、P269、P271、P272、P273、P276、P277、P278、P279、P280、P300、P314、P316、P332、P343、P348、P350、P351、P360、P367、P369、P370、P373、P380、P383、P387、P388、P390、P395、P396。
example B10: sea ash wing night moth (Spodoptera littoralis) (Egypt cotton leaf worm)
Test compounds were pipetted from 10,000 ppm DMSO stock solution into 24 well plates and mixed with agar. Lettuce seeds were placed on agar and the multiwell plates were blocked with another plate also containing agar. After 7 days, the roots absorbed the compound and lettuce grew into the cover. These lettuce leaves were then cut into cover plates. The spodoptera eggs were pipetted through a plastic template onto a wet gel blotting paper and the cover plate was closed with it. After 6 days of infestation, these samples were evaluated for mortality, antifeedant effect and growth inhibition compared to untreated samples.
The following compounds gave at least 80% effect of at least one of the three categories (mortality, antifeedant, or growth inhibition) at a test rate of 12.5 ppm:
P5。
example B11: green peach aphid:
test compounds prepared from 10,000 ppm DMSO stock solutions were applied to 96 well microtiter plates by a liquid handling robot and mixed with sucrose solutions. Paraffin film was stretched over a 96-well microtiter plate and a plastic template with 96 wells was placed on the plate. Aphid screening holes were directly onto the parafilm. The infested plates were blocked with gel blot cards and a second plastic template, and then inverted. 5 days after infestation, these samples were evaluated for mortality.
The following compounds gave at least 80% mortality at 50ppm application rates:
P5、P6、P46、P103。
example B12: plutella xylostella (Plutella xylostella) (plutella xylostella (diamond back) Moth)):
96-well microtiter plates containing artificial feed were treated by a liquid handling robot with aqueous test solutions prepared from 10,000 ppm DMSO stock solutions. After drying, eggs (about 30 per well) were infested onto a mesh cover that was suspended over the feed. These eggs hatch and the L1 larvae move down to the feed. These samples were evaluated for mortality 9 days after infestation.
The following compounds gave an effect of at least 80% of the average mortality at an application rate of 500 ppm:
P4、P5、P6。
example B13: tetranychus urticae (Tetranychus urticae) (Two-spotted spider) mite)), by: feeding/contact activity:
bean leaf discs on agar in 24 well microtiter plates were sprayed with aqueous test solutions prepared from 10,000 ppm DMSO stock solutions. After drying, leaf discs were infested with mite populations of mixed ages. After 8 days of infestation, these samples were evaluated for mortality in the mixed population (active phase).
The following compounds gave at least 80% mortality at an application rate of 200 ppm:
P277。
Abbreviations for synthetic schemes and preparation examples
CAN acetonitrile
Boc t-Butoxycarbonyl group
DBU 1, 8-diazabicyclo [5.4.0] undec-7-ene
DCM dichloromethane
DDQ 2, 3-dichloro-5, 6-dicyano-1, 4-benzoquinone
DMSO dimethyl sulfoxide
DMSO-d6 deuterated dimethyl sulfoxide
DPEN diphenyl ethylenediamine
Et 3 N-triethylamine
EtOAc ethyl acetate
MeCN acetonitrile
MeOH ethanol
Ms methanesulfonyl (methanesulfonyl)
n-Bu n-butyl
NHC N-heterocyclic carbenes
NPhth phthalimide-1-yl
OMs mesylate groups
OTf triflate group
OTs tosylate radical
PdCl2dppf 1,1' -bis (diphenylphosphino) ferrocene ] palladium (II) dichloride
TBME tertiary butyl methyl ether
TEA triethylamine
TEMPO (2, 6-tetramethylpiperidin-1-yl) oxy-nitrogen radical
Tf trifluoromethanesulfonyl (trifluoromethanesulfonyl)
TFA trifluoroacetic acid
THF tetrahydrofuran
Ts p-toluenesulfonyl (tosyl)
X-Phos 2-dicyclohexylphosphino-2 ',4',6' -triisopropyldiphenyl
aq. Water-based
Degree centigrade
equiv. Equivalent weight
h hours
LC/MS or LC-MS liquid chromatography mass spectrometry
M mole
MHz megahertz (MHz)
min
mp or M.P. melting point
NMR nuclear magnetic resonance
ppm parts per million
RT room temperature
Rt retention time
RBF round bottom flask

Claims (19)

1. A compound of formula I
Wherein:
x is O or S;
q is
T is phenyl, pyridine, pyrimidine, pyrazine, pyridazine or a five-or nine-membered heteroaromatic ring; or (b)
T is phenyl, pyridine, pyrimidine, pyrazine, pyridazine or a five-or nine-membered heteroaromatic ring, each independently of the other being selected from R independently of the others from one to three 2 Is substituted by a substituent of (a);
R 1a and R is 1b Independently selected from hydrogen, C 1 -C 6 Alkyl groups independently selected from CN, C 1 -C 3 Alkoxy, C (O) NH 2 、C(O)OH、NO 2 and-Si (CH) 3 ) 3 C substituted by one substituent of (C) 1 -C 6 Alkyl, C 1 -C 6 Haloalkyl, C 2 -C 6 Alkenyl, C 2 -C 6 Haloalkenyl, C 2 -C 6 Alkynyl, C 2 -C 6 Haloalkynyl, C 3 -C 4 cycloalkyl-C 1 -C 2 Alkyl, C substituted by 1 or 2 halogen atoms 3 -C 4 cycloalkyl-C 1 -C 2 Alkyl, oxetan-3-yl-CH 2 -，C 1 -C 6 Alkylcarbonyl, C 1 -C 6 Alkoxycarbonyl, phenyloxycarbonyl, benzyloxycarbonyl, benzyl and groups selected from halogen, C independently from 1 to 3 1 -C 6 Alkoxy and C 1 -C 6 A benzyl group substituted with a substituent of a haloalkyl group; or (b)
R 1a And R is 1b Taken together is selected from- (CH) 2 ) 2 -、-(CH 2 ) 3 -、-CH 2 -O-CH 2 -、-CH 2 -S-CH 2 -、-CH 2 -S(＝O)-CH 2 -、-CH 2 -SO 2 -CH 2 -and-CH 2 -N(R Y )-CH 2 -, to form a 5-or 6-membered ring with the nitrogen atom to which they are attached;
R 1b and T together with the nitrogen atom forms a nine or ten membered bicyclic heterocycle which may be substituted with one to three substituents independently selected from: c (C) 1 -C 3 Alkyl, C 1 -C 3 Haloalkyl, C 1 -C 3 Alkoxy, C 3 -C 4 Cycloalkyl, halogen, hydroxy, cyano and C 1 -C 3 Haloalkoxy groups;
R 2 independently selected from: c (C) 1 -C 3 Alkyl, C 1 -C 3 Haloalkyl, C 1 -C 3 Haloalkylthio, C 1 -C 3 Alkoxy, C 1 -C 3 Haloalkoxy, halo, NO 2 、SF 5 、CN、C(O)NR 7 R 8 、C(O)OH、C(S)NH 2 、C 1 -C 4 Alkylsulfonylamino, aminosulfonyl, C 1 -C 4 Alkylaminosulfonyl, di (C) 1 -C 4 Alkyl) sulfamoyl, C 3 -C 6 Cycloalkyl sulfamoyl, C 3 -C 6 Cycloalkyl, independently selected from one to three of R x C substituted by substituent(s) 3 -C 6 Cycloalkyl, C 3 -C 6 Cycloalkyl carbonyl, phenyl, independently selected from one to three of R x Phenyl, heteroaryl substituted with one to three substituents independently selected from R x Heteroaryl groups substituted with substituents OR 6 Piperidin-2-one-1-yl, one to two independently selected from R x Piperidin-2-one-1-yl, pyridin-2-one-1-yl substituted with one or two substituents independently selected from R x Pyridin-2-one-1-yl, azetidin-1-yl, substituted with one or two substituents independently selected from R x Azetidin-1-yl, pyrrolidin-1-yl substituted with one or two substituents independently selected from R x Pyrrolidin-1-yl, C, substituted by substituents of (2) 3 -C 6 Cycloalkyl C 1 -C 4 Alkyl, independently selected from one to two of R z C substituted by substituent(s) 3 -C 6 Cycloalkyl C 1 -C 4 Alkyl, C 3 -C 6 Cycloalkyl C 1 -C 3 Alkoxy, one to two independently selected from R x C substituted by substituent(s) 3 -C 6 Cycloalkyl C 1 -C 3 Alkoxy, C 1 -C 5 Cyanoalkyl, C 1 -C 5 Cyanoalkoxy, C 1 -C 4 Alkylsulfonyl, one to two independently selected from R x C substituted by substituent(s) 1 -C 4 Alkylsulfonyl, C 1 -C 4 Alkylsulfinyl groups, one to two of which are independently selected from R x C substituted by substituent(s) 1 -C 4 Alkylsulfinyl, C 3 -C 6 Cycloalkyl sulfanyl, C 3 -C 6 Cycloalkyl sulfinyl, C 3 -C 6 Cycloalkyl sulfonyl; a divalent group selected from the group consisting of-O-C 1 -C 2 haloalkyldi-O-, -CH 2 -C(CH 3 ) 2 -O-、-CH 2 -C(CH 3 ) 2 -S-、-CH 2 -C(CH 3 ) 2 -SO 2 -wherein the divalent group is linked to T via two adjacent ring members of T; and an eight to twelve membered spiro heterocycle, which ring may be substituted with one or two substituents selected from the group consisting of: halo, C 1 -C 3 Alkyl, C 1 -C 3 Haloalkyl, and C 1 -C 3 An alkoxy group; or (b)
R 3 Is C 1 -C 3 Alkyl or C 1 -C 3 A haloalkyl group;
R 4 is pyridine, pyrimidine, pyrazine or pyridazine; or (b)
R 4 Is pyridine, pyrimidine, pyrazine or pyridazine, each independently of the other being substituted by one to two substituents independently selected from the group consisting of: c (C) 1 -C 3 Alkyl, C 1 -C 3 Haloalkyl, C 1 -C 3 Alkoxy, C 3 -C 4 Cycloalkyl, halo, hydroxy, CN, C 1 -C 6 Haloalkoxy, C 2 -C 6 Haloalkenyloxy, C 2 -C 6 Haloalkynyloxy, C 3 -C 4 Halogenated cycloalkoxy, NH 2 C(O)-、NH 2 C(S)-、(OH)N＝C(NH 2 ) -and a 5-membered heteroaryl ring optionally substituted with 1 to 3 substituents independently selected from: halogen, C 1 -C 3 Alkyl, C 1 -C 3 Haloalkyl, C 1 -C 3 Alkoxy and C 1 -C 3 Haloalkoxy compoundsA base;
R 4 is thiazol-2-yl, thiazol-4-yl, thiazol-5-yl, isothiazol-3-yl, isothiazol-4-yl, isothiazol-5-yl, 1,2, 4-thiadiazol-3-yl, 1,3, 4-thiadiazol-2-yl or 1,2, 4-thiadiazol-5-yl; or (b)
R 4 Is thiazol-2-yl, thiazol-4-yl, thiazol-5-yl, isothiazol-3-yl, isothiazol-4-yl, isothiazol-5-yl, 1,2, 4-thiadiazol-3-yl, 1,3, 4-thiadiazol-2-yl or 1,2, 4-thiadiazol-5-yl, each of which is independently substituted with one to two substituents independently selected from the group consisting of: c (C) 1 -C 3 Alkyl, C 1 -C 3 Haloalkyl, C 1 -C 3 Alkoxy, C 3 -C 4 Cycloalkyl, halo, hydroxy, CN, C 1 -C 6 Haloalkoxy, C 2 -C 6 Haloalkenyloxy, C 2 -C 6 Haloalkynyloxy, C 3 -C 4 Halogenated cycloalkoxy, NH 2 C(O)-、NH 2 C(S)-、(OH)N＝C(NH 2 ) -and a 5-membered heteroaryl ring optionally substituted with 1 to 3 substituents independently selected from: halogen, C 1 -C 3 Alkyl, C 1 -C 3 Haloalkyl, C 1 -C 3 Alkoxy and C 1 -C 3 Haloalkoxy groups;
R 4a is pyridine, pyrimidine, pyrazine or pyridazine; or (b)
R 4a Is pyridine, pyrimidine, pyrazine or pyridazine, each independently of the other being substituted by one to three substituents independently selected from the group consisting of: c (C) 1 -C 3 Alkyl, C 1 -C 3 Haloalkyl, C 1 -C 3 Alkoxy, C 3 -C 4 Cycloalkyl, halogen, hydroxy, cyano and C 1 -C 3 Haloalkoxy groups; or (b)
R 4a Is Y1, Y2, Y3 or Y4
Wherein R 'is' 4a 、R’ 4b And R'. 4c Independently of each other and independently of Y1 to Y4, from hydrogen, halogen, CN, C 1 -C 3 Alkyl, C 1 -C 3 Haloalkyl, C 3 -C 4 Cycloalkyl, C 1 -C 3 Alkoxy and C 1 -C 3 Haloalkoxy groups;
R 4a is thiazol-2-yl, thiazol-4-yl, thiazol-5-yl, isothiazol-3-yl, isothiazol-4-yl, isothiazol-5-yl, 1,2, 4-thiadiazol-3-yl, 1,3, 4-thiadiazol-2-yl or 1,2, 4-thiadiazol-5-yl; or (b)
R 4a Is thiazol-2-yl, thiazol-4-yl, thiazol-5-yl, isothiazol-3-yl, isothiazol-4-yl, isothiazol-5-yl, 1,2, 4-thiadiazol-3-yl, 1,3, 4-thiadiazol-2-yl or 1,2, 4-thiadiazol-5-yl, each of which is independently substituted with one to two substituents independently selected from the group consisting of: c (C) 1 -C 3 Alkyl, C 1 -C 3 Haloalkyl, C 1 -C 3 Alkoxy, C 3 -C 4 Cycloalkyl, halogen, hydroxy, cyano, and C 1 -C 3 Haloalkoxy groups; r is R 5 Is hydrogen, C 1 -C 3 Alkyl, C 1 -C 3 Haloalkyl, C 3 -C 4 Cycloalkyl, C 1 -C 3 Alkoxy, C 3 -C 4 Alkoxy C (O) -, (C) 1 -C 3 Alkoxy group) 2 CH-, halogen, CN, NH 2 C (O), amino (i.e., NH) 2 )、(C 1 -C 3 Alkyl) amino, di (C) 1 -C 3 Alkyl) amino, hydroxy, C 3 -C 4 Halogenated cycloalkyl, C 3 -C 4 Cyanocycloalkyl, C 2 -C 6 Alkenyl, C 2 -C 6 Haloalkenyl, C 2 -C 6 Alkynyl, C 2 -C 6 Haloalkynyl, C 1 -C 4 Haloalkyl sulfanyl, C 1 -C 4 Haloalkyl sulfinyl, C 1 -C 4 Haloalkyl sulfonyl, C 1 -C 4 Alkyl sulfanyl, C 1 -C 4 Alkylsulfinyl, C 1 -C 4 Alkylsulfonyl group,C 1 -C 3 alkoxy-C 1 -C 3 Alkyl, C 1 -C 3 alkoxy-C 1 -C 3 alkoxy-C 1 -C 3 Alkyl, (C) 1 -C 3 Alkyl) sulfonylamino, (C 1 -C 3 Alkyl) sulfonyl (C) 1 -C 3 Alkyl) amino, (C 1 -C 3 Alkyl) NHC (O), (C 1 -C 3 Alkyl group 2 NC(O)、(C 1 -C 3 Cycloalkyl) NHC (O), (C 1 -C 3 Cycloalkyl) (C) 1 -C 3 Alkyl) NC (O), (C 1 -C 3 Alkyl) C (O) (C 1 -C 3 Alkyl) N, (C 1 -C 3 Alkyl) C (O) NH, (C) 1 -C 3 Alkyl) C (O), (C 1 -C 3 Alkoxy) C (O), HC (O), benzophenone imine and C 1 -C 3 Haloalkoxy, phenyl, or a 5-membered heteroaromatic ring; or (b)
R 5 Is phenyl substituted with one to three substituents selected from the group consisting of: c (C) 1 -C 3 Alkyl, C 1 -C 3 Haloalkyl, C 1 -C 3 Alkoxy, C 3 -C 4 Cycloalkyl, halogen, CN, and hydroxy; or (b)
R 5 Is a 5-membered heteroaromatic ring substituted with one to three substituents selected from the group consisting of: c (C) 1 -C 3 Alkyl, C 1 -C 3 Haloalkyl, C 1 -C 3 Alkoxy, C 3 -C 4 Cycloalkyl, halogen, CN, and hydroxy;
R 5a and R is 5b Independently of each other selected from hydrogen, halogen, CN, C 1 -C 3 Alkyl, C 1 -C 3 Haloalkyl, C 3 -C 4 Cycloalkyl, C 1 -C 3 Alkoxy and C 1 -C 3 Haloalkoxy groups;
R 6 is phenyl, benzyl, heteroaryl, C 3 -C 6 Cycloalkyl, or C 3 -C 6 Cycloalkyl C 1 -C 3 An alkyl group; or (b)
R 6 Is phenyl groupBenzyl, heteroaryl, C 3 -C 6 Cycloalkyl, or C 3 -C 6 Cycloalkyl C 1 -C 3 Alkyl groups, each independently of the other, are selected from R x Is substituted by a substituent of (a);
R 7 is hydrogen, C 1 -C 3 Alkyl or C 3 -C 6 Cycloalkyl; or (b)
R 7 Is C 1 -C 3 Alkyl or C 3 -C 6 Cycloalkyl groups, each independently of the other, are selected from R independently of the others from one to three z Is substituted by a substituent of (a);
R 8 is hydrogen, C 1 -C 3 Alkyl or C 3 -C 6 Cycloalkyl; or (b)
R 8 Is C 1 -C 3 Alkyl or C 3 -C 6 Cycloalkyl groups, each independently of the other, are selected from R independently of the others from one to three z Is substituted by a substituent of (a); or (b)
R 7 And R is 8 Together are- (CH) 2 ) 2 -O-(CH 2 ) 2 -and forms a 6-membered ring with the nitrogen atom;
R x independently selected from halogen, C 1 -C 3 Alkyl, C 1 -C 3 Haloalkyl, C 1 -C 3 Alkoxy, C 1 -C 3 Haloalkoxy, NO 2 、SF 5 、CN、C(O)NH 2 、C(S)NH 2 、C 3 -C 6 Cycloalkyl, C 1 -C 4 Haloalkyl sulfanyl, C 1 -C 4 Haloalkyl sulfinyl, C 1 -C 4 Haloalkyl sulfonyl, C 1 -C 4 Alkyl sulfanyl, C 1 -C 4 Alkylsulfinyl and C 1 -C 4 An alkylsulfonyl group;
R Y is C 1 -C 4 Alkyl, C 3 -C 5 Alkenyl, C 3 -C 4 Cycloalkyl, C 2 -C 5 Alkynyl, or benzyl;
R z selected from oxo, halogen, C 1 -C 3 Alkyl, C 1 -C 3 Haloalkyl, C 1 -C 3 Alkoxy, C 1 -C 3 Haloalkoxy and CN; or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer and N-oxide of the compound of formula I.
2. The compound of claim 1, wherein X is oxygen.
3. The compound of claim 1, wherein X is sulfur.
4. A compound according to any one of claims 1 to 3, wherein R 3 Is C 1 -C 2 Alkyl or C 1 -C 2 A haloalkyl group.
5. The compound of any one of claims 1 to 4, wherein R 1a And R is 1b Independently of one another, hydrogen, methyl, ethyl, cyanomethyl, methoxymethyl, cyclopropyl-methyl, allyl, propargyl, benzyloxycarbonyl, or benzyl, or R 1a And R is 1b Taken together is-CH 2 -O-CH 2 -。
6. A compound according to any one of claims 1 to 5, wherein T is phenyl, pyridine, pyrimidine, pyrazine, pyridazine or a heteroaromatic ring selected from: j-13, J-16, J-22, J-25, J-26, J-27, J-28, J-31, J-36, J-37, J-38, J-39, J-40, J-41, thieno [2,3-d ] ]Pyrimidinyl, [1,2,4 ]]Triazolo [1,5-a ]]Pyrimidinyl, and indazolyl, which are independently of each other unsubstituted or are selected from R, independently of one to three 2 Is substituted by a substituent of (a).
7. The compound of any one of claims 1 to 6, wherein R 2 Independently of one another, from halogen, C 1 -C 3 Alkyl, C 1 -C 3 Haloalkyl, C 1 -C 3 Alkoxy, C 1 -C 3 Haloalkoxy, CN, C 3 -C 4 Cycloalkyl, C 3 -C 6 Cycloalkyl carbonyl, phenyl, heteroaryl selected from J-1 and J-41-C 3 -C 4 Cycloalkyl, phenyl or heteroaryl are each, independently of one another, each by one to three substituents R x Substituted, OR 6 Piperidin-2-one-1-yl, pyridin-2-one-1-yl, optionally substituted with R x Substituted azetidin-1-yl, pyrrolidin-1-yl, substituted by one or two substituents R Z Substituted C 3 -C 6 Cycloalkyl C 1 -C 4 Alkyl, optionally R x Substituted C 3 -C 6 Cycloalkyl C 1 -C 3 Alkoxy, C 1 -C 5 Cyanoalkyl, C 1 -C 5 Cyanoalkoxy, optionally substituted with one to three substituents R x Substituted C 1 -C 4 Alkylsulfanyl, optionally substituted by one to three substituents R x Substituted C 1 -C 4 Alkylsulfonyl, optionally substituted by one to three substituents R x Substituted C 1 -C 4 Alkylsulfinyl, C (O) NR 7 R 8 ，C 1 -C 4 Alkylsulfonylamino, aminosulfonyl, C 1 -C 4 Alkylaminosulfonyl, di (C) 1 -C 4 Alkyl) sulfamoyl, C 3 -C 6 Cycloalkyl sulfamoyl, -O-C 1 -C 2 haloalkyl-O-, and 10 membered optionally substituted spiroheterocycle.
8. The compound of any one of claims 1 to 7, wherein Q is selected from Q a -1 to Q a -16 and Q b -1 to Q b -13。
9. The compound of any one of claims 1 to 8, wherein R 4 (where Q is Q a -1 to Q a Independent of Q in the case of one of 16 a ) Is pyridine or pyrimidine, wherein the pyridine or pyrimidine are independently of each other optionally substituted with one substituent selected from the group consisting of: c (C) 1 -C 3 Alkyl group,C 1 -C 3 Haloalkyl, C 1 -C 3 Alkoxy, C 3 -C 4 Cycloalkyl, halo, hydroxy, CN, C 1 -C 6 Haloalkoxy, C 2 -C 6 Haloalkenyloxy, C 2 -C 6 Haloalkynyloxy, C 3 -C 4 Halogenated cycloalkoxy, C 3 -C 6 Cycloalkyl C 1 -C 4 Haloalkoxy, NH 2 C(O)-、NH 2 C(S)-、(OH)N＝C(NH 2 ) -, optionally by C 1 -C 3 Haloalkyl-substituted J-13, optionally C 1 -C 3 Haloalkyl substituted J-20, and 1H-tetrazol-5-yl.
10. The compound of any one of claims 1 to 8, wherein R 4a (where Q is Q b -1 to Q b Independent of Q in the case of one of 13 b ) Is pyridine or pyrimidine, wherein the pyridine or pyrimidine is optionally substituted with one substituent selected from the group consisting of: cyclopropyl, F, cl, br, CN, trifluoromethoxy, difluoromethoxy, 2-difluoroethoxy and 2, 2-trifluoroethoxy, or R 4a Selected from Y1 to Y4.
11. The compound of claim 1, wherein the formula I is represented by:
therein T, R 1a 、R 1b 、R 3 Is as defined in any one of claims 1 and 4 to 7, and Q 1 Is as defined for Q in any one of claims 1, 9 and 10.
12. The compound of claim 11, wherein Q1 is selected from Q aa To Q ag And Q ba To Q bf 。
13. A composition comprising a compound as defined in any one of claims 1 to 12, one or more adjuvants and diluents, and optionally one or more other active ingredients.
14. A method is that
(i) A method for combating and controlling insects, acarines, nematodes or molluscs which comprises applying to a pest, to a locus of a pest, or to a plant susceptible to attack by a pest an insecticidally, acaricidally, nematicidally or molluscicidally effective amount of a compound as defined in any one of claims 1 to 12 or a composition as defined in claim 13; or (b)
(ii) A method for protecting plant propagation material from attack by insects, acarines, nematodes or molluscs which comprises treating the propagation material or the locus in which the propagation material is grown with an effective amount of a compound as defined in any one of claims 1 to 12 or a composition as defined in claim 13; or (b)
(iii) A method for controlling parasites in or on animals in need thereof, which comprises administering an effective amount of a compound as defined in any one of claims 1 to 12 or a composition as defined in claim 13.
15. Plant propagation material, such as a seed, comprising a compound as defined in any one of claims 1 to 12 or a composition as defined in claim 13, or treated with said compound or said composition, or having said compound or said composition adhered thereto.
16. A compound having formula III
Wherein X is oxygen or sulfur, and R 3 And Q is as defined in any one of claims 1, 4, 8, 9, 10, 11 and 12.
17. A compound having formula IV
Wherein X is oxygen or sulfur, and R 1a And Q is as defined in any one of claims 1, 5, 8, 9, 10, 11 and 12.
18. A compound having formula VII
Wherein X is oxygen or sulfur, and R 1b And T is as defined in any one of claims 1, 5 and 6, and when T is one to three independently selected from R 2 R when substituted by substituent(s) 2 Is as defined in any one of claims 1 and 7.
19. A compound of formula XIII or a compound of formula XVI
Wherein T and R 3 Is as defined in any one of claims 1 and 4, and when T is one to three independently selected from R 2 R when substituted by substituent(s) 2 Is as defined in any one of claims 1 and 7.
CN202280011073.3A 2021-01-23 2022-01-19 Pesticidally active heteroaromatic compounds Pending CN117412961A (en)

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