HERBICIDE COMPOSITIONS, USE OF PICOLINIC ACIDS AND SUBSTITUTED PYRIMIDINE-4-CARBOXYLIC ACIDS, AND ME

专利摘要:
Abstract: "Picolinic acids and substituted pyrimidine-4-carboxylic acids, method for their production and use as herbicides and plant growth regulators". The present invention relates to a carboxylic acid derivative of benzoeterocyclyl pyridines and benzoeterocyclyl pyrimidines of formula (I) and their use as herbicides. (i) in said formula (i), x means n or ch. a means a benzofused heterocycle, and r 1, r 2, r 3 and r 4 mean groups such as hydrogen and organic groups such as alkyl.
公开号:BR112014001882B1
申请号:R112014001882-0
申请日:2012-07-24
公开日:2019-05-07
发明作者:Michael Gerhard Hoffmann；Marco Brünjes；Uwe Döller；Hans-Jörg Dietrich；Isolde Häuser-Hahn；Christopher Hugh Rosinger；Elmar GATZWEILER；Ines Heinemann
申请人:Bayer Intellectual Property Gmbh；
IPC主号:

专利说明:

Invention Patent Descriptive Report for HERBICIDIC COMPOSITIONS, USE OF PICOLINIC ACIDS AND SUBSTITUTED PYRIMIDIN-4-CARBOXYLIC ACIDS, AND METHOD TO CONTROL UNWANTED PLANTS.
[001] The present invention relates to the technical field of herbicides, in particular that of herbicides for the selective control of broadleaf weeds and weeds in useful plant crops.
[002] Several publications describe that substituted picolinic acid derivatives and pyrimidine-4-carboxylic acid derivatives have herbicidal properties: WO 2003/011853 A1 describes polysubstituted 6-phenylpicolinic acid derivatives having herbicidal action. W02009 / 029735 A1 and WO2010 / 125332 A1 describe herbicidal effects for derivatives of polysubstituted 2-phenyl-4-pyrimidinecarboxylic acid. Heteroaromatically substituted picoline- and pyrimidinecarboxylic acids that have herbicidal properties are described in WO 2009/138712 A2. WO 2007/080382 A1 and WO 2009/007751 A2 describe heteroaromatically substituted picoline- and pyrimidinecarboxylic acids that have pharmacological activities.
[003] However, the compounds described in these publications often have insufficient herbicidal activity and / or insufficient selectivity in crops of useful plants.
[004] Substituted picolinic acids and pyrimidine-4-carboxylic acids have been found which are particularly suitable as herbicides.
[005] The present invention provides picolinic acids and pyrimidine-4-carboxylic acids of the General Formula (I), their N-oxides or their salts
Petition 870180143799, of 10/23/2018, p. 16/411
2/134 to Α20,
on what :
A represents a radical of the group consisting of A1

A5 A6 A7 A8
A9 A10 A11 A12
A17 A18 A19 A20
R ¹ represents hydrogen or (C 1 -C 4) -alkyl,
R ² represents chlorine,
R ³ represents hydrogen,
Petition 870180143799, of 10/23/2018, p. 17/411
3/134
R ⁴ represents hydrogen,
R ⁵ represents hydrogen, halogen, OH, NH2, CN, (C1C3) -alkyl, (C1-C3) -alkoxy, C1-C3) -alkylamino or cyclopropyl,
R ⁶ represents hydrogen, halogen, OH, NH2, CN, (C1C3) -alkyl, (Ci-C3) -alkoxy, cyclopropyl or vinyl, R ⁷ represents hydrogen, halogen, (Ci-C3) -alkyl, (Ci-C3 ) -alkoxy, (C1-C3) -alkylthio, cyclopropyl, (C1-C3) -alkylamino or phenyl,
R ⁸ represents hydrogen, (C 1 -C 3) -alkyl, phenyl or (C 1 -C 3) alkylcarbonyl,
X represents N, CH, CCI, CF or CBr, n represents 0, 1 or 2.
[006] Alkyl means straight or branched, saturated hydrocarbon radicals having 1 to 10 carbon atoms, for example, C1-Ce-alkyl such as methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl , 1,1-dimethylethyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, hexyl, 1,1dimethylpropyl, 1,2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl , 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1ethylbutyl, 2-ethylbutyl, 1,1,2 -trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethyl-1methylpropyl and 1-ethyl-2-methylpropyl.
[007] Haloalkyl means straight chain or branched alkyl groups having 1 to 8 carbon atoms, where in these groups some or all of the hydrogen atoms can be replaced by halogen atoms, for example, C 1 -C 2 haloalkyl as chloromethyl, bromomethyl , dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 1-chloroethyl, 1-bromoethyl, 1-fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2-difluoroethyl, 2,2,2-triforo -2-fluoroethyl, 2-chloro, 2-difluoroethyl, 2,2dichloro-2-fluoroethyl, 2,2,2-trichloroethyl, pentafluoroethyl and 1,1,1
Petition 870180143799, of 10/23/2018, p. 18/411
4/134 trifluoroprop-2-yl.
[008] Alkenyl means straight or branched, unsaturated hydrocarbon radicals having 2 to 8 carbon atoms and a double bond in any position, for example, C2-Ce-alkenyl such as ethylene, 1-propenyl, 2-propenyl, 1-methylethyl, 1-butenyl, 2butenyl, 3-butenyl, 1-methyl-1-propenyl, 2-methyl-1-propenyl, 1-methyl-2propenyl, 2-methyl-2-propenyl, 1-pentenyl, 2- pentenyl, 3-pentenyl, 4pentenyl, 1-methyl-1-butyl, 2-methyl-1-butenyl, 3-methyl-1-butenyl, 1methyl-2-butenyl, 2-methyl-2-butenyl, 3-methyl- 2-butenyl, 1-methyl-3-butenyl, 2-methyl-3-butenyl, 3-methyl-3-butenyl, 1,1-dimethyl-2-propenyl, 1,2-dimethyl-1-propenyl, 1,2 -dimethyl-2-propenyl, 1-ethyl-1-propenyl, 1-ethyl2-propenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, 1-methyl-1-pentenyl, 2 -methyl-1-pentenyl, 3-methyl-1-pentenyl, 4-methyl-1pentenyl, 1-methyl-2-pentenyl, 2-methyl-2-pentenyl, 3-methyl-2-pentenyl,
4-methyl-2-pentenyl, 1-methyl-3-pentenyl, 2-methyl-3-pentenyl, 3-methyl-3pentenyl, 4-methyl-3-pentenyl, 1-methyl-4-pentenyl, 2-methyl- 4-pentenyl,
3-methyl-4-pentenyl, 4-methyl-4-pentenyl, 1,1-dimethyl-2-butenyl, 1.1- dimethyl-3-butenyl, 1,2-dimethyl-1-butyl, 1,2-dimethyl-2-butenyl, 1.2- dimethyl-3-butenyl, 1,3-dimethyl-1-butyl, 1,3-dimethyl-2-butenyl, 1.3- dimethyl-3-butenyl, 2,2-dimethyl-3-butenyl, 2,3-dimethyl-1-butyl, 2.3- dimethyl-2-butenyl, 2,3-dimethyl-3-butenyl, 3,3-dimethyl-1-butyl, 3.3-
1-ethyl-1-butenyl, 1-ethyl-2-butenyl, 1-ethyl-3-butenyl, 2dimethyl-2-butenyl, ethyl-1-butenyl, 2-ethyl-2-butenyl, 2-ethyl-3- butenyl, 1,1,2-trimethyl-2 propenyl, 1-ethyl-1-methyl-2-propenyl, 1-ethyl-2-methyl-1-propenyl and 1-ethyl-2methyl-2-propenyl.
[009] Alquinyl means straight chain or branched hydrocarbon radicals having 2 to 8 carbon atoms and a triple bond in any position, for example, C2-C6-alkynyl such as ethynyl, 1propynyl, 2-propynyl (or propargyl), 1 -butinyl, 2-butynyl, 3-butynyl, 1methyl-2-propynyl, 1-pententyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, 3-methyl
Petition 870180143799, of 10/23/2018, p. 19/411
5/134
1-butynyl, 1-methyl-2-butynyl, 1-methyl-3-butynyl, 2-methyl-3-butynyl, 1,1dimethyl-2-propynyl, 1-ethyl-2-propynyl, 1-hexynyl, 2- hexynyl, 3-hexynyl, 4hexinyl, 5-hexynyl, 3-methyl-1-pentinyl, 4-methyl-1-pentinyl, 1-methyl-2pentinyl, 4-methyl-2-pentinyl, 1-methyl-3-pentynyl, 2-methyl-3-pentynyl, 1methyl-4-pentynyl, 2-methyl-4-pentynyl, 3-methyl-4-pentynyl, 1,1-dimethyl-2-butynyl, 1,1-dimethyl-3-butynyl, 1, 2-dimethyl-3-butynyl, 2,2-dimethyl-3butynyl, 3,3-dimethyl-1-butynyl, 1-ethyl-2-butynyl, 1-ethyl-3-butynyl, 2-ethyl-3butynyl and 1 - ethyl-1-methyl-2-propynyl.
[0010] Aloxy means straight or branched, saturated alkoxy radicals having 1 to 8 carbon atoms, for example, C 1 -C alkoxy such as methoxy, ethoxy, propoxy, 1-methylethoxy, butoxy, 1-methylpropoxy, 2- methylpropoxy, 1,1-dimethyloxy, pentoxy, 1methylbutoxy, 2-methylbutoxy, 3-methylbutoxy, 2,2-dimethylpropoxy, 1ethylpropoxy, hexoxy, 1,1-dimethylpropoxy, 1,2-dimethylpropoxy, 1-methylpentoxy, 2-methylpentoxy, 2-methylpenthoxy methylpentoxy, 4-methyl pentoxy, 1,1-dimethyl-butoxy, 1,2-dimethyl-butoxy, 1,3-dimethyl-butoxy, 2,2-dimethyl-butoxy, 2,3-dimethyl-butoxy, 3,3-dimethyl-butoxy, 1-ethyl-butoxy, 2-ethyl-butoxy, 1,1 , 2-trimethylpropoxy, 1,2,2-trimethylpropoxy, 1-ethyl-1-methylpropoxy and 1-ethyl-2methylpropoxy;
[0011] haloalkoxy means straight chain or branched alkoxy groups having 1 to 8 carbon atoms (as mentioned above), where in these groups some or all of the hydrogen atoms can be replaced by halogen atoms as mentioned above, for example, C1-C2 haloalkoxy such as chloromethoxy, bromomethoxy, dichloromethoxy, trichloromethoxy, fluoromethoxy, difluoromethoxy, trifluoromethoxy, chlorofluoromethoxy, dichlorofluoromethoxy, chlorodifluoromethoxy, 1-chloroethoxy, 2-chloroethoxy, 1-chloroethoxy, 2-chloroethoxy, 1 2-trifluoroethoxy, 2-chloro-2-fluoroethoxy, 2-chloro-2-difluoroethoxy, 2,2-dichloro-2-fluoroethoxy, 2,2,2-trichloroethoxy, pentafluoroethoxy and 1,1,1-trifluoroprope-2-oxy.
Petition 870180143799, of 10/23/2018, p. 20/411
6/134 [0012] Alkylthio means straight or branched, saturated alkylthio radicals having 1 to 8 carbon atoms, for example, C 1 -C-alkylthio such as methylthio, ethylthio, propylthio, 1-methylethylthio, butylthio, 1- methylpropylthio, 2-methylpropylthio, 1,1-dimethylethylthio, pentylthio, 1methylbutylthio, 2-methylbutylthio, 3-methylbutylthio, 2,2-dimethylpropylthio, 1ethylpropylthio, hexylthio, 1,1-dimethylpropylthio, 1,2-dimethylpropylthio, 2-methylethylthio methylpentylthio, 3-methylpentylthio, 4-methylpentylthio, 1,1dimethylbutylthio, 1,2-dimethylbutylthio, 1,3-dimethylbutylthio, 2,2-dimethylbutylthio,
2,3-dimethylbutylthio, 3,3-dimethylbutylthio, 1-ethylbutylthio, 2-ethylbutylthio, 1,1,2trimethylpropylthio, 1,2,2-trimethylpropylthio, 1-ethyl-1-methylpropylthio and 1-ethyl-2methylpropylthio;
[0013] haloalkylthio means straight chain or branched alkylthio groups having 1 to 8 carbon atoms (as mentioned above), where in these groups some or all of the hydrogen atoms can be replaced by halogen atoms as mentioned above, for example, C1-C2-haloalkylthio such as chloromethylthio, bromomethylthio, dichloromethylthio, trichloromethylthio, fluoromethylthio, difluoromethylthio, trifluoromethylthio, chlorofluoromethylthio, dichlorofluoromethylthio, chlorodifluoromethylthio, 1-chloroethylthio, 1-chloroethylthio, 1-chloroethylthio, 1 , 2-trifluoroethylthio, 2-chloro-2-fluoroethylthio, 2-chloro, 2-difluoroethylthio, 2,2-dichloro-2-fluoroethylthio, 2,2,2-trichlorethylthio, pentafluoroethylthio and 1,1,1 -trifluoroprope-2 -thio.
[0014] Arila means phenyl or naphthyl.
[0015] Depending, among other things, on the nature of the substituents, the compounds of Formula (I) may be present as geometric and / or optical isomers or mixtures of isomers of variable composition which, if desired, can be separated in a usual manner . The present invention provides both pure isomers and mixtures of isomers, their preparation and use and compositions comprising them. In view of simplicity, however, compounds
Petition 870180143799, of 10/23/2018, p. 21/411
7/134 of Formula (I) are always referred to below, although both pure compounds and also, if appropriate, mixtures having different proportions of appropriate isomeric compounds, mixtures having different proportions of isomeric compounds are desired. [0016] A metal ion equivalent is a metal ion that has a positive charge, such as Na ⁺ , K ⁺ , (Mg ²⁺ ) i / 2, (Ca ²⁺ ) i / 2, MgH ⁺ , CaH ⁺ , (AI ³⁺ ) i / 3 (Fe ²⁺ ) i / 2 or (Fe ³⁺ ) i / ₃ .
[0017] Halogen is fluorine, chlorine, bromine or iodine.
[0018] Where a group is replaced by a plurality of radicals, this means that this group is replaced by one or more representatives identical or different from the radicals mentioned.
[0019] Depending on the nature of the substituents defined above, the compounds of Formula (I) have acidic or basic properties and can form salts, if appropriate, also internal salts, or adducts with inorganic or organic acids or with bases or with metal ions . If the compounds of Formula (I) carry amino, alkylamino or other groups, which induce basic properties, these compounds can be reacted with acids to provide salts, or they are directly obtained as salts in the synthesis.
[0020] Examples of inorganic acids are hydrohalic acids, such as hydrogen fluoride, hydrogen chloride, hydrogen bromide and hydrogen iodide, sulfuric acid, phosphoric acid and nitric acid, and acidic salts, such as NaHSO4 and KHSO4. Suitable organic acids are, for example, formic acid, carbonic acid and alkanoic acids, such as acetic acid, trifluoroacetic acid, trichloroacetic acid and propionic acid, as well as glycolic acid, thiocyanic acid, lactic acid, succinic acid, citric acid, benzoic acid , cinnamic acid, oxalic acid, alkylsulfonic acids (sulfonic acids having straight or branched alkyl radicals of 1 to 20 carbon atoms), arylsulfonic acids or aryldisulfonic acids (radicals
Petition 870180143799, of 10/23/2018, p. 22/411
8/134 aromatics, such as phenyl and naphthyl, which transport one or two groups of sulfonic acid), alkylphosphonic acids (phosphonic acids that have linear or branched alkyl radicals of 1 to 20 carbon atoms), arylphosphonic acids or arylphosphonic acids (aromatic radicals, such as phenyl and naphthyl, which carry one or two phosphonic acid radicals), where the alkyl and aryl radicals can carry other substituents, for example, p-toluenesulfonic acid, salicylic acid, p-aminosalicylic acid, 2 -phenoxybenzoic, 2-acetoxybenzoic acid, etc.
[0021] Suitable metal ions are, in particular, the ions of the elements of the second main group, in particular calcium and magnesium, of the third and four main groups, in particular aluminum, tin and lead, and also of the first to the eighth group of transition, in particular chromium, manganese, iron, cobalt, nickel, copper, zinc and others. Particular preference is given to the metal ions of the elements of the fourth period. Here, metals can be present in the various valences they can assume.
[0022] If the compounds of Formula (I) carry hydroxyl, carboxyl or other groups, which induce acidic properties, these compounds can be reacted with bases to provide salts. Suitable bases are, for example, hydroxides, carbonates, bicarbonates of alkali metals and alkaline earth metals, in particular those of sodium, potassium, magnesium and calcium, in addition to ammonia, primary, secondary and tertiary amines, having groups (CiC4) - alkyl, mono-, di- and (C 1 -C 4) -alkanols, choline and also chlorocholine.
[0023] Depending on the nature and the bonding of the substituents, the compounds of the general Formula (I) may be present as stereoisomers. If, for example, one or more asymmetrically substituted carbon atoms or sulfoxides are present, there may be
Petition 870180143799, of 10/23/2018, p. 23/411
9/134 enantiomers and diastereomers. Stereoisomers can be obtained from mixtures that result from the preparation using standard separation methods, for example, by chromatographic separation techniques. It is also possible to prepare stereoisomers selectively using stereoselective reactions using optically active starting materials and / or auxiliaries. The invention also relates to all stereoisomers and mixtures thereof covered by general Formula (I) but not specifically defined.
[0024] In all Formulas below, the substituents and symbols have the same definition, as described under Formula (I), unless otherwise defined.
[0025] Compounds of Formula (I) can be prepared, for example, according to the scheme below by a palladium-catalyzed coupling reaction of a halogen (II) compound with a boronic acid derivative (III). In this scheme Het represents the heterocycles of groups A1 to A24 fused to the phenyl ring. R represents hydrogen or (C 1 -C 3) -alkyl.

COOR ¹

[0026] The halogen compounds of Formula (II) are known, for example, from W02001051468 A1 and W02007082076 A1, or they can be prepared by methods known per se, by the person skilled in the art. The boronic acid derivatives of Formula (III) are either commercially available or can be prepared by known methods of persi, by the person skilled in the art.
[0027] Preference is given to the compounds of Formula (I) listed
Petition 870180143799, of 10/23/2018, p. 24/411
10/134 in Tables 1 to 44, whose compounds can be prepared analogously to the methods mentioned here. The abbreviations used denote:
Et = ethyl Me = methyl Pr = propyl Ph = Phenyl
Table 1: Compounds according to the invention of Formula (I) in which X represents CH, A represents A1, R ³ and R ⁴ each represents hydrogen and R ² represents chlorine:
Ex. No. R1 R5 R16 R26 R17 R27 1,001 H H H H H H 1,002 H F H H H H 1,003 H F H H Cl H 1,004 H F H H H Cl 1,005 H F H H Cl Cl 1,006 H F H H Ph H 1,007 H F H H Ph Cl 1,008 H F H H Ph F 1,009 H F H H Me H 1,010 H F H H Me Cl 1,011 H F H H Me F 1,012 Me H H H H H 1,013 Me F H H H H 1,014 Me F H H Cl H 1,015 Me F H H H Cl 1,016 Me F H H Cl Cl 1,017 Me F H H H F 1,018 Me F H H Ph H 1,019 Me F H H Ph Cl 1,020 Me F H H Ph F 1,021 Me F H H Me H 1,022 Me F H H Me Cl 1,023 Me F H H Me F
Petition 870180143799, of 10/23/2018, p. 25/411
11/134
Ex. No. R1 R5 R16 R26 R17 R27 1,024 Et H H H H H 1,025 Et Cl H H H H 1,026 Et Cl H H Cl H 1,027 Et Cl H H H Cl 1,028 Et Cl H H Cl Cl 1,029 Et Cl H H H F 1,030 Et Cl H H Ph H 1,031 Et Cl H H Ph Cl 1,032 Et Cl H H Ph F 1,033 Et Cl H H Me H 1,034 Et Cl H H Me Cl 1,035 Et Cl H H Me F 1,036 H F F H H H 1,037 H F H F H H 1,038 Me H F H H H 1,039 H H F H H H 1,040 K H F H H H 1,041 Me H Cl H H H 1,042 H H Cl H H H 1,043 K H Cl H H H 1,044 Me H H F H H 1,045 H H H F H H 1,046 K H H F H H 1,047 Me H H Cl H H 1,048 H H H Cl H H 1,049 K H H Cl H H 1,050 K F H H H H 1,051 Me Cl H H H H 1,052 H Cl H H H H 1,053 At Cl H H H H Table 2: Comoostosd and according to the invention of Formula (I) in which
X represents CH, A represents A2, R ³ and R ⁴ each represents hydrogen and R ² represents chlorine:
Petition 870180143799, of 10/23/2018, p. 26/411
12/134
Ex. No. R ¹ R ⁵ R1 ⁶ r ₂ ⁶ R1 ⁷ R2 ⁷ 2,001 H H H H H H 2,002 H F H H H H 2,003 H F H H Cl H 2,004 H F H H H Cl 2,005 H F H H Cl Cl 2,006 H F H H Ph H 2,007 H F H H Ph Cl 2,008 H F H H Ph F 2,009 H F H H Me H 2,010 H F H H Me Cl 2,011 H F H H Me F 2,012 Me H H H H H 2,013 Me F H H H H 2,014 Me F H H Cl H 2,015 Me F H H H Cl 2,016 Me F H H Cl Cl 2,017 Me F H H H F 2,018 Me F H H Ph H 2,019 Me F H H Ph Cl 2,020 Me F H H Ph F 2,021 Me F H H Me H 2,022 Me F H H Me Cl 2,023 Me F H H Me F 2,024 Et H H H H H 2,025 Et Cl H H H H 2,026 Et Cl H H Cl H 2,027 Et Cl H H H Cl
Petition 870180143799, of 10/23/2018, p. 27/411
13/134
Ex. No. R ¹ R ⁵ R1 ⁶ R2 ⁶ R1 ⁷ R2 ⁷ 2,028 Et Cl H H Cl Cl 2,029 Et Cl H H H F 2,030 Et Cl H H Ph H 2,031 Et Cl H H Ph Cl 2,032 Et Cl H H Ph F 2,033 Et Cl H H Me H 2,034 Et Cl H H Me Cl 2,035 Et Cl H H Me F 2,036 H F F H H H 2,037 H F H F H H 2,038 Me H F H H H 2,039 H H F H H H 2,040 K H F H H H 2,041 Me H Cl H H H 2,042 H H Cl H H H 2,043 K H Cl H H H 2,044 Me H H F H H 2,045 H H H F H H 2,046 K H H F H H 2,047 Me H H Cl H H 2,048 H H H Cl H H 2,049 K H H Cl H H 2,050 K F H H H H 2,051 Me Cl H H H H 2,052 H Cl H H H H 2,053 K Cl H H H H Table 3: Comp ostos de wake up : om the inv < Section of Formula ( I) in which
X represents CH, A represents A3, R ³ and R ⁴ each represents hydrogen and R ² represents chlorine:
Petition 870180143799, of 10/23/2018, p. 28/411
14/134
Ex. No. R ¹ R ⁵ R1 ⁶ r ₂ ⁶ R1 ⁷ R2 ⁷ R ⁸ 3,001 H H H H H H H 3,002 H F H H H H Me 3,003 H F H H Cl H H 3,004 H F H H H Cl Me 3,005 H F H H Cl Cl Me 3,006 H F H H Ph H Me 3,007 H F H H Ph Cl H 3,008 H F H H Ph F H 3,009 H F H H Me H H 3,010 H F H H Me Cl Me 3,011 H F H H Me F Me 3,012 Me H H H H H Me 3,013 Me F H H H H H 3,014 Me F H H Cl H H 3,015 Me F H H H Cl Me 3,016 Me F H H Cl Cl Me 3,017 Me F H H H F Me 3,018 Me F H H Ph H H 3,019 Me F H H Ph Cl H 3,020 Me F H H Ph F H 3,021 Me F H H Me H H 3,022 Me F H H Me Cl Me 3,023 Me F H H Me F H 3,024 Et H H H H H Me 3,025 Et Cl H H H H Me 3,026 Et Cl H H Cl H Me 3,027 Et Cl H H H Cl Me 3,028 Et Cl H H Cl Cl Me
Petition 870180143799, of 10/23/2018, p. 29/411
15/134
Ex. No. R ¹ R ⁵ R1 ⁶ R2 ⁶ R1 ⁷ R2 ⁷ R ⁸ 3,029 Et Cl H H H F Me 3,030 Et Cl H H Ph H H 3,031 Et Cl H H Ph Cl H 3,032 Et Cl H H Ph F H 3,033 Et Cl H H Me H H 3,034 Et Cl H H Me Cl H 3,035 Et Cl H H Me F Me 3,036 H F F H H H H 3,037 H F H F H H H
Table 4: Compounds according to the invention of Formula (I) in which X represents CH, A represents A4, R ³ and R ⁴ each represents hydrogen and R ² represents chlorine:
Ex. No. R ¹ R ⁵ R1 ⁶ R2 ⁶ R ⁷ 4,001 H H H H H 4,002 H F H H H 4,003 H F H H F 4,004 H F H H Cl 4,005 H F H H Me 4,006 H Cl H H H 4,007 H Cl H H F 4,008 H Cl H H Cl 4,009 H Cl H H Me 4,010 Me H H H H 4,011 Me F H H H 4,012 Me F H H F 4,013 Me F H H Cl 4,014 Me Cl H H H
Petition 870180143799, of 10/23/2018, p. 4/30
16/134
Ex. No. R ¹ R ⁵ R1 ⁶ R2 ⁶ R ⁷ 4,015 Me Cl H H F 4,016 Me Cl H H Cl 4,017 Me Cl H H Me 4,018 Et H H H H 4,019 Et F H H H 4,020 Et Cl H H H 4,021 Et F H H Me 4,022 Et Cl H H Me 4,023 H F F H H 4,024 H F H F H Table 5: Comoos acoi tos with the invention ( 1st Formula (1) where
X represents CH, A represents A5, R ³ and R ⁴ each represents hydrogen and R ² represents chlorine:
Ex. No. R ¹ R ⁵ R1 ⁶ R2 ⁶ R ⁷ 5,001 H H H H H 5,002 H F H H H 5,003 H F H H F 5,004 H F H H Cl 5,005 H F H H F 5,006 H Cl H H H 5,007 H Cl H H F 5,008 H Cl H H Cl 5,009 H Cl H H Me 5,010 Me H H H H 5,011 Me F H H H 5,012 Me F H H Cl 5,013 Me Cl H H H
Petition 870180143799, of 10/23/2018, p. 4/31
17/134
Ex. No. R ¹ R ⁵ R1 ⁶ r ₂ ⁶ R ⁷ 5,014 Me Cl H H F 5,015 Me Cl H H Cl 5,016 Me Cl H H Me 5,017 Et H H H H 5,018 Et F H H H 5,019 Et Cl H H H 5,020 Et F H H Me 5,021 Et Cl H H Me 5,022 H F F H H 5,023 H F H F H Table 6: Comoos acoi tos with the invention ( la Formula (1) where
X represents CH, A represents A6, R ⁸ , R ³ and R ⁴ each represents hydrogen and R ² represents chlorine:
Ex. No. R ¹ R ⁵ R1 ⁶ r ₂ ⁶ R ⁷ 6,001 H H H H H 6,002 H F H H H 6,003 H F H H Me 6,004 H F H H Et 6,005 H H H H Me 6,006 H Cl H H H 6,007 H Cl H H Me 6,008 H Cl H H Et 6,009 Me H H H H 6,010 Me H H H Me 6,011 Me F H H H 6,012 Me F H H Me 6,013 Me F H H Et
Petition 870180143799, of 10/23/2018, p. 32/411
18/134
Ex. No. R ¹ R ⁵ R1 ⁶ r ₂ ⁶ R ⁷ 6,014 Me Cl H H H 6,015 Me Cl H H Me 6,016 Me Cl H H Et 6,017 Me H H H Me 6,018 Et H H H H 6,019 Et H H H Me 6,020 Et H H H Et 6,021 Et F H H H 6,022 Et F H H Me 6,023 Et F H H Et 6,024 Et Cl H H H 6,025 Et Cl H H Me 6,026 Et Cl H H Et 6,027 H F F H H 6,028 H F H F H Table 7: Comoos acoi tos with the invention < la Formula (1) where
X represents CH, A represents A6, R ³ and R ⁴ each represent hydrogen, R ⁸ represents methyl and R ² represents chlorine:
Ex. No. R ¹ R ⁵ R1 ⁶ r ₂ ⁶ R ⁷ 7,001 H H H H H 7,002 H F H H H 7,003 H F H H Me 7,004 H F H H Et 7,005 H H H H Me 7,006 H Cl H H H 7,007 H Cl H H Me 7,008 H Cl H H Et
Petition 870180143799, of 10/23/2018, p. 33/411
19/134
Ex. No. R ¹ R ⁵ R1 ⁶ r ₂ ⁶ R ⁷ 7,009 Me H H H H 7,010 Me H H H Me 7,011 Me F H H H 7,012 Me F H H Me 7,013 Me F H H Et 7,014 Me Cl H H H 7,015 Me Cl H H Me 7,016 Me Cl H H Et 7,017 Me H H H Me 7,018 Et H H H H 7,019 Et H H H Me 7,020 Et H H H Et 7,021 Et F H H H 7,022 Et F H H Me 7,023 Et F H H Et 7,024 Et Cl H H H 7,025 Et Cl H H Me 7,026 Et Cl H H Et 7,027 H F F H H 7,028 H F H F H Table 8: Comoos acoi tos with the invention ( 1st Formula (1) where
X represents CH, A represents A7, R ³ and R ⁴ each represents hydrogen and R ² represents chlorine:
Ex. No. R ¹ R ⁵ R1 ⁶ r ₂ ⁶ R ⁷ 8,001 H H H H H 8,002 H H H H Me 8,003 H H H H Ph
Petition 870180143799, of 10/23/2018, p. 34/411
20/134
Ex. No. R ¹ R ⁵ R1 ⁶ R2 ⁶ R ⁷ 8,004 H H H H SMe 8,005 H F H H H 8,006 H F H H Me 8,007 H F H H Ph 8,008 H F H H SMe 8,009 H Cl H H H 8,010 H Cl H H Me 8,011 H Cl H H Ph 8,012 H Cl H H SMe 8,013 Me H H H H 8,014 Me H H H Me 8,015 Me H H H Ph 8,016 Me H H H SMe 8,017 Me F H H H 8,018 Me F H H Me 8,019 Me F H H Ph 8,020 Me F H H SMe 8,021 Me Cl H H H 8,022 Me Cl H H Me 8,023 Me Cl H H Ph 8,024 Me Cl H H SMe 8,025 Et H H H H 8,026 Et H H H Me 8,027 Et H H H Ph 8,028 Et H H H SMe 8,029 Et F H H H 8,030 Et F H H Me 8,031 Et F H H Ph 8,032 Et F H H SMe 8,033 Et Cl H H H 8,034 Et Cl H H Me 8,035 Et Cl H H Ph
Petition 870180143799, of 10/23/2018, p. 35/411
21/134
Ex. No. R ¹ R ⁵ R1 ⁶ r ₂ ⁶ R ⁷ 8,036 Et Cl H H SMe 8,037 H F F H H 8,038 H F H F H
Table 9: Compounds according to the invention of Formula (I) in which X represents CH, A represents A8, R ³ and R ⁴ each represents hydrogen and R ² represents chlorine:
Ex. No. R ¹ R ⁵ R1 ⁶ r ₂ ⁶ R ⁷ 9,001 H H H H H 9,002 H H H H Me 9,003 H H H H Ph 9,004 H H H H SMe 9,005 H F H H H 9,006 H F H H Me 9,007 H F H H Ph 9,008 H F H H SMe 9,009 H Cl H H H 9,010 H Cl H H Me 9,011 H Cl H H Ph 9,012 H Cl H H SMe 9,013 Me H H H H 9,014 Me H H H Me 9,015 Me H H H Ph 9,016 Me H H H SMe 9,017 Me F H H H 9,018 Me F H H Me 9,019 Me F H H Ph 9,020 Me F H H SMe 9,021 Me Cl H H H
Petition 870180143799, of 10/23/2018, p. 36/411
22/134
Ex. No. R ¹ R ⁵ R1 ⁶ R2 ⁶ R ⁷ 9,022 Et H H H H 9,023 Et H H H Me 9,024 Et H H H Ph 9,025 Et H H H SMe 9,026 Et F H H H 9,027 Et F H H Me 9,028 Et F H H Ph 9,029 Et F H H SMe 9,030 Et Cl H H H 9,031 Et Cl H H Me 9,032 Et Cl H H Ph 9,033 Et Cl H H SMe 9,034 H F F H H 9,035 H F H F H
Table 10: Compounds according to the invention of Formula (I) in which X represents CH, A represents A9, R ³ and R ⁴ each represents hydrogen and R ² represents chlorine:
R
Ex. No. R ¹ R ⁵ R1 ⁶ R2 ⁶ R ⁷ 10,001 H H H H H 10,002 H H H H Me 10,003 H H H H Ph 10,004 H H H H SMe 10,005 H F H H H 10,006 H F H H Me 10,007 H F H H Ph 10,008 H F H H SMe 10,009 H Cl H H H
Petition 870180143799, of 10/23/2018, p. 37/411
23/134
Ex. No. R ¹ R ⁵ R1 ⁶ R2 ⁶ R ⁷ 10,010 H Cl H H Me 10,011 H Cl H H Ph 10,012 H Cl H H SMe 10,013 Me H H H H 10,014 Me H H H Me 10,015 Me H H H Ph 10,016 Me H H H SMe 10,017 Me F H H H 10,018 Me F H H Me 10,019 Me F H H Ph 10,020 Me F H H SMe 10,021 Me Cl H H H 10,022 Me Cl H H Me 10,023 Me Cl H H Ph 10,024 Me Cl H H SMe 10,025 Et H H H H 10,026 Et H H H Me 10,027 Et H H H Ph 10,028 Et H H H SMe 10,029 Et F H H H 10,030 Et F H H Me 10,031 Et F H H Ph 10,032 Et F H H SMe 10,033 Et Cl H H H 10,034 Et Cl H H Me 10,035 Et Cl H H Ph 10,036 Et Cl H H SMe 10,037 H F F H H 10,038 H F H F H
Table 11: Compounds according to the invention of Formula (I) in which X represents CH, A represents A10, R ³ and R ⁴ each represents hydrogen and R ² represents chlorine:
Petition 870180143799, of 10/23/2018, p. 38/411
24/134
Ex. No. R ¹ R ⁵ R1 ⁶ r ₂ ⁶ R ⁷ 11,001 H H H H H 11,002 H H H H Me 11,003 H H H H Ph 11,004 H H H H SMe 11,005 H F H H H 11,006 H F H H Me 11,007 H F H H Ph 11,008 H F H H SMe 11,009 H Cl H H H 11,010 H Cl H H Me 11,011 H Cl H H Ph 11,012 H Cl H H SMe 11,013 Me H H H H 11,014 Me H H H Me 11,015 Me H H H Ph 11,016 Me H H H SMe 11,017 Me F H H H 11,018 Me F H H Me 11,019 Me F H H Ph 11,020 Me F H H SMe 11,021 Me Cl H H H 11,022 Et H H H H 11,023 Et H H H Me 11,024 Et H H H Ph 11,025 Et H H H SMe 11,026 Et F H H H 11,027 Et F H H Me
Petition 870180143799, of 10/23/2018, p. 39/411
25/134
Ex. No. R ¹ R ⁵ R1 ⁶ r ₂ ⁶ R ⁷ 11,028 Et F H H Ph 11,029 Et F H H SMe 11,030 Et Cl H H H 11,031 Et Cl H H Me 11,032 Et Cl H H Ph 11,033 Et Cl H H SMe 11,034 H F F H H 11,035 H F H F H
Table 12: Compounds according to the invention of Formula (I) in which X represents CH, A represents A11, R ³ and R ⁴ each represents hydrogen and R ² represents chlorine:
Ex. No. R ¹ R ⁵ R1 ⁶ r ₂ ⁶ R ⁷ R ⁸ 12,001 H H H H H H 12,002 H F H H H H 12,003 H F H H H Me 12,004 H F H H Me H 12,005 H F H H Me Me 12,006 H Cl H H H H 12,007 H Cl H H H Me 12,008 H Cl H H Me H 12,009 H Cl H H Me Me 12,010 H H H H Ph H 12,011 H H H H Ph Me 12,012 H F H H Ph H 12,013 H F H H Ph Me 12,014 H Cl H H Ph H 12,015 H Cl H H Ph Me
Petition 870180143799, of 10/23/2018, p. 40/411
26/134
Ex. No. R ¹ R ⁵ R1 ⁶ r ₂ ⁶ R ⁷ R ⁸ 12,016 H H H H Me H 12,017 H H H H H Me 12,018 H H H H Me Me 12,019 Me H H H H H 12,020 Me F H H H H 12,021 Me F H H H Me 12,022 Me F H H Me H 12,023 Me F H H Me Me 12,024 Me Cl H H H H 12,025 Me Cl H H H Me 12,026 Me Cl H H Me H 12,027 Me Cl H H Me Me 12,028 Me H H H Ph H 12,029 Me H H H Ph Me 12,030 Me F H H Ph H 12,031 Me F H H Ph Me 12,032 Me Cl H H Ph H 12,033 Me Cl H H Ph Me 12,034 Me H H H Me H 12,035 Me H H H H Me 12,036 Me H H H Me Me 12,037 Et H H H H H 12,038 Et F H H H H 12,039 Et F H H H Me 12,040 Et F H H Me H 12,041 Et F H H Me Me 12,042 Et Cl H H H H 12,043 Et Cl H H H Me 12,044 Et Cl H H Me H 12,045 Et H H H Ph H 12,046 Et H H H Ph Me 12,047 Et F H H Ph H
Petition 870180143799, of 10/23/2018, p. 41/411
27/134
Ex. No. R ¹ R ⁵ R1 ⁶ R2 ⁶ R ⁷ R ⁸ 12,048 Et F H H Ph Me 12,049 Et Cl H H Ph H 12,050 Et Cl H H Ph Me 12,051 Et H H H Me H 12,052 Et H H H H Me 12,053 Me H H H Me Me 12,054 H F F H H H 12,055 H F H F H H Table 13: Con C items and wake up the with nvention da Formi jla (I) in
that X represents CH, A represents A12, R ³ and R ⁴ each represent hydrogen and R ² represents chlorine:
NH.
Cl
COOR ¹
R '
Ex. No. R ¹ R ⁵ R1 ⁶ R2 ⁶ R ⁷ R ⁸ 13,001 H H H H H Me 13,002 H F H H H Me 13,003 H F H H Me Me 13,004 H Cl H H H Me 13,005 H Cl H H Me Me 13,006 H H H H Ph Me 13,007 H F H H Ph Me 13,008 H Cl H H Ph Me 13,009 H H H H H Me 13,010 Me H H H H Me 13,011 Me F H H H Me 13,012 Me H H H Me Me 13,013 Me F H H Me Me 13,014 Me Cl H H H Me 13,015 Me Cl H H Me Me
Petition 870180143799, of 10/23/2018, p. 42/411
28/134
Ex. No. R ¹ R ⁵ R1 ⁶ R2 ⁶ R ⁷ R ⁸ 13,016 Me H H H Ph Me 13,017 Me F H H Ph Me 13,018 Me Cl H H Ph Me 13,019 Et F H H H Me 13,020 Et F H H Me Me 13,021 Et Cl H H H Me 13,022 Et H H H Ph Me 13,023 Et F H H Ph Me 13,024 Et Cl H H Ph Me 13,025 Et H H H H Me 13,026 Me H H H Me Me 13,027 Et Cl H H Me Me 13,028 H F F H H H 13,029 H F H F H H Table 14: Corr 1 gas stations and wake up the with nvention da Formi jla (I) in
that X represents CH, A represents A13, R ³ and R ⁴ each represent hydrogen and R ² represents chlorine:
Ex. No. R ¹ R ⁵ R1 ⁶ R2 ⁶ R1 ⁷ R2 ⁷ 14,001 H H H H H H 14,002 H H H H H Cl 14,003 H H H H H F 14,004 H H H H H Me 14,005 H H H H F H 14,006 H H H H F Cl 14,007 H H H H F F 14,008 H H H H F Me 14,009 H H H H Cl H
Petition 870180143799, of 10/23/2018, p. 43/411
29/134
Ex. No. R ¹ R ⁵ R1 ⁶ R2 ⁶ R1 ⁷ R2 ⁷ 14,010 H H H H Cl F 14,011 H H H H Cl Cl 14,012 H H H H Cl Me 14,013 H H H H Me H 14,014 H H H H Me Cl 14,015 H H H H Me F 14,016 H H H H Me Me 14,017 H H H H Ph H 14,018 H H H H Ph Cl 14,019 H H H H Ph F 14,020 H H H H Ph Me 14,021 H F H H H H 14,022 H F H H H Cl 14,023 H F H H H F 14,024 H F H H H Me 14,025 H F H H F H 14,026 H F H H F F 14,027 H F H H F Cl 14,028 H F H H F Me 14,029 H F H H Cl H 14,030 H F H H Cl Cl 14,031 H F H H Cl F 14,032 H F H H Cl Me 14,033 H F H H Me H 14,034 H F H H Me Cl 14,035 H F H H Me F 14,036 H F H H Me Me 14,037 H F H H Ph H 14,038 H F H H Ph Cl 14,039 H F H H Ph F 14,040 H F H H Ph Me 14,041 H Cl H H H H
Petition 870180143799, of 10/23/2018, p. 44/411
30/134
Ex. No. R ¹ R ⁵ R1 ⁶ r ₂ ⁶ R1 ⁷ r ₂ ⁷ 14,042 H Cl H H H Cl 14,043 H Cl H H H F 14,044 H Cl H H H Me 14,045 H Cl H H F H 14,046 H Cl H H F Cl 14,047 H Cl H H F F 14,048 H Cl H H F Me 14,049 H Cl H H Cl H 14,050 H Cl H H Cl F 14,051 H Cl H H Cl Cl 14,052 H Cl H H Cl Me 14,053 H Cl H H Me H 14,054 H Cl H H Me Cl 14,055 H Cl H H Me F 14,056 H Cl H H Me Me 14,057 H Cl H H Ph H 14,058 H Cl H H Ph Cl 14,059 H Cl H H Ph F 14,060 H Cl H H Ph Me 14,061 Me H H H H H 14,062 Me H H H H Cl 14,063 Me H H H H F 14,064 Me H H H H Me 14,065 Me H H H F H 14,066 Me H H H F Cl 14,067 Me H H H F F 14,068 Me H H H F Me 14,069 Me H H H Cl H 14,070 Me H H H Cl F 14,071 Me H H H Cl Cl 14,072 Me H H H Cl Me 14,073 Me H H H Me H
Petition 870180143799, of 10/23/2018, p. 45/411
31/134
Ex. No. R ¹ R ⁵ R1 ⁶ R2 ⁶ R1 ⁷ R2 ⁷ 14,074 Me H H H Me Cl 14,075 Me H H H Me F 14,076 Me H H H Me Me 14,077 Me H H H Ph H 14,078 Me H H H Ph Cl 14,079 Me H H H Ph F 14,080 Me H H H Ph Me 14,081 Me F H H H H 14,082 Me F H H H Cl 14,083 Me F H H H F 14,084 Me F H H H Me 14,085 Me F H H F H 14,086 Me F H H F Cl 14,087 Me F H H F F 14,088 Me F H H F Me 14,089 Me F H H Cl H 14,090 Me F H H Cl F 14,091 Me F H H Cl Cl 14,092 Me F H H Cl Me 14,093 Me F H H Me H 14,094 Me F H H Me Cl 14,095 Me F H H Me F 14,096 Me F H H Me Me 14,097 Me F H H Ph H 14,098 Me F H H Ph Cl 14,099 Me F H H Ph F 14,100 Me F H H Ph Me 14,101 Me Cl H H H H 14,102 Me Cl H H H Cl 14,103 Me Cl H H H F 14,104 Me Cl H H H Me 14,105 Me Cl H H F H
Petition 870180143799, of 10/23/2018, p. 46/411
32/134
Ex. No. R ¹ R ⁵ R1 ⁶ r ₂ ⁶ R1 ⁷ r ₂ ⁷ 14,106 Me Cl H H F Cl 14,107 Me Cl H H F F 14,108 Me Cl H H F Me 14,109 Me Cl H H Cl H 14,110 Me Cl H H Cl F 14,111 Me Cl H H Cl Cl 14,112 Me Cl H H Cl Me 14,113 Me Cl H H Me H 14,114 Me Cl H H Me Cl 14,115 Me Cl H H Me F 14,116 Me Cl H H Me Me 14,117 Me Cl H H Ph H 14,118 Me Cl H H Ph Cl 14,119 Me Cl H H Ph F 14,120 Me Cl H H Ph Me 14,121 Et H H H H H 14,122 Et H H H H Cl 14,123 Et H H H H F 14,124 Et H H H H Me 14,125 Et H H H F H 14,126 Et H H H F Cl 14,127 Et H H H F F 14,128 Et H H H F Me 14,129 Et H H H Cl H 14,130 Et H H H Cl F 14,131 Et H H H Cl Cl 14,132 Et H H H Cl Me 14,133 Et H H H Me H 14,134 Et H H H Me Cl 14,135 Et H H H Me F 14,136 Et H H H Me Me 14,137 Et H H H Ph H
Petition 870180143799, of 10/23/2018, p. 47/411
33/134
Ex. No. R ¹ R ⁵ Rl ⁶ R2 ⁶ R1 ⁷ R2 ⁷ 14,138 Et H H H Ph Cl 14,139 Et H H H Ph F 14,140 Et H H H Ph Me 14,141 Et F H H H H 14,142 Et F H H H Cl 14,143 Et F H H H F 14,144 Et F H H H Me 14,145 Et F H H F H 14,146 Et F H H F Cl 14,147 Et F H H F F 14,148 Et F H H F Me 14,149 Et F H H Cl H 14,150 Et F H H Cl F 14,151 Et F H H Cl Cl 14,152 Et F H H Cl Me 14,153 Et F H H Me H 14,154 Et F H H Me Cl 14,155 Et F H H Me F 14,156 Et F H H Me Me 14,157 Et F H H Ph H 14,158 Et F H H Ph Cl 14,159 Et F H H Ph F 14,160 Et F H H Ph Me 14,161 Et Cl H H H H 14,162 Et Cl H H H Cl 14,163 Et Cl H H H F 14,164 Et Cl H H H Me 14,165 Et Cl H H F H 14,166 Et Cl H H F Cl 14,167 Et Cl H H F F 14,168 Et Cl H H F Me 14,169 Et Cl H H Cl H
Petition 870180143799, of 10/23/2018, p. 48/411
34/134
Ex. No. R ¹ R ⁵ R1 ⁶ R2 ⁶ R1 ⁷ R2 ⁷ 14,170 Et Cl H H Cl F 14,171 Et Cl H H Cl Cl 14,172 Et Cl H H Cl Me 14,173 Et Cl H H Me H 14,174 Et Cl H H Me Cl 14,175 Et Cl H H Me F 14,176 Et Cl H H Me Me 14,177 Et Cl H H Ph H 14,178 Et Cl H H Ph Cl 14,179 Et Cl H H Ph F 14,180 Et Cl H H Ph Me 14,181 H F F H H H 14,182 H F H F H H 14,183 Me H F H H H 14,184 H H F H H H 14,185 K H F H H H 14,186 Me H Cl H H H 14,187 H H Cl H H H 14,188 K H Cl H H H 14,189 Me H H F H H 14,190 H H H F H H 14,191 K H H F H H 14,192 Me H H Cl H H 14,193 H H H Cl H H 14,194 K H H Cl H H 14,195 K F H H H H 14,196 K Cl H H H H Table 15: Color npositions c ie acorc the with invention da Formi jla (I) in
that X represents CH, A represents A14, R ³ and R ⁴ each represent hydrogen and R ² represents chlorine:
Petition 870180143799, of 10/23/2018, p. 49/411
35/134
Ex. No. R ¹ R ⁵ R1 ⁶ R2 ⁶ R1 ⁷ R2 ⁷ 15,001 H H H H H H 15,002 H H H H H Cl 15,003 H H H H H F 15,004 H H H H H Me 15,005 H H H H F H 15,006 H H H H F Cl 15,007 H H H H F F 15,008 H H H H F Me 15,009 H H H H Cl H 15,010 H H H H Cl F 15,011 H H H H Cl Cl 15,012 H H H H Cl Me 15,013 H H H H Me H 15,014 H H H H Me Cl 15,015 H H H H Me F 15,016 H H H H Me Me 15,017 H H H H Ph H 15,018 H H H H Ph Cl 15,019 H H H H Ph F 15,020 H H H H Ph Me 15,021 H F H H H H 15,022 H F H H H Cl 15,023 H F H H H F 15,024 H F H H H Me 15,025 H F H H F H 15,026 H F H H F Cl 15,027 H F H H F F 15,028 H F H H F Me
Petition 870180143799, of 10/23/2018, p. 50/411
36/134
Ex. No. R ¹ R ⁵ R1 ⁶ r ₂ ⁶ R1 ⁷ R2 ⁷ 15,029 H F H H Cl H 15,030 H F H H Cl F 15,031 H F H H Cl Cl 15,032 H F H H Cl Me 15,033 H F H H Me H 15,034 H F H H Me Cl 15,035 H F H H Me F 15,036 H F H H Me Me 15,037 H F H H Ph H 15,038 H F H H Ph Cl 15,039 H F H H Ph F 15,040 H F H H Ph Me 15,041 H Cl H H H H 15,042 H Cl H H H Cl 15,043 H Cl H H H F 15,044 H Cl H H H Me 15,045 H Cl H H F H 15,046 H Cl H H F Cl 15,047 H Cl H H F F 15,048 H Cl H H F Me 15,049 H Cl H H Cl H 15,050 H Cl H H Cl F 15,051 H Cl H H Cl Cl 15,052 H Cl H H Cl Me 15,053 H Cl H H Me H 15,054 H Cl H H Me Cl 15,055 H Cl H H Me F 15,056 H Cl H H Me Me 15,057 H Cl H H Ph H 15,058 H Cl H H Ph Cl 15,059 H Cl H H Ph F 15,060 H Cl H H Ph Me
Petition 870180143799, of 10/23/2018, p. 51/411
37/134
Ex. No. R ¹ R ⁵ R1 ⁶ R2 ⁶ R1 ⁷ R2 ⁷ 15,061 Me H H H H H 15,062 Me H H H H Cl 15,063 Me H H H H F 15,064 Me H H H H Me 15,065 Me H H H F H 15,066 Me H H H F Cl 15,067 Me H H H F F 15,068 Me H H H F Me 15,069 Me H H H Cl H 15,070 Me H H H Cl F 15,071 Me H H H Cl Cl 15,072 Me H H H Cl Me 15,073 Me H H H Me H 15,074 Me H H H Me Cl 15,075 Me H H H Me F 15,076 Me H H H Me Me 15,077 Me H H H Ph H 15,078 Me H H H Ph Cl 15,079 Me H H H Ph F 15,080 Me H H H Ph Me 15,081 Me F H H H H 15,082 Me F H H H Cl 15,083 Me F H H H F 15,084 Me F H H H Me 15,085 Me F H H F H 15,086 Me F H H F Cl 15,087 Me F H H F F 15,088 Me F H H F Me 15,089 Me F H H Cl H 15,090 Me F H H Cl F 15,091 Me F H H Cl Cl 15,092 Me F H H Cl Me
Petition 870180143799, of 10/23/2018, p. 52/411
38/134
Ex. No. R ¹ R ⁵ R1 ⁶ r ₂ ⁶ R1 ⁷ r ₂ ⁷ 15,093 Me F H H Me H 15,094 Me F H H Me Cl 15,095 Me F H H Me F 15,096 Me F H H Me Me 15,097 Me F H H Ph H 15,098 Me F H H Ph Cl 15,099 Me F H H Ph F 15,100 Me F H H Ph Me 15,101 Me Cl H H H H 15,102 Me Cl H H H Cl 15,103 Me Cl H H H F 15,104 Me Cl H H H Me 15,105 Me Cl H H F H 15,106 Me Cl H H F Cl 15,107 Me Cl H H F F 15,108 Me Cl H H F Me 15,109 Me Cl H H Cl H 15,110 Me Cl H H Cl F 15,111 Me Cl H H Cl Cl 15,112 Me Cl H H Cl Me 15,113 Me Cl H H Me H 15,114 Me Cl H H Me Cl 15,115 Me Cl H H Me F 15,116 Me Cl H H Me Me 15,117 Me Cl H H Ph H 15,118 Me Cl H H Ph Cl 15,119 Me Cl H H Ph F 15,120 Me Cl H H Ph Me 15,121 Et H H H H H 15,122 Et H H H H Cl 15,123 Et H H H H F 15,124 Et H H H H Me
Petition 870180143799, of 10/23/2018, p. 53/411
39/134
Ex. No. R ¹ R ⁵ R1 ⁶ R2 ⁶ R1 ⁷ R2 ⁷ 15,125 Et H H H F H 15,126 Et H H H F Cl 15,127 Et H H H F F 15,128 Et H H H F Me 15,129 Et H H H Cl H 15,130 Et H H H Cl F 15,131 Et H H H Cl Cl 15,132 Et H H H Cl Me 15,133 Et H H H Me H 15,134 Et H H H Me Cl 15,135 Et H H H Me F 15,136 Et H H H Me Me 15,137 Et H H H Ph H 15,138 Et H H H Ph Cl 15,139 Et H H H Ph F 15,140 Et H H H Ph Me 15,141 Et F H H H H 15,142 Et F H H H Cl 15,143 Et F H H H F 15,144 Et F H H H Me 15,145 Et F H H F H 15,146 Et F H H F Cl 15,147 Et F H H F F 15,148 Et F H H F Me 15,149 Et F H H Cl H 15,150 Et F H H Cl F 15,151 Et F H H Cl Cl 15,152 Et F H H Cl Me 15,153 Et F H H Me H 15,154 Et F H H Me Cl 15,155 Et F H H Me F 15,156 Et F H H Me Me
Petition 870180143799, of 10/23/2018, p. 54/411
40/134
Ex. No. R ¹ R ⁵ R1 ⁶ r ₂ ⁶ R1 ⁷ r ₂ ⁷ 15,157 Et F H H Ph H 15,158 Et F H H Ph Cl 15,159 Et F H H Ph F 15,160 Et F H H Ph Me 15,161 Et Cl H H H H 15,162 Et Cl H H H Cl 15,163 Et Cl H H H F 15,164 Et Cl H H H Me 15,165 Et Cl H H F H 15,166 Et Cl H H F Cl 15,167 Et Cl H H F F 15,168 Et Cl H H F Me 15,169 Et Cl H H Cl H 15,170 Et Cl H H Cl F 15,171 Et Cl H H Cl Cl 15,172 Et Cl H H Cl Me 15,173 Et Cl H H Me H 15,174 Et Cl H H Me Cl 15,175 Et Cl H H Me F 15,176 Et Cl H H Me Me 15,177 Et Cl H H Ph H 15,178 Et Cl H H Ph Cl 15,179 Et Cl H H Ph F 15,180 Et Cl H H Ph Me 15,181 H F F H H H 15,182 H F H F H H 15,183 Me H F H H H 15,184 H H F H H H 15,185 K H F H H H 15,186 Me H Cl H H H 15,187 H H Cl H H H 15,188 K H Cl H H H
Petition 870180143799, of 10/23/2018, p. 55/411
41/134
Ex. No. R ¹ R ⁵ R1 ⁶ R2 ⁶ R1 ⁷ R2 ⁷ 15,189 Me H H F H H 15,190 H H H F H H 15,191 K H H F H H 15,192 Me H H Cl H H 15,193 H H H Cl H H 15,194 K H H Cl H H 15,195 K F H H H H 15,196 K Cl H H H H Table 16: Color npositions c ie acorc the with invention da Formi jla (I) in
that X represents CH, A represents A15, R ⁸ , R ³ and R ⁴ each represents hydrogen and R ² represents chlorine:
NH,
Cl
COOR ^1
R 1
Ex. No. R ¹ R ⁵ R1 ⁶ R2 ⁶ R1 ⁷ R2 ⁷ 16,001 H H H H H H 16,002 H H H H H Cl 16,003 H H H H H F 16,004 H H H H H Me 16,005 H H H H F H 16,006 H H H H F Cl 16,007 H H H H F F 16,008 H H H H F Me 16,009 H H H H Cl H 16,010 H H H H Cl F 16,011 H H H H Cl Cl 16,012 H H H H Cl Me 16,013 H H H H Me H 16,014 H H H H Me Cl
Petition 870180143799, of 10/23/2018, p. 56/411
42/134
Ex. No. R ¹ R ⁵ R1 ⁶ r ₂ ⁶ R1 ⁷ R2 ⁷ 16,015 H H H H Me F 16,016 H H H H Me Me 16,017 H H H H Ph H 16,018 H H H H Ph Cl 16,019 H H H H Ph F 16,020 H H H H Ph Me 16,021 H F H H H H 16,022 H F H H H Cl 16,023 H F H H H F 16,024 H F H H H Me 16,025 H F H H F H 16,026 H F H H F Cl 16,027 H F H H F F 16,028 H F H H F Me 16,029 H F H H Cl H 16,030 H F H H Cl F 16,031 H F H H Cl Cl 16,032 H F H H Cl Me 16,033 H F H H Me H 16,034 H F H H Me Cl 16,035 H F H H Me F 16,036 H F H H Me Me 16,037 H F H H Ph H 16,038 H F H H Ph Cl 16,039 H F H H Ph F 16,040 H F H H Ph Me 16,041 H Cl H H H H 16,042 H Cl H H H Cl 16,043 H Cl H H H F 16,044 H Cl H H H Me 16,045 H Cl H H F H 16,046 H Cl H H F Cl
Petition 870180143799, of 10/23/2018, p. 57/411
43/134
Ex. No. R ¹ R ⁵ R1 ⁶ r ₂ ⁶ R1 ⁷ R2 ⁷ 16,047 H Cl H H F F 16,048 H Cl H H F Me 16,049 H Cl H H Cl H 16,050 H Cl H H Cl F 16,051 H Cl H H Cl Cl 16,052 H Cl H H Cl Me 16,053 H Cl H H Me H 16,054 H Cl H H Me Cl 16,055 H Cl H H Me F 16,056 H Cl H H Me Me 16,057 H Cl H H Ph H 16,058 H Cl H H Ph Cl 16,059 H Cl H H Ph F 16,060 H Cl H H Ph Me 16,061 Me H H H H H 16,062 Me H H H H Cl 16,063 Me H H H H F 16,064 Me H H H H Me 16,065 Me H H H F H 16,066 Me H H H F Cl 16,067 Me H H H F F 16,068 Me H H H F Me 16,069 Me H H H Cl H 16,070 Me H H H Cl F 16,071 Me H H H Cl Cl 16,072 Me H H H Cl Me 16,073 Me H H H Me H 16,074 Me H H H Me Cl 16,075 Me H H H Me F 16,076 Me H H H Me Me 16,077 Me H H H Ph H 16,078 Me H H H Ph Cl
Petition 870180143799, of 10/23/2018, p. 58/411
44/134
Ex. No. R ¹ R ⁵ Rl ⁶ R2 ⁶ R1 ⁷ R2 ⁷ 16,079 Me H H H Ph F 16,080 Me H H H Ph Me 16,081 Me F H H H H 16,082 Me F H H H Cl 16,083 Me F H H H F 16,084 Me F H H H Me 16,085 Me F H H F H 16,086 Me F H H F Cl 16,087 Me F H H F F 16,088 Me F H H F Me 16,089 Me F H H Cl H 16,090 Me F H H Cl F 16,091 Me F H H Cl Cl 16,092 Me F H H Cl Me 16,093 Me F H H Me H 16,094 Me F H H Me Cl 16,095 Me F H H Me F 16,096 Me F H H Me Me 16,097 Me F H H Ph H 16,098 Me F H H Ph Cl 16,099 Me F H H Ph F 16,100 Me F H H Ph Me 16,101 Me Cl H H H H 16,102 Me Cl H H H Cl 16,103 Me Cl H H H F 16,104 Me Cl H H H Me 16,105 Me Cl H H F H 16,106 Me Cl H H F Cl 16,107 Me Cl H H F F 16,108 Me Cl H H F Me 16,109 Me Cl H H Cl H 16,110 Me Cl H H Cl F
Petition 870180143799, of 10/23/2018, p. 59/411
45/134
Ex. No. R ¹ R ⁵ R1 ⁶ R2 ⁶ R1 ⁷ R2 ⁷ 16,111 Me Cl H H Cl Cl 16,112 Me Cl H H Cl Me 16,113 Me Cl H H Me H 16,114 Me Cl H H Me Cl 16,115 Me Cl H H Me F 16,116 Me Cl H H Me Me 16,117 Me Cl H H Ph H 16,118 Me Cl H H Ph Cl 16,119 Me Cl H H Ph F 16,120 Me Cl H H Ph Me 16,121 Et H H H H H 16,122 Et H H H H Cl 16,123 Et H H H H F 16,124 Et H H H H Me 16,125 Et H H H F H 16,126 Et H H H F Cl 16,127 Et H H H F F 16,128 Et H H H F Me 16,129 Et H H H Cl H 16,130 Et H H H Cl F 16,131 Et H H H Cl Cl 16,132 Et H H H Cl Me 16,133 Et H H H Me H 16,134 Et H H H Me Cl 16,135 Et H H H Me F 16,136 Et H H H Me Me 16,137 Et H H H Ph H 16,138 Et H H H Ph Cl 16,139 Et H H H Ph F 16,140 Et H H H Ph Me 16,141 Et F H H H H 16,142 Et F H H H Cl
Petition 870180143799, of 10/23/2018, p. 60/411
46/134
Ex. No. R ¹ R ⁵ R1 ⁶ r ₂ ⁶ R1 ⁷ r ₂ ⁷ 16,143 Et F H H H F 16,144 Et F H H H Me 16,145 Et F H H F H 16,146 Et F H H F Cl 16,147 Et F H H F F 16,148 Et F H H F Me 16,149 Et F H H Cl H 16,150 Et F H H Cl F 16,151 Et F H H Cl Cl 16,152 Et F H H Cl Me 16,153 Et F H H Me H 16,154 Et F H H Me Cl 16,155 Et F H H Me F 16,156 Et F H H Me Me 16,157 Et F H H Ph H 16,158 Et F H H Ph Cl 16,159 Et F H H Ph F 16,160 Et F H H Ph Me 16,161 Et Cl H H H H 16,162 Et Cl H H H Cl 16,163 Et Cl H H H F 16,164 Et Cl H H H Me 16,165 Et Cl H H F H 16,166 Et Cl H H F Cl 16,167 Et Cl H H F F 16,168 Et Cl H H F Me 16,169 Et Cl H H Cl H 16,170 Et Cl H H Cl F 16,171 Et Cl H H Cl Cl 16,172 Et Cl H H Cl Me 16,173 Et Cl H H Me H 16,174 Et Cl H H Me Cl
Petition 870180143799, of 10/23/2018, p. 61/411
47/134
Ex. No. R ¹ R ⁵ R1 ⁶ R2 ⁶ R1 ⁷ R2 ⁷ 16,175 Et Cl H H Me F 16,176 Et Cl H H Me Me 16,177 Et Cl H H Ph H 16,178 Et Cl H H Ph Cl 16,179 Et Cl H H Ph F 16,180 Et Cl H H Ph Me 16,181 H F F H H H 16,182 H F H F H H Table 17: Con npositions c and wake up the with invention da Formi jla (I) in
that X represents CH, A represents A15, R ⁸ represents methyl, R ³ and R ⁴ each represent hydrogen and R ² represents chlorine:
Ex. No. R ¹ R ⁵ R1 ⁶ R2 ⁶ R1 ⁷ R2 ⁷ 17,001 H H H H H H 17,002 H H H H H Cl 17,003 H H H H H F 17,004 H H H H H Me 17,005 H H H H F H 17,006 H H H H F Cl 17,007 H H H H F F 17,008 H H H H F Me 17,009 H H H H Cl H 17,010 H H H H Cl F 17,011 H H H H Cl Cl 17,012 H H H H Cl Me 17,013 H H H H Me H 17,014 H H H H Me Cl 17,015 H H H H Me F
Petition 870180143799, of 10/23/2018, p. 62/411
48/134
Ex. No. R ¹ R ⁵ R1 ⁶ r ₂ ⁶ R1 ⁷ R2 ⁷ 17,016 H H H H Me Me 17,017 H H H H Ph H 17,018 H H H H Ph Cl 17,019 H H H H Ph F 17,020 H H H H Ph Me 17,021 H F H H H H 17,022 H F H H H Cl 17,023 H F H H H F 17,024 H F H H H Me 17,025 H F H H F H 17,026 H F H H F Cl 17,027 H F H H F F 17,028 H F H H F Me 17,029 H F H H Cl H 17,030 H F H H Cl F 17,031 H F H H Cl Cl 17,032 H F H H Cl Me 17,033 H F H H Me H 17,034 H F H H Me Cl 17,035 H F H H Me F 17,036 H F H H Me Me 17,037 H F H H Ph H 17,038 H F H H Ph Cl 17,039 H F H H Ph F 17,040 H F H H Ph Me 17,041 H Cl H H H H 17,042 H Cl H H H Cl 17,043 H Cl H H H F 17,044 H Cl H H H Me 17,045 H Cl H H F H 17,046 H Cl H H F Cl 17,047 H Cl H H F F
Petition 870180143799, of 10/23/2018, p. 63/411
49/134
Ex. No. R ¹ R ⁵ R1 ⁶ r ₂ ⁶ R1 ⁷ r ₂ ⁷ 17,048 H Cl H H F Me 17,049 H Cl H H Cl H 17,050 H Cl H H Cl F 17,051 H Cl H H Cl Cl 17,052 H Cl H H Cl Me 17,053 H Cl H H Me H 17,054 H Cl H H Me Cl 17,055 H Cl H H Me F 17,056 H Cl H H Me Me 17,057 H Cl H H Ph H 17,058 H Cl H H Ph Cl 17,059 H Cl H H Ph F 17,060 H Cl H H Ph Me 17,061 Me H H H H H 17,062 Me H H H H Cl 17,063 Me H H H H F 17,064 Me H H H H Me 17,065 Me H H H F H 17,066 Me H H H F Cl 17,067 Me H H H F F 17,068 Me H H H F Me 17,069 Me H H H Cl H 17,070 Me H H H Cl F 17,071 Me H H H Cl Cl 17,072 Me H H H Cl Me 17,073 Me H H H Me H 17,074 Me H H H Me Cl 17,075 Me H H H Me F 17,076 Me H H H Me Me 17,077 Me H H H Ph H 17,078 Me H H H Ph Cl 17,079 Me H H H Ph F
Petition 870180143799, of 10/23/2018, p. 64/411
50/134
Ex. No. R ¹ R ⁵ R1 ⁶ R2 ⁶ R1 ⁷ R2 ⁷ 17,080 Me H H H Ph Me 17,081 Me F H H H H 17,082 Me F H H H Cl 17,083 Me F H H H F 17,084 Me F H H H Me 17,085 Me F H H F H 17,086 Me F H H F Cl 17,087 Me F H H F F 17,088 Me F H H F Me 17,089 Me F H H Cl H 17,090 Me F H H Cl F 17,091 Me F H H Cl Cl 17,092 Me F H H Cl Me 17,093 Me F H H Me H 17,094 Me F H H Me Cl 17,095 Me F H H Me F 17,096 Me F H H Me Me 17,097 Me F H H Ph H 17,098 Me F H H Ph Cl 17,099 Me F H H Ph F 17,100 Me F H H Ph Me 17,101 Me Cl H H H H 17,102 Me Cl H H H Cl 17,103 Me Cl H H H F 17,104 Me Cl H H H Me 17,105 Me Cl H H F H 17,106 Me Cl H H F Cl 17,107 Me Cl H H F F 17,108 Me Cl H H F Me 17,109 Me Cl H H Cl H 17,110 Me Cl H H Cl F 17,111 Me Cl H H Cl Cl
Petition 870180143799, of 10/23/2018, p. 65/411
51/134
Ex. No. R ¹ R ⁵ R1 ⁶ r ₂ ⁶ R1 ⁷ R2 ⁷ 17,112 Me Cl H H Cl Me 17,113 Me Cl H H Me H 17,114 Me Cl H H Me Cl 17,115 Me Cl H H Me F 17,116 Me Cl H H Me Me 17,117 Me Cl H H Ph H 17,118 Me Cl H H Ph Cl 17,119 Me Cl H H Ph F 17,120 Me Cl H H Ph Me 17,121 Et H H H H H 17,122 Et H H H H Cl 17,123 Et H H H H F 17,124 Et H H H H Me 17,125 Et H H H F H 17,126 Et H H H F Cl 17,127 Et H H H F F 17,128 Et H H H F Me 17,129 Et H H H Cl H 17,130 Et H H H Cl F 17,131 Et H H H Cl Cl 17,132 Et H H H Cl Me 17,133 Et H H H Me H 17,134 Et H H H Me Cl 17,135 Et H H H Me F 17,136 Et H H H Me Me 17,137 Et H H H Ph H 17,138 Et H H H Ph Cl 17,139 Et H H H Ph F 17,140 Et H H H Ph Me 17,141 Et F H H H H 17,142 Et F H H H Cl 17,143 Et F H H H F
Petition 870180143799, of 10/23/2018, p. 66/411
52/134
Ex. No. R ¹ R ⁵ R1 ⁶ r ₂ ⁶ R1 ⁷ r ₂ ⁷ 17,144 Et F H H H Me 17,145 Et F H H F H 17,146 Et F H H F Cl 17,147 Et F H H F F 17,148 Et F H H F Me 17,149 Et F H H Cl H 17,150 Et F H H Cl F 17,151 Et F H H Cl Cl 17,152 Et F H H Cl Me 17,153 Et F H H Me H 17,154 Et F H H Me Cl 17,155 Et F H H Me F 17,156 Et F H H Me Me 17,157 Et F H H Ph H 17,158 Et F H H Ph Cl 17,159 Et F H H Ph F 17,160 Et F H H Ph Me 17,161 Et Cl H H H H 17,162 Et Cl H H H Cl 17,163 Et Cl H H H F 17,164 Et Cl H H H Me 17,165 Et Cl H H F H 17,166 Et Cl H H F Cl 17,167 Et Cl H H F F 17,168 Et Cl H H F Me 17,169 Et Cl H H Cl H 17,170 Et Cl H H Cl F 17,171 Et Cl H H Cl Cl 17,172 Et Cl H H Cl Me 17,173 Et Cl H H Me H 17,174 Et Cl H H Me Cl 17,175 Et Cl H H Me F
Petition 870180143799, of 10/23/2018, p. 67/411
53/134
Ex. No. R ¹ R ⁵ R1 ⁶ R2 ⁶ R1 ⁷ R2 ⁷ 17,176 Et Cl H H Me Me 17,177 Et Cl H H Ph H 17,178 Et Cl H H Ph Cl 17,179 Et Cl H H Ph F 17,180 Et Cl H H Ph Me 17,181 H F F H H H 17,182 H F H F H H Table 18: Color npositions c ie acorc the with invention da Formi jla (I) in
that X represents CH, A represents A16, R ³ and R ⁴ each represent hydrogen and R ² represents chlorine:
Ex. No. R ¹ R ⁵ R1 ⁶ R2 ⁶ R ⁷ 18,001 H H H H H 18,002 H H H H Me 18,003 H H H H Ph 18,004 H H H H F 18,005 H H H H Cl 18,006 H Cl H H H 18,007 H Cl H H Me 18,008 H Cl H H Ph 18,009 H Cl H H F 18,010 H Cl H H Cl 18,011 H F H H H 18,012 H F H H Me 18,013 H F H H Ph 18,014 H F H H F 18,015 H F H H Cl 18,016 Me H H H H 18,017 Me H H H Me
Petition 870180143799, of 10/23/2018, p. 68/411
54/134
Ex. No. R ¹ R ⁵ R1 ⁶ R2 ⁶ R ⁷ 18,018 Me H H H Ph 18,019 Me H H H F 18,020 Me H H H Cl 18,021 Me Cl H H H 18,022 Me Cl H H Me 18,023 Me Cl H H Ph 18,024 Me Cl H H F 18,025 Me Cl H H Cl 18,026 Et H H H H 18,027 Et H H H Me 18,028 Et H H H Ph 18,029 Et H H H F 18,030 Et H H H Cl 18,031 Et F H H H 18,032 Et F H H Me 18,033 Et F H H Ph 18,034 Et F H H F 18,035 Et F H H Cl 18,036 Et Cl H H H 18,037 Et Cl H H Me 18,038 Et Cl H H Ph 18,039 Et Cl H H F 18,040 Et Cl H H Cl 18,041 H F F H H 18,042 H F H F H
Table 19: Compounds according to the invention of Formula (I) in which X represents CH, A represents A17, R ³ and R ⁴ each represents hydrogen and R ² represents chlorine:
Petition 870180143799, of 10/23/2018, p. 69/411
55/134
Ex. No. R ¹ R ⁵ R1 ⁶ R2 ⁶ R ⁷ 19,001 H H H H H 19,002 H H H H Me 19,003 H H H H Ph 19,004 H H H H F 19,005 H H H H Cl 19,006 H Cl H H H 19,007 H Cl H H Me 19,008 H Cl H H Ph 19,009 H Cl H H F 19,010 H Cl H H Cl 19,011 H F H H H 19,012 H F H H Me 19,013 H F H H Ph 19,014 H F H H F 19,015 H F H H Cl 19,016 Me H H H H 19,017 Me H H H Me 19,018 Me H H H Ph 19,019 Me H H H F 19,020 Me H H H Cl 19,021 Me Cl H H H 19,022 Me Cl H H Me 19,023 Me Cl H H Ph 19,024 Me Cl H H F 19,025 Me Cl H H Cl 19,026 Et H H H H 19,027 Et H H H Me 19,028 Et H H H Ph 19,029 Et H H H F 19,030 Et H H H Cl 19,031 Et F H H H 19,032 Et F H H Me
Petition 870180143799, of 10/23/2018, p. 70/411
56/134
Ex. No. R ¹ R ⁵ R1 ⁶ r ₂ ⁶ R ⁷ 19,033 Et F H H Ph 19,034 Et F H H F 19,035 Et F H H Cl 19,036 Et Cl H H H 19,037 Et Cl H H Me 19,038 Et Cl H H Ph 19,039 Et Cl H H F 19,040 Et Cl H H Cl 19,041 H F F H H 19,042 H F H F H
Table 20: Compounds according to the invention of Formula (I) where X represents CH, A represents A18, R ³ and R ⁴ each represents hydrogen and R ² represents chlorine:
Ex. No. R ¹ R ⁵ R1 ⁶ r ₂ ⁶ R ⁷ R ⁸ 20,001 H H H H H H 20,002 H H H H Me H 20,003 H H H H Ph H 20,004 H H H H F Me 20,005 H H H H Cl H 20,006 H Cl H H H Me 20,007 H Cl H H Me Me 20,008 H Cl H H Ph Me 20,009 H Cl H H F H 20,010 H Cl H H Cl H 20,011 H F H H H Me 20,012 H F H H Me H 20,013 H F H H Ph H
Petition 870180143799, of 10/23/2018, p. 71/411
57/134
Ex. No. R ¹ R ⁵ R1 ⁶ R2 ⁶ R ⁷ R ⁸ 20,014 H F H H F Me 20,015 H F H H Cl Me 20,016 Me H H H H Et 20,017 Me H H H Me Et 20,018 Me H H H Ph Et 20,019 Me H H H F Et 20,020 Me H H H Cl Et 20,021 Me Cl H H H Me 20,022 Me Cl H H Me H 20,023 Me Cl H H Ph H 20,024 Me Cl H H F H 20,025 Me Cl H H Cl Et 20,026 Et H H H H Me 20,027 Et H H H Me Me 20,028 Et H H H Ph Me 20,029 Et H H H F H 20,030 Et H H H Cl H 20,031 Et F H H H Me 20,032 Et F H H Me Me 20,033 Et F H H Ph H 20,034 Et F H H F Et 20,035 Et F H H Cl Et 20,036 Et Cl H H H H 20,037 Et Cl H H Me H 20,038 Et Cl H H Ph H 20,039 Et Cl H H F Me 20,040 Et Cl H H Cl H 20,041 H F F H H H 20,042 H F H F H H
Table 21: Compounds according to the invention of Formula (I) in which X represents CH, A represents A19, R ³ and R ⁴ each represent hydrogen and R ² represents chlorine:
Petition 870180143799, of 10/23/2018, p. 72/411
58/134
nh ₂τ ^{, β} _X CI R ₂ ι'Τ N ^ COOR ^r -n> ⁵
ν = ν
Ex. No. R ¹ R ⁵ R1 ⁶ r ₂ ⁶ R ⁸ 21,001 H H H H H 21,002 H H H H Me 21,003 H H H H Et 21,004 H F H H H 21,005 H F H H Me 21,006 H F H H Et 21,007 H Cl H H H 21,008 H Cl H H Me 21,009 H Cl H H Et 21,010 Me H H H H 21,011 Me H H H Me 21,012 Me H H H Et 21,013 Me F H H H 21,014 Me F H H Me 21,015 Me F H H Et 21,016 Me Cl H H H 21,017 Me Cl H H Me 21,018 Me Cl H H Et 21,019 Et H H H H 21,020 Et H H H Me 21,021 Et H H H Et 21,022 Et F H H H 21,023 Et F H H Me 21,024 Et F H H Et 21,025 Et Cl H H H 21,026 Et Cl H H Me 21,027 Et Cl H H Et
Petition 870180143799, of 10/23/2018, p. 73/411
59/134
Ex. No. R ¹ R ⁵ R1 ⁶ R2 ⁶ R ⁸ 21,028 H F F H H 21,029 H F H F H
Table 22: Compounds according to the invention of Formula (I) in which X represents CH, A represents A20, R ³ and R ⁴ each represents hydrogen and R ² represents chlorine:
Ex. No. R ¹ R ⁵ R1 ⁶ R2 ⁶ R ⁸ 22,001 H H H H H 22,002 H H H H Me 22,003 H H H H Et 22,004 H F H H H 22,005 H F H H Me 22,006 H F H H Et 22,007 H Cl H H H 22,008 H Cl H H Me 22,009 H Cl H H Et 22,010 Me H H H H 22,011 Me H H H Me 22,012 Me H H H Et 22,013 Me F H H H 22,014 Me F H H Me 22,015 Me F H H Et 22,016 Me Cl H H H 22,017 Me Cl H H Me 22,018 Me Cl H H Et 22,019 Et H H H H 22,020 Et H H H Me 22,021 Et H H H Et 22,022 Et F H H H
Petition 870180143799, of 10/23/2018, p. 74/411
60/134
Ex. No. R ¹ R ⁵ R1 ⁶ R2 ⁶ R ⁸ 22,023 Et F H H Me 22,024 Et F H H Et 22,025 Et Cl H H H 22,026 Et Cl H H Me 22,027 Et Cl H H Et 22,028 H F F H H 22,029 H F H F H
Table 23: Compounds according to the invention of Formula (I) in which X represents N, A represents A1, R ³ and R ⁴ each represents hydrogen and R ² represents chlorine:
Ex. No. R ¹ R ⁵ R1 ⁶ R2 ⁶ R1 ⁷ R2 ⁷ 23,001 H H H H H H 23,002 H F H H H H 23,003 H F H H Cl H 23,004 H F H H H Cl 23,005 H F H H Cl Cl 23,006 H F H H Ph H 23,007 H F H H Ph Cl 23,008 H F H H Ph F 23,009 H F H H Me H 23,010 H F H H Me Cl 23,011 H F H H Me F 23,012 Me H H H H H 23,013 Me F H H H H 23,014 Me F H H Cl H 23,015 Me F H H H Cl 23,016 Me F H H Cl Cl
Petition 870180143799, of 10/23/2018, p. 75/411
61/134
Ex. No. R ¹ R ⁵ R1 ⁶ R2 ⁶ R1 ⁷ R2 ⁷ 23,017 Me F H H H F 23,018 Me F H H Ph H 23,019 Me F H H Ph Cl 23,020 Me F H H Ph F 23,021 Me F H H Me H 23,022 Me F H H Me Cl 23,023 Me F H H Me F 23,024 Et H H H H H 23,025 Et Cl H H H H 23,026 Et Cl H H Cl H 23,027 Et Cl H H H Cl 23,028 Et Cl H H Cl Cl 23,029 Et Cl H H H F 23,030 Et Cl H H Ph H 23,031 Et Cl H H Ph Cl 23,032 Et Cl H H Ph F 23,033 Et Cl H H Me H 23,034 Et Cl H H Me Cl 23,035 Et Cl H H Me F 23,036 H F F H H H 23,037 H F H F H H Table 24: Color npositions c ie acorc the with invention da Formi jla (I) in
that X represents N, A represents A2, R ³ and R ⁴ each represents hydrogen and R ² represents chlorine:
Ex. No. R ¹ R ⁵ R1 ⁶ R2 ⁶ R1 ⁷ R2 ⁷ 24,001 H H H H H H 24,002 H F H H H H
Petition 870180143799, of 10/23/2018, p. 76/411
62/134
Ex. No. R ¹ R ⁵ R1 ⁶ R2 ⁶ R1 ⁷ R2 ⁷ 24,003 H F H H Cl H 24,004 H F H H H Cl 24,005 H F H H Cl Cl 24,006 H F H H Ph H 24,007 H F H H Ph Cl 24,008 H F H H Ph F 24,009 H F H H Me H 24,010 H F H H Me Cl 24,011 H F H H Me F 24,012 Me H H H H H 24,013 Me F H H H H 24,014 Me F H H Cl H 24,015 Me F H H H Cl 24,016 Me F H H Cl Cl 24,017 Me F H H H F 24,018 Me F H H Ph H 24,019 Me F H H Ph Cl 24,020 Me F H H Ph F 24,021 Me F H H Me H 24,022 Me F H H Me Cl 24,023 Me F H H Me F 24,024 Et H H H H H 24,025 Et Cl H H H H 24,026 Et Cl H H Cl H 24,027 Et Cl H H H Cl 24,028 Et Cl H H Cl Cl 24,029 Et Cl H H H F 24,030 Et Cl H H Ph H 24,031 Et Cl H H Ph Cl 24,032 Et Cl H H Ph F 24,033 Et Cl H H Me H 24,034 Et Cl H H Me Cl
Petition 870180143799, of 10/23/2018, p. 77/411
63/134
Ex. No. R ¹ R ⁵ R1 ⁶ R2 ⁶ R1 ⁷ R2 ⁷ 24,035 Et Cl H H Me F 24,036 H F F H H H 24,037 H F H F H H
Table 25: Compounds according to the invention of Formula (I) in which X represents N, A represents A3, R ³ and R ⁴ each represents hydrogen and R ² represents chlorine:
Ex. No. R ¹ R ⁵ R1 ⁶ R2 ⁶ R1 ⁷ R2 ⁷ R ⁸ 25,001 H H H H H H H 25,002 H F H H H H H 25,003 H F H H Cl H H 25,004 H F H H H Cl Me 25,005 H F H H Cl Cl Me 25,006 H F H H Ph H Me 25,007 H F H H Ph Cl H 25,008 H F H H Ph F H 25,009 H F H H Me H H 25,010 H F H H Me Cl Me 25,011 H F H H Me F Me 25,012 Me H H H H H H 25,013 Me F H H H H H 25,014 Me F H H Cl H H 25,015 Me F H H H Cl Me 25,016 Me F H H Cl Cl Me 25,017 Me F H H H F Me 25,018 Me F H H Ph H H 25,019 Me F H H Ph Cl H 25,020 Me F H H Ph F H
Petition 870180143799, of 10/23/2018, p. 78/411
64/134
Ex. No. R ¹ R ⁵ R1 ⁶ R2 ⁶ R1 ⁷ R2 ⁷ R ⁸ 25,021 Me F H H Me H H 25,022 Me F H H Me Cl Me 25,023 Me F H H Me F H 25,024 Et H H H H H H 25,025 Et Cl H H H H Me 25,026 Et Cl H H Cl H Me 25,027 Et Cl H H H Cl Me 25,028 Et Cl H H Cl Cl Me 25,029 Et Cl H H H F Me 25,030 Et Cl H H Ph H H 25,031 Et Cl H H Ph Cl H 25,032 Et Cl H H Ph F H 25,033 Et Cl H H Me H H 25,034 Et Cl H H Me Cl H 25,035 Et Cl H H Me F Me 25,036 H F F H H H H 25,037 H F H F H H H
Table 26: Compounds according to the invention of Formula (I) in which X represents Ν, A represents A4, R ³ and R ⁴ each represents hydrogen and R ² represents chlorine:
Ex. No. R ¹ R ⁵ R1 ⁶ R2 ⁶ R ⁷ 26,001 H H H H H 26,002 H F H H H 26,003 H F H H F 26,004 H F H H Cl 26,005 H F H H Me 26,006 H Cl H H H
Petition 870180143799, of 10/23/2018, p. 79/411
65/134
Ex. No. R ¹ R ⁵ R1 ⁶ R2 ⁶ R ⁷ 26,007 H Cl H H F 26,008 H Cl H H Cl 26,009 H Cl H H Me 26,010 Me H H H H 26,011 Me F H H H 26,012 Me F H H F 26,013 Me F H H Cl 26,014 Me Cl H H H 26,015 Me Cl H H F 26,016 Me Cl H H Cl 26,017 Me Cl H H Me 26,018 Et H H H H 26,019 Et F H H H 26,020 Et Cl H H H 26,021 Et F H H Me 26,022 Et Cl H H Me 26,023 H F F H H 26,024 H F H F H
Table 27: Compounds according to the invention of Formula (I) in which X represents N, A represents A5, R ³ and R ⁴ each represents hydrogen and R ² represents chlorine:
Ex. No. R ¹ R ⁵ R1 ⁶ R2 ⁶ R ⁷ 27,001 H H H H H 27,002 H F H H H 27,003 H F H H F 27,004 H F H H Cl 27,005 H F H H F
Petition 870180143799, of 10/23/2018, p. 80/411
66/134
Ex. No. R ¹ R ⁵ R1 ⁶ R2 ⁶ R ⁷ 27,006 H Cl H H H 27,007 H Cl H H F 27,008 H Cl H H Cl 27,009 H Cl H H Me 27,010 Me H H H H 27,011 Me F H H H 27,012 Me F H H Cl 27,013 Me Cl H H H 27,014 Me Cl H H F 27,015 Me Cl H H Cl 27,016 Me Cl H H Me 27,017 Et H H H H 27,018 Et F H H H 27,019 Et Cl H H H 27,020 Et F H H Me 27,021 Et Cl H H Me 27,022 H F F H H 27,023 H F H F H
Table 28: Compounds according to the invention of Formula (I) where X represents N, A represents A6, R ⁸ , R ³ and R ⁴ each represents hydrogen and R ² represents chlorine:
Ex. No. R ¹ R ⁵ R1 ⁶ R2 ⁶ R ⁷ 28,001 H H H H H 28,002 H F H H H 28,003 H F H H Me 28,004 H F H H Et 28,005 H H H H Me
Petition 870180143799, of 10/23/2018, p. 81/411
67/134
Ex. No. R ¹ R ⁵ R1 ⁶ R2 ⁶ R ⁷ 28,006 H Cl H H H 28,007 H Cl H H Me 28,008 H Cl H H Et 28,009 Me H H H H 28,010 Me H H H Me 28,011 Me F H H H 28,012 Me F H H Me 28,013 Me F H H Et 28,014 Me Cl H H H 28,015 Me Cl H H Me 28,016 Me Cl H H Et 28,017 Me H H H Me 28,018 Et H H H H 28,019 Et H H H Me 28,020 Et H H H Et 28,021 Et F H H H 28,022 Et F H H Me 28,023 Et F H H Et 28,024 Et Cl H H H 28,025 Et Cl H H Me 28,026 Et Cl H H Et 28,027 H F F H H 28,028 H F H F H
Table 29: Compounds according to the invention of Formula (I) where X represents N, A represents A6, R ³ and R ⁴ each represents hydrogen, R ⁸ represents methyl and R ² represents chlorine:
Petition 870180143799, of 10/23/2018, p. 82/411
68/134
Ex. No. R ¹ R ⁵ RT R2 ⁶ R ⁷ 29,001 H H H H H 29,002 H F H H H 29,003 H F H H Me 29,004 H F H H Et 29,005 H H H H Me 29,006 H Cl H H H 29,007 H Cl H H Me 29,008 H Cl H H Et 29,009 Me H H H H 29,010 Me H H H Me 29,011 Me F H H H 29,012 Me F H H Me 29,013 Me F H H Et 29,014 Me Cl H H H 29,015 Me Cl H H Me 29,016 Me Cl H H Et 29,017 Me H H H Me 29,018 Et H H H H 29,019 Et H H H Me 29,020 Et H H H Et 29,021 Et F H H H 29,022 Et F H H Me 29,023 Et F H H Et 29,024 Et Cl H H H 29,025 Et Cl H H Me 29,026 Et Cl H H Et 29,027 H F F H H 29,028 H F H F H
Table 30: Compounds according to the invention of Formula (I) in which X represents N, A represents A7, R ³ and R ⁴ each represents hydrogen and R ² represents chlorine:
Petition 870180143799, of 10/23/2018, p. 83/411
69/134
Ex. No. R ¹ R ⁵ R1 ⁶ R2 ⁶ R ⁷ 30,001 H H H H H 30,002 H H H H Me 30,003 H H H H Ph 30,004 H H H H SMe 30,005 H F H H H 30,006 H F H H Me 30,007 H F H H Ph 30,008 H F H H SMe 30,009 H Cl H H H 30,010 H Cl H H Me 30,011 H Cl H H Ph 30,012 H Cl H H SMe 30,013 Me H H H H 30,014 Me H H H Me 30,015 Me H H H Ph 30,016 Me H H H SMe 30,017 Me F H H H 30,018 Me F H H Me 30,019 Me F H H Ph 30,020 Me F H H SMe 30,021 Me Cl H H H 30,022 Me Cl H H Me 30,023 Me Cl H H Ph 30,024 Me Cl H H SMe 30,025 Et H H H H 30,026 Et H H H Me 30,027 Et H H H Ph
Petition 870180143799, of 10/23/2018, p. 84/411
70/134
Ex. No. R ¹ R ⁵ R1 ⁶ R2 ⁶ R ⁷ 30,028 Et H H H SMe 30,029 Et F H H H 30,030 Et F H H Me 30,031 Et F H H Ph 30,032 Et F H H SMe 30,033 Et Cl H H H 30,034 Et Cl H H Me 30,035 Et Cl H H Ph 30,036 Et Cl H H SMe 30,037 H F F H H 30,038 H F H F H
Table 31: Compounds according to the invention of Formula (I) in which X represents N, A represents A8, R ³ and R ⁴ each represents hydrogen and R ² represents chlorine:
Ex. No. R ¹ R ⁵ R1 ⁶ R2 ⁶ R ⁷ 31,001 H H H H H 31,002 H H H H Me 31,003 H H H H Ph 31,004 H H H H SMe 31,005 H F H H H 31,006 H F H H Me 31,007 H F H H Ph 31,008 H F H H SMe 31,009 H Cl H H H 31,010 H Cl H H Me 31,011 H Cl H H Ph 31,012 H Cl H H SMe
Petition 870180143799, of 10/23/2018, p. 85/411
71/134
Ex. No. R ¹ R ⁵ R1 ⁶ R2 ⁶ R ⁷ 31,013 Me H H H H 31,014 Me H H H Me 31,015 Me H H H Ph 31,016 Me H H H SMe 31,017 Me F H H H 31,018 Me F H H Me 31,019 Me F H H Ph 31,020 Me F H H SMe 31,021 Me Cl H H H 31,022 Et H H H H 31,023 Et H H H Me 31,024 Et H H H Ph 31,025 Et H H H SMe 31,026 Et F H H H 31,027 Et F H H Me 31,028 Et F H H Ph 31,029 Et F H H SMe 31,030 Et Cl H H H 31,031 Et Cl H H Me 31,032 Et Cl H H Ph 31,033 Et Cl H H SMe 31,034 H F F H H 31,035 H F H F H
Table 32: Compounds according to the invention of Formula (I) in which X represents N, A represents A9, R ³ and R ⁴ each represents hydrogen and R ² represents chlorine:
Petition 870180143799, of 10/23/2018, p. 86/411
72/134
Ex. No. R ¹ R ⁵ R1 ⁶ R2 ⁶ R ⁷ 32,001 H H H H H 32,002 H H H H Me 32,003 H H H H Ph 32,004 H H H H SMe 32,005 H F H H H 32,006 H F H H Me 32,007 H F H H Ph 32,008 H F H H SMe 32,009 H Cl H H H 32,010 H Cl H H Me 32,011 H Cl H H Ph 32,012 H Cl H H SMe 32,013 Me H H H H 32,014 Me H H H Me 32,015 Me H H H Ph 32,016 Me H H H SMe 32,017 Me F H H H 32,018 Me F H H Me 32,019 Me F H H Ph 32,020 Me F H H SMe 32,021 Me Cl H H H 32,022 Me Cl H H Me 32,023 Me Cl H H Ph 32,024 Me Cl H H SMe 32,025 Et H H H H 32,026 Et H H H Me 32,027 Et H H H Ph 32,028 Et H H H SMe 32,029 Et F H H H 32,030 Et F H H Me 32,031 Et F H H Ph 32,032 Et F H H SMe
Petition 870180143799, of 10/23/2018, p. 87/411
73/134
Ex. No. R ¹ R ⁵ R1 ⁶ R2 ⁶ R ⁷ 32,033 Et Cl H H H 32,034 Et Cl H H Me 32,035 Et Cl H H Ph 32,036 Et Cl H H SMe 32,037 H F F H H 32,038 H F H F H
Table 33: Compounds according to the invention of Formula (I) where X represents N, A represents A10, R ³ and R ⁴ each represents hydrogen and R ² represents chlorine:
Ex. No. R ¹ R ⁵ R1 ⁶ R2 ⁶ R ⁷ 33,001 H H H H H 33,002 H H H H Me 33,003 H H H H Ph 33,004 H H H H SMe 33,005 H F H H H 33,006 H F H H Me 33,007 H F H H Ph 33,008 H F H H SMe 33,009 H Cl H H H 33,010 H Cl H H Me 33,011 H Cl H H Ph 33,012 H Cl H H SMe 33,013 Me H H H H 33,014 Me H H H Me 33,015 Me H H H Ph 33,016 Me H H H SMe 33,017 Me F H H H
Petition 870180143799, of 10/23/2018, p. 88/411
74/134
Ex. No. R ¹ R ⁵ R1 ⁶ R2 ⁶ R ⁷ 33,018 Me F H H Me 33,019 Me F H H Ph 33,020 Me F H H SMe 33,021 Me Cl H H H 33,022 Et H H H H 33,023 Et H H H Me 33,024 Et H H H Ph 33,025 Et H H H SMe 33,026 Et F H H H 33,027 Et F H H Me 33,028 Et F H H Ph 33,029 Et F H H SMe 33,030 Et Cl H H H 33,031 Et Cl H H Me 33,032 Et Cl H H Ph 33,033 Et Cl H H SMe 33,034 H F F H H 33,035 H F H F H
Table 34: Compounds according to the invention of Formula (I) in which X represents N, A represents A11, R ³ and R ⁴ each represents hydrogen and R ² represents chlorine:
Ex. No. R ¹ R ⁵ R1 ⁶ R2 ⁶ R ⁷ R ⁸ 34,001 H H H H H H 34,002 H F H H H H 34,003 H F H H H Me 34,004 H F H H Me H 34,005 H F H H Me Me
Petition 870180143799, of 10/23/2018, p. 89/411
75/134
Ex. No. R ¹ R ⁵ R1 ⁶ R2 ⁶ R ⁷ R ⁸ 34,006 H Cl H H H H 34,007 H Cl H H H Me 34,008 H Cl H H Me H 34,009 H Cl H H Me Me 34,010 H H H H Ph H 34,011 H H H H Ph Me 34,012 H F H H Ph H 34,013 H F H H Ph Me 34,014 H Cl H H Ph H 34,015 H Cl H H Ph Me 34,016 H H H H Me H 34,017 H H H H H Me 34,018 H H H H Me Me 34,019 Me H H H H H 34,020 Me F H H H H 34,021 Me F H H H Me 34,022 Me F H H Me H 34,023 Me F H H Me Me 34,024 Me Cl H H H H 34,025 Me Cl H H H Me 34,026 Me Cl H H Me H 34,027 Me Cl H H Me Me 34,028 Me H H H Ph H 34,029 Me H H H Ph Me 34,030 Me F H H Ph H 34,031 Me F H H Ph Me 34,032 Me Cl H H Ph H 34,033 Me Cl H H Ph Me 34,034 Me H H H Me H 34,035 Me H H H H Me 34,036 Me H H H Me Me 34,037 Et H H H H H
Petition 870180143799, of 10/23/2018, p. 90/411
76/134
Ex. No. R ¹ R ⁵ R1 ⁶ R2 ⁶ R ⁷ R ⁸ 34,038 Et F H H H H 34,039 Et F H H H Me 34,040 Et F H H Me H 34,041 Et F H H Me Me 34,042 Et Cl H H H H 34,043 Et Cl H H H Me 34,044 Et Cl H H Me H 34,045 Et H H H Ph H 34,046 Et H H H Ph Me 34,047 Et F H H Ph H 34,048 Et F H H Ph Me 34,049 Et Cl H H Ph H 34,050 Et Cl H H Me Me 34,051 Et H H H Me H 34,052 Et H H H H Me 34,053 Et H H H Me Me 34,054 H F F H H H 34,055 H F H F H H Table 35: Con C items and wake up the with nvention da Formi jla (I) in
that X represents N, A represents A12, R ³ and R ⁴ each represent hydrogen and R ² represents chlorine:
Cl
COOR ¹
R '
Ex. No. R ¹ R ⁵ R1 ⁶ R2 ⁶ R ⁷ R ⁸ 35,001 H H H H H Me 35,002 H F H H H Me 35,003 H F H H Me Me 35,004 H Cl H H H Me 35,005 H Cl H H Me Me
Petition 870180143799, of 10/23/2018, p. 91/411
77/134
Ex. No. R ¹ R ⁵ R1 ⁶ R2 ⁶ R ⁷ R ⁸ 35,006 H H H H Ph Me 35,007 H F H H Ph Me 35,008 H Cl H H Ph Me 35,009 H H H H H Me 35,010 Me H H H H Me 35,011 Me F H H H Me 35,012 Me H H H Me Me 35,013 Me F H H Me Me 35,014 Me Cl H H H Me 35,015 Me Cl H H Me Me 35,016 Me H H H Ph Me 35,017 Me F H H Ph Me 35,018 Me Cl H H Ph Me 35,019 Et F H H H Me 35,020 Et F H H Me Me 35,021 Et Cl H H H Me 35,022 Et H H H Ph Me 35,023 Et F H H Ph Me 35,024 Et Cl H H Ph Me 35,025 Et H H H H Me 35,026 Et H H H Me Me 35,027 Et Cl H H Me Me 35,028 H F F H H H 35,029 H F H F H H Table 36: Con C items and wake up the with nvention da Formi jla (I) in
that X represents N, A represents A13, R ³ and R ⁴ each represent hydrogen and R ² represents chlorine:
Petition 870180143799, of 10/23/2018, p. 92/411
78/134
Ex. No. R ¹ R ⁵ R1 ⁶ R2 ⁶ R1 ⁷ R2 ⁷ 36,001 H H H H H H 36,002 H H H H H Cl 36,003 H H H H H F 36,004 H H H H H Me 36,005 H H H H F H 36,006 H H H H F Cl 36,007 H H H H F F 36,008 H H H H F Me 36,009 H H H H Cl H 36,010 H H H H Cl F 36,011 H H H H Cl Cl 36,012 H H H H Cl Me 36,013 H H H H Me H 36,014 H H H H Me Cl 36,015 H H H H Me F 36,016 H H H H Me Me 36,017 H H H H Ph H 36,018 H H H H Ph Cl 36,019 H H H H Ph F 36,020 H H H H Ph Me 36,021 H F H H H H 36,022 H F H H H Cl 36,023 H F H H H F 36,024 H F H H H Me 36,025 H F H H F H 36,026 H F H H F Cl 36,027 H F H H F F 36,028 H F H H F Me 36,029 H F H H Cl H 36,030 H F H H Cl F 36,031 H F H H Cl Cl 36,032 H F H H Cl Me
Petition 870180143799, of 10/23/2018, p. 93/411
79/134
Ex. No. R ¹ R ⁵ RT R2 ⁶ R1 ⁷ R2 ⁷ 36,033 H F H H Me H 36,034 H F H H Me Cl 36,035 H F H H Me F 36,036 H F H H Me Me 36,037 H F H H Ph H 36,038 H F H H Ph Cl 36,039 H F H H Ph F 36,040 H F H H Ph Me 36,041 H Cl H H H H 36,042 H Cl H H H Cl 36,043 H Cl H H H F 36,044 H Cl H H H Me 36,045 H Cl H H F H 36,046 H Cl H H F Cl 36,047 H Cl H H F F 36,048 H Cl H H F Me 36,049 H Cl H H Cl H 36,050 H Cl H H Cl F 36,051 H Cl H H Cl Cl 36,052 H Cl H H Cl Me 36,053 H Cl H H Me H 36,054 H Cl H H Me Cl 36,055 H Cl H H Me F 36,056 H Cl H H Me Me 36,057 H Cl H H Ph H 36,058 H Cl H H Ph Cl 36,059 H Cl H H Ph F 36,060 H Cl H H Ph Me 36,061 Me H H H H H 36,062 Me H H H H Cl 36,063 Me H H H H F 36,064 Me H H H H Me
Petition 870180143799, of 10/23/2018, p. 94/411
80/134
Ex. No. R ¹ R ⁵ R1 ⁶ R2 ⁶ R1 ⁷ R2 ⁷ 36,065 Me H H H F H 36,066 Me H H H F Cl 36,067 Me H H H F F 36,068 Me H H H F Me 36,069 Me H H H Cl H 36,070 Me H H H Cl F 36,071 Me H H H Cl Cl 36,072 Me H H H Cl Me 36,073 Me H H H Me H 36,074 Me H H H Me Cl 36,075 Me H H H Me F 36,076 Me H H H Me Me 36,077 Me H H H Ph H 36,078 Me H H H Ph Cl 36,079 Me H H H Ph F 36,080 Me H H H Ph Me 36,081 Me F H H H H 36,082 Me F H H H Cl 36,083 Me F H H H F 36,084 Me F H H H Me 36,085 Me F H H F H 36,086 Me F H H F Cl 36,087 Me F H H F F 36,088 Me F H H F Me 36,089 Me F H H Cl H 36,090 Me F H H Cl F 36,091 Me F H H Cl Cl 36,092 Me F H H Cl Me 36,093 Me F H H Me H 36,094 Me F H H Me Cl 36,095 Me F H H Me F 36,096 Me F H H Me Me
Petition 870180143799, of 10/23/2018, p. 95/411
81/134
Ex. No. R ¹ R ⁵ R1 ⁶ R2 ⁶ R1 ⁷ R2 ⁷ 36,097 Me F H H Ph H 36,098 Me F H H Ph Cl 36,099 Me F H H Ph F 36,100 Me F H H Ph Me 36,101 Me Cl H H H H 36,102 Me Cl H H H Cl 36,103 Me Cl H H H F 36,104 Me Cl H H H Me 36,105 Me Cl H H F H 36,106 Me Cl H H F Cl 36,107 Me Cl H H F F 36,108 Me Cl H H F Me 36,109 Me Cl H H Cl H 36,110 Me Cl H H Cl F 36,111 Me Cl H H Cl Cl 36,112 Me Cl H H Cl Me 36,113 Me Cl H H Me H 36,114 Me Cl H H Me Cl 36,115 Me Cl H H Me F 36,116 Me Cl H H Me Me 36,117 Me Cl H H Ph H 36,118 Me Cl H H Ph Cl 36,119 Me Cl H H Ph F 36,120 Me Cl H H Ph Me 36,121 Et H H H H H 36,122 Et H H H H Cl 36,123 Et H H H H F 36,124 Et H H H H Me 36,125 Et H H H F H 36,126 Et H H H F Cl 36,127 Et H H H F F 36,128 Et H H H F Me
Petition 870180143799, of 10/23/2018, p. 96/411
82/134
Ex. No. R ¹ R ⁵ R1 ⁶ R2 ⁶ R1 ⁷ R2 ⁷ 36,129 Et H H H Cl H 36,130 Et H H H Cl F 36,131 Et H H H Cl Cl 36,132 Et H H H Cl Me 36,133 Et H H H Me H 36,134 Et H H H Me Cl 36,135 Et H H H Me F 36,136 Et H H H Me Me 36,137 Et H H H Ph H 36,138 Et H H H Ph Cl 36,139 Et H H H Ph F 36,140 Et H H H Ph Me 36,141 Et F H H H H 36,142 Et F H H H Cl 36,143 Et F H H H F 36,144 Et F H H H Me 36,145 Et F H H F H 36,146 Et F H H F Cl 36,147 Et F H H F F 36,148 Et F H H F Me 36,149 Et F H H Cl H 36,150 Et F H H Cl F 36,151 Et F H H Cl Cl 36,152 Et F H H Cl Me 36,153 Et F H H Me H 36,154 Et F H H Me Cl 36,155 Et F H H Me F 36,156 Et F H H Me Me 36,157 Et F H H Ph H 36,158 Et F H H Ph Cl 36,159 Et F H H Ph F 36,160 Et F H H Ph Me
Petition 870180143799, of 10/23/2018, p. 97/411
83/134
Ex. No. R ¹ R ⁵ R1 ⁶ R2 ⁶ R1 ⁷ R2 ⁷ 36,161 Et Cl H H H H 36,162 Et Cl H H H Cl 36,163 Et Cl H H H F 36,164 Et Cl H H H Me 36,165 Et Cl H H F H 36,166 Et Cl H H F Cl 36,167 Et Cl H H F F 36,168 Et Cl H H F Me 36,169 Et Cl H H Cl H 36,170 Et Cl H H Cl F 36,171 Et Cl H H Cl Cl 36,172 Et Cl H H Cl Me 36,173 Et Cl H H Me H 36,174 Et Cl H H Me Cl 36,175 Et Cl H H Me F 36,176 Et Cl H H Me Me 36,177 Et Cl H H Ph H 36,178 Et Cl H H Ph Cl 36,179 Et Cl H H Ph F 36,180 Et Cl H H Ph Me 36,181 H F F H H H 36,182 H F H F H H Table 37: Color npositions c ie acorc the with invention da Formi jla (I) in
that X represents N, A represents A14, R ³ and R ⁴ each represent hydrogen and R ² represents chlorine:
Petition 870180143799, of 10/23/2018, p. 98/411
84/134
Ex. No. R ¹ R ⁵ R1 ⁶ R2 ⁶ R1 ⁷ R2 ⁷ 37,002 H H H H H Cl 37,003 H H H H H F 37,004 H H H H H Me 37,005 H H H H F H 37,006 H H H H F Cl 37,007 H H H H F F 37,008 H H H H F Me 37,009 H H H H Cl H 37,010 H H H H Cl F 37,011 H H H H Cl Cl 37,012 H H H H Cl Me 37,013 H H H H Me H 37,014 H H H H Me Cl 37,015 H H H H Me F 37,016 H H H H Me Me 37,017 H H H H Ph H 37,018 H H H H Ph Cl 37,019 H H H H Ph F 37,020 H H H H Ph Me 37,021 H F H H H H 37,022 H F H H H Cl 37,023 H F H H H F 37,024 H F H H H Me 37,025 H F H H F H 37,026 H F H H F Cl 37,027 H F H H F F 37,028 H F H H F Me 37,029 H F H H Cl H 37,030 H F H H Cl F 37,031 H F H H Cl Cl 37,032 H F H H Cl Me 37,033 H F H H Me H
Petition 870180143799, of 10/23/2018, p. 99/411
85/134
Ex. No. R ¹ R ⁵ R1 ⁶ R2 ⁶ R1 ⁷ R2 ⁷ 37,034 H F H H Me Cl 37,035 H F H H Me F 37,036 H F H H Me Me 37,037 H F H H Ph H 37,038 H F H H Ph Cl 37,039 H F H H Ph F 37,040 H F H H Ph Me 37,041 H Cl H H H H 37,042 H Cl H H H Cl 37,043 H Cl H H H F 37,044 H Cl H H H Me 37,045 H Cl H H F H 37,046 H Cl H H F Cl 37,047 H Cl H H F F 37,048 H Cl H H F Me 37,049 H Cl H H Cl H 37,050 H Cl H H Cl F 37,051 H Cl H H Cl Cl 37,052 H Cl H H Cl Me 37,053 H Cl H H Me H 37,054 H Cl H H Me Cl 37,055 H Cl H H Me F 37,056 H Cl H H Me Me 37,057 H Cl H H Ph H 37,058 H Cl H H Ph Cl 37,059 H Cl H H Ph F 37,060 H Cl H H Ph Me 37,061 Me H H H H H 37,062 Me H H H H Cl 37,063 Me H H H H F 37,064 Me H H H H Me 37,065 Me H H H F H
Petition 870180143799, of 10/23/2018, p. 100/411
86/134
Ex. No. R ¹ R ⁵ R1 ⁶ R2 ⁶ R1 ⁷ R2 ⁷ 37,066 Me H H H F Cl 37,067 Me H H H F F 37,068 Me H H H F Me 37,069 Me H H H Cl H 37,070 Me H H H Cl F 37,071 Me H H H Cl Cl 37,072 Me H H H Cl Me 37,073 Me H H H Me H 37,074 Me H H H Me Cl 37,075 Me H H H Me F 37,076 Me H H H Me Me 37,077 Me H H H Ph H 37,078 Me H H H Ph Cl 37,079 Me H H H Ph F 37,080 Me H H H Ph Me 37,081 Me F H H H H 37,082 Me F H H H Cl 37,083 Me F H H H F 37,084 Me F H H H Me 37,085 Me F H H F H 37,086 Me F H H F Cl 37,087 Me F H H F F 37,088 Me F H H F Me 37,089 Me F H H Cl H 37,090 Me F H H Cl F 37,091 Me F H H Cl Cl 37,092 Me F H H Cl Me 37,093 Me F H H Me H 37,094 Me F H H Me Cl 37,095 Me F H H Me F 37,096 Me F H H Me Me 37,097 Me F H H Ph H
Petition 870180143799, of 10/23/2018, p. 101/411
87/134
Ex. No. R ¹ R ⁵ R1 ⁶ R2 ⁶ R1 ⁷ R2 ⁷ 37,098 Me F H H Ph Cl 37,099 Me F H H Ph F 37,100 Me F H H Ph Me 37,101 Me Cl H H H H 37,102 Me Cl H H H Cl 37,103 Me Cl H H H F 37,104 Me Cl H H H Me 37,105 Me Cl H H F H 37,106 Me Cl H H F Cl 37,107 Me Cl H H F F 37,108 Me Cl H H F Me 37,109 Me Cl H H Cl H 37,110 Me Cl H H Cl F 37,111 Me Cl H H Cl Cl 37,112 Me Cl H H Cl Me 37,113 Me Cl H H Me H 37,114 Me Cl H H Me Cl 37,115 Me Cl H H Me F 37,116 Me Cl H H Me Me 37,117 Me Cl H H Ph H 37,118 Me Cl H H Ph Cl 37,119 Me Cl H H Ph F 37,120 Me Cl H H Ph Me 37,121 Et H H H H H 37,122 Et H H H H Cl 37,123 Et H H H H F 37,124 Et H H H H Me 37,125 Et H H H F H 37,126 Et H H H F Cl 37,127 Et H H H F F 37,128 Et H H H F Me 37,129 Et H H H Cl H
Petition 870180143799, of 10/23/2018, p. 102/411
88/134
Ex. No. R ¹ R ⁵ R1 ⁶ R2 ⁶ R1 ⁷ R2 ⁷ 37,130 Et H H H Cl F 37,131 Et H H H Cl Cl 37,132 Et H H H Cl Me 37,133 Et H H H Me H 37,134 Et H H H Me Cl 37,135 Et H H H Me F 37,136 Et H H H Me Me 37,137 Et H H H Ph H 37,138 Et H H H Ph Cl 37,139 Et H H H Ph F 37,140 Et H H H Ph Me 37,141 Et F H H H H 37,142 Et F H H H Cl 37,143 Et F H H H F 37,144 Et F H H H Me 37,145 Et F H H F H 37,146 Et F H H F Cl 37,147 Et F H H F F 37,148 Et F H H F Me 37,149 Et F H H Cl H 37,150 Et F H H Cl F 37,151 Et F H H Cl Cl 37,152 Et F H H Cl Me 37,153 Et F H H Me H 37,154 Et F H H Me Cl 37,155 Et F H H Me F 37,156 Et F H H Me Me 37,157 Et F H H Ph H 37,158 Et F H H Ph Cl 37,159 Et F H H Ph F 37,160 Et F H H Ph Me 37,161 Et Cl H H H H
Petition 870180143799, of 10/23/2018, p. 103/411
89/134
Ex. No. R ¹ R ⁵ R1 ⁶ R2 ⁶ R1 ⁷ R2 ⁷ 37,162 Et Cl H H H Cl 37,163 Et Cl H H H F 37,164 Et Cl H H H Me 37,165 Et Cl H H F H 37,166 Et Cl H H F Cl 37,167 Et Cl H H F F 37,168 Et Cl H H F Me 37,169 Et Cl H H Cl H 37,170 Et Cl H H Cl F 37,171 Et Cl H H Cl Cl 37,172 Et Cl H H Cl Me 37,173 Et Cl H H Me H 37,174 Et Cl H H Me Cl 37,175 Et Cl H H Me F 37,176 Et Cl H H Me Me 37,177 Et Cl H H Ph H 37,178 Et Cl H H Ph Cl 37,179 Et Cl H H Ph F 37,180 Et Cl H H Ph Me 37,181 H F F H H H 37,182 H F H F H H Table 38: Color npositions c ie acorc the with invention da Formi jla (I) in
that X represents N, A represents A15, R ⁸ , R ³ and R ⁴ each represents hydrogen and R ² represents chlorine:
Ex. No. R ¹ R ⁵ R1 ⁶ R2 ⁶ R1 ⁷ R2 ⁷ 38,001 H H H H H H 38,002 H H H H H Cl
Petition 870180143799, of 10/23/2018, p. 104/411
90/134
Ex. No. R ¹ R ⁵ R1 ⁶ R2 ⁶ R1 ⁷ R2 ⁷ 38,003 H H H H H F 38,004 H H H H H Me 38,005 H H H H F H 38,006 H H H H F Cl 38,007 H H H H F F 38,008 H H H H F Me 38,009 H H H H Cl H 38,010 H H H H Cl F 38,011 H H H H Cl Cl 38,012 H H H H Cl Me 38,013 H H H H Me H 38,014 H H H H Me Cl 38,015 H H H H Me F 38,016 H H H H Me Me 38,017 H H H H Ph H 38,018 H H H H Ph Cl 38,019 H H H H Ph F 38,020 H H H H Ph Me 38,021 H F H H H H 38,022 H F H H H Cl 38,023 H F H H H F 38,024 H F H H H Me 38,025 H F H H F H 38,026 H F H H F Cl 38,027 H F H H F F 38,028 H F H H F Me 38,029 H F H H Cl H 38,030 H F H H Cl F 38,031 H F H H Cl Cl 38,032 H F H H Cl Me 38,033 H F H H Me H 38,034 H F H H Me Cl
Petition 870180143799, of 10/23/2018, p. 105/411
91/134
Ex. No. R ¹ R ⁵ RT R2 ⁶ R1 ⁷ R2 ⁷ 38,035 H F H H Me F 38,036 H F H H Me Me 38,037 H F H H Ph H 38,038 H F H H Ph Cl 38,039 H F H H Ph F 38,040 H F H H Ph Me 38,041 H Cl H H H H 38,042 H Cl H H H Cl 38,043 H Cl H H H F 38,044 H Cl H H H Me 38,045 H Cl H H F H 38,046 H Cl H H F Cl 38,047 H Cl H H F F 38,048 H Cl H H F Me 38,049 H Cl H H Cl H 38,050 H Cl H H Cl F 38,051 H Cl H H Cl Cl 38,052 H Cl H H Cl Me 38,053 H Cl H H Me H 38,054 H Cl H H Me Cl 38,055 H Cl H H Me F 38,056 H Cl H H Me Me 38,057 H Cl H H Ph H 38,058 H Cl H H Ph Cl 38,059 H Cl H H Ph F 38,060 H Cl H H Ph Me 38,061 Me H H H H H 38,062 Me H H H H Cl 38,063 Me H H H H F 38,064 Me H H H H Me 38,065 Me H H H F H 38,066 Me H H H F Cl
Petition 870180143799, of 10/23/2018, p. 106/411
92/134
Ex. No. R ¹ R ⁵ R1 ⁶ R2 ⁶ R1 ⁷ R2 ⁷ 38,067 Me H H H F F 38,068 Me H H H F Me 38,069 Me H H H Cl H 38,070 Me H H H Cl F 38,071 Me H H H Cl Cl 38,072 Me H H H Cl Me 38,073 Me H H H Me H 38,074 Me H H H Me Cl 38,075 Me H H H Me F 38,076 Me H H H Me Me 38,077 Me H H H Ph H 38,078 Me H H H Ph Cl 38,079 Me H H H Ph F 38,080 Me H H H Ph Me 38,081 Me F H H H H 38,082 Me F H H H Cl 38,083 Me F H H H F 38,084 Me F H H H Me 38,085 Me F H H F H 38,086 Me F H H F Cl 38,087 Me F H H F F 38,088 Me F H H F Me 38,089 Me F H H Cl H 38,090 Me F H H Cl F 38,091 Me F H H Cl Cl 38,092 Me F H H Cl Me 38,093 Me F H H Me H 38,094 Me F H H Me Cl 38,095 Me F H H Me F 38,096 Me F H H Me Me 38,097 Me F H H Ph H 38,098 Me F H H Ph Cl
Petition 870180143799, of 10/23/2018, p. 107/411
93/134
Ex. No. R ¹ R ⁵ R1 ⁶ R2 ⁶ R1 ⁷ R2 ⁷ 38,099 Me F H H Ph F 38,100 Me F H H Ph Me 38,101 Me Cl H H H H 38,102 Me Cl H H H Cl 38,103 Me Cl H H H F 38,104 Me Cl H H H Me 38,105 Me Cl H H F H 38,106 Me Cl H H F Cl 38,107 Me Cl H H F F 38,108 Me Cl H H F Me 38,109 Me Cl H H Cl H 38,110 Me Cl H H Cl F 38,111 Me Cl H H Cl Cl 38,112 Me Cl H H Cl Me 38,113 Me Cl H H Me H 38,114 Me Cl H H Me Cl 38,115 Me Cl H H Me F 38,116 Me Cl H H Me Me 38,117 Me Cl H H Ph H 38,118 Me Cl H H Ph Cl 38,119 Me Cl H H Ph F 38,120 Me Cl H H Ph Me 38,121 Et H H H H H 38,122 Et H H H H Cl 38,123 Et H H H H F 38,124 Et H H H H Me 38,125 Et H H H F H 38,126 Et H H H F Cl 38,127 Et H H H F F 38,128 Et H H H F Me 38,129 Et H H H Cl H 38,130 Et H H H Cl F
Petition 870180143799, of 10/23/2018, p. 108/411
94/134
Ex. No. R ¹ R ⁵ R1 ⁶ R2 ⁶ R1 ⁷ R2 ⁷ 38,131 Et H H H Cl Cl 38,132 Et H H H Cl Me 38,133 Et H H H Me H 38,134 Et H H H Me Cl 38,135 Et H H H Me F 38,136 Et H H H Me Me 38,137 Et H H H Ph H 38,138 Et H H H Ph Cl 38,139 Et H H H Ph F 38,140 Et H H H Ph Me 38,141 Et F H H H H 38,142 Et F H H H Cl 38,143 Et F H H H F 38,144 Et F H H H Me 38,145 Et F H H F H 38,146 Et F H H F Cl 38,147 Et F H H F F 38,148 Et F H H F Me 38,149 Et F H H Cl H 38,150 Et F H H Cl F 38,151 Et F H H Cl Cl 38,152 Et F H H Cl Me 38,153 Et F H H Me H 38,154 Et F H H Me Cl 38,155 Et F H H Me F 38,156 Et F H H Me Me 38,157 Et F H H Ph H 38,158 Et F H H Ph Cl 38,159 Et F H H Ph F 38,160 Et F H H Ph Me 38,161 Et Cl H H H H 38,162 Et Cl H H H Cl
Petition 870180143799, of 10/23/2018, p. 109/411
95/134
Ex. No. R ¹ R ⁵ R1 ⁶ R2 ⁶ R1 ⁷ R2 ⁷ 38,163 Et Cl H H H F 38,164 Et Cl H H H Me 38,165 Et Cl H H F H 38,166 Et Cl H H F Cl 38,167 Et Cl H H F F 38,168 Et Cl H H F Me 38,169 Et Cl H H Cl H 38,170 Et Cl H H Cl F 38,171 Et Cl H H Cl Cl 38,172 Et Cl H H Cl Me 38,173 Et Cl H H Me H 38,174 Et Cl H H Me Cl 38,175 Et Cl H H Me F 38,176 Et Cl H H Me Me 38,177 Et Cl H H Ph H 38,178 Et Cl H H Ph Cl 38,179 Et Cl H H Ph F 38,180 Et Cl H H Ph Me 38,181 H F F H H H 38,182 H F H F H H Table 39: Color npositions c ie acorc the with invention da Formi jla (I) in
that X represents N, A represents A15, R ⁸ represents methyl, R ³ and R ⁴ each represent hydrogen and R ² represents chlorine:
Ex. No. R ¹ R ⁵ R1 ⁶ R2 ⁶ R1 ⁷ R2 ⁷ 39,001 H H H H H H 39,002 H H H H H Cl 39,003 H H H H H F
Petition 870180143799, of 10/23/2018, p. 110/411
96/134
Ex. No. R ¹ R ⁵ R1 ⁶ R2 ⁶ R1 ⁷ R2 ⁷ 39,004 H H H H H Me 39,005 H H H H F H 39,006 H H H H F Cl 39,007 H H H H F F 39,008 H H H H F Me 39,009 H H H H Cl H 39,010 H H H H Cl F 39,011 H H H H Cl Cl 39,012 H H H H Cl Me 39,013 H H H H Me H 39,014 H H H H Me Cl 39,015 H H H H Me F 39,016 H H H H Me Me 39,017 H H H H Ph H 39,018 H H H H Ph Cl 39,019 H H H H Ph F 39,020 H H H H Ph Me 39,021 H F H H H H 39,022 H F H H H Cl 39,023 H F H H H F 39,024 H F H H H Me 39,025 H F H H F H 39,026 H F H H F Cl 39,027 H F H H F F 39,028 H F H H F Me 39,029 H F H H Cl H 39,030 H F H H Cl F 39,031 H F H H Cl Cl 39,032 H F H H Cl Me 39,033 H F H H Me H 39,034 H F H H Me Cl 39,035 H F H H Me F
Petition 870180143799, of 10/23/2018, p. 111/411
97/134
Ex. No. R ¹ R ⁵ R1 ⁶ R2 ⁶ R1 ⁷ R2 ⁷ 39,036 H F H H Me Me 39,037 H F H H Ph H 39,038 H F H H Ph Cl 39,039 H F H H Ph F 39,040 H F H H Ph Me 39,041 H Cl H H H H 39,042 H Cl H H H Cl 39,043 H Cl H H H F 39,044 H Cl H H H Me 39,045 H Cl H H F H 39,046 H Cl H H F Cl 39,047 H Cl H H F F 39,048 H Cl H H F Me 39,049 H Cl H H Cl H 39,050 H Cl H H Cl F 39,051 H Cl H H Cl Cl 39,052 H Cl H H Cl Me 39,053 H Cl H H Me H 39,054 H Cl H H Me Cl 39,055 H Cl H H Me F 39,056 H Cl H H Me Me 39,057 H Cl H H Ph H 39,058 H Cl H H Ph Cl 39,059 H Cl H H Ph F 39,060 H Cl H H Ph Me 39,061 Me H H H H H 39,062 Me H H H H Cl 39,063 Me H H H H F 39,064 Me H H H H Me 39,065 Me H H H F H 39,066 Me H H H F Cl 39,067 Me H H H F F
Petition 870180143799, of 10/23/2018, p. 112/411
98/134
Ex. No. R ¹ R ⁵ R1 ⁶ R2 ⁶ R1 ⁷ R2 ⁷ 39,068 Me H H H F Me 39,069 Me H H H Cl H 39,070 Me H H H Cl F 39,071 Me H H H Cl Cl 39,072 Me H H H Cl Me 39,073 Me H H H Me H 39,074 Me H H H Me Cl 39,075 Me H H H Me F 39,076 Me H H H Me Me 39,077 Me H H H Ph H 39,078 Me H H H Ph Cl 39,079 Me H H H Ph F 39,080 Me H H H Ph Me 39,081 Me F H H H H 39,082 Me F H H H Cl 39,083 Me F H H H F 39,084 Me F H H H Me 39,085 Me F H H F H 39,086 Me F H H F Cl 39,087 Me F H H F F 39,088 Me F H H F Me 39,089 Me F H H Cl H 39,090 Me F H H Cl F 39,091 Me F H H Cl Cl 39,092 Me F H H Cl Me 39,093 Me F H H Me H 39,094 Me F H H Me Cl 39,095 Me F H H Me F 39,096 Me F H H Me Me 39,097 Me F H H Ph H 39,098 Me F H H Ph Cl 39,099 Me F H H Ph F
Petition 870180143799, of 10/23/2018, p. 113/411
99/134
Ex. No. R ¹ R ⁵ R1 ⁶ R2 ⁶ R1 ⁷ R2 ⁷ 39,100 Me F H H Ph Me 39,101 Me Cl H H H H 39,102 Me Cl H H H Cl 39,103 Me Cl H H H F 39,104 Me Cl H H H Me 39,105 Me Cl H H F H 39,106 Me Cl H H F Cl 39,107 Me Cl H H F F 39,108 Me Cl H H F Me 39,109 Me Cl H H Cl H 39,110 Me Cl H H Cl F 39,111 Me Cl H H Cl Cl 39,112 Me Cl H H Cl Me 39,113 Me Cl H H Me H 39,114 Me Cl H H Me Cl 39,115 Me Cl H H Me F 39,116 Me Cl H H Me Me 39,117 Me Cl H H Ph H 39,118 Me Cl H H Ph Cl 39,119 Me Cl H H Ph F 39,120 Me Cl H H Ph Me 39,121 Et H H H H H 39,122 Et H H H H Cl 39,123 Et H H H H F 39,124 Et H H H H Me 39,125 Et H H H F H 39,126 Et H H H F Cl 39,127 Et H H H F F 39,128 Et H H H F Me 39,129 Et H H H Cl H 39,130 Et H H H Cl F 39,131 Et H H H Cl Cl
Petition 870180143799, of 10/23/2018, p. 114/411
100/134
Ex. No. R ¹ R ⁵ R1 ⁶ R2 ⁶ R1 ⁷ R2 ⁷ 39,132 Et H H H Cl Me 39,133 Et H H H Me H 39,134 Et H H H Me Cl 39,135 Et H H H Me F 39,136 Et H H H Me Me 39,137 Et H H H Ph H 39,138 Et H H H Ph Cl 39,139 Et H H H Ph F 39,140 Et H H H Ph Me 39,141 Et F H H H H 39,142 Et F H H H Cl 39,143 Et F H H H F 39,144 Et F H H H Me 39,145 Et F H H F H 39,146 Et F H H F Cl 39,147 Et F H H F F 39,148 Et F H H F Me 39,149 Et F H H Cl H 39,150 Et F H H Cl F 39,151 Et F H H Cl Cl 39,152 Et F H H Cl Me 39,153 Et F H H Me H 39,154 Et F H H Me Cl 39,155 Et F H H Me F 39,156 Et F H H Me Me 39,157 Et F H H Ph H 39,158 Et F H H Ph Cl 39,159 Et F H H Ph F 39,160 Et F H H Ph Me 39,161 Et Cl H H H H 39,162 Et Cl H H H Cl 39,163 Et Cl H H H F
Petition 870180143799, of 10/23/2018, p. 115/411
101/134
Ex. No. R ¹ R ⁵ R1 ⁶ R2 ⁶ R1 ⁷ R2 ⁷ 39,164 Et Cl H H H Me 39,165 Et Cl H H F H 39,166 Et Cl H H F Cl 39,167 Et Cl H H F F 39,168 Et Cl H H F Me 39,169 Et Cl H H Cl H 39,170 Et Cl H H Cl F 39,171 Et Cl H H Cl Cl 39,172 Et Cl H H Cl Me 39,173 Et Cl H H Me H 39,174 Et Cl H H Me Cl 39,175 Et Cl H H Me F 39,176 Et Cl H H Me Me 39,177 Et Cl H H Ph H 39,178 Et Cl H H Ph Cl 39,179 Et Cl H H Ph F 39,180 Et Cl H H Ph Me 39,181 H F F H H H 39,182 H F H F H H Table 40: Color npositions c ie acorc the with invention da Formi jla (I) in
that X represents N, A represents A16, R ³ and R ⁴ each represent hydrogen and R ² represents chlorine:
AT THE
Ex. No. R ¹ R ⁵ R1 ⁶ R2 ⁶ R ⁷ 40,001 H H H H H 40,002 H H H H Me 40,003 H H H H Ph 40,004 H H H H F
Petition 870180143799, of 10/23/2018, p. 116/411
102/134
Ex. No. R ¹ R ⁵ RT R2 ⁶ R ⁷ 40,005 H H H H Cl 40,006 H Cl H H H 40,007 H Cl H H Me 40,008 H Cl H H Ph 40,009 H Cl H H F 40,010 H Cl H H Cl 40,011 H F H H H 40,012 H F H H Me 40,013 H F H H Ph 40,014 H F H H F 40,015 H F H H Cl 40,016 Me H H H H 40,017 Me H H H Me 40,018 Me H H H Ph 40,019 Me H H H F 40,020 Me H H H Cl 40,021 Me Cl H H H 40,022 Me Cl H H Me 40,023 Me Cl H H Ph 40,024 Me Cl H H F 40,025 Me Cl H H Cl 40,026 Et H H H H 40,027 Et H H H Me 40,028 Et H H H Ph 40,029 Et H H H F 40,030 Et H H H Cl 40,031 Et F H H H 40,032 Et F H H Me 40,033 Et F H H Ph 40,034 Et F H H F 40,035 Et F H H Cl 40,036 Et Cl H H H
Petition 870180143799, of 10/23/2018, p. 117/411
103/134
Ex. No. R ¹ R ⁵ R1 ⁶ R2 ⁶ R ⁷ 40,037 Et Cl H H Me 40,038 Et Cl H H Ph 40,039 Et Cl H H F 40,040 Et Cl H H Cl 40,041 H F F H H 40,042 H F H F H
Table 41: Compounds according to the invention of Formula (I) where X represents N, A represents A17, R ³ and R ⁴ each represents hydrogen and R ² represents chlorine:
Ex. No. R ¹ R ⁵ R1 ⁶ R2 ⁶ R ⁷ 41,001 H H H H H 41,002 H H H H Me 41,003 H H H H Ph 41,004 H H H H F 41,005 H H H H Cl 41,006 H Cl H H H 41,007 H Cl H H Me 41,008 H Cl H H Ph 41,009 H Cl H H F 41,010 H Cl H H Cl 41,011 H F H H H 41,012 H F H H Me 41,013 H F H H Ph 41,014 H F H H F 41,015 H F H H Cl 41,016 Me H H H H 41,017 Me H H H Me
Petition 870180143799, of 10/23/2018, p. 118/411
104/134
Ex. No. R ¹ R ⁵ R1 ⁶ R2 ⁶ R ⁷ 41,018 Me H H H Ph 41,019 Me H H H F 41,020 Me H H H Cl 41,021 Me Cl H H H 41,022 Me Cl H H Me 41,023 Me Cl H H Ph 41,024 Me Cl H H F 41,025 Me Cl H H Cl 41,026 Et H H H H 41,027 Et H H H Me 41,028 Et H H H Ph 41,029 Et H H H F 41,030 Et H H H Cl 41,031 Et F H H H 41,032 Et F H H Me 41,033 Et F H H Ph 41,034 Et F H H F 41,035 Et F H H Cl 41,036 Et Cl H H H 41,037 Et Cl H H Me 41,038 Et Cl H H Ph 41,039 Et Cl H H F 41,040 Et Cl H H Cl 41,041 H F F H H 41,042 H F H F H
Table 42: Compounds according to the invention of Formula (I) in which X represents N, A represents A18, R ³ and R ⁴ each represents hydrogen and R ² represents chlorine:
Petition 870180143799, of 10/23/2018, p. 119/411
105/134
Ex. No. R ¹ R ⁵ R1 ⁶ R2 ⁶ R ⁷ R ⁸ 42,001 H H H H H H 42,002 H H H H Me H 42,003 H H H H Ph H 42,004 H H H H F Me 42,005 H H H H Cl H 42,006 H Cl H H H Me 42,007 H Cl H H Me Me 42,008 H Cl H H Ph Me 42,009 H Cl H H F H 42,010 H Cl H H Cl H 42,011 H F H H H Me 42,012 H F H H Me H 42,013 H F H H Ph H 42,014 H F H H F Me 42,015 H F H H Cl Me 42,016 Me H H H H Et 42,017 Me H H H Me Et 42,018 Me H H H Ph Et 42,019 Me H H H F Et 42,020 Me H H H Cl Et 42,021 Me Cl H H H Me 42,022 Me Cl H H Me H 42,023 Me Cl H H Ph H 42,024 Me Cl H H F H 42,025 Me Cl H H Cl Et 42,026 Et H H H H Me 42,027 Et H H H Me Me 42,028 Et H H H Ph Me 42,029 Et H H H F H 42,030 Et H H H Cl H 42,031 Et F H H H Me 42,032 Et F H H Me Me
Petition 870180143799, of 10/23/2018, p. 120/411
106/134
Ex. No. R ¹ R ⁵ R1 ⁶ R2 ⁶ R ⁷ R ⁸ 42,033 Et F H H Ph H 42,034 Et F H H F Et 42,035 Et F H H Cl Et 42,036 Et Cl H H H H 42,037 Et Cl H H Me H 42,038 Et Cl H H Ph H 42,039 Et Cl H H F Me 42,040 Et Cl H H Cl H 42,041 H F F H H H 42,042 H F H F H H Table 43: Con C items and wake up the with nvention da Formi ila (I) in
that X represents N, A represents A19, R ³ and R ⁴ each represent hydrogen and R ² represents chlorine:
Ex. No. R ¹ R ⁵ R1 ⁶ R2 ⁶ R ⁸ 43,001 H H H H H 43,002 H H H H Me 43,003 H H H H Et 43,004 H F H H H 43,005 H F H H Me 43,006 H F H H Et 43,007 H Cl H H H 43,008 H Cl H H Me 43,009 H Cl H H Et 43,010 Me H H H H 43,011 Me H H H Me 43,012 Me H H H Et 43,013 Me F H H H
Petition 870180143799, of 10/23/2018, p. 121/411
107/134
Ex. No. R ¹ R ⁵ R1 ⁶ R2 ⁶ R ⁸ 43,014 Me F H H Me 43,015 Me F H H Et 43,016 Me Cl H H H 43,017 Me Cl H H Me 43,018 Me Cl H H Et 43,019 Et H H H H 43,020 Et H H H Me 43,021 Et H H H Et 43,022 Et F H H H 43,023 Et F H H Me 43,024 Et F H H Et 43,025 Et Cl H H H 43,026 Et Cl H H Me 43,027 Et Cl H H Et 43,028 H F F H H 43,029 H F H F H
Table 44: Compounds according to the invention of Formula (I) in which X represents N, A represents A20, R ³ and R ⁴ each represents hydrogen and R ² represents chlorine:
Ex. No. R ¹ R ⁵ R1 ⁶ R2 ⁶ R ⁸ 44,001 H H H H Me 44,002 H H H H Et 44,003 H F H H Me 44,004 H F H H Et 44,005 H Cl H H Me 44,006 H Cl H H Et 44,007 Me H H H Me
Petition 870180143799, of 10/23/2018, p. 122/411
108/134
Ex. No. R ¹ R ⁵ R1 ⁶ R2 ⁶ R ⁸ 44,008 Me H H H Et 44,009 Me F H H Me 44,010 Me F H H Et 44,011 Me Cl H H Me 44,012 Me Cl H H Et 44,013 Et H H H Me 44,014 Et H H H Et 44,015 Et F H H Me 44,016 Et F H H Et 44,017 Et Cl H H Me 44,018 Et Cl H H Et 44,019 H F F H Me 44,020 H F H F Me
[0028] Collections of compounds of Formula (I) and / or salts thereof that can be synthesized by the reactions mentioned above, can also be prepared in a parallel manner, making it possible for this to occur in a manual, partially automated or completely automated manner . In this regard, it is, for example, possible to automate the reaction procedure, the preparation or the purification of the products and / or intermediates. In general, this is understood to mean a procedure as described, for example, by D. Tiebes in Combinatorial Chemistry Synthesis, Analysis, Screening (editor Günther Jung), Verlag Wiley 1999, on pages 1 to 34.
[0029] For the parallel reaction and preparation procedure, it is possible to use a number of commercially available instruments, for example, the Calpyso Barnstead International reaction blocks,
Dubuque, Iowa 52004-0797, USA or Radleys reaction stations,
Shirehill, Saffron Walden, Essex, CB 11 3AZ, England or MultiPROBE
Automated Workstations from Perkin Elmer, Waltham, Massachusetts
02451, USA. For the parallel purification of compounds of Formula (I)
Petition 870180143799, of 10/23/2018, p. 123/411
109/134 and salts thereof or intermediates produced during preparation, are available, among other things, chromatography apparatus, for example, from ISCO, Inc., 4700 Superior Street, Lincoln, NE 68504, USA.
[0030] The listed apparatus leads to a modular procedure in which the individual process steps are automated, but between the process steps manual operations must be performed. This can be avoided by using partially or completely integrated automation systems, in which the respective automation modules are operated, for example, by robots. Automation systems of this type can be purchased, for example, from Caliper, Hopkinton, MA 01748, USA.
[0031] The implementation of individual or diverse synthesis steps can be sustained through the use of polymer-supported resins / reagents. The specialist literature describes a series of experimental protocols, for example, in ChemFiles, Vol. 4, No. 1, Polimer-Supported Scavengers and Reagents for Solution-Phase Synthesis (Sigma-Aldrich).
[0032] In addition to the methods described here, the preparation of compounds of Formula (I) and salts thereof, can occur completely or partially by methods supported by solid phase. For this purpose, individual intermediates or all intermediates in the synthesis or a synthesis adapted for the corresponding procedure are bonded to a synthetic resin. Synthesis methods supported by solid phase are sufficiently described in the specialist literature, for example, Barry A. Bunin in The Combinatorial Index, Academic Press, 1998 and Combinatorial Chemistry - Synthesis, Analysis, Screening (editor Günther Jung), Wiley, 1999. O The use of solid-phase synthesis methods allows a series of protocols known in the literature, which
Petition 870180143799, of 10/23/2018, p. 124/411
110/134 performed manually or in an automated manner. Reactions can be carried out, for example, by IRORI technology methods on micro-reactors from Nexus Biosystems, 12140 Community Road, Poway, CA92064, USA.
[0033] Both in a solid phase and in a liquid phase, the procedure of individual or diverse synthesis steps can be sustained through the use of microwave technology. The specialist literature describes a series of experimental protocols, for example, in Microwaves in Organic and Medicinal Chemistry (editor C. O. Kappe and A. Stadler), Wiley, 2005.
[0034] The preparation, according to the processes described here, produces compounds of Formula (I) and their salts in the form of collections of substance which are called libraries. The present invention also provides libraries that comprise at least two compounds of Formula (I) and their salts.
[0035] The compounds of Formula (I) according to the invention (and / or their salts), hereinafter also referred to together as compounds according to the invention, have excellent herbicidal efficacy against a wide spectrum of monocotyledonous and dicotyledonous annual nocturnal plants economically important. The active compounds act efficiently even on perennial harmful plants that produce rhizome shoots, root stumps and other perennial organs that are difficult to control.
The present invention, therefore, also relates to a method for controlling unwanted plants or for regulating plant growth, preferably in plant harvests, where one or more compound (s) according to the invention is / are applied to plants (for example, harmful plants, such as monocots or dicots or unwanted crop plants), to seed (for example, grains, seeds or propagules
Petition 870180143799, of 10/23/2018, p. 125/411
111/134 vegetative areas such as tubers or bud parts with buds) or the area in which the plants grow (for example, the area under cultivation). In this context, the compounds according to the invention can be applied, for example, pre-sowing (if appropriate, also by incorporation into the soil), pre-emergence or post-emergence. Specific examples can be mentioned of some representative of the monocotyledonous and dicotyledonous weed flora that can be controlled by the compounds according to the invention, without the enumeration being restricted to certain species.
[0037] Harmful monocotyledonous plants of the genera: Aegilops, Agropyron, Agrostis, Alopecurus, Apera, Avena, Brachiaria, Bromus, Cenchrus, Commelina, Cynodon, Cyperus, Dactyloctenium, Digitaria, Echinochloa, Eleocharisis, Eleusine, Erusine, Erusine, Erusine, , Heteranthera, Imperata, Ischaemum, Leptochloa, Lolium, Monochoria, Panicum, Paspalum, Phalaris, Phleum, Poa, Rottboellia, Sagittaria, Scirpus, Setaria, Sorghum.
[0038] Dicotyledonous weeds of the genera: Abutilon, Amarandesse mode, Ambrosia, Anoda, Anthemis, Aphanes, Artemisia, Atriplex, Bellis, Bidens, Capsella, Carduus, Cassia, Centaurea, Chenopodium, Cirsium, Convolvulus, Datura, Desmodium, Emex, Erysimum, Euphorbia, Galeopsis, Galinsoga, Galium, Hibiscus, Ipomoea, Kochia, Lamium, Lepidium, Lindernia, Matricaria, Mentha, Mercurialis, Mullugo, Myosotis, Papaver, Pharbitis, Plantago, Poligonum, Portulaca, Ranunculus, Raphanus, Rhan Rumex, Salsola, Senecio, Sesbania, Sida, Sinapis, Solanum, Sonchus, Sphenoclea, Stellaria, Taraxacum, Thlaspi, Trifolium, Urtica, Veronica, Viola, Xanthium.
[0039] If the compounds according to the invention are applied to the earth's surface before germination, the weed seedlings are either completely prevented from emerging or the weeds
Petition 870180143799, of 10/23/2018, p. 126/411
They grow until they reach the cotyledon stage, but then their growth stops, and eventually, after three to four weeks have elapsed, they die completely.
[0040] If the active compounds are applied after emergence to the green parts of the plants, the growth stops after treatment, and the harmful plants remain in the growth stage of the application time point, or they die completely after a certain time, so that in this way the competition for weeds, which is harmful to harvest plants, is eliminated very early and in a prolonged way.
[0041] Although the compounds according to the invention have an important herbicidal activity against monocotyledonous and dicotyledonous weeds, economically important crop harvesting plants, for example, dicotyledonous crops of the genera Arachis, Beta, Brassica, Cucumis, Cucurbita, Heliandesse mode , Daucus, Glycine, Gossypium, Ipomoea, Lactuca, Linum, Lycopersicon, Nicotiana, Phaseolus, Pisum, Solanum, Vicia, or monocot crops of the genera Allium, Arianas, Asparagus, Avena, Hordeum, Oryza, Panicum, Saccharum, Secale, Sorale, Sorale Triticale, Triticum, Zea, in particular Zea and Triticus, are damaged only to an insignificant extent, or in any way, depending on the structure of the respective compound, according to the invention and its rate of application. That is, since the present compounds are highly suitable for the selective control of unwanted plant growth in plant crops, such as agriculturally useful or ornamental plants.
[0042] In addition, the compounds according to the invention (depending on their respective structure and the rate of application applied) have regulatory properties of outstanding growth in crop plants. They get involved in the metabolism of a plant's
Petition 870180143799, of 10/23/2018, p. 127/411
113/134 in a regulatory manner and can therefore be used to influence, in a targeted manner, plant constituents and to facilitate harvesting, such as, for example, initiating desiccation and stunted growth. In addition, they are also suitable to generally control and inhibit unwanted vegetative growth, without destroying plants in the process. The inhibition of vegetative growth plays an important role in many monocotyledon and dicotyledon crops since, for example, housing can be reduced, or completely prevented, through it.
[0043] Due to their herbicidal and plant growth regulatory properties, active compounds can also be used to control nocturnal plants in crops of known genetically modified plants or genetically modified plants yet to be developed. In general, transgenic plants are distinguished by particularly advantageous properties, for example, by resistance to certain pesticides, especially certain herbicides, resistance to plant diseases or organisms that cause plant diseases, such as certain insects or microorganisms, such as fungi, bacteria or viruses. Other particular properties refer, for example, to the material harvested with respect to quantity, quality, storage capacity, composition and specific constituents. In this way, transgenic plants are known, whose starch content is increased, or whose starch quality is altered, or those where the harvested material has a different fatty acid composition. Other particular properties may be tolerant or resistant to abiotic stressors, for example, heat, low temperatures, drought, salinity and ultraviolet radiation.
[0044] It is preferred to use the compounds of Formula (I) according to
Petition 870180143799, of 10/23/2018, p. 128/411
114/134 the invention or the salts thereof, in economically important transgenic crops of useful plants and ornamental plants, for example, cereals such as wheat, barley, rye, oats, sorghum and millet, rice, cassava and maize or else harvests of sugar beet, cotton, soy, rapeseed, potatoes, tomatoes, peas and other vegetables.
[0045] It is preferred to employ the compounds of Formula (I) as herbicides in crops of useful plants that are resistant, or have been made resistant by recombinant methods, to the phytotoxic effects of the herbicides.
[0046] Conventional methods of generating new plants that have modified properties compared to plants that occur until this date consist, for example, of traditional reproduction methods and the generation of mutants. Alternatively, new plants with altered properties can be generated with the aid of recombinant methods (see, for example, EP 0221044, EP 0131624). For example, the following have been described in several cases:
- genetic modifications of crop plants for the purposes of modifying the starch synthesized in plants (for example, WO 92/011376 A, WO 92/014827 A, WO 91/019806 A),
- transgenic crop plants that are resistant to certain glufosinate type herbicides (as per, for example, EP 0242236 A, EP 0242246 A) or glyphosate type (WO 92/000377 A) or sulfonylurea type (EP 0257993 A, US 5,013,659 ) or combinations or mixtures of these herbicides by means of gene stacking, such as transgenic crop plants, for example, maize or soybeans with the trade name or brand Optimum ™ GAT ™ (tolerant to glyphosate ALS),
- transgenic crop plants, for example, cotton,
Petition 870180143799, of 10/23/2018, p. 129/411
115/134 which is capable of producing Bacillus thuringiensis toxins (Bt toxins), which make plants resistant to certain pests (EP 0142924 A, EP 0193259 A),
- transgenic crop plants with a modified fatty acid composition (WO 91/013972 A),
- crop plants genetically modified with new constituents or secondary metabolites, for example, new phytoalexins, which provide increased resistance to disease (EP 0309862 A, EP 0464461 A),
- genetically modified plants with reduced photorespiration that characterize higher yields and greater tolerance to stress (EP 0305398 A),
- transgenic crop plants that produce pharmaceutically or diagnostically important proteins (molecular pharming),
- transgenic crop plants that are distinguished by higher yields or better quality,
- transgenic crop plants that are distinguished by a combination, for example, of the new properties mentioned above (gene stacking).
[0047] A large number of molecular biological techniques by methods by which new transgenic plants with modified properties can be generated are known in principle; see, for example, I. Potrykus and G. Spangenberg (eds.) Gene Transferto Plants, Springer Lab Manual (1995), Springer Verlag Berlin, Heidelberg. or Christou, Trends in Plant Science 1 (1996) 423-431.
[0048] To perform such recombinant manipulations, nucleic acid molecules that allow mutagenesis or a sequence change by recombination of DNA sequences can be introduced into plasmids. For example, standard methods allow
Petition 870180143799, of 10/23/2018, p. 130/411
116/134 base changes are made, substrings are removed, or natural or synthetic sequences to be added. For joining the DNA fragments to one another, adapters or linkers can be attached to the fragments; see, for example, Sambrook et al., 1989, Molecular Cloning, A Laboratory Manual, 2a. edition, Cold Spring Harbor Laboratory Press, Cold Spring Harbor, NY; or Winnacker Gene und Klone, VCH Weinheim 2a. 1996 edition.
[0049] For example, the generation of plant cells with reduced activity of a gene product can be obtained by expressing at least one corresponding antisense RNA, a sense RNA to obtain a co-suppression effect or by expressing at least one ribozyme appropriately that specifically cleaves transcripts of the aforementioned gene product.
[0050] For this purpose, it is possible to use DNA molecules that span the entire coding sequence of a gene product including any flanking sequences that may be present, and also DNA molecules that only span portions of the coding sequence, being necessary for these portions to be long enough to have an antisense effect on the cells. The use of DNA sequences that have a high degree of homology for the coding sequences of a gene product, but are not completely identical to them, is also possible.
[0051] When expressing nucleic acid molecules in plants, the synthesized protein can be located in any desired compartment of the plant cell. However, to obtain location in a particular compartment, it is possible, for example, to link the coding region with DNA sequences that guarantee the location in a particular compartment. Such sequences are known to the person skilled in the art (see, for example, Braun et al., EMBO J. 11 (1992), 3219-3227; Wolter et al., Proc. Natl. Acad.
Petition 870180143799, of 10/23/2018, p. 131/411
117/134
Know. USA 85 (1988), 846-850; Sonnewald et al., Plant J. 1 (1991), 95106). Nucleic acid molecules can also be expressed in the organelles of plant cells.
[0052] Transgenic plant cells can be regenerated by known techniques to produce whole plants. In principle, transgenic plants can be plants of any desired plant species, that is, not only monocotyledonous plants, but also dicotyledonous plants.
[0053] In this way, transgenic plants can be obtained, whose properties are altered by overexpression, suppression or inhibition of homologous (= natural) genes or gene sequences or the expression of heterologous (= foreign) genes or gene sequences.
[0054] It is preferred to use the compounds (I) according to the invention in transgenic crops that are resistant to growth regulators, such as, for example, 2.4 D, dicamba, or to herbicides that inhibit essential plant enzymes, for example, acetolactate synthases (ALS), EPSP synthases, glutamine synthases (GS) or hydroxyphenylpyruvate dioxigenases (HPPD), or to the herbicides of the sulfonylurea group, glyphosate, glufosinate or benzoylisoxazoles and analogous active compounds, or any combinations of these active compounds. [0055] Particularly preferably, the compounds according to the invention can be used in transgenic crop plants that are resistant to a combination of glyphosates and glufosinates, glyphosates and sulfonylureas or imidazolinones. Most particularly preferably, the compounds according to the invention can be used in transgenic crop plants such as, for example, corn or soybeans with the trade name or brand Optimum ™ GAT ™ (tolerant to glyphosate ALS).
[0056] When the active compounds according to the invention are used in transgenic crops, the effects are often
Petition 870180143799, of 10/23/2018, p. 132/411
118/134 observed - in addition to the effects on harmful plants that can be observed in other crops - which are specific to the application in the GM crop in question, for example, a modified or specifically broadened spectrum of weeds that can be application rates modified, controlled that can be used for application, preferably good combinability with the herbicides to which the GM crop is resistant, and an effect on the growth and production of the GM crop plants. [0057] The invention, therefore, also relates to the use of the compounds of Formula (I) according to the invention as herbicides for the control of harmful plants in transgenic crop plants. [0058] The compounds according to the invention can be used in the form of wetting powders, emulsifiable concentrates, sprayable solutions, dusting products or granules in the usual formulations. The invention, therefore, also provides herbicidal and plant growth regulating compositions comprising the compounds according to the invention.
[0059] The compounds according to the invention can be formulated in several ways, according to which biological and / or physicochemical parameters are required. Possible formulations include, for example: wetting powders (WP), water-soluble powders (SP), water-soluble concentrates, emulsifiable concentrates (EC), emulsions (EW) such as oil-in-water and water-in-oil emulsions, sprayable solutions, suspension concentrates (SC), oil or water based dispersions, oil miscible solutions, capsule suspensions (CS), dusting products (DP), seed fertilizer products, granules for dispersion and application to soil, granules ( GR) in the form of microgranules, spray granules, coated granules and adsorption granules, water dispersible granules (WG), water soluble granules (SG), ULV formulations,
Petition 870180143799, of 10/23/2018, p. 133/411
119/134 microcapsules and waxes.
[0060] These individual types of formulation are known in principle and are described, for example, in: Winnacker-Küchler, Chemische Technologie [Chemical technology], volume 7, C. Hanser Verlag Munich, 4th ed. 1986; Wade van Valquenburg, Pesticide Formulations, Marcei Dekker, N.Y., 1973; K. Martens, Spray Drying Handbook, 3a. edition, 1979, G. Goodwin Ltd. London.
[0061] The necessary formulation aids, such as inert materials, surfactants, solvents and other additives, are also known and are described, for example, in: Watkins, Handbook of Insecticide Dust Diluents and Carriers, 2nd Ed., Darland Books, Caldwell NJ, Hv Olphen, Introduction to Clay Colloid Chemistry; 2a. edition, J. Wiley & Sons, N.Y .; C. Marsden, Solvents Guide; 2a. edition, Interscience, N.Y. 1963, McCutcheon's Detergents and Emulsifiers Annual, MC Publ. Corp., Ridgewood N.J .; Sisley eWood, Encyclopedia of Surface Active Agents, Chem. Publ. Co. Inc., N.Y. 1964; Schõnfeldt, Grenzflãchenaktive Ãthylenoxidaddukte [Interface-active Etilene Oxide Adducts], Wiss. Verlagsgesell., Stuttgart 1976; WinnackerKüchler, Chemische Technologie, volume 7, C. Hanser Verlag Munich, 4th. edition, 1986.
[0062] Based on these formulations, it is also possible to produce combinations with other pesticide-active compounds, such as, for example, insecticides, acaricides, herbicides, fungicides, and also with protectors, fertilizers and / or growth regulators, for example, in form of a finished formulation or as a tank mix. Suitable protectors are, for example, mefenpir-diethyl, cyprosulfamide, isoxadifen-ethyl, cloquintocet-mexila and diclormide. [0063] Wetting powders are preparations that can be dispersed evenly in water and, like the active compound, the part of a diluent or inert substance, also comprise surfactants of the
Petition 870180143799, of 10/23/2018, p. 134/411
120/134 ionic and / or non-ionic type (wetting agents, dispersants), for example, polyoxyethylated alkylphenols, polyoxyethylated fatty alcohols, polyoxyethylated fatty amines, polyglycol sulfates fatty alcohol ether, alkanesulphonates, alkylbenzenesulphonates, sodium lignosulphonates 'dinaftimethane-6,6'-disulfonate, sodium dibutylnaphthalenessulfonate or sodium oleoylmethyltaurinate. To prepare the wetting powders, the herbicidally active compounds are finely ground, for example, in usual apparatuses, such as hammer mills, blow mills and air jet mills, and simultaneously or subsequently mixed with the formulation aids.
[0064] Emulsifiable concentrates are prepared by dissolving the active compound in an organic solvent, for example, butanol, cyclohexanone, dimethylformamide, xylene or relatively high boiling hydrocarbons or aromatics or mixtures of organic solvents, with the addition of one or more ionic and / or non-ionic surfactants (emulsifiers). The emulsifiers used may, for example, be: calcium alkylarylsulfonate salts, such as calcium dodecylbenzenesulfonate, or non-ionic emulsifiers, such as fatty acid polyglycol esters, alkylaryl polyglycol ethers, fatty alcohol polyglyol ethers, condensation of propylene oxide-ethylene oxide, alkyl polyethers, sorbitan esters, for example, sorbitan fatty acid esters, or polyoxyethylene sorbitan esters, for example, polyoxyethylene sorbitan fatty acid esters.
[0065] Powders are obtained by grinding the active compound with finely distributed solid substances, for example talc, natural clays, such as kaolin, bentonite and pyrophyllite, or diatomaceous earth.
[0066] Suspension concentrates can be based on water or oil. They can be prepared, for example, by wet grinding
Petition 870180143799, of 10/23/2018, p. 135/411
121/134 by commercial bed mill methods and optional addition of surfactants as already, for example, listed above for the other types of formulation.
[0067] Emulsions, for example, oil in water (EW) emulsions, can be prepared, for example, by agitator methods, colloid mills and / or static mixers using aqueous organic solvents and optionally surfactants, as they have been, for example , listed above for other types of formulation.
[0068] The granules can be prepared by spraying the active compound on granular inert material capable of adsorption or by applying active compound concentrates to the surface of carrier substances, such as sand, kaolinite or granulated inert material, by adhesive methods, for example, polyvinyl alcohol, sodium polyacrylate or mineral oils. Suitable active compounds can also be granulated in the usual way for the production of fertilizer granules - if desired as a mixture with fertilizers.
[0069] Water-dispersible granules are usually prepared by the usual processes, such as spray drying, fluidized bed granulation, pan granulation, mixing with high-speed mixers and extrusion without solid inert material. [0070] For the production of pot granules, fluidized bed granules, extruder granules and spray granules, see, for example, processes in Spray-Drying Handbook 3a. edition, 1979, G. Goodwin Ltd., London; J.E. Browning, Agglomeration, Chemical and Engineering 1967, pages 147 ff .; Perry's Chemical Engineer's Handbook, 5th. edition, McGraw-HilI, New York 1973, pp. 8-57.
[0071] For further details regarding the formulation of crop protection compositions, see, for example, GC Klingman, Weed Control as a Science, John Wiley and Sons, Inc., New York, 1961, pages 81-96 and JD Freyer, SA Evans, Weed Control
Petition 870180143799, of 10/23/2018, p. 136/411
122/134
Handbook, 5th. edition, Blackwell Scientific Publications, Oxford, 1968, pages 101-103.
[0072] Agrochemical formulations generally contain from 0.1 to 99% by weight, in particular from 0.1 to 95% by weight, of compounds according to the invention.
[0073] In wetting powders, the concentration of active compound is, for example, from about 10 to 90% by weight, the rest up to 100% by weight consisting of usual formulation components. In the case of emulsifiable concentrates, the concentration of active compound can be from about 1 to 90, preferably from 5 to 80,% by weight. Formulations in powder form comprise from 1 to 30% by weight of active compound, preferably usually from 5 to 20% by weight of active compound; sprayable solutions contain from about 0.05 to 80% by weight, preferably from 2 to 50% by weight of active compound. In the case of water-dispersible granules, the active compound content depends partly on whether the active compound is present in liquid or solid form, and which granulation aids, fillers, etc., are used. In water-dispersible granules, the content of active compound is, for example, between 1 and 95% by weight, preferably between 10 and 80% by weight.
[0074] In addition, the active compound formulations mentioned optionally comprise respectively the usual adhesives, wetting agents, dispersants, emulsifiers, penetrants, preservatives, antifreeze agents and solvents, fillers, vehicles and pigments, defoamers, evaporation inhibitors and agents that influence pH and viscosity.
[0075] Based on these formulations, it is also possible to produce combinations with other pesticide-active compounds, such as, for example, insecticides, acaricides, herbicides, fungicides, and also with protectors, fertilizers and / or growth regulators, for
Petition 870180143799, of 10/23/2018, p. 137/411
123/134 example, in the form of a finished formulation or as a tank mixture.
[0076] Active compounds that can be used in combination with the compounds according to the invention in mixed formulations or in the tank mixture are, for example, known active compounds that are based on the inhibition of, for example, acetolactate synthase, acetyl- CoA carboxylase, cellulose synthase, enolpyruvylchiquimate-3-phosphate synthase, glutamine synthetase, phydroxyphenylpyruvate dioxigenase, phyteno desaturase, photosystem I, photosystem II, protoporphyrinogen oxidase, as described, for example, in Weed Research 26 (1986) 441-445 Manual Pesticide, 15a. edition, The British Crop Protection Council and the Royal Soc. of Chemistry, 2009 and the literature cited here. Known herbicides or plant growth regulators that can be combined with the compounds according to the invention are, for example, the following active compounds (the compounds are or are designated by the common name, according to the International Organization for Standardization (ISO) or by chemical name, or by code number) and always comprise all forms of use, such as acids, salts, esters and isomers, such as stereoisomers and optical isomers. Here, by way of example, one and in some cases, a plurality of forms of use are mentioned:
[0077] acetochlor, acibenzolar, acibenzolar-S-methyl, acifluorfen, acifluorfen sodium, aclonifene, alachlor, alidochlor, aloxidim, aloxidim sodium, ametrine, amicarbazone, amidochlor, amidosulfurone, aminocyclidyridine, aminopyridine, aminolyridine , anilofos, asulam, atrazine, azafenidin, azimsulfurone, aziprotrin, beflubutamid, benazolin, benazolin-ethyl, bencarbazone, benfluralin, benfuresate, bensulide, bensulfurone, bensulfuron-methyl, bentazone, benzofen, benzofendone, benzofen
Petition 870180143799, of 10/23/2018, p. 138/411
124/134 benzoilprope, bicyclopyrone, bifenox, bilanafos, bilanafos sodium, bispiribac, bispiribac sodium, bromacila, bromobutide, bromophenoxim, bromoxynil, bromuron, bumina, busoxynone, butachlor, butafenacil, butafenacil, butafenacil, butafenacil, butafenacil, butafenacil, butafenacil, butafenacil, butafenacil , carbetamide, carfentrazone, carfentrazone-ethyl, clomethoxyfen, chlorambene, chlorazifop, chlorazifop-butyl, chlorobromuron, chlororbam, chlorfenac, sodium chlorfenac, chlorfenprope, chlorflurenol, chlorflurenolmethyl, chloridon, chloridon, chlorimuron, chlorimuron, chlorimuron chlortal-dimethyl, chlortoluron, chlorsulfurone, cinidon, cinidon-ethyl, cinmetilina, cinosulfurone, cletodim, clodinafope, clodinafop-propargila, clofencete, clomazone, clomeprope, cloprope, clopyralide, chloransulam, chloramide, chloramide, chloramide cycloate, cyclosulfamuron, cycloxidim, cycluron, cihalofope, cihalofope-butyl, cyperquat, ciprazine, ciprazole, 2,4-D, 2 , 4DB, daimuron / dimron, dalapon, daminozide, dazomet, n-decanol, demedifam, desmetrina, detosil-pyrazolate (DTP), dialate, dicamba, diclobenyl, dichlorprope, dichlorprope-P, diclofope, diclofope-metil, diclofope-metil, diclofope-metil, diclofope-metil, diclofope-metil, diclofope-dila methyl, diclosulam, diethyl, diethyl-ethyl, diphenoxurone, difenzoquat, diflufenican, diflufenzopyr, diflufenzopyr sodium, dimefuron, dicegulac sodium, dimefuron, dimepiperate, dimetachlor, dimetamethrine, dimethamine, dinetamine, dimethamine, dimethamine, dimethamine, dinoterb, diphenamid, dipropetrin, diquat, diquat dibromide, dithiopir, diuron, DNOC, eglinazine-ethyl, endothal, EPTC, esprocarb, etalfluralin, etametsulfuron, etametsulfuron-methyl, etefon, etidimurene, ethoxy, ethoxy, ethoxy, ethoxy ethoxysulfurone, etobenzanide, F-5331, i.e., N- [2-chloro-4-fluoro-5- [4- (3-fluoropropyl) -4,5-dihydro-5-oxo1H-tetrazol-1-yl] phenyl ] ethanesulfonamide, F-7967, that is, 3- [7-chloro-5fluoro-2- (trifluoromethyl) -1 H-benzimidazol-4-yl] -1 -m ethyl-6 (trifluoromethyl) pyrimidine-2,4 (1 H, 3H) -dione, fenoprope, phenoxaprope,
Petition 870180143799, of 10/23/2018, p. 139/411
125/134 fenoxaprope-P, fenoxaprope-ethyl, fenoxaprope-P-ethyl, fenoxasulfone, fentrazamide, fenuron, flamprope, flamprope-M-isopropyl, flampropeM-methyl, flazasulfurone, florasulam, fluazifope, fluazifope-P, fluazifeb -butyl, fluazolate, flucarbazone, flucarbazone sodium, flucosulfurone, flucloraline, flufenacet (thiafluamide), flufenpir, flufenpirethyl, flumetraline, flumetsulam, flumichloracet, flumicloracentil, flumichlorofluorine, fluofluorin, fluofluorin flupoxam, flupropacil, flupropanate, flupirsulfurone, flupirsulfuron-methyl-sodium, flurenol, flurenolbutyl, fluridone, flurochloridone, fluroxypyr, fluroxypyron, flurprimidine, flutiacetam, flutiacetam, flutiacetam, flutiacetam, flutiacetam, flutiacetone gibberellic acid, glufosinate, glufosinate ammonium, glufosinate-P, glufosinate-P-ammonium, glufosinate-P-sodium, glyphosate, glyphosate-isopropylammon io, H-9201, that is, O- (2,4-dimethyl-6-nitrophenyl) isopropylphosphoramidothioate O-ethyl, halosafen, halosulfurone, halosulfuron-methyl, haloxifop, haloxypop-P, haloxypop-ethoxy, haloxifop-P-ethoxy ethoxyethyl, haloxifopemethyl, haloxifop-P-methyl, hexazinone, HW-02, i.e., 1 (dimethoxyphosphoryl) ethyl (2,4-dichlorophenoxy) acetate, imazametabenz, imazametabenz-methyl, imazamox, imazamox, imazapamine, imazapap, imazapap, -isopropylammonium, imazaquine, imazaquine-ammonium, imazetapyr, imazetapyr-ammonium, imazosulfurone, inabenfide, indanophane, indaziflam, indoleacetic acid (IAA), 4-indol-3-ylbutyric acid (IBA), iodosulfurone, iodosulfurone, iodosulfurone, , ipfencarbazone, isocarbamide, isopropalin, isoproturon, isouron, isoxaben, isoxaclortol, isoxaflutol, isoxapyrifope, KUH-043, that is, 3 - ({[5 (difluoromethyl) -l-methyl-3- (trifluoromethyl) -1 -4-yl] methyl} sulfonyl) -5,5dimethyl-4,5-dihydro-1,2-oxazole, carbutylate, ketoespiradox, lactophen, lenacil, linuron, hi maleic drazide, MCPA, MCPB, MCPB-methyl, -ethyl and -sodium, mecoprope, mecoprope-sodium, mecoprope-butotyl,
Petition 870180143799, of 10/23/2018, p. 140/411
126/134 mecoprope-P-butotyl, mecoprope-P-dimethylammonium, mecoprope-P-2ethylhexyl, mecoprope-P-potassium, mefenacet, mefluidide, mepiquat chloride, mesosulfurone, mesosulfuron-methyl, mesotrione, metenztiazuron, metenztiazuron, , metazachlor, metazasulfurone, metazol, methypyrosulfurone, methozoline, methoxyfenone, methyldinrone, 1-methylcyclopropene, methyl isothiocyanate, metobenzurone, metobromuron, metolachlor, S-metolachlor, metosulam, methoxyuron, mometuron, methoxyuron, methoxuron, methoxuron, , monocarbamide dihydrogen sulfate, monolinuron, monosulfurone, monosulfurone ester, monuron, MT128, that is, 6-chloro-N - [(2E) -3-chloroprope-2-en-1-yl] -5-methyl-N-phenylpyridazine-3 -amine, MT-5950, that is, N- [3-chloro-4- (1-methylethyl) phenyl] -
2-methylpentanamide, NGGC-011, naproanilide, napropamide, naptalam, NC-310, i.e. 4- (2,4-dichlorobenzoyl) -1-methyl-5-benzyloxypyrazole, neburon, nicosulfurone, nipyraclofen, nitralin, nitrofen, sodode nitrophenolate (isomer mixture), nitrofluorphene, non-anionic acid, norflurazon, orbencarb, ortosulfamuron, oryzine, oxadiargyl, oxadiazone, oxasulfurone, oxazyclomephone, oxyfluorphene, paclobutrazol, paraquat, pendant, paraquatalin, dichloride, paraquat penoxsulam, pentanochlor, pentoxazone, perfluidone, petoxamide, fenisofam, fenmedifam, fenmedifam-ethyl, picloram, picolinafen, pinoxadene, piperophos, pyriphenope, pyriphenope-butyl, pretilachlor, primisulfurine, prisulfenine, prysulfurone, proline profoxidim, proexadione, proexadion calcium, proidrojasmona, prometeona, prometrina, propachlor, propanila, propaquizafope, propazine, profam, propisochlor, propoxycarbazone, propoxicarb sodium azone, propyrisulfurone, propizamide, prosulfaline, prosulfocarb, prosulfurone, prinachlor, pyraclonyl, piraflufene, piraflufene-ethyl, pyrasulfotol, pyrazolinate (pyrazolate), pyrazosulfurone,
Petition 870180143799, of 10/23/2018, p. 141/411
127/134 pyrazosulfuron-ethyl, pyrazoxifene, piribambenzo, pyribambenzoisopropyl, pyribambenzo-propyl, piribenzoxim, pyributicarb, pyridafol, pyridate, pyriftalide, pyriminobac, pyriminobaco-methyl, pyrimisulfan, pyrioloxin, pyroxoxaminoxin, pyroxoxaminoxin , quizalofope, quizalofope-ethyl, quizalofopeP, quizalofope-P-ethyl, quizalofope-P-tefuril, rinsulfurone, saflufenacil, secbumeton, setoxidim, siduron, simazine, symmetry, SN-106279, that is, ((2R) -2 - ((2R) -2 - 7- [2-chloro-4- (trifluoromethyl) phenoxy] -2-naphthyl} oxy) methyl propanoate, sulcotrione, sulfalate (CDEC), sulfentrazone, sulfometuron, sulfometuron-methyl, sulfosate (glyphosate-trimesium), sulfosulfurone, SYN -523, SYP-249, i.e., 1-ethoxy-3-methyl-1-oxobut-3-en-2-yl 5- [2-chloro-4- (trifluoromethyl) phenoxy] -2-nitrobenzoate, SYP-300, that is, 1- [7fluoro-3-oxo-4- (prope-2-in-1-yl) -3,4-dihydro-2H-1,4-benzoxazin-6-yl] -3propyl-2-thioxoimidazolidine -4,5-diona, tebutam, tebutiuron, tecnaze no, tefuriltrione, tembotrione, tepraloxidim, terbacil, terbucarb, terbuclor, terbumeton, terbutilazine, terbutrin, tenilchlor, thiafluamide, thiazafluron, thiazopyr, tidiazimin, tidiazuron, tiencarbone, tencarbazone, tencarbazone, tencarbazone, tencarbazone tralcoxidim, trialate, triasulfurone, triaziflam, triazophenamide, tribenuron, tribenuron-methyl, trichloroacetic acid (TCA), triclopyr, tridiphane, trietazine, trifloxysulfurone, trifloxysulfurine, triflurine, triflurine, triflurine, triflurine, triflurine tritosulfurone, tsitodef, uniconazole, uniconazole-P, vernolate, ZJ-0862, i.e., 3,4-dichloro-N- {2 [(4,6-dimethoxypyrimidin-2-yl) oxy] benzyl} aniline, and the following compounds:
Petition 870180143799, of 10/23/2018, p. 142/411
128/134

[0078] For application, formulations present in commercial form are, if appropriate, diluted in a usual manner, for example, in the case of wetting powders, emulsifiable concentrates, dispersions and granules dispersible in water with water. Preparations in the form of powders, granules for application to the earth or granules for spreading and vaporisable solutions are usually undiluted or with other inert substances before application.
[0079] The required application rate of the compounds of Formula (I) varies according to external conditions, such as, among other things, temperature, humidity and the type of herbicide used. It can vary within wide limits, for example, between 0.001 and 1.0 kg / ha or more of active substance; however, it is preferably between 0.005 and 750 g / ha.
[0080] The examples below illustrate the invention:
A. Chemical examples
1. Preparation of methyl 4-amino-3-chloro-6- (7-fluoro-2-phenyl-1,3benzoxazol-6-yl) pyridine-2-carboxylate (Example No. 8.019) [0081] 0.024 g ( 0.03 mmol) of (PPh3) 2PdCb is added to a solution of 0.3 g (1.13 mmol) of methyl 4-amino-6-bromo-3-chloropyridine-2-carboxylate in 20 mL of dioxane, and this The mixture is stirred at room temperature (RT) for 30 minutes. In succession, 0.35 g (1.35 mmol) of boronic acid (7-fluoro-2-phenyl-1,3-benzoxazol-6-yl), 0.47 g (3.4 mmol) of K2CO3 and 2 g ( 111 mmol) of H2O are then added
Petition 870180143799, of 10/23/2018, p. 143/411
129/134 to this mixture, which is then stirred under reflux for 6 hours. The mixture is allowed to remain at room temperature for another 12 hours and then added to 40 ml of H2O. This mixture is extracted repeatedly with CH2 Cl2, and the combined organic phase is dried over Na2 SO4 and then concentrated. Purification by chromatography on silica gel using the heptane / ethyl acetate (3/7) mobile phase provides 0.16 g (36%) of product. ¹ H-NMR (CDCh): δ 8.30, 8.00, 7.55 (3m, 5H, C ₆ H ₅ ), 7.60, 7.55 (2d, 2H, benzoxazole ring), 7.30 (s, 1H, pyridine) 4.85 (bs, 2H, NH ₂ ), 4.00 (S, 3H, COOCH3).
2. Preparation of methyl 4-amino-3-chloro-6- (1,3-benzoxazol-6-yl) pyridine2-carboxylate (Example No. 8,013) [0082] 0.024 g (0.03 mmol) of (PPh3 ) 2PdCh is added to a solution of 0.3 g (1.13 mmol) of methyl 4-amino-6-bromo-3-chloropyridine2-carboxylate in 20 ml of dioxane, and this mixture is stirred at room temperature for 30 minutes . In succession, 0.28 g (1.13 mmol) of 6- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -1,3-benzoxazole, 0.47 g (3.4 mmol) K2CO3 and 2 g (111 mmol) H2O are then added to this mixture, which is then stirred under reflux for 6 hours. The mixture is allowed to remain at room temperature for another 12 hours and then added to 40 ml of H2O. This mixture is extracted repeatedly with CH2 Cl2, and the combined organic phase is dried over Na2 SO4 and then concentrated. Purification by silica gel chromatography using the heptane / ethyl acetate (3/7) mobile phase provides 0.1 g (29%) of product. ¹ H-NMR (CDCh): δ 8.25 (s, 1H, benzoxazole), 8.15 (s, 1H, benzoxazole), 7.90, 7.80 (2d, 2H, benzoxazole), 7.20 ( s, 1H, pyridine), 4.80 (bs, 2H, NH ₂ ), 4.00 (s, 3H, COOCH3).
3. Preparation of methyl 6-amino-5-chloro-2- (2-methyl-1,3-benzoxazol-5yl) pyrimidine-4-carboxylate (Example No. 30.014) [0083] 0.024 g (0.03 mmol ) of (PPh3) 2PdCl2 is added to a solution of 0.3 g (1.13 mmol) of 6-amino-2-bromo-5-chloropyridine-4
Petition 870180143799, of 10/23/2018, p. 144/411
130/134 methyl carboxylate in 20 ml of dioxane, and this mixture is stirred at room temperature for 30 minutes. 0.29 g (1.13 mmol) of 2-methyl-5- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -1,3-benzoxazole, 0.47 g (3, 4 mmol) K2CO3 and 2 g (111 mmol) H2O are then added, and the mixture is then stirred under reflux for 6 hours. The reaction mixture is allowed to remain at room temperature for another 12 hours and then added to 40 mL of H2O. This mixture is extracted repeatedly with CH2 Cl2, and the combined organic phase is dried over Na2 SO4 and then concentrated. Purification by chromatography on silica gel using the heptane / ethyl acetate (3/7) mobile phase provides 0.06 g (17%) of product. ¹ H-NMR (CDCb): δ 8.65 (d, 1H, benzoxazole), 8.40 (dd, 1H, benzoxazole), 7.50 (d, 1H, benzoxazole), 5.55 (bs, 2H, NH ₂ ), 4, 05 (s, 3H, COOCH3) 2.70 (s, 3H, -CH ₃ ).
[0084] In the table below, the NMR data of some compounds, according to the invention, are listed for characterization.
Ex. No. ¹ H-NMR δ (ppm) 1,012 CDCl3: 8.40d, 1H; 7.83d, 1H; 7.65, 1H; 7.53d, 1H; 7.12s, 1H; 4.80bs, 2H, NH2; 4.05s, 3H, COOMe 1,038 CDCl3: 8.40d, 1H; 7.62d, 1H; 7.57d, 1H; 7.20s, 1H; 6.70d, 1H; 4.80bs, 2H, NH2; 4.00s, 3H, COOMe 2,012 CDCb: 8.40d, 1H; 7.92d, 1H; 7.88dd, 1H; 7.46d, 1H; 7.39d, 1H; 7.18s, 1H; 4.8bs, NH ₂ ; 4.02s, 3H, COOMe 2,038 CDCl3: 8.40d, 1H; 7.60d, 1H; 7.40d, 1H; 7.35d, 1H; 7.25s, 1H; 4.85bs, 2H, NH2; 4.00s, 3H, COOMe 8,007 DMSO-de: 8.45d, 2H; 8.20m, 1H; 7.80s, 1H; 7.70m, 3H; 7.40m;1H 8,013 CDCb: 8.30s, 1H; 8.13s, 1H; 8.05d, 2H; 7.62d, 1H; 7.13s, 1H; 4.82bs, NH ₂ ; 4, Os, 3H, COOMe 8,014 CDCb: 8.10s, 1H; 7.90d, 1H; 7.50d, 1H; 7.10s, 1H; 4.70bs, 2H, NH ₂ ; 4.00s, 3H, COOMe; 2.65s, 3H, CH ₃ 8,019 CDCb: 8.30m, 2H; 8.15m, 1H; 7.59m, 4H; 7.18m, 1H; 4.95bs,
Petition 870180143799, of 10/23/2018, p. 145/411
131/134
Ex. No. ¹ H-NMR δ (ppm)2H, NH ₂ ; 4.05s, 3H, COOMe 8,039 CDCh: 7.85s, 1H; 7.70d, 1H; 7.30d, 1H; 7.10s, 1H; 4.95bs, 2H, NH ₂ ; 4.80bs, 2H, NH ₂ ; 4.00s, 3H, COOMe 9,013 CDCh: 9.00s, 1H; 8.60s, 1H; 8.12d, 1H; 8.00d, 1H; 7.20s, 1H; 4.85bs, 2H, NH ₂ ; 4.00s, 3H, COOMe 9,014 CDCh: 8.40s, 1H; 8.00d, 1H; 7.85d, 1H; 7.18s, 1H; 4.80bs, 2H, NH ₂ ; 4.00s, 3H, COOMe 10.013 CDCh: 8.25s, 1H; 8.15s, 1H; 8.92d, 1H; 8.82d, 1H; 7.18s, 1H; 4.80bs, 2H, NH ₂ ; 4.00s, 3H, COOMe 10.014 CDCh: 8.10 s, 1H; 7.82d, 1H; 7.68d, 1H; 7.14s, 1H; 4.80bs, 2H, NH ₂ ; 4.00s, 3H, COOMe; 2.68s, 3H, CH ₃ 10.019 CDCh: 8.30m, 2H; 8.00dd, 1H; 7.60d, 1H; 7.57m, 3H; 7.30s, 1H; 4.85bs, 2H, NH ₂ ; 4.00s 3H, COOMe 10.023 CDCh: 8.30m, 2H; 7.73d, 1H; 7.67s, 1H; 7.60m, 3H; 7.14s, 1H; 4.90bs, 2H, NH ₂ ; 4.00s, 3H, COOMe 11,014 CDCh: 8.50s, 1H; 7.98d, 1H; 7.90d, 1H; 7.15s, 1H; 4.85bs, 2H, NH ₂ ; 4.00s, 3H, COOMe; 2.85s, 3H, CH ₃ 14,061 CDCl3: 8.20s, 1H; 7.80d, 1H; 7.65d, 1H; 7.60d, 1H; 7.15s, 1H;6.78d, 1H; 4.80bs, 2H, NH2; 4.02s, 3H, COOMe 14,081 CDCl3: 7.85dd, 1H; 7.70d, 2H; 7.40d, 2H; 7.30s, 1H; 6.70d, 1H; 4.80bs, 2H, NH2; 4.00s, 3H, COOMe 15,061 CDCl3: 8.50s, 1H; 7.89d, 1H; 7.85d, 1H; 7.50d, 1H; 7.35d, 1H;7.20s, 1H; 4.80bs, 2H, NH2; 4.03s, 3H, COOMe 16,064 CDCh: 8.10 s, 1H; 8.00bs, 1H, NH; 7.60m, 2H; 7.20s, 1H; 7.00s, 1H; 4.70bs, 2H, NH ₂ ; 4.00s, 3H, COOMe; 2.35s, 3H, CH ₃ 16,073 CDCh: 8.10bs, 1H, NH; 7.95s, 1H; 7.50m, 2H; 7.10s, 1H; 6.20s, 1H; 4.75bs, 2H; NH ₂ ; 4.00s, 3H, COOMe; 2.45s, 3H, CH ₃ 24,012 CDCh: 8.84s, 1H; 8.35d, 1H; 7.93d, 1H; 7.48d, 1H; 7.42d, 1H; 5.60bs, 2H, NH ₂ ; 4.00s, 3H; COOMe 30,014 CDCh: 8.65s, 1H; 8.40d, 1H; 7.50d, 1H; 5.60bs, 2H, NH ₂ ; 4.05s, 3H, COOMe; 2.70s, 3H, CH ₃
Petition 870180143799, of 10/23/2018, p. 146/411
132/134
Ex. No. ¹ H-NMR δ (ppm) 31,013 CDCh: 9.15 s, 1H; 9.05s, 1H; 8.50d, 1H; 8.00d, 1H; 5.60bs, 2H, NH ₂ ; 4.05s, 3H, COOMe 32,013 CDCh: 8.60s, 1H; 8.45d, 1H; 8.18s, 1H; 7.70d, 1H; 5.60bs, 2H, NH ₂ ; 4.05s, 3H, COOMe 33,014 CDCh: 8.85s, 1H; 8.45d, 1H; 7.95d, 1H; 5.60bs, 2H, NH ₂ ; 4.00s, 3H; COOMe; 2.85s, 3H, CH ₃ 38,061 CDCh: 8.48s, 1H; 8.30bs, NH; 8.15d, 1H; 7.70d, 1H; 7.30d, 1H; 6.60d, 1H; 5.50bs, 2H, NH ₂ ; 4.00s, 3H, COOMe
B. Formulation examples
1. Powders [0085] A powder is obtained by mixing 10 parts by weight of a compound of the General Formula (I) and 90 parts by weight of talc as an inert substance and fragmenting the mixture in a hammer mill.
2. Dispersible powder [0086] A humectable powder that is easily dispersible in water is obtained by mixing 25 parts by weight of a compound of the General formula (I), 64 parts by weight of quartz containing kaolin as an inert substance, 10 parts in weight of potassium lignosulfonate and 1 part by weight of sodium oleoylmethyltaurate as a wetting and dispersing agent, and grinding the mixture in a stapled disc mill.
3. Dispersion Concentrate [0087] A dispersion concentrate easily dispersible in water is obtained by mixing 20 parts by weight of a compound of the General Formula (I) with 6 parts by weight of alkyl phenol polyglycol ether (®Triton X 207), 3 parts by weight of isotridecanol polyglycol ether (8 EO) and 71 parts by weight of paraffinic mineral oil (boiling range, for example, approximately 155 to above 277Ό) and grinding the mixture in a ball mill to a fineness below 5 microns.
4. Emulsifiable concentrate [0088] An emulsifiable concentrate is obtained from 15 parts by weight
Petition 870180143799, of 10/23/2018, p. 147/411
133/134 of a compound of the general Formula (I), 75 parts by weight of cyclohexanone as a solvent and 10 parts by weight of oxetylated nonylphenol as an emulsifier.
5. Water-dispersible granules
Water-dispersible granules are obtained by mixing:
parts by weight of a compound of the General Formula (I), calcium lignosulfonate, sodium lauryl sulfate, polyvinyl alcohol and kaolin, grinding the mixture in a stapled disc mill, and granulating the powder in a fluidized bed by vaporizing water as a granulation liquid.
[0089] Water-dispersible granules are also obtained by homogenizing and prefragmenting, in a colloid mill, parts by weight of a compound of the General Formula (I),
5 II 2,2'-dinaftymethane-6,6'-disulfonate sodium, 2 II of sodium oleoylmethyltaurinate,1 II of polyvinyl alcohol,17 II of calcium carbonate and50 II of water,
subsequently grinding the mixture in a bead mill and atomising and drying the resulting suspension in a spray tower using a single substance nozzle.
C. Biological examples
1. Pre-emergence herbicidal action against harmful plants [0090] Seeds or rhizome pieces of harmful mono- and dicotyledonous plants are placed on sandy clay soil in pots with a diameter of 9 to 13 cm and covered with soil. Herbicides,
Petition 870180143799, of 10/23/2018, p. 148/411
134/134 formulated as emulsifiable powders or concentrates, they are then applied in various dosages as aqueous dispersions or suspensions or emulsions at an application rate of 300 to 800 I of water / ha (converted) to the surface of the covering land. For other plant cultivation, the pots are then kept under ideal conditions in a greenhouse. After the test plants are allowed to remain in the greenhouse for 3 to 4 weeks under ideal growth conditions, the activity of the compounds according to the invention is classified visually. Thus, for example, the compounds of nos. 1,012, 1,038, 14,061 and 15,061 each show, at an application rate of 320 grams per hectare, an activity of at least 90% against Echinocloa crus galli, Abutilon theophrasti, Amaranthus retroflexus, Matricaria inodora, Stellaria media and Verônica persica.
2. Post-emergence herbicidal action against harmful plants [0091] Seeds of harmful monocotyledonous and dicotyledonous plants are placed on sandy clay soil in cardboard pots, covered with soil and grown in a greenhouse under good growing conditions. Two to three weeks after sowing, the test plants are treated in the three-leaf stage. The compounds according to the invention, formulated as wettable powders or as emulsion concentrates, are sprayed on the surface of the green parts of the plants at an application rate of 600 to 800 I of water / ha (converted). After the test plants are allowed to remain in the greenhouse for 3 to 4 weeks under ideal growth conditions, the effect of the compounds according to the invention is classified visually. Thus, for example, the compounds of nos. 1,012, 14,061 and 15,061 each show, at an application rate of 80 grams per hectare, an activity of at least 90% against Echinocloa crus galli, Abutilon theophrasti, Amaranthus retroflexus and Matricaria inodora.

权利要求:
Claims (9)
[1]
1. Herbicidal compositions, characterized by the fact that they comprise a herbicidally effective amount of at least one compound of Formula (I), its N-oxides or their salts
COOR ¹ (l) in which
A represents a radical of the group consisting of:
R ¹ represents hydrogen or (C 1 -C 4) -alkyl,
R ² represents chlorine,
R ³ represents hydrogen,
R ⁴ represents hydrogen,
R ⁵ represents hydrogen, halogen, OH, NH2, CN, (C1-C3) alkyl, (C1-C3) -alkoxy, (C1-C3) -alkylamino or cyclopropyl,
R ⁶ represents hydrogen, halogen, OH, NH2, CN, (C1-C3) alkyl, (C1-C3) -alkoxy, cyclopropyl or vinyl,
R ⁷ represents hydrogen, halogen, (C1-C3) -alkyl, (C1-C3) alkoxy, (C1-C3) -alkylthio, cyclopropyl, (C1-C3) -alkylamino or phenyl,
R ⁸ represents hydrogen, (C 1 -C 3) -alkyl, phenyl or (C 1 -C 3) alkylcarbonyl,
X represents CF, n represents 0, 1 or 2.
[2]
2. Herbicidal compositions according to claim 1,
Petition 870180143799, of 10/23/2018, p. 163/411
2/2 characterized by the fact that they are in a mixture with formulation aids.
[3]
3. Herbicidal compositions according to claim 1 or 2, characterized by the fact that they comprise at least one other pesticidally active compound from the group of insecticides, acaricides, herbicides, fungicides, protectors and growth regulators.
[4]
4. Herbicidal compositions according to claim 3, characterized by the fact that they comprise a protector.
[5]
5. Herbicidal compositions according to claim 4, characterized in that they comprise another herbicide.
[6]
6. Method for controlling unwanted plants, characterized by the fact that an effective amount of at least one compound of Formula (I), as defined in claim 1, is applied to the plants or on the growth site of the unwanted plant.
[7]
7. Use of compounds of Formula (I), as defined in claim 1, characterized by the fact that it is to control unwanted plants.
[8]
8. Use according to claim 7, characterized by the fact that the compounds of Formula (I) are used to control unwanted plants in crops of useful plants.
[9]
9. Use according to claim 8, characterized by the fact that the useful plants are useful transgenic plants.

类似技术:

---

公开号 | 公开日 | 专利标题

---

AU2017204231B2|2018-11-29|Substituted picolinic acids and pyrimidine-4-carboxylic acids, method for the production thereof, and use thereof as herbicides and plant growth regulators

---

JP5651602B2|2015-01-14|4-Phenyl substituted pyridazinones with herbicidal and insecticidal effects

---

EP2691379B1|2016-11-02|Herbicidally and fungicidally active 3-phenylisoxazoline-5-carboxamides and 3-phenylisoxazoline-5-thioamides

---

CA2830089A1|2012-09-20|N-|-, n-|- and n-|bicycloarylcarboxamides and their use as herbicides

---

WO2011045271A1|2011-04-21|Herbicidally active, heterocyclyl-substituted pyridazinones

---

CA2809492C|2018-12-18|Herbicidally active ketosultams and diketopyridines

---

US20120065065A1|2012-03-15|Herbicidally active pyridylketosultams

---

AU2018219470A1|2019-08-22|Substituted benzyl-4-aminopicolinic esters and pyrimidino-4-carboxylic esters, methods for the production thereof, and use thereof as herbicides and plant growth regulators

同族专利:

---

公开号 | 公开日

---

AU2017204231A1|2017-07-13|

---

CA2842830A1|2013-01-31|

---

ES2561887T3|2016-03-01|

---

JP2014524927A|2014-09-25|

---

BR112014001882A2|2017-02-21|

---

ZA201400557B|2015-09-30|

---

WO2013014165A1|2013-01-31|

---

RU2734460C9|2021-04-05|

---

CA2842830C|2018-12-04|

---

CN103827102B|2016-04-27|

---

CN103827102A|2014-05-28|

---

JP6039667B2|2016-12-07|

---

AU2012288895A1|2014-02-20|

---

PL2736897T3|2016-04-29|

---

RU2734460C2|2020-10-16|

---

MX2014000950A|2014-02-27|

---

HUE028580T2|2016-12-28|

---

AU2017204231B2|2018-11-29|

---

AU2019201365A1|2019-03-21|

---

EP2736897A1|2014-06-04|

---

US9179676B2|2015-11-10|

---

AR087349A1|2014-03-19|

---

EP2736897B1|2015-11-25|

---

UA111084C2|2016-03-25|

---

IN2014CN00473A|2015-04-03|

---

RU2612301C2|2017-03-06|

---

RU2014107104A|2015-09-10|

---

AU2021202032A1|2021-04-29|

---

AU2017204231C1|2021-04-15|

---

MX370455B|2019-12-13|

---

US20150005165A1|2015-01-01|

---

RU2017104715A3|2020-03-25|

---

AU2017204231C9|2021-05-13|

---

RU2017104715A|2019-01-18|

引用文献:

---

公开号 | 申请日 | 公开日 | 申请人 | 专利标题

---

---

WO1984002919A1|1983-01-17|1984-08-02|Monsanto Co|Plasmids for transforming plant cells|

---

BR8404834A|1983-09-26|1985-08-13|Agrigenetics Res Ass|METHOD TO GENETICALLY MODIFY A PLANT CELL|

---

BR8600161A|1985-01-18|1986-09-23|Plant Genetic Systems Nv|CHEMICAL GENE, HYBRID, INTERMEDIATE PLASMIDIO VECTORS, PROCESS TO CONTROL INSECTS IN AGRICULTURE OR HORTICULTURE, INSECTICIDE COMPOSITION, PROCESS TO TRANSFORM PLANT CELLS TO EXPRESS A PLANTINIDE TOXIN, PRODUCED BY CULTURES, UNITED BY BACILLA|

---

AT80182T|1985-10-25|1992-09-15|Monsanto Co|PLANT VECTORS.|

---

ES2018274T5|1986-03-11|1996-12-16|Plant Genetic Systems Nv|VEGETABLE CELLS RESISTANT TO GLUTAMINE SYNTHETASE INHIBITORS, PREPARED BY GENETIC ENGINEERING.|

---

JPH01503663A|1986-05-01|1989-12-07|

---

US5013659A|1987-07-27|1991-05-07|E. I. Du Pont De Nemours And Company|Nucleic acid fragment encoding herbicide resistant plant acetolactate synthase|

---

IL83348A|1986-08-26|1995-12-08|Du Pont|Nucleic acid fragment encoding herbicide resistant plant acetolactate synthase|

---

DE3733017A1|1987-09-30|1989-04-13|Bayer Ag|Stilbene synthase gene|

---

WO1991013972A1|1990-03-16|1991-09-19|Calgene, Inc.|Plant desaturases - compositions and uses|

---

AT212670T|1990-06-18|2002-02-15|Monsanto Technology Llc|INCREASED STRENGTH IN PLANTS|

---

AU655197B2|1990-06-25|1994-12-08|Monsanto Technology Llc|Glyphosate tolerant plants|

---

DE4107396A1|1990-06-29|1992-01-02|Bayer Ag|STYLE SYNTHASE GENES FROM VINEYARD|

---

SE467358B|1990-12-21|1992-07-06|Amylogene Hb|GENETIC CHANGE OF POTATISE BEFORE EDUCATION OF AMYLOPECT TYPE STARCH|

---

DE4104782B4|1991-02-13|2006-05-11|Bayer Cropscience Gmbh|Novel plasmids containing DNA sequences that cause changes in carbohydrate concentration and carbohydrate composition in plants, as well as plants and plant cells containing these plasmids|

---

AR026836A1|2000-01-14|2003-02-26|Dow Agrosciences Llc|4-AMYNOPYCHOLINATES AND ITS USE AS HERBICIDES|

---

AR037228A1|2001-07-30|2004-11-03|Dow Agrosciences Llc|ACID COMPOUNDS 6- -4-AMYNOPYCOLINIC, HERBICIDE COMPOSITION THAT UNDERSTANDS AND METHOD TO CONTROL UNWANTED VEGETATION|

---

TWI355894B|2003-12-19|2012-01-11|Du Pont|Herbicidal pyrimidines|

---

CN101171237B|2005-05-06|2011-04-20|杜邦公司|Method for preparation of optionally 2-substituted 1,6-dihydro-6-oxo-4-pyrimidinecarboxylic acids|

---

EP1979325A1|2006-01-11|2008-10-15|AstraZeneca AB|Morpholino pyrimidine derivatives and their use in therapy|

---

EP1971579B1|2006-01-13|2010-07-28|Dow AgroSciences LLC|2--6-amino-5-halo-4-pyrimidinecarboxylic acids and their use as herbicides|

---

EP1973881B1|2006-01-13|2009-10-28|Dow Agrosciences LLC|6--4-aminopicolinates and their use as herbicides|

---

BRPI0706884A2|2006-02-02|2011-04-12|Du Pont|method of inhibiting cotton plant foliage growth, mixing to cause prolonged defoliation of cotton plant and agricultural compositions|

---

CA2646143A1|2006-04-10|2007-10-25|E. I. Du Pont De Nemours And Company|Herbicidal mixtures|

---

CA2657745C|2006-07-21|2015-02-17|Novartis Ag|Pyrimidine derivatives and their use as pesticides|

---

EP1916240A1|2006-10-25|2008-04-30|Syngeta Participations AG|Pyridazine derivatives|

---

CA2692725A1|2007-07-09|2009-01-15|Astrazeneca Ab|Compound - 946|

---

ES2400405T3|2007-08-13|2013-04-09|Dow Agrosciences Llc|2- -6-amino-5-chloro-4-pyrimidinecarboxylates and their use as herbicides|

---

UA94351C2|2007-08-27|2011-04-26|ДАУ АГРОСАЙЕНСИЗ ЭлЭлСи|Synergistic herbicidal composition comprising certain pyridine or pyrimidine carboxylic acids and certain herbicides for cereals and rice|

---

WO2009029735A1|2007-08-30|2009-03-05|Dow Agrosciences Llc|2--6-amino-5-alkoxy, thioalkoxy and aminoalkyl-4-pyrimidinecarboxylates and their use as herbicides|

---

MX2010003464A|2007-10-02|2010-04-27|Dow Agrosciences Llc|2-substituted-6-amino-5-alkyl, alkenyl or alkynyl-4-pyrimidinecar boxylic acids and 6-substituted-4-amino-3- alkyl, alkenyl or alkynyl picolinic acids and their use as herbicides.|

---

PL2279178T3|2008-04-18|2015-10-30|Dow Agrosciences Llc|2--6-hydroxy- or alkoxy-5-substituted-4-pyrimidinecarboxylates and their use as herbicides|

---

GB0808664D0|2008-05-13|2008-06-18|Syngenta Ltd|Chemical compounds|

---

US8647594B2|2008-07-18|2014-02-11|Accuri Cytometers, Inc.|Wellplate handler system for a flow cytometer|

---

EP2191719A1|2008-11-29|2010-06-02|Bayer CropScience AG|Herbicide safener combination|

---

GB0907625D0|2009-05-01|2009-06-10|Syngenta Ltd|Method of controlling undesired vegetation|

---

BR112013009703A2|2010-10-22|2018-05-22|Bayer Ip Gmbh|substituted picolinic acids, their salts and acid derivatives, as well as their use as herbicides.|

---

KR20140037804A|2010-12-16|2014-03-27|바이엘 인텔렉쳐 프로퍼티 게엠베하|6-picolinates and their use as herbicides|

---

US9637505B2|2013-03-15|2017-05-02|Dow Agrosciences Llc|4-amino-6-picolinates and 6-amino-2-pyrimidine-4-carboxylates and their use as herbicides|US9637505B2|2013-03-15|2017-05-02|Dow Agrosciences Llc|4-amino-6-picolinates and 6-amino-2-pyrimidine-4-carboxylates and their use as herbicides|

---

ES2811084T3|2013-03-15|2021-03-10|Dow Agrosciences Llc|4-Amino-6-picolinates and 6-amino-2-pyrimidine-4-carboxylates and their use as herbicides|

---

WO2014151008A1|2013-03-15|2014-09-25|Dow Agrosciences Llc|4-amino-6-picolinates and 6-amino-2-pyrimidine-4-carboxylates and their use as herbicides|

---

TWI689251B|2014-09-15|2020-04-01|美商陶氏農業科學公司|Synergistic weed control from applications of pyridine carboxylic acid herbicides and synthetic auxin herbicides and/or auxin transport inhibitors|

---

TWI689252B|2014-09-15|2020-04-01|美商陶氏農業科學公司|Synergistic weed control from applications of pyridine carboxylic acid herbicides and als inhibitors|

---

TWI694770B|2014-09-15|2020-06-01|美商陶氏農業科學公司|Safened herbicidal compositions comprising a pyridine carboxylic acid herbicide|

---

US10455836B2|2014-09-15|2019-10-29|Dow Agrosciences Llc|Synergistic weed control from applications of pyridine carboxylic acid herbicides and photosystem II inhibitors|

---

TWI685302B|2014-09-15|2020-02-21|美商陶氏農業科學公司|Safened herbicidal compositions comprising pyridine carboxylic acids|

---

EP3360872A1|2017-02-13|2018-08-15|Bayer CropScience Aktiengesellschaft|Substituted benzyl-4-aminopicolinic acid esters and pyrimidin-4-carboxylic acid ester, process for their preparation and use as herbicides and regulators of plant growth|

---

AU2018219470A1|2017-02-13|2019-08-22|Bayer Aktiengesellschaft|Substituted benzyl-4-aminopicolinic esters and pyrimidino-4-carboxylic esters, methods for the production thereof, and use thereof as herbicides and plant growth regulators|

---

KR20200015532A|2017-05-10|2020-02-12|다우 아그로사이언시즈 엘엘씨|4-amino-6-picolinate and 6-amino-2-pyrimidine-4-carboxylate, and their use as herbicides|

---

WO2019046667A1|2017-09-01|2019-03-07|Dow Agrosciences Llc|Herbicidal compositions containing pyridine carboxylic acids or derivatives thereof, with pds and vlcfa inhibitors, or derivatives thereof|

---

EP3675635A4|2017-09-01|2021-05-19|Dow Agrosciences LLC|Herbicidal compositions containing pyridine carboxylic acids or derivatives thereof, with glyphosate or glufosinate, or derivatives thereof|

---

TW202010408A|2018-04-04|2020-03-16|美商陶氏農業科學公司|Improved weed control from applications of pyridine carboxylic acid herbicides and acetyl CoA carboxylaseinhibitors|

---

TW202002784A|2018-04-04|2020-01-16|美商陶氏農業科學公司|Weed control from applications of pyridine carboxylic acid herbicides and 4-hydroxyphenyl-pyruvate dioxygenaseinhibitors|

---

CA3118680A1|2018-11-06|2020-05-14|Corteva Agriscience Llc|Compositions comprising pyridine carboxylate herbicides and azole carboxylate safeners|

---

EP3876722A1|2018-11-06|2021-09-15|Corteva Agriscience LLC|Safened compositions comprising pyridine carboxylate herbicides and cloquintocet|

---

US20220000109A1|2018-11-06|2022-01-06|Corteva Agriscience Llc|Safened compositions comprising pyridine carboxylate herbicides and isoxadifen|

---

CN113329627A|2018-11-07|2021-08-31|科迪华农业科技有限责任公司|Compositions comprising a carboxypyridine herbicide and an acetyl-CoA carboxylaseinhibitor herbicide|

---

EP3876734A1|2018-11-07|2021-09-15|Corteva Agriscience LLC|Compositions comprising pyridine carboxylate herbicides and plant growth regulators|

---

WO2020096928A1|2018-11-07|2020-05-14|Dow Agrosciences Llc|Compositions comprising pyridine carboxylate herbicides with glyphosate or glufosinate|

---

EA202191269A1|2018-11-07|2021-07-26|КОРТЕВА АГРИСАЙЕНС ЭлЭлСи|COMPOSITIONS CONTAINING HERBICIDES BASED ON PYRIDINCARBOXYLATE AND HERBICIDE-INHIBITORS OF FATTY ACID SYNTHESIS WITH A VERY LONG CHAIN |

---

CA3118596A1|2018-11-07|2020-05-14|Corteva Agriscience Llc|Compositions comprising pyridine carboxylate herbicides with pds inhibitor herbicides|

---

CA3118579A1|2018-11-07|2020-05-14|Corteva Agriscience Llc|Compositions comprising pyridine carboxylate herbicides and cellulose biosynthesis inhibitor herbicides|

---

AU2019375944A1|2018-11-07|2021-05-27|Corteva Agriscience Llc|Compositions comprising a pyridine carboxylate herbicide and protoporphyrinogen oxidaseinhibitor herbicides|

---

BR112021008843A2|2018-11-07|2021-08-17|Corteva Agriscience Llc|compositions comprising pyridine carboxylate herbicides with photosystem ii and optional hppd inhibiting herbicides|

---

EP3876727A1|2018-11-07|2021-09-15|Corteva Agriscience LLC|Compositions comprising pyridine carboxylate herbicides with synthetic auxin herbicides or auxin transport inhibitors|

---

AU2019377056A1|2018-11-07|2021-05-06|Corteva Agriscience Llc|Compositions comprising pyridine carboxylate herbicides with acetolactate synthaseinhibitor herbicides|

---

WO2020096939A1|2018-11-07|2020-05-14|Dow Agrosciences Llc|Compositions comprising pyridine carboxylate herbicides and fatty acid and lipid synthesis inhibitor herbicides|

---

JP2022506680A|2018-11-07|2022-01-17|コルテバ アグリサイエンス エルエルシー|A composition comprising a pyridinecarboxylic acid herbicide and a 4-hydroxyphenyl-pyruvate dioxygenaseinhibitory herbicide.|

法律状态:
2017-05-30| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

---

2018-08-07| B07A| Technical examination (opinion): publication of technical examination (opinion) [chapter 7.1 patent gazette]|

---

2019-03-06| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

---

2019-05-07| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 24/07/2012, OBSERVADAS AS CONDICOES LEGAIS. (CO) 20 (VINTE) ANOS CONTADOS A PARTIR DE 24/07/2012, OBSERVADAS AS CONDICOES LEGAIS |

---

2019-11-19| B17A| Notification of administrative nullity (patentee has 60 days time to reply to this notification)|Free format text: REQUERENTE DA NULIDADE: DOW AGROSCIENCES LLC - 870190050466 - 29/05/2019 |

优先权:

---

申请号 | 申请日 | 专利标题

---

EP11175511.2|2011-02-27|

---

EP11175511|2011-07-27|

---

PCT/EP2012/064519|WO2013014165A1|2011-07-27|2012-07-24|Substituted picolinic acids and pyrimidine-4-carboxylic acids, method for the production thereof, and use thereof as herbicides and plant growth regulators|

---