EP3325446A1 - Hydrazides substitués d'acide arylcarboxylique et hétéroarylcarboxylique ou leurs sels, et leur utilisation pour accroître la tolérance au stress chez les végétaux - Google Patents

Hydrazides substitués d'acide arylcarboxylique et hétéroarylcarboxylique ou leurs sels, et leur utilisation pour accroître la tolérance au stress chez les végétaux

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Publication number
EP3325446A1
EP3325446A1 EP16738448.6A EP16738448A EP3325446A1 EP 3325446 A1 EP3325446 A1 EP 3325446A1 EP 16738448 A EP16738448 A EP 16738448A EP 3325446 A1 EP3325446 A1 EP 3325446A1
Authority
EP
European Patent Office
Prior art keywords
alkyl
aryl
heteroaryl
cycloalkyl
alkoxycarbonyl
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP16738448.6A
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German (de)
English (en)
Inventor
Jens Frackenpohl
Guido Bojack
Marco BRÜNJES
Hendrik Helmke
Isabelle Adelt
Stefan Lehr
Peter BRÜCHNER
Jan Dittgen
Dirk Schmutzler
Ines Heinemann
Udo Bickers
Martin Jeffrey Hills
Juan Pedro RUIZ-SANTAELLA MORENO
Harry STREK
Philippe Desbordes
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Bayer CropScience AG
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Bayer CropScience AG
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Publication date
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Publication of EP3325446A1 publication Critical patent/EP3325446A1/fr
Withdrawn legal-status Critical Current

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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
    • A01N43/42—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings condensed with carbocyclic rings
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/18—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing the group —CO—N<, e.g. carboxylic acid amides or imides; Thio analogues thereof
    • A01N37/28—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing the group —CO—N<, e.g. carboxylic acid amides or imides; Thio analogues thereof containing the group; Thio analogues thereof
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/34—Nitriles
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/36—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a singly bound oxygen or sulfur atom attached to the same carbon skeleton, this oxygen or sulfur atom not being a member of a carboxylic group or of a thio analogue, or of a derivative thereof, e.g. hydroxy-carboxylic acids
    • A01N37/38—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a singly bound oxygen or sulfur atom attached to the same carbon skeleton, this oxygen or sulfur atom not being a member of a carboxylic group or of a thio analogue, or of a derivative thereof, e.g. hydroxy-carboxylic acids having at least one oxygen or sulfur atom attached to an aromatic ring system
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/44—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a nitrogen atom attached to the same carbon skeleton by a single or double bond, this nitrogen atom not being a member of a derivative or of a thio analogue of a carboxylic group, e.g. amino-carboxylic acids
    • A01N37/48—Nitro-carboxylic acids; Derivatives thereof
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C243/00—Compounds containing chains of nitrogen atoms singly-bound to each other, e.g. hydrazines, triazanes
    • C07C243/24—Hydrazines having nitrogen atoms of hydrazine groups acylated by carboxylic acids
    • C07C243/38—Hydrazines having nitrogen atoms of hydrazine groups acylated by carboxylic acids with acylating carboxyl groups bound to carbon atoms of six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C255/00—Carboxylic acid nitriles
    • C07C255/49—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
    • C07C255/57—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing cyano groups and carboxyl groups, other than cyano groups, bound to the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C255/00—Carboxylic acid nitriles
    • C07C255/63—Carboxylic acid nitriles containing cyano groups and nitrogen atoms further bound to other hetero atoms, other than oxygen atoms of nitro or nitroso groups, bound to the same carbon skeleton
    • C07C255/65—Carboxylic acid nitriles containing cyano groups and nitrogen atoms further bound to other hetero atoms, other than oxygen atoms of nitro or nitroso groups, bound to the same carbon skeleton with the nitrogen atoms further bound to nitrogen atoms
    • C07C255/66—Carboxylic acid nitriles containing cyano groups and nitrogen atoms further bound to other hetero atoms, other than oxygen atoms of nitro or nitroso groups, bound to the same carbon skeleton with the nitrogen atoms further bound to nitrogen atoms having cyano groups and nitrogen atoms being part of hydrazine or hydrazone groups bound to the same carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C281/00—Derivatives of carbonic acid containing functional groups covered by groups C07C269/00 - C07C279/00 in which at least one nitrogen atom of these functional groups is further bound to another nitrogen atom not being part of a nitro or nitroso group
    • C07C281/02—Compounds containing any of the groups, e.g. carbazates
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C317/00—Sulfones; Sulfoxides
    • C07C317/44—Sulfones; Sulfoxides having sulfone or sulfoxide groups and carboxyl groups bound to the same carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C317/00—Sulfones; Sulfoxides
    • C07C317/44—Sulfones; Sulfoxides having sulfone or sulfoxide groups and carboxyl groups bound to the same carbon skeleton
    • C07C317/46—Sulfones; Sulfoxides having sulfone or sulfoxide groups and carboxyl groups bound to the same carbon skeleton the carbon skeleton being further substituted by singly-bound oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/61—Halogen atoms or nitro radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C07D213/86—Hydrazides; Thio or imino analogues thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D217/00—Heterocyclic compounds containing isoquinoline or hydrogenated isoquinoline ring systems
    • C07D217/12—Heterocyclic compounds containing isoquinoline or hydrogenated isoquinoline ring systems with radicals, substituted by hetero atoms, attached to carbon atoms of the nitrogen-containing ring
    • C07D217/14—Heterocyclic compounds containing isoquinoline or hydrogenated isoquinoline ring systems with radicals, substituted by hetero atoms, attached to carbon atoms of the nitrogen-containing ring other than aralkyl radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
    • C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
    • C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
    • C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D241/00—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings
    • C07D241/02—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings
    • C07D241/10—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
    • C07D241/14—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D241/24—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a chain containing hetero atoms as chain links

Definitions

  • the invention relates to substituted aryl and heteroarylcarboxylic acid hydrazides or their salts and their use for increasing the stress tolerance in plants to abiotic stress, as well as for increasing plant growth and / or increasing the plant yield.
  • substituted azinylcarboxamides such as, for example, substituted 4- (trifluoromethyl) nicotinamides, possess insecticidal properties (cf., for example, EP185256, WO2001 / 014373, WO2002 / 022583, JP07010841, JP07025853, WO2005 / 1 13553).
  • N-substituted Azinylalkylazincarboxamide and their insecticidal activity are described in DE102008041214, wherein as N-substituents of the amides in question, for example, alkyl, arylcarbonyl, alkylcarbonyl,
  • Hydride reagents are known from J. Org. Chem. 1956, 21, 1177, while the hydrogenolysis mediated by Raney Nickel mediates the nitrogen bonding in
  • Signal transduction chains e.g., transcription factors, kinases, phosphatases
  • a physiological response of the plant cell e.g., ion transport, detoxification of reactive oxygen species.
  • the signal chain genes of the abiotic stress reaction include, among others. Transcription factors of classes DREB and CBF (Jaglo-Ottosen et al., 1998,
  • the response to salt stress involves phosphatases of the ATPK and MP2C types. Furthermore, in salt stress the biosynthesis of osmolytes such as proline or sucrose is often activated. For example, sucrose synthase and proline transporters (Hasegawa et al., 2000, Annu Rev Plant Physiol Plant Mol Biol 51: 463-499). The stress control of plants against cold and
  • Late Embryogenesis Abundant Proteins which include dehydrins as an important class, is known (Ingram and Bartels, 1996, Annu Rev Plant Physiol Plant Mol Biol 47: 277-403, Close, 1997, Physiol Plant 100: 291-296). These are chaperones that stabilize vesicles, proteins and membrane structures in stressed plants (Bray, 1993, Plant Physiol 103: 1035-1040). Moreover, induction of aldehyde dehydrogenases, which detoxify the reactive oxygen species (ROS) produced by oxidative stress, is often used (Kirch et al., 2005, Plant Mol Biol 57: 315-332).
  • ROS reactive oxygen species
  • HSF Heat Shock Factors
  • HSP Heat Shock Proteins
  • Substances or their stable synthetic derivatives and derived structures are also effective in external application to plants or seed dressing and activate defense reactions that result in an increased stress or pathogen tolerance of the plant [Sembdner, and Parthier, 1993, Ann. Rev. Plant Physiol. Plant Mol. Biol. 44: 569-589].
  • naphthylsulfonamide (4-bromo-N- (pyridin-2-ylmethyl) naphthalene-1-sulfonamide) influences the germination of plant seeds in the same manner as abscisic acid (Park et al., Science 2009, 324, 1068-1071).
  • a naphthylsulfamidocarboxylic acid (N - [(4-bromo-1-naphthyl) sulfonyl] -5-methoxynorvaline) exhibits a mode of action in biochemical receptor assays that react with 4-bromo-N- (pyridin-2-ylmethyl) naphthalene-1-sulfonamide is comparable (Melcher et al., Nature Structural & Molecular Biology 2010, 17, 1, 102-1 108).
  • Xanthines for increasing the abiotic stress tolerance in plants has already been described (Bergmann et al., DD277832, Bergmann et al., DD277835).
  • the molecular causes of the anti-stress effects of these substances are largely unknown.
  • the object of the present invention was to provide compounds which further increase the tolerance to abiotic stress in plants, cause a strengthening of plant growth and / or contribute to the increase of the plant yield.
  • tolerance to abiotic stress for example, tolerance to cold, heat,
  • Drought stress stress caused by drought and / or lack of water
  • salting and flooding understood.
  • Heteroarylcarbonklahydrazide can be used to increase the stress tolerance in plants to abiotic stress, as well as to increase plant growth and / or increase the plant yield.
  • Wonn R ⁇ R 2 and R 7 independently of one another represent hydrogen, halogen, cyano, nitro,
  • (Ci-C 8) -Haloalkylthio- (Ci-C 8) alkyl, (Ci-C8) alkylcarbonyl (C, -C 8) alkyl, COOR 23, CONR 2 R 22, COR 23, -C NOR 23 , R 23 is OOC- (C 1 -C 8 ) -alkyl, aryl- (C 1 -C 8 ) -alkynyl, heteroaryl- (C 1 -C 8 ) -alkynyl, heterocyclyl- (C 1 -C 8 ) -alkynyl.
  • X 1 , X 2 , X 3 and X 4 are the same or different and are independently N
  • W is O (oxygen) or S (sulfur),
  • a 1 , A 2 , A 3 , A 4 and A 5 are the same or different and are independently N (nitrogen) or the group CR 7 , but in no case more than two N atoms are adjacent, and wherein R 7 in the group CR 7 has the same or different meanings as defined above, R 3 is (CrC 8) alkyl, cyano (dC 8) -alkyl, (C 2 -C 8) alkenyl, (C 2 -C 8) -alkynyl, (C1-C10) - haloalkyl, (C 2 -C 8 ) -haloalkenyl, (C 2 -C 8 ) -haloalkynyl, (C 3 -Cio) -cycloalkyl,
  • R 4 is hydrogen, (C 1 -C 8 ) -alkyl, (C 2 -C 8 ) -alkenyl, (C 2 -C 8 ) -alkyny, (C 1 -C 10) -haloalkyl, (C 2 -C 8 ) -haloalkenyl , (C 2 -C 8 ) -haloalkynyl, (C 3 -Cio) -cycloalkyl,
  • R 5 and R 6 independently of one another represent hydrogen, (C 1 -C 8 ) -alkyl, (C 2 -C 8 ) -alkenyl, (C 2 -C 8 ) -alkynyl, (C 1 -C 10) -haloalkyl, (C 2 -) C 8 ) haloalkenyl.
  • a 1 and A 2 when both represent a group CR 7 , with the atoms to which they
  • a 2 and A 3 when both represent a group CR 7 , with the atoms to which they
  • R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 and R 9 are each the
  • a 5 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 and R 19 are each independently hydrogen, (Ci-C 8 ) alkyl, (C 2 -C 8) alkenyl, (C 2 -C 8) -alkynyl, (CrCio) -haloalkyl, (C 2 -C 8) -haloalkenyl, (C 2 -C 8) haloalkynyl, ( C 3 -Cio) cycloalkyl, aryl, aryl (Ci-Ce) - alkyl, heteroaryl, heteroaryl (Ci-C 8) alkyl, (C 3 -C 8) -cycloalkyl- (Ci-C8) - alkyl, heterocyclyl, heterocyclyl (-C 8) alkyl, (Ci-C 8) alkoxy
  • the compounds of general formula (I) may be prepared by addition of a suitable inorganic or organic acid such as, for example, mineral acids such as HCl, HBr, H 2 S0, H 3 P0 4 or HNO 3 , or organic acids, e.g.
  • a suitable inorganic or organic acid such as, for example, mineral acids such as HCl, HBr, H 2 S0, H 3 P0 4 or HNO 3 , or organic acids, e.g.
  • carboxylic acids such as formic acid, acetic acid, propionic acid, oxalic acid, lactic acid or salicylic acid or sulfonic acids such as p-toluenesulfonic acid to form a basic group such as amino, alkylamino, dialkylamino, piperidino, morpholino or pyridino, salts.
  • These salts then contain the conjugate base of the acid as an anion.
  • Sulfonic acids certain sulfonic acid amides or carboxylic acids are present, internal salts can in turn form protonatable groups, such as amino groups. Salt formation can also be effected by the action of a base on compounds of the
  • Suitable bases are, for example, organic amines, such as trialkylamines, morpholine, piperidine and pyridine, and ammonium, alkali or alkaline earth metal hydroxides, carbonates and bicarbonates, in particular sodium and potassium hydroxide, sodium and potassium carbonate and sodium and
  • Hydrogen is replaced by a cation suitable for agriculture, for example metal salts, in particular alkali metal salts or alkaline earth metal salts, in particular sodium and potassium salts, or ammonium salts, salts with organic amines or quaternary ammonium salts, for example with cations of the formula [NR a R b R c R d ] + , wherein R a to R d each independently represent an organic radical, in particular alkyl, aryl, aralkyl or alkylaryl.
  • metal salts in particular alkali metal salts or alkaline earth metal salts, in particular sodium and potassium salts, or ammonium salts, salts with organic amines or quaternary ammonium salts, for example with cations of the formula [NR a R b R c R d ] + , wherein R a to R d each independently represent an organic radical, in particular alkyl, aryl, aralkyl or alkylaryl.
  • alkylsulfonium and Alkylsulfoxoniumsalze such as (Ci-C4) - trialkylsulfonium and (Ci-C 4) -Trialkylsulfoxoniumsalze.
  • aryl and heteroarylcarboxylic acid hydrazides of the formula (I) according to the invention may be present in various tautomeric structures, depending on external conditions such as pH, solvent and temperature, and X 1 , X 2 , X 3 and X 4 , all of the general formula (I) should be included.
  • Preferred subject of the invention are compounds of the general formula (I) wherein
  • R 1 , R 2 and R 7 independently of one another represent hydrogen, halogen, cyano, nitro,
  • (C 1 -C 7 ) -haloalkylthio (C 1 -C 7 ) -alkyl, (C 1 -C 7 ) -alkylcarbonyl- (C 1 -C 7 ) -alkyl, COOR 23 , CONR 21 R 22 , COR 23 , -C NOR 23 , R 23 OOC- (C 1 -C 7 ) -alkyl, aryl- (C 1 -C 7 ) -alkynyl, heteroaryl- (C 1 -C 7 ) -alkynyl, heterocyclyl- (C 1 -C 7 ) -alkynyl, tris [ !
  • X 1 , X 2 , X 3 and X 4 are the same or different and are independently N
  • W is O (oxygen) or S (sulfur),
  • a 1 , A 2 , A 3 , A 4 and A 5 are the same or different and are independently N (nitrogen) or the group CR 7 , but in no case more than two N atoms are adjacent, and wherein R 7 in the grouping CR 7 each has identical or different meanings according to the above definition, is (Ci-C7) alkyl, cyano (Ci-C7) alkyl, (C 2 -C 7) alkenyl, ( C 2 -C 7 ) -alkynyl, (C 1 -C 10) -haloalkyl, (C 2 -C 7 ) -haloalkenyl, (C 2 -C 7 ) -haloalkynyl, (C 3 -C 10) -cycloalkyl,
  • R 5 and R 6 are each independently hydrogen, (Ci-C7) alkyl, (C 2 -C 7) alkenyl, (C 2 -C 7) alkynyl, (Ci-Cio) -haloalkyl, (C 2 -C 7 ) -Haloalkenyi, (C 2 -C 7 ) -Haioalkinyl, (C 3 -Cio) -cycloalkyl.
  • R 5 and R 6 with the atom to which they are attached form a fully saturated or partially saturated, optionally interrupted by heteroatoms and optionally further substituted 5-7 membered ring, R 1 and X 1 , when X 1 is a group CR 2 , with the atoms to which they are attached, a fully saturated, partially saturated or completely
  • X 1 and X 2 when both represent a group CR 2 , with the atoms to which they belong
  • a 1 and A 2 when both represent a group CR 7 , with the atoms to which they belong
  • a 2 and A 3 when both represent a group CR 7 , with the atoms to which they belong
  • a 3 and A 4 when both represent a group CR 7 , with the atoms to which they belong
  • R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 and R 19 independently of one another are hydrogen, (C 1 -C 7 ) -alkyl, ( C 2 -C 7) alkenyl, (C 2 -C 7) alkynyl, (Ci-Cio) -haloalkyl, (C 2 -C 7) haloalkenyl, (C 2 -C 7) haloalkynyl, (C 3 -Cio) cycloalkyl, aryl, aryl (dC 7) - alkyl, heteroaryl, heteroaryl (dC 7) alkyl, (C 3 -C 7) cycloalkyl (Ci-C7) alkyl, heterocyclyl, heterocyclyl - (Ci-C7) alkyl, (Ci-C7) alkoxy (Ci-C7) al
  • R 21 and R 22 are the same or different and independently of each other
  • (C 1 -C 6 ) -haloalkylthio (C 1 -C 6 ) -alkyl, (C 1 -C 6 ) -alkylcarbonyl- (C 1 -C 6 ) -alkyl, COOR 23 , CONR 21 R 22 , COR 23 , -C NOR 23 , R 23 OOC- (C 1 -C 6 ) -alkyl, aryl- (C 1 -C 6 ) -alkynyl, heteroaryl- (C 1 -C 6 ) -alkynyl, heterocyclyl - (Ci-C 6) -alkynyl, tris - [(Ci-C6) alkyl] silyl (C 2 -C 6) alkynyl, - bis [(Ci-C6) alkyl] (aryl) silyl - (C2-C6) alkynyl-aryl i bis [(Ci-C 6)
  • X 1 , X 2 , X 3 and X 4 are the same or different and are independently N
  • W is O (oxygen) or S (sulfur),
  • a 1 , A 2 , A 3 , A 4 and A 5 are the same or different and are independently N (nitrogen) or the group CR 7 , but in no case more than two N atoms are adjacent, and wherein R 7 in the group CR 7 has the same or different meanings as defined above,
  • R 3 is (CrC 6) alkyl, cyano- (CrC 6) alkyl, (C 2 -C 6) alkenyl, (C2-C6) -alkynyl, (Ci-C 6) - haloalkyl, (C 2 -C 6) haloalkenyl, (C 2 -C 6) haloalkynyl, (C 3 -C 6) -cycloalkyl, (C3-C10) - halocycloalkyl, (C 4 -Cio) cycloalkenyl, (C 4 -Cio) -Halocycloalkenyl, (Ca-Ce) -cycloalkyl- (C 1 -C 6 ) -alkyl, heterocyclyl, heterocyclyl- (C 1 -C 6 ) -alkyl, (C 1 -C 6 ) -alkoxy- (C 1 -C 6 ) -
  • R 5 and R 6 are each independently hydrogen, (Ci-C6) -Alkyi, (C2-C6) alkenyl, (C2-C6) -alkynyl, (Ci-Cio) -haloalkyl, (C 2 -C 6) -Haloaikenyi, (C 2 -C 6 ) -haloalkynyl, (C 3 -C 10) -cycloalkyl, (C 3 -C 10) -aiocycloalkyl, (C 4 -C 10) -cycloalkenyl, (C 4 -C 10) -halocycioalkenyl, aryl, aryl (C 1 -C 6 ) -alkyl, heteroaryl, heteroaryl- (C 1 -C 6 ) -alkyl, (C 3 -C 6 ) -cycloalkyl- (C 1 -C 6 ) -alkyl, heterocyclyl
  • R 5 and R 6 with the atom to which they are attached form a fully saturated or partially saturated, optionally interrupted by heteroatoms and optionally further substituted 5-7 membered ring, R 1 and X 1 , when X 1 is a group CR 2 , with the atoms to which they are attached, a fully saturated, partially saturated or completely
  • X 1 and X 2 when both represent a group CR 2 , with the atoms to which they belong
  • a 1 and A 2 when both represent a group CR 7 , with the atoms to which they belong
  • a 2 and A 3 when both represent a group CR 7 , with the atoms to which they belong
  • a 3 and A 4 when both represent a group CR 7 , with the atoms to which they belong
  • R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 and R 19 independently of one another are hydrogen, (C 1 -C 6 ) -alkyl, ( C 2 -C 6 ) alkenyl, (C 2 -C 6 ) alkynyl, (C 1 -C 6 ) haloalkyl, (C 2 -C 6 ) haloalkenyl, (C 2 -C 6 ) haloalkynyl, (C 3 -Cio) cycloalkyl, aryl, aryl (CrC 6) - alkyl, heteroaryl, heteroaryl (Ci-C 6) alkyl, (C3-C6) cycloalkyl (Ci-C 6) alkyl, heterocyclyl, Heterocyclyl (C 1 -C 6 ) -alkyl, (C 1 -
  • R 21 and R 22 are the same or different and independently of each other
  • R 1, R 2 and R 7 independently of one another represent hydrogen, fluorine, chlorine, bromine, iodine,
  • Trifluoromethoxymethyl trifluoromethoxyethyl, trifluoromethoxy-n-propyl,
  • NOR 23 R 23 OOC- (C 1 -C 6 ) -alkyl, aryl- (C 1 -C 6 ) -alkynyl, heteroaryl- (C 1 -C 6) -alkynyl, heterocyclyl- (C 1 -C 6) -alkynyl, trimethylsilylethynyl, triethylsilylethynyl, tris - (iso-propyl) silylethynyl, (Ca-Ce) - cycloalkyl, (C2-C6) alkynyl, aryl (C 2 -C 6) alkenyl, heteroaryl (C 2 -C 6) alkenyl, heterocyclyl - (C2-C6) alkenyl, (C3-C6) cycloalkyl (C2-C6) alkenyl, (Ci-C 6) - Alkylaminosulfonylamino
  • X 1 , X 2 , X 3 and X 4 are the same or different and are independently N
  • W is O (oxygen) or S (sulfur),
  • a 1 , A 2 , A 3 , A 4 and A 5 are the same or different and are independently N (nitrogen) or the group CR 7 , but in no case more than two N atoms are adjacent, and wherein R 7 in the group CR 7 has the same or different meanings as defined above,
  • R 3 is methyl, ethyl, n-propyl, 1-methylethyl, n-butyl, 1-methylpropyl, 2-
  • 2-ethylbutyl 1, 1, 2-trimethylpropyl, 1, 2,2-trimethylpropyl, 1-ethyl-1-methylpropyl and 1-ethyl-2-methylpropyl, cyanomethyl, cyanoethyl, cyano-n-propyl, cyano-n- butyl, ethenyl, 1-propenyl, 2-propenyl, 1-methyl-ethenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1-propenyl, 2-methyl-1-propenyl, 1-methyl 2-propenyl, 2-methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-ethyl-butenyl, 2-methyl-1-butenyl, 3-methyl-1-butenyl , 1-methyl-2-butenyl, 2-methyl-2-butenyl, 3-methyl-1-butenyl, 1-methyl-2-butenyl,
  • Trifluoromethoxymethyl trifluoromethoxyethyl, trifluoromethoxy-n-propyl,
  • R 5 and R 6 with the atom to which they are attached form a fully saturated or partially saturated, optionally interrupted by heteroatoms and optionally further substituted 5-7 membered ring,
  • R 1 and X 1 when X 1 is a group CR 2 , with the atoms to which they are attached, a fully saturated, partially saturated or completely form unsaturated, optionally interrupted by heteroatoms and optionally further substituted 5-7 membered ring,
  • X 1 and X 2 when both represent a group CR 2 , with the atoms to which they are attached form a fully saturated, partially saturated or fully unsaturated, optionally interrupted by heteroatoms and optionally further substituted 5-7 membered ring,
  • a 1 and A 2 when both represent a group CR 7 , with the atoms to which they are attached form a fully saturated, partially saturated or completely unsaturated, optionally interrupted by heteroatoms and optionally further substituted 5-7 membered ring,
  • a 2 and A 3 when both represent a group CR 7 , with the atoms to which they are attached form a fully saturated, partially saturated or completely unsaturated, optionally interrupted by heteroatoms and optionally further substituted 5-7 membered ring,
  • a 3 and A 4 when both represent a group CR 7 , with the atoms to which they are attached form a fully saturated, partially saturated or fully unsaturated, optionally interrupted by heteroatoms and optionally further substituted 5-7 membered ring,
  • R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 and R 19 are each the
  • R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 and R 19 independently of one another represent hydrogen, fluorine, methyl, ethyl, n-propyl, iso -propyl, n -butyl, iso -butyl, tert -butyl, ethenyl, 1 -propenyl, 2-propenyl, 1-methyl-ethenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1 -propenyl, 2-methyl-1-propenyl, 1-methyl-2-propenyl, 2-methyl-2-propenyl, ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl,
  • Trifluoromethoxymethyl trifluoromethoxyethyl, trifluoromethoxy-n-propyl,
  • Difluoromethoxy-n-propyl 2,2-difluoroethoxymethyl, 2,2-difluoroethoxyethyl, 2,2-difluoroethoxy-n-propyl, 2,2,2-trifluoroethoxymethyl, 2,2,2-trifluoroethoxyethyl, 2,2,2-trifluoroethoxy-n-propyl, pentafluoroethoxymethyl, pentafluoroethoxyethyl, pentafluoroethoxy-n-propyl, methylthiomethyl, methylthioethyl, ethylthioethyl, methylthio-n-propyl, ethylthio-n-propyl, trifluoromethylthiomethyl,
  • octan-2-yl bicyclo [3.2.2] nonan-2-yl, adamantan-1-yl, adamantan-2-yl, 1-ethylcyclopropyl, 2-methylcyclopropyl, 2,2-dimethylcyclopropyl, 2,3-dimethylcyclopropyl, 1, 1 !
  • Bromodifluoromethyl dichlorofluoromethyl, iododifluoromethyl, bromofluoromethyl, 1-fluoroethyl, 2-fluoroethyl, fluoromethyl, difluoromethyl, 2,2-difluoroethyl.
  • R 1, R 2 and R 7 independently of one another represent hydrogen, fluorine, chlorine, bromine, iodine,
  • R 23 is OOC- (C 1 -C 6 ) -alkyl, aryl- (C 1 -C 6 ) -alkynyl, heteroaryl- (C 1 -C 6 ) -alkynyl, heterocyclyl- (C 1 -C 6 ) -alkynyl , trimethylsilylethynyl, Triethylsilylethinyl, tris (iso-propyl) silylethynyl, cyclopropylethynyl, Cyclobutylethinyl, Cyclopentylethinyl, cyclohexylethynyl, aryl (C2-Cr>) alkenyl, heteroaryl (C2-C6) alkenyl, heterocyclyl (C2-C € >) - alkenyl, (C 1 -C 6) -alkylaminosulfonylamino, (C 1 -
  • X 1 , X 2 , X 3 and X 4 are the same or different and are independently N
  • W is O (oxygen) or S (sulfur), preferably O (oxygen),
  • a 1 , A 2 , A 3 , A 4 and A 5 are the same or different and are independently N (nitrogen) or the group CR 7 , but in no case more than two N atoms are adjacent, and wherein R 7 in the group CR 7 has the same or different meanings as defined above,
  • R 5 and R 6 independently of one another are hydrogen, methyl, ethyl, n-propyl, 1-methylethyl, n-butyl, 1-methylpropyl, 2-methylpropyl, 1, 1-dimethylethyl, n-pentyl, 1-methylbutyl, 2 Methylbutyl, 3-methylbutyl, 1, 1-dimethylpropyl, 1, 2-dimethylpropyl, 2,2-dimethylpropyl, 1-ethylpropyl, n-hexyl, cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl, cyclohexylmethyl, cyanomethyl,
  • R 5 and R 6 with the atom to which they are attached form a fully saturated or partially saturated, optionally interrupted by heteroatoms and optionally further substituted 5-7 membered ring,
  • R 1 and X 1 when X 1 is a group CR 2 , with the atoms to which they are attached, a fully saturated, partially saturated or completely
  • X 1 and X 2 when both represent a group CR 2 , with the atoms to which they belong
  • a 1 and A 2 when both represent a group CR 7 , with the atoms to which they belong
  • a 2 and A 3 when both represent a group CR 7 , with the atoms to which they are attached form a fully saturated, partially saturated or completely unsaturated, optionally interrupted by heteroatoms and optionally further substituted 5-7 membered ring,
  • a 3 and A 4 when both represent a group CR 7 , with the atoms to which they belong
  • R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 and R 19 independently of one another represent hydrogen, fluorine, methyl, ethyl, n-propyl, iso- Propyl, n-butyl, iso-butyl, t-butyl, ethenyl, 1-propenyl, 2-propenyl, 1-methyl-ethenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1-propenyl , 2-methyl-1-propenyl, 1-methyl-2-propenyl, 2-methyl-2-propenyl, ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-methyl 2-propynyl, trifluoromethyl, pentafluoroethyl, 1,1,2,2-t
  • Hydrogen methyl, ethyl, n -propyl, 1-methylethyl, n-butyl, 1-methylpropyl, 2-methylpropyl, 1, 1-dimethylethyl, n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1. 1-dimethylpropyl, 1, 2-dimethylpropyl.
  • Difluoromethoxy-n-propyl 2,2-difluoroethoxymethyl, 2,2-difluoroethoxyethyl, 2,2-difluoroethoxy-n-propyl, 2,2,2-trifluoroethoxymethyl, 2,2,2-trifluoromethoxyethyl, 2,2,2-trifluoroethoxy-n-propyl, pentafluoroethoxymethyl, pentafluoroethoxyethyl, pentafluoroethoxy-n-propyl, methylthiomethyl, methylthioethyl, ethylthioethyl, methylthio-n-propyl, ethylthio-n-propyl, trifluoromethylthiomethyl,
  • Methoxycarbonylmethyl ethoxycarbonylmethyl, n-propyloxycarbonylmethyl, isopropyloxycarbonylmethyl, tert-butyloxycarbonylmethyl,
  • Methoxycarbonylmethyl ethoxycarbonylmethyl, n-propyloxycarbonylmethyl, isopropyloxycarbonylmethyl, tert-butyloxycarbonylmethyl,
  • Allyloxycarbonylethyl, allyloxycarbonyl-n-propyl, aryl (d-C6) alkoxycarbonyl (C CeJ alkyl, hydroxycarbonyl (C Cr>) alkyl, heterocyclic, heterocyclyl (Ci-C6) - alkyl represents and R 24 is hydrogen, methyl, ethyl, n-propyl, 1-methylethyl, n-butyl, 1-methylpropyl, 2-methylpropyl, 1 .1 -dimethylethyl.
  • n-pentyl 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1, 1-dimethylpropyl, 1, 2-dimethylpropyl, 2.2-dimethylpropyl, 1-ethylpropyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 3 Methylpentyl, 4-methylpentyl, 1, 1-dimethylbutyl, 1, 2-dimethylbutyl, 1, 3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1, 1, 2-trimethylpropyl, 1, 2,2-trimethylpropyl, 1-ethyl-1-methylpropyl and 1-ethyl-2-methylpropyl, cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl, cyclohexylmethyl, cyanomethyl
  • R 1 , R 2 and R 7 independently of one another represent hydrogen, fluorine, chlorine, bromine, iodine,
  • X 1 , X 2 , X 3 and X 4 are the same or different and are independently N
  • W is O (oxygen) or S (sulfur), preferably O (oxygen),
  • a 1 , A 2 , A 3 , A 4 and A 5 are the same or different and are independently N (nitrogen) or the group CR 7 , but in no case more than two N atoms are adjacent, and wherein R 7 in the group CR 7 has the same or different meanings as defined above,
  • R 5 and R 6 independently of one another represent hydrogen, methyl, ethyl, n-propyl, 1-methylethyl, n-butyl, cyclopropylmethyl, cyclopropyl, cyclobutyl, cyclopentyl,
  • R 5 and R 6 with the atom to which they are attached form a fully saturated or partially saturated, optionally interrupted by heteroatoms and optionally further substituted 5-7 membered ring,
  • R 1 and X 1 when X 1 is a group CR 2 , with the atoms to which they are attached, a fully saturated, partially saturated or completely
  • X 1 and X 2 when both represent a group CR 2 , with the atoms to which they belong
  • a 1 and A 2 when both represent a group CR 7 , with the atoms to which they belong
  • a 2 and A 3 when both represent a group CR 7 , with the atoms to which they belong
  • a 3 and A 4 when both represent a group CR 7 , with the atoms to which they belong
  • Y is a bond or groups Y-1 to Y-2
  • R 8 , R 9 , R 10 , R 11 , R 12 and R 13 are independently hydrogen, methyl.
  • Residue definitions apply both to the end products of the general formula (I) and correspondingly to the starting material or preparation required in each case for the preparation Intermediates. These remainder definitions can be combined with one another as desired, ie also between the specified preferred ranges.
  • arylsulfonyl is optionally substituted phenylsulfonyl or optionally substituted polycyclic arylsulfonyl, here in particular optionally substituted naphthylsulfonyl, for example substituted by fluorine, chlorine, bromine, iodine, cyano, nitro, alkyl, haloalkyl, haloalkoxy, amino,
  • Alkylamino, alkylcarbonylamino, dialkylamino or alkoxy groups
  • cycloalkylsulfonyl alone or as part of a chemical group - is optionally substituted Cycloalkylsulfonyl, preferably having 3 to 6 carbon atoms such as cyclopropylsulfonyl, cyclobutylsulfonyl, cyclopentylsulfonyl or cyclohexylsulfonyl.
  • alkylsulfonyl by itself or as part of a chemical group, represents straight-chain or branched alkylsulfonyl, preferably of 1 to 8, or of 1 to 6 carbon atoms, e.g.
  • alkylsulfonyl such as methylsulfonyl, ethylsulfonyl, propylsulfonyl, 1-methylethylsulfonyl, butylsulfonyl, 1-methylpropylsulfonyl, 2-methylpropylsulfonyl, 1, 1-dimethylethylsulfonyl, pentylsulfonyl, 1-methylbutylsulfonyl, 2-methylbutylsulfonyl, 3-methyl-butylsulfonyl, 1, 1-dimethylpropylsulfonyl, 1, 2-dimethylpropylsulfonyl.
  • heteroarylsulfonyl is optionally substituted
  • Alkylcarbonylamino, dialkylamino or alkoxy groups Alkylcarbonylamino, dialkylamino or alkoxy groups.
  • alkylthio alone or as part of a chemical group - represents straight-chain or branched S-alkyl, preferably having 1 to 8, or having 1 to 6 carbon atoms, such as (C 1 -C 10) -, (C 1 -C 4) - or (C 1 -C 4 ) -alkylthio, for example (but not limited to) C 1 -C 6 -alkylthio, such as methylthio, ethylthio, propylthio, 1-methylethylthio, butylthio, 1-methylpropylthio, 2-methylpropylthio, 1, 1-dimethylethylthio, Pentylthio, 1-methylbutylthio, 2-methylbutylthio, 3-methylbutylthio, 1, 1-dimethylpropylthio, 1, 2-dimethylpropylthio, 2,2-dimethylpropylthio, 1-ethylpropylthio,
  • alkenylthio means an alkenyl radical bonded via a sulfur atom
  • alkynylthio means an alkynyl radical bonded via a sulfur atom
  • cycloalkylthio means a cycloalkyl radical bonded via a sulfur atom
  • cycloalkenylthio means a cycloalkenyl radical bonded via a sulfur atom
  • (ci-Ce) alkylsulfinyl such as methylsulfinyl, ethylsulfinyl, propylsulfinyl, 1-methylethylsulfinyl, butylsulfinyl, 1-methylpropylsulfinyl, 2-methylpropylsulfinyl, 1,1-dimethylethylsulfinyl, pentylsulfinyl, 1-methylbutylsulfinyl, 2- Methylbutylsulfinyl, 3-methylbutylsulfinyl, 1, 1-dimethylpropylsulfinyl, 1, 2-dimethylpropylsulfinyl, 2,2-dimethylpropylsulfinyl, 1-ethyl-propylsulfinyl, hexylsulfinyl, 1-methylpentylsulfinyl,
  • Alkoxy means an alkyl radical bonded through an oxygen atom, for example (but not limited to) (C 1 -C 6) -alkoxy, such as methoxy, ethoxy, propoxy, 1-methylethoxy, butoxy, 1-methylpropoxy, 2-ethylpropoxy , 1, 1-dimethylethoxy, pentoxy, 1-methylbutoxy, 2-methylbutoxy, 3-ethylbutoxy, 1, 1-dimethylpropoxy, 1, 2-dimethylpropoxy, 2,2-dimethylpropoxy, 1-ethylpropoxy, hexoxy, 1-methylpentoxy , 2-methylpentoxy, 3-methylpentoxy, 4-methylpentoxy, 1, 1-dimethylbutoxy, 1, 2-dimethylbutoxy, 1, 3-dimethylbutoxy, 2,2-dimethylbutoxy, 2,3-dimethylbutoxy, 3,3- Dimethylbutoxy, 1-ethylbutoxy, 2-ethylbutoxy, 1, 1, 2-trimethylpropoxy, 1, 2, 2-trimethylpropoxy, 1-e
  • Alkoxy-bonded alkynyl such as (C 2 -C 10) -, (Cz-Ce) - or (C 2 -C 4 ) -alkenoxy or (C 3 -C 10) -, (C 3 -C 6 ) - or (C 3 -C 4 ) alkynoxy.
  • Cycloalkyloxy means a cycloalkyl group bonded via an oxygen atom
  • cycloalkenyloxy means a cycloalkenyl radical bonded via an oxygen atom.
  • the number of C atoms refers to the Alkyirest in the alkylcarbonyl group.
  • the number of C atoms refers to the alkenyl or alkynyl radical in the alkenyl or alkynylcarbonyl group.
  • Alkyl radicals which are bonded to the skeleton via -O-C ( O) -, such as (C 1 -C 10) -, (d-Ce) - or (C 1 -C 4 ) -alkoxycarbonyl.
  • the number of C atoms refers to the alkyl radical in the alkoxycarbonyl group.
  • the number of C atoms refers to the alkenyl or alkynyl radical in the alkene or
  • alkynyloxycarbonyl alkynyloxycarbonyl.
  • the number of C atoms here refers to the alkyl radical in the alkylcarbonyloxy group.
  • the number of C atoms refers to the alkenyl or alkynyl radical in the alkenyl or alkynylcarbonyloxy group.
  • aryl means an optionally substituted mono-, bi- or polycyclic aromatic system having preferably 6 to 14, in particular 6 to 10 ring C atoms, for example phenyl, naphthyl, anthryl, phenanthrenyl, and the like, preferably phenyl.
  • optionally substituted aryl also includes polycyclic systems, such as tetrahydronaphthyl, indenyl, indanyl, fluorenyl, biphenylyl, where the binding site is on the aromatic system
  • Rule also includes the term "optionally substituted phenyl”.
  • Preferred aryl substituents here are, for example, hydrogen, halogen, alkyl, cycloalkyl, cycloalkylalkyl, cycloalkenyl, halocycloalkyl, alkenyl, alkynyl, aryl,
  • heterocyclic ring preferably contains 3 to 9 ring atoms, especially 3 to 6
  • Ring atoms, and one or more, preferably 1 to 4, in particular 1, 2 or 3 heteroatoms in the heterocyclic ring, preferably from the group N, O, and S, but not two oxygen atoms should be directly adjacent, as
  • 2- or 3-tetrahydrothiophenyl 2,3-dihydrothiophene-2- or 3- or 4- or 5-yl; 2,5-dihydrothiophene-2 or 3-yl; Tetrahydro-2H-thiopyran-2- or 3- or 4-yl; 3,4-dihydro-2H-thiopyran-2 or 3 or 4 or 5 or 6-yl; 3,6-dihydro-2H-thiopyran-2 or 3 or 4 or 5 or 6-yl; 2H-thiopyran-2 or 3 or 4 or 5 or 6-yl; 4H-thiopyran-2- or 3- or 4-yl.
  • Preferred 3- and 4-ring heterocycles are, for example, 1- or 2-aziridinyl, oxiranyl, thiiranyl, 1- or 2- or 3-azetidinyl, 2- or 3-oxetanyl, 2- or 3-thietanyl, 1, 3 -Dioxetan-2-yl. Further examples of
  • Heterocyclyl are a partially or fully hydrogenated heterocyclic radical having two heteroatoms from the group N, O and S, such as 1- or 2- or 3- or 4-pyrazolidinyl; 4,5-dihydro-3H-pyrazole-3 or 4 or 5-yl; 4,5-dihydro-1H-pyrazole-1 or 3 or 4 or 5-yl; 2,3-dihydro-1H-pyrazole-1 - or 2- or 3- or 4- or 5-yl; 1- or 2- or 3- or 4-imidazolidinyl; 2,3-dihydro-1H-imidazole-1 - or 2- or 3- or 4-yl; 2,5-dihydro-1H-imidazole-1 - or 2- or 4- or 5-yl; 4,5-dihydro-1H-imidazole-1 - or 2- or 4- or 5-yl; Hexahydropyridazine-1 or 2- or 3- or 4-yl; 1,2,3,4-tetrahydropyridazine-1 - or 5-
  • heterocyclyl are a partially or fully hydrogenated heterocyclic radical having 3 heteroatoms from the group consisting of N, O and S, such as 1,2,2-dioxazolidin-2- or 3- or 5-yl; 1,2,2-dioxazol-3 or 5-yl; 1,2,2-dioxazinan-2- or -3- or 5- or 6-yl; 5,6-dihydro-1,2,2,2-dioxazine-3- or 5- or 6-yl; 1, 4.2-dioxazine-3- or 5- or 6-yl; 1, 4,2-Dioxazepan-2 or 3 or 5 or
  • heterocycles listed above are preferably, for example, hydrogen, halogen, alkyl, haloalkyl, hydroxy, alkoxy, cycloalkoxy, aryloxy, alkoxyalkyl, Alkoxyalkoxy, cycloalkyl, halocycloalkyl, aryl, arylalkyl, heteroaryl, heterocyclyl, alkenyl, alkylcarbonyl, cycloalkylcarbonyl, arylcarbonyl, heteroarylcarbonyl,
  • Suitable substituents for a substituted heterocyclic radical are the substituents mentioned below, in addition to oxo and thioxo.
  • Oxo group as a substituent on a ring C atom then means, for example, a carbonyl group in the heterocyclic ring.
  • lactones and lactams are preferably also included.
  • the oxo group can also occur at the hetero ring atoms, which can exist in different oxidation states, for example at N and S, and then form, for example, the divalent groups N (O), S (O) (also SO for short) and S (O) 2 (also short S0 2 ) in the heterocyclic ring.
  • N (O), S (O) (also SO for short) and S (O) 2 also short S0 2
  • both enantiomers are included.
  • heteroaryl is heteroaromatic
  • Compounds ie fully unsaturated aromatic heterocyclic Compounds, preferably for 5- to 7-membered rings having 1 to 4, preferably 1 or 2 identical or different heteroatoms, preferably O, S or N.
  • Heteroaryls of the invention are, for example, 1H-pyrrol-1-yl; 1H-pyrrol-2-yl; 1H-pyrrol-3-yl; Furan-2-yl; Furan-3-yl; Thien-2-yl; Thien-3-yl, 1H-imidazole-1-yl; 1 H-imidazol-2-yl; 1 H -imidazol-4-yl; 1 H -imidazol-5-yl; 1H-pyrazole-1-yl; 1H-pyrazol-3-yl; 1H-pyrazol-4-yl; 1 H-pyrazol-5-yl, 1 H-1, 2,3-triazol-1-yl, 1 H-1, 2,3-triazol-4-yl, 1 H-1, 2,3-triazole-5 yl, 2H-1, 2,3-triazol-2-yl, 2H-1, 2,3-triazol-4-yl, 1H-1, 2,4-triazol-1-y
  • 2,3-oxadiazol-4-yl, 1, 2.3-oxadiazol-5-yl 1, 2,5-oxadiazol-3-yl, azepinyl, pyridin-2-yl, pyridin-3-yl, pyridin-4-yl, pyrazine-2-yl, pyrazine-3-yl, pyrimidin-2-yl, Pyrimidin-4-yl, pyrimidin-5-yl, pyridazin-3-yl, pyridazin-4-yl, 1, 3,5-triazin-2-yl, 1, 2,4-triazin-3-yl, 1, 2,4-triazin-5-yl, 1, 2,4-triazin-6-yl, 1, 2,3-triazin-4-yl, 1, 2,3-triazin-5-yl, 1, 2,4-, 1 3,2-, 1, 3,6- and 1, 2,6-oxazinyl, isoxazol-3-yl, isoxazol-4-y
  • heteroaryl groups according to the invention may furthermore be substituted by one or more identical or different radicals. If two adjacent carbon atoms are part of another aromatic ring, these are annelated heteroaromatic systems, such as benzo-fused or multiply fused heteroaromatics.
  • quinolines for example quinolin-2-yl, quinolin-3-yl, quinolin-4-yl, quinolin-5-yl, quinolin-6-yl, quinolin-7-yl, quinolin-8-yl
  • Isoquinolines e.g., isoquinolin-1-yl, isoquinolin-3-yl, isoquinolin-4-yl, isoquinolin-5-yl, isoquinolin-6-yl, isoquinolin-7-yl, isoquinolin-8-yl
  • quinoxaline for example quinolin-2-yl, quinolin-3-yl, quinolin-4-yl, quinolin-5-yl, quinolin-6-yl, quinolin-7-yl, quinolin-8-yl
  • quinoxaline e.g., isoquinolin-1-yl, isoquinolin-3-yl, isoquinolin-4-yl, isoquinolin-5-
  • quinazoline cinnoline; 1,5-naphthyridine; 1,6-naphthyridine; 1,7-naphthyridine; 1,8-naphthyridine; 2,6-naphthyridine; 2,7-naphthyridine; phthalazine; Pyridopyrazine;
  • heteroaryl are also 5- or 6-membered benzo-fused rings from the group 1H-indol-1-yl, 1H-indol-2-yl, 1H-indol-3-yl, 1H-indole-4 yl, 1H-indol-5-yl, 1H-indol-6-yl, 1H-indol-7-yl, 1-benzofuran-2-yl, 1-benzofuran-3-yl, 1-benzofuran-4 -yl, 1-benzofuran-5-yl, 1-benzofuran-6-yl, 1-benzofuran-7-yl, 1-benzothiophen-2-yl, 1-benzothiophen-3-yl, 1-benzothiophen-4-yl , 1-benzothiophene-5-yl, 1-benzothiophene
  • halogen means, for example, fluorine, chlorine, bromine or iodine.
  • halogen means, for example, a fluorine, chlorine, bromine or iodine atom.
  • alkyl means a straight-chain or branched, open-chain, saturated hydrocarbon radical which is optionally monosubstituted or polysubstituted and is referred to in the latter case as “substituted alkyl”.
  • Substituents are halogen atoms, alkoxy, haloalkoxy, cyano, alkylthio,
  • Haloalkylthio, amino or nitro groups particularly preferred are methoxy, methyl, fluoroalkyl, cyano, nitro, fluorine, chlorine, bromine or iodine.
  • the prefix "bis" also includes the combination of different alkyl radicals, for example, methyl (ethyl) or
  • Polyhaloalkyl such. B. CH2CHFCI, CF2CCIFH, CF 2 CBrFH, CH2CF3;
  • perhaloalkyl also encompasses the term perfluoroalkyl.
  • Partially fluorinated alkyl means a straight-chain or branched, saturated
  • Hydrocarbon which is mono- or polysubstituted by fluorine, wherein the corresponding fluorine atoms as substituents on one or more different carbon atoms of the straight-chain or branched hydrocarbon chain may be such.
  • B. CHFCH 3 , CH 2 CH 2 F, CH 2 CH 2 CF 3 , CHF 2 , CH 2 F, CHFCF 2 CF 3
  • Partially fluorinated haloalkyl means a straight-chain or branched, saturated hydrocarbon which is substituted by various halogen atoms having at least one fluorine atom , all other possibly existing ones
  • Halogen atoms are selected from the group fluorine, chlorine or bromine, iodine.
  • the corresponding halogen atoms may be present as substituents on one or more different carbon atoms of the straight-chain or branched hydrocarbon chain.
  • Partially fluorinated haloalkyl also includes the
  • Haloalkoxy is, for example, OCF 3 , OCHF 2 , OCH 2 F, OCF 2 CF 3 , OCH 2 CF 3 and OCH 2 CH 2 Cl;
  • (Ci-C 4 ) -Alky exemplified here means a
  • Carbon atoms corresponding to the range for C atoms, d. H. includes the radicals methyl, ethyl, 1-propyl, 2-propyl, 1-butyl, 2-butyl, 2-methylpropyl or tert-butyl.
  • General alkyl radicals having a larger specified range of carbon atoms eg. B. "(d-Ce) - alkyl”, accordingly also include straight-chain or branched alkyl radicals having a larger number of C atoms, d. H. according to example, the alkyl radicals with 5 and 6 carbon atoms.
  • hydrocarbon radicals such as alkyl, alkenyl and alkynyl radicals, even in assembled radicals, are lower
  • Alkyl radicals including in the assembled radicals such as alkoxy, haloalkyl, etc., mean, for example, methyl, ethyl, n- or i-propyl, n-, i-, t- or 2-butyl, pentyls, hexyls, such as n-hexyl, i -Hexyl and 1, 3-dimethylbutyl, heptyls such as n-heptyl, 1-methylhexyl and 1, 4-dimethylpentyl; Alkenyl and alkynyl radicals have the meaning of the possible unsaturated radicals corresponding to the Aikylresten, wherein at least one double bond or triple bond is included. Preference is given to radicals having a double bond or triple bond.
  • alkenyl also includes straight-chain or branched open-chain hydrocarbon radicals having more than one double bond, such as 1,3-butadienyl and 1,4-pentadienyl, but also allenyl or cumulenyl radicals having one or more cumulative double bonds, such as For example, allenyl (1,2-propadienyl), 1, 2-butadienyl and 1, 2, 3-pentatrienyl.
  • Alkenyl is, for example, vinyl, which may optionally be substituted by further alkyl radicals, for example (but not limited to) (C2 -Cr>) - alkenyl such as ethenyl, 1-propenyl, 2-propenyl, 1 -Methylethenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1 -propenyl, 2-methyl-1 -propenyl, 1 -Methyl-2-propenyl, 2-methyl-2-propenenyl, 2-
  • alkynyl in particular also includes straight-chain or branched open-chain hydrocarbon radicals having more than one triple bond or else having one or more triple bonds and one or more double bonds, for example 1,3-butatrienyl or 3-penten-1-yn-1 -yl.
  • (C2-Ce) alkynyl means, for example, ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-methyl-2-propynyl, 1-pentynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, 1-methyl-2-butynyl, 1-methyl-3 butinyl, 2-methyl-3-butynyl, 3-methyl-1-butynyl, 1, 1-dimethyl-2-propynyl, 1-ethyl-2-propynyl, 1-hexynyl, 2-hexynyl, 3-hexynyl, 4- Hexynyl, 5-hexynyl, 1-ethyl-2-pentynyl, 1-methyl-3-pentynyl, 1-methyl-4-pentynyl, 2-methyl-3-pentynyl, 2-e
  • cycloalkyl means a carbocyclic, saturated ring system preferably having 3-8 ring C atoms, eg cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl, which is optionally further substituted, preferably by hydrogen, alkyl, alkoxy, cyano, nitro, alkylthio , Haloalkylthio, halogen, alkenyl, alkynyl,
  • Haloalkyl ino, alkylamino, bisalkylamino, alkocycarbonyl, hydroxycarbonyl, arylalkoxycarbonyl, aminocarbonyl, alkylaminocarbonyl, cycloalkylaminocarbonyl.
  • substituents having a double bond on
  • Cycloalkyl, z As an alkylidene group such as methylidene, are included.
  • optionally substituted cycloalkyl it also encompasses polycyclic aliphatic systems such as bicyclo [1, 1] -butan-1-yl, bicyclo [1, 1] -butan-2-yl, bicyclo [2.1.0] pentane 1-yl, bicyclo [1 .1 .1] pentan-1-yl, bicyclo [2.1.0] pentan-2-yl,
  • (C 3 -C 7) -cycloalkyl means a
  • substituted cycloalkyl are also spirocyclic aliphatic
  • Cycloalkenyl means a carbocyclic, non-aromatic, partially unsaturated ring system preferably having 4-8 C atoms, eg 1-cyclobutenyl, 2-cyclobutenyl, 1-cyclopentenyl, 2-cyclopentenyl, 3-cyclopentenyl, or 1-cyclohexenyl, 2- Cyclohexenyl, 3-cyclohexenyl, 1, 3-cyclohexadienyl or 1, 4-cyclohexadienyl, wherein also substituents having a double bond on the cycloalkenyl, z. Legs
  • Alkylidene group such as methylidene, are included. In case of if necessary
  • Cycloalkylidene means a carbocyclic radical which is bonded via a double bond. If the compounds can form tautomers by hydrogen shift which would not be structurally formally recognized by the formula (I), these tautomers are nevertheless encompassed by the definition of the compounds of the formula (I) according to the invention, unless a particular tautomer is the subject of
  • the compounds of the general formula (I) can exist as stereoisomers.
  • the possible stereoisomers defined by their specific spatial form, such as enantiomers, diastereomers, Z and E isomers, are all encompassed by the formula (I). If, for example, one or more alkenyl groups are present, diastereomers (Z and E isomers) can occur. For example, if one or more asymmetric carbon atoms are present, enantiomers and diastereomers may occur.
  • Stereoisomers can be obtained from the resulting mixtures in the preparation by conventional separation methods. The chromatographic separation can be used both on an analytical scale for
  • stereoisomers can be prepared by using stereoselective Reactions can be selectively prepared using optically active starting materials and / or auxiliaries.
  • the invention thus also relates to all stereoisomers which comprises the general formula (I) but are not specified with their specific stereoform, and mixtures thereof.
  • aryl and heteroarylcarboxylic acid hydrazides of general formula (I) can be prepared by known methods (see Tetrahedron 2003, 59, 7733, J. Organomet Chem 2001, 617, J. Org. Chem. 1962, 27, 2640; IT2000M I0292; J. Heterocyclic Chem. 1981, 18, 319).
  • Various literature known See Tetrahedron 2003, 59, 7733, J. Organomet Chem 2001, 617, J. Org. Chem. 1962, 27, 2640; IT2000M I0292; J. Heterocyclic Chem. 1981, 18, 319).
  • Heteroarylcarbonchure chloride if this is not commercially available, and this then with a corresponding '' disubstituted hydrazine using a suitable base (eg triethylamine (EtaN)), di-iso-propylethylamine) in a suitable polar-aproti see solvent (For example, tetrahydrofuran (THF) or dichloromethane (DCM)) to an aryl or Heteroarylcarbonklazid (A).
  • a suitable base eg triethylamine (EtaN)
  • EtaN triethylamine
  • DCM dichloromethane
  • Heteroarylcarboxylic acid hydrazide (A) can also be prepared by direct reaction with suitable reagents (eg 1-hydroxybenzotriazole (HOBt), N- (3-dimethylaminopropyl) -N'-ethylcarbodiimide hydrochloride (EDC) or 2,4,6-tripropyl).
  • suitable reagents eg 1-hydroxybenzotriazole (HOBt), N- (3-dimethylaminopropyl) -N'-ethylcarbodiimide hydrochloride (EDC) or 2,4,6-tripropyl.
  • EDC N- (3-dimethylaminopropyl) -N'-ethylcarbodiimide hydrochloride
  • T3P 1, 3,5,2,4,6-trioxatriphosphorinane-2,4,6-trioxide
  • T3P 1, 3,5,2,4,6-trioxatriphosphorinane-2,4,6-tri
  • optionally further substituted aryl or heteroarylcarboxylic acid with a 1, 1 '-disubstituted hydrazine in a suitable polar aprotic solvent eg, dichloromethane, acetonitrile or tetrahydrofuran
  • a suitable polar aprotic solvent eg, dichloromethane, acetonitrile or tetrahydrofuran
  • Arylalkyihalogenids or Heteroaryialkyihalogenids and a suitable base eg, sodium hydride or triethylamine (EtaN)
  • a suitable solvent eg, tetrahydrofuran, ⁇ , ⁇ -dimethylformamide (DMF) or dichloromethane
  • R ⁇ R 3 , R 4 , R 5 and R 6 and A 1 , A 2 , A 3 , A 4 , A 5 , X 1 , X 2 , X 3 and Y have the meanings defined above and W is exemplified, but not limiting, in the following Scheme 1 for oxygen.
  • Substituted aryl- or heteroarylcarboxylic acid hydrazides of the general formula (I) can alternatively also be prepared via the reduction of hydrazones (B), provided that the radical R 6 is hydrogen.
  • an appropriately substituted aldehyde or an appropriately substituted ketone is reacted with a corresponding 1, 1 '-disubstituted hydrazine to Hydrazon fundamentalhand (B), then with the aid of a suitable reagent (eg., Triethylsilan, BHa, sodium cyanoborohydride, sodium borohydride or Hydrogen on palladium / carbon) in a suitable solvent into the corresponding hydrazine intermediate (C), which in the final reaction step with an optionally further substituted aryl or heteroarylcarbonyl chloride in a suitable polar aprotic solvent (eg., Tetra hydrofuran or dichloromethane in a substituted aryl or heteroarylcarbox
  • Unsymmetrically substituted aryl- or heteroaryl-carboxylic acid hydrazides (I) on the second hydrazide nitrogen (NR 3 R 4 ) can also be prepared using tert-butyl-1-methylhydrazinecarboxylate (Scheme 3). The person in question
  • aryl- or heteroarylcarboxylic acid is thereby converted into the corresponding aryl- or -formane with the aid of a suitable chlorinating agent (eg oxalyl chloride or thionyl chloride) in an aprotic solvent (for example toluene)
  • a suitable chlorinating agent eg oxalyl chloride or thionyl chloride
  • an aprotic solvent for example toluene
  • Heteroarylcarbonklarechlorid transferred, if this is not commercially available, and this with tert-butyl-1 -methylhydrazincarboxylat using a suitable base (eg triethylamine (EtaN)), di-iso-propylethylamine) in a suitable polar-aproti see solvent (eg Tetrahydrofuran (THF) or
  • Heteroarylcarboxylic acid hydrazide (D) can also be prepared by direct reaction with suitable reagents (eg 1-hydroxybenzotriazole (HOBt), N- (3-dimethylaminopropyl) -N'-ethylcarbodiimide hydrochloride (EDC) or 2.4.6-tripropyl-1, 3,5,2,4,6-trioxatriphosphorinane-2,4,6-trioxide (T3P) together with a suitable base such as triethylamine or di-iso-propylethylamine) mediated coupling of a suitable reagents (eg 1-hydroxybenzotriazole (HOBt), N- (3-dimethylaminopropyl) -N'-ethylcarbodiimide hydrochloride (EDC) or 2.4.6-tripropyl-1, 3,5,2,4,6-trioxatriphosphorinane-2,4,6-trioxide (T3P) together with
  • Heteroarylalkyl halide and a suitable base e.g., sodium hydride or triethylamine (EtaN)
  • a suitable solvent e.g., tetrahydrofuran, N, N-dimethylformamide (DMF) or dichloromethane
  • Heteroarylcarbonsaurehydrazid (If) transferred (Scheme 3).
  • the tert-butyloxycarbonyl protecting group can then be removed by treatment of the substituted aryl or
  • Heteroarylcarboxylic acid hydrazide (If) with a suitable acid e.g.
  • Trifluoroacetic acid in a polar aprotic solvent (e.g., dichloromethane) to the N-mono-substituted aryl or heteroarylcarboxylic hydrazide (ie).
  • a suitable alkyl halide e.g., ethyl iodide in Scheme 3 below
  • a suitable base e.g., sodium hydride or potassium carbonate
  • Pat an inventive optionally further substituted aryl or Heteroarylcarbonklarehydrazid by way of example but not limiting (Ib) in the following Scheme 3, be converted with unsymmetrical groups on the second hydrazide nitrogen.
  • R ⁇ R 5 and R 6 and A 1, A 2, A 3, A 4, A 5, X 1, X 2, X 3 and Y have the previously defined
  • R 3 is exemplary, but not limiting, in the following Scheme 3 for methyl and W is exemplary, but not limiting, for oxygen.
  • N-Boc-protected aryl or heteroarylcarboxylic acid hydrazides (ff) can also be prepared starting from a reaction of an appropriately substituted arylalkyl halide or heteroarylayl halide with tert-butyl-1-methylhydrazinecarboxylate using a suitable base in a suitable polar aprotic solvent (eg dichloromethane , Acetonitrile or tetrahydrofuran).
  • a suitable polar aprotic solvent eg dichloromethane , Acetonitrile or tetrahydrofuran.
  • Example numbers correspond to the numbers given in Tables A1 to H1 below.
  • N ', N'-dimethyl-2- (trifluoromethyl) benzohydrazide as a colorless solid (405 mg, 69% of theory).
  • H-NMR 400 MHz, CDC ⁇ , ppm
  • N ', N'-Dimethyl-2- (trifluoromethyl) benzohydrazide 150 mg, 0.65 mmol was dissolved in abs.
  • Tetra hydrofu ran (5 ml) under argon and treated at room temperature with sodium hydride (28 mg, 0.71 mmol, 60% dispersion). After stirring at room temperature for 30 minutes, addition of 2- (chloromethyl) -3-methylpyridine (91 mg, 0.65 mmol) was performed, and the resulting reaction mixture was allowed to stand for 3 hours
  • N ', N'-Dimethyl-2- (trifluoromethyl) benzohydrazide (350 mg, 1.51 mmol) was dissolved in abs. N, N-dimethylformamide (5 ml) under argon and at room temperature with
  • N'.N'-Dimethyl-2- (trifluoromethyl) benzohydrazide 100 mg, 0.43 mmol was dissolved in a mixture of abs. Acetone and abs. N.N-dimethylformamide (20: 1, 10.5 ml) was dissolved under argon and treated at room temperature with potassium carbonate (1 19 mg, 0.86 mmol). After stirring at room temperature for 30 minutes, 2-chloro-5- (chloromethyl) pyridine (84 mg, 0.52 mmol) was added, and the resulting reaction mixture was stirred at reflux for six hours. After cooling to room temperature, sat. Sodium bicarbonate solution, water and dichloromethane added. The aqueous phase was repeatedly intensively with
  • N ', N'-Dimethyl-2- (trifluoromethyl) benzohydrazide 150 mg, 0.65 mmol was dissolved in abs. Dissolved tetrahydrofuran (7 ml) under argon and at room temperature with sodium hydride (28 mg, 0.71 mmol, 60% dispersion). After stirring at room temperature for 30 minutes, addition of 3- (chloromethyl) isoquinoline (15 mg, 0.65 mmol) was performed, and the resulting reaction mixture was stirred at reflux for two and a half hours. After cooling to room temperature, sat. Sodium bicarbonate solution, water and dichloromethane added.
  • N'.N'-Dimethyl-2- (trifluoromethyl) benzohydrazide 200 mg, 0.86 mmol was dissolved in abs. Tetra hydrofu ran (10 ml) under argon and treated at room temperature with sodium hydride (38 mg, 0.95 mmol, 60% dispersion). After stirring for 30 minutes
  • N- [3- (4-chlorophenyl) propyl] -N ⁇ N'-dimethyl-2- (trifluoromethyl) benzohydrazide was isolated as a viscous oil (137 mg, 41% of theory).
  • H NMR 400 MHz, CDC 6, ppm) 7.62 (m, 1H), 7.53 (m, 1H), 7.47 (m, 1H), 7.37 (m, 1H), 7.28 (d, 2H) , 7.14 (d, 2H), 3.76-3.71 (m, 2H), 3.40 (s, 6H), 2.70 (m, 2H, 2.19 (m, 2H).
  • N'.N'-Dimethyl-2- (trifluoromethyl) benzohydrazide 300mg, 1.29mmol was dissolved in abs. Dissolve N, N-dimethylformamide (10 mL) under argon and add sodium hydride (62 mg, 1.55 mmol, 60% dispersion) at room temperature. After stirring at room temperature for 30 minutes, addition of 3- (2,6-difluorophenyl) propyl bromide (304 mg, 1.29 mmol) was performed and the resulting reaction mixture was stirred at reflux for two and a half hours. After cooling to room temperature, sat. Sodium bicarbonate solution, water and dichloromethane added. The aqueous phase was repeatedly intensively with
  • N'.N'-diethyl-2- (trifluoromethyl) benzohydrazide was isolated as a colorless solid (900 mg, 84% of theory).
  • H NMR 400 MHz, CDCl 3 O, ppm) 7.71 (m, 1H), 7.61-7.54 (m, 3H), 6.23 (br.s, 1H, NH), 3.14 (m, 2H), 2.89 (m, 2H), 1 .33 (m, 3H), 1 .21 (m, 3H).
  • N ', N'-Diethyl-2- (trifluoromethyl) benzohydrazide 150 mg, 0.58 mmol was dissolved in abs.
  • N'.N'-Diethyl 2- (trifluoromethyl) benzohydrazide 300 mg, 1.15 mmol was dissolved in abs. Dissolved ethanol (10 ml) under argon and at room temperature with potassium carbonate (239 mg, 1 .73 mmol) was added. After stirring at room temperature for 15 minutes, the addition of 2,3-dichlorobenzyl chloride (332 mg, 1 .36 mmol) was performed and the resulting reaction mixture was stirred at reflux for 8 hours. After cooling to room temperature, sat. Sodium bicarbonate solution, water and dichloromethane added.
  • the reaction mixture was stirred at a temperature of 50 ° C for one and one-half hours. After cooling to room temperature, sat.
  • N ', N'-Dimethyl-4- (1, 2,3-benzothiadiazolyl) -carboxylic acid hydrazide 120 mg, 0.54 mmol was dissolved in abs.
  • Tetrahydrofuran (5 ml) was dissolved under argon and treated at room temperature with sodium hydride (43 mg, 1 .08 mmol, 60% pure). After stirring at room temperature for 30 minutes, the addition of 3-picolyl chloride hydrochloride (93 mg, 0.57 mmol) and the resulting
  • N ', N'-Dimethyl-4- (1, 2,3-benzothiadiazolyl) -carboxylic acid hydrazide (1 10 mg, 0.49 mmol) was dissolved in abs. Tetrahydrofuran (4 ml) was dissolved under argon and treated at room temperature with sodium hydride (24 mg, 0.59 mmol, 60% pure). After stirring at room temperature for 30 minutes, 2-chloromethylbenzonitrile (79 mg, 0.52 mmol) was added, and the resulting reaction mixture was stirred under reflux conditions for two and a half hours. After cooling to room temperature, sat. Sodium bicarbonate solution, water and dichloromethane added.
  • N ', N'-diethyl-4- (trifluoromethyl) -nicotinohydrazid be isolated in the form of a colorless solid (880 mg, 64% of theory).
  • H-NMR 400 MHz, de-DMSO ⁇ , ppm
  • N ', N'-Diethyl-4- (trifluoromethyl) -nicotinohydrazide (1 10 mg, 0.42 mmol) was dissolved in abs. Tetrahydrofuran (10 ml) was dissolved under argon and at room temperature with
  • 6-chlorodifluoromicotinic acid 500 mg, 2.41 mmol was heated in a
  • 3,6-Dichloropyridazine-4-carboxylic acid 700 mg, 3.63 mmol was dissolved in abs. Dissolve dichloromethane (10 ml) and add triethylamine (0.33 ml, 1.52 mmol). After stirring at room temperature for 5 minutes, NN-dimethylhydrazine (0.33 ml, 4.35 mmol) and 2,4,6-tripropyl-1, 3,5,2,4,6-trioxatriphosphorinane-2,4,6- were added. trioxide (3.24 ml, 5.44 mmol, 50% solution in tetrahydrofuran). The resulting reaction mixture was stirred for 30 minutes at room temperature and then washed with water, sat.
  • Tetra hydrofu ran (4 ml) under argon and treated at room temperature with sodium hydride (28 mg, 0.69 mmol, 60% purity). After stirring for 15 minutes
  • a 2 , A 3 , A 4 , A 5 correspond to the definitions (Nos 1 to 681, corresponding to compounds A9-1 to A9-681) in Table 1 above.
  • A1 1.
  • Compounds A1 1 -1 to A1 1 -681 of the general formula (Ia7) in which R 5 , R 6 , Y, A 1 , A 2 , A 3 , A 4 , A 5 are as defined (Nos 1 to 681; A1 1 -1 to A1 1 -681) in Table 1 above.
  • a 2 , A 3 , A 4 , A 5 are the definitions (Nos 1 to 681, corresponding to compounds B6-1 to B6-681) in the above
  • a 2 , A 3 , A 4 , A 5 correspond to the definitions (Nos 1 to 681, corresponding to compounds B7-1 to B7-681) in Table 1 above.
  • NMR peak list method The H-NMR data of selected examples are noted in terms of H-NMR peak lists. For each signal peak, first the ⁇ value in ppm and then the signal intensity in round brackets are listed. The ⁇ -value signal intensity number pairs of different signal peaks are listed separated by semicolons. The peak list of a corresponding example therefore has the form: ⁇ (intensity ⁇ ; ⁇ 2 (intensity.2);; ⁇ , (intensity *;; ⁇ ⁇ (intensity);
  • the intensity of sharp signals correlates with the height of the signals in a printed example of an NMR spectrum in cm and shows the true ratios of the signal intensities. For broad signals, multiple peaks or the center of the signal and their relative intensity can be shown compared to the most intense signal in the spectrum.
  • Solvent peaks for example peaks of DMSO in DMSO-de and the peak of water, which are usually of high intensity on average.
  • Impurities usually have on average a lower intensity than the peaks of the target compounds (for example with a purity of> 90%). Such stereoisomers and / or impurities may be typical of each

Abstract

L'invention concerne des hydrazides substitués d'acide arylcarboxylique et hétéroarylcarboxylique de formule générale (I) ou leurs sels, les restes de la formule (I) répondant aux définitions mentionnées dans la description, pour augmenter la tolérance des plantes au stress abiotique et pour renforcer la croissance des plantes et/ou pour augmenter le rendement des plantes.
EP16738448.6A 2015-07-17 2016-07-14 Hydrazides substitués d'acide arylcarboxylique et hétéroarylcarboxylique ou leurs sels, et leur utilisation pour accroître la tolérance au stress chez les végétaux Withdrawn EP3325446A1 (fr)

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CN111170983B (zh) * 2019-12-26 2021-07-09 中国农业大学 一种苄硫基乙酰胺类化合物及其制备方法与应用
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BR112018000989A2 (pt) 2018-09-11
JP2018526338A (ja) 2018-09-13
UY36800A (es) 2017-01-31

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