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EP1228050A1 - Azadioxacycloalcenes - Google Patents

Azadioxacycloalcenes

Info

Publication number
EP1228050A1
EP1228050A1 EP00972907A EP00972907A EP1228050A1 EP 1228050 A1 EP1228050 A1 EP 1228050A1 EP 00972907 A EP00972907 A EP 00972907A EP 00972907 A EP00972907 A EP 00972907A EP 1228050 A1 EP1228050 A1 EP 1228050A1
Authority
EP
European Patent Office
Prior art keywords
alkyl
methyl
compounds
halogen
substituents
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Withdrawn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
EP00972907A
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German (de)
English (en)
Inventor
Markus Gewehr
Hubert Sauter
Andreas Gypser
Wassilios Grammenos
Jordi Tormo I Blasco
Arne Ptock
Bernd Müller
Oliver Cullmann
Thomas Grote
Eberhard Ammermann
Siegfried Strathmann
Gisela Lorenz
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.)
BASF SE
Original Assignee
BASF SE
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Publication of EP1228050A1 publication Critical patent/EP1228050A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D273/00—Heterocyclic compounds containing rings having nitrogen and oxygen atoms as the only ring hetero atoms, not provided for by groups C07D261/00 - C07D271/00
    • 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
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/88—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms six-membered rings with three ring hetero atoms

Definitions

  • the present invention relates to azadioxacycloalkenes of the general formula I,
  • R 2 C ⁇ -C 4 -alkyl, C 4 haloalkyl, C 3 -C 4 alkenyl, C 3 -C 4 -Halo- genalkenyl, C 3 -C 4 -alkynyl or C 3 -C 4 haloalkynyl;
  • C ⁇ -C 4 alkyl C 2 -C 6 alkenyloxy-C ⁇ -C 4 alkyl, C 2 -C 6 -Halogenalke- nyloxy-C ⁇ -C 4 alkyl, C 2 -C 6 alkynyloxy-C ⁇ -C alkyl, C 2 -C 6 haloalkynyloxy-C 1 -C 4 alkyl,
  • C ⁇ -C4 alkyl aryl-C 2 -C 4 alkenyl, aryl-C 2 -C 4 -alkynyl, aryloxy C ⁇ -C 4 alkyl, heterocyclyl containing from 5 to 8 ring atoms and 1,2,3 or 4 heteroatoms selected from nitrogen, oxygen and sulfur,
  • R 5 which are the same or different and which are selected from: halogen, cyano, nitro, hydroxy, amino, formyl, carboxyl, aminocarbonyl, amino-thiocarbonyl, Ci-C ö alkyl, -C-C 6 -Halogenalkyl, C -C 6 -alkenyl, C 2 -C 4 -haloalkenyl, C 2 -C 6 -alkynyl or C 2 -C 6 -haloalkynyl, -C-C 6 -alkoxy, -C-C 6 -haloalkoxy, C ⁇ - C 6 alkylcarbonyl, C ⁇ -C 6 haloalkylcarbonyl, Ci-C ö haloalkylcarbonyloxy, Ci-C ⁇ -alkylcarbonyloxy, C ⁇ -C 6 -alkoxycarbonyl, Ci-C ⁇ -haloalkoxycarbonyl, C ⁇ -C 6 -C 6
  • two substituents R 5 bonded to adjacent ring atoms can also form a bridge which contains three or four members selected from the group: 3 or 4 carbon atoms, 2 to 3 carbon atoms and 1 or 2 nitrogen, oxygen and / or sulfur atoms, these being Bridge together with the ring to which it is attached can form a partially unsaturated or aromatic radical and furthermore the carbon atoms of the bridge can be partially or completely substituted by halogen atoms or methyl groups;
  • R 4 nitro, cyano, halogen, -CC 6 alkyl, Ci-C ß -haloalkyl or
  • n is greater than 1
  • a bridge bonded to two adjacent ring atoms which has three or four members selected from the group: 3 or 4 carbon atoms, 2 or 3 carbon atoms and 1 or 2 nitrogen, oxygen and / or Contains sulfur atoms, this bridge together with the ring to which it is attached can form a partially unsaturated or aromatic radical and furthermore the carbon atoms of the bridge can be partially or completely substituted by halogen atoms or methyl groups;
  • n 0, 1, 2, 3 or 4, where the substituents R 4 can be different if n is greater than 1;
  • R 6 is halogen, C ⁇ -C 4 -alkyl, C alkylthio, C 1 -C 4 -Alkylanu.no or di-C ⁇ -C alkylamino, and means 4 means unsubstituted or by R 7 mono- or disubstituted -CC 3 alkylene, wherein
  • R 7 is halogen, cyano, C 4 -alkyl, C 4 haloalkyl, C 2 -C 4 alkenyl, C 2 -C 4 haloalkenyl, C 2 -C 4 alkynyl or C 2 -C 4 -Halogenalkynyl, -C-C 4 -alkoxy, C ⁇ -C 4 -haloalkoxy, C 2 -C 4 -alkenyloxy, C 2 -C -haloalkenyloxy, C 2 -C 4 -alkynyloxy or C 2 -C 4 -haloalkynyloxy, -C-C 4 alkylcarbonyloxy is.
  • the invention further relates to compositions for controlling harmful fungi and animal pests which contain the compounds of the formula I and / or their agriculturally acceptable salts, and to the use of the compounds I and their salts for controlling harmful fungi and animal pests.
  • WO 95/04728 and WO 97/27189 describe 2-aza-1,4-dioxacycloalkenes which are linked in the 3 position via an 1,1-alkanediyl unit to an orthosubstituted (het) aryloxy group.
  • the compounds described in the abovementioned documents are used as crop protection agents against harmful fungi and in some cases. suitable against animal pests.
  • the present invention is therefore based on the object of providing compounds with improved activity against harmful fungi and / or animal pests.
  • the invention thus also relates to processes for the preparation of the compounds I and the uses tion of the compounds I found to combat harmful fungi and animal pests.
  • the invention further relates to agents which contain at least one compound of the formula I or an agriculturally useful salt thereof and which are suitable for controlling harmful fungi and animal pests.
  • the compounds of formula I and their agriculturally useful salts are distinguished in particular by their fungicidal activity.
  • the compounds of the formula I can be in the form of stereoisomers. They can contain one or more centers of chirality and are then available as mixtures of enantiomers or diastereomers.
  • the invention relates both to the pure enantiomers or diastereomers and to their mixtures.
  • the compounds I can be obtained in the preparation as E / Z isomer mixtures which are e.g. can separate into the individual compounds by crystallization or chromatography in the usual way.
  • isomer mixtures are obtained in the synthesis, however, a separation is generally not absolutely necessary, since the individual isomers can partially convert into one another during preparation for use or during use (e.g. under the action of light, acid or base). Corresponding conversions can also take place after use, for example in the treatment of plants in the treated plant or in the harmful fungus or animal pest to be controlled.
  • Agriculturally useful salts include, in particular, the salts of those cations or the acid addition salts of those acids whose cations or anions do not adversely affect the action of the compounds I according to the invention.
  • cations in particular the ions of the alkali metals, preferably sodium and potassium, the alkaline earth metals, preferably calcium, magnesium and barium, and the transition metals, preferably manganese, copper, zinc and iron, and the ammonium ion, if desired one to four C ⁇ -C 4 alkyl and / or a phenyl or benzyl substituent, preferably diisopropylammonium, tetramethylammonium, tetrabutylammonium, trimethylbenzylammonium, further phosphonium ions, sulfonium ions, preferably Tri (-CC 4 alkyl) sulfonium and sulfoxonium ions, preferably tri (-C 4 alkyl) sulfoxon
  • Anions of useful acid addition salts are primarily chloride, bromide, fluoride, hydrogen sulfate, sulfate, dihydrogen phosphate, hydrogen phosphate, phosphate, nitrate, hydrogen carbonate, carbonate, hexafluorosilicate, hexafluorophosphate, benzoate, and the anions of C 1 -C 4 -alkanoic acids, preferably Formate, acetate, propionate and butyrate. They can be formed by reacting I with an acid of the corresponding anion, preferably hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid or nitric acid.
  • Cx-C ß -haloalkylthio and C ⁇ -C 6 -haloalkylsulfonyl for: a C ⁇ -C 6 -alkyl radical as mentioned above, which is partially or completely substituted by fluorine, chlorine, bromine and / or iodine, for example for one of the radicals mentioned under C ⁇ -C 4 -haloalkyl or for 5-fluoro-1-pentyl, 5-chloro-1-pentyl, - * 5 5-bromo-1-pentyl, 5-iodo-1-pentyl, 5.5 , 5-trichloro-l-penyl, undecafluoropentyl, 6-fluoro-l-hexyl, 6-chloro-l-hexyl, 6-bromo-l-hexyl, 6-iodo-l-hexyl, 6, 6, 6 Trichloro-l-hexyl or do-decafluorohexy
  • Ethenyl n-penten-1-yl, n-penten-2-yl, n-penten-3-yl, n-penten-4-yl, 1-methyl-but-l-en-l-yl, 2-methyl-but-l-en-l-yl, 3-methyl-but-l-en-l-yl, l-methyl-but-2-en-l-yl, 2-methyl-but-2- en-l-yl, 3-methyl-but-2-en-l-yl, l-methyl-but-3-en-l-yl,
  • halogen atoms as mentioned above, in particular fluorine, chlorine and bromine, are replaced, e.g. 2-chloroallyl, 3-chloroallyl, 2,3-dichlorallyl, 3,3-dichlorallyl, 2,3, 3-trichlorallyl, 2,3-dichlorobut-2-enyl, 2-bromoallyl, 3-bromoallyl, 2,3- Dibromoallyl, 3,3-dibromoallyl, 2, 3,3-tribromoallyl or 2,3-dibromo-
  • OCH (CH 3 ) 2 n-butoxy, OCH (CH 3 ) -C 2 H 5 , OCH 2 -CH (CH 3 ) 2 or C (CH 3 ) 3 preferably for OCH 3 , OC 2 H 5 or OCH ( CH 3 ) 2 ;
  • C ⁇ -C 4 alkoxy radical as mentioned above, the is partially or completely substituted by fluorine, chlorine, bromine and / or iodine, for example OCH 2 F, OCHF 2 , 0CF 3 , 0CH 2 C1, 0CH (C1) 2 , 0C (C1) 3 , chlorofluoromethoxy, dichlorofluoromethoxy, Chlorodifluoromethoxy, 2-fluoroethoxy, 2-chloroethoxy,
  • n-pentoxy 1-methylbutoxy, 2-methylbutoxy, 3-methylbutoxy, 2, 2-dimethylpropoxy, 1-ethylpropoxy, n-hexoxy, 1, 1-dimethylpropoxy, 1, 2-dimethylpropoxy, 1-methylpentoxy, 2- Methylpentoxy, 3-methylpentoxy, 4-methylpenoxy, 1, 1-dimethylbutoxy, 1, 2-dimethylbutoxy, 1, 3-dimethylbutoxy, 2, 2-dimethylbutoxy, 2, 3-dimethylbutoxy, 3, 3-dimethyl butoxy, 1-ethylbutoxy, 2-ethylbutoxy, 1, 1, 2-trimethylpropoxy, 1, 2, 2-trimethylpropoxy, 1-ethyl-l-methylpropoxy or l-ethyl-2-methylpropoxy, preferably for 0CH 3 , OC 2 H 5 , OCH 2 -C 2 H 5 , OCH (CH 3 ) 2 , n-butoxy, OC (CH 3 ) 3 , n-pentoxy or n-
  • Ci-C ß -alkoxy radical as mentioned above, which is partially or completely substituted by fluorine, chlorine, bromine and / or iodine is, for example one of the radicals mentioned under C ⁇ -C 4 -haloalkoxy or for 5-fluoro-1-pentoxy, 5-chloro-1-pentoxy,
  • 5-bromo-1-pentoxy 5-iodo-1-pentoxy, 5,5,5-trichloro-1-pentoxy, undecafluoropentoxy, 6-fluoro-1-hexoxy, 6-chloro-1-hexoxy, 6-bromo l-hexoxy, 6-iodo-l-hexoxy, 6, 6,6-trichloro-l-hexoxy or dodecafluorohexoxy;
  • C ⁇ -C 6 -alkoxy-C ⁇ -C 4 -alkyl for: C ⁇ -C 6 -alkoxy - as mentioned above - substituted C ⁇ -C 4 alkyl, for example for CH 2 -OCH 3 , CH 2 -OC 2 H 5 , n-propoxymethyl, CH 2 -OCH (CH 3 ) 2 , n-butoxymethyl, (l-methylpropoxy) methyl, (2-methylpropoxy) methyl, CH 2 -OC (CH 3 ) 3 , 2- ( Methoxy) ethyl, 2- (ethoxy) ethyl, 2- (n-propoxy) ethyl, 2- (l-methylethoxy) ethyl, 2- (n-butoxy) ethyl, 2- (l-methylpropoxy) ethyl, 2 - (2-Methylpropoxy) ethyl, 2- (l, l-dimethylethoxy) ethyl, 2- (me
  • C ⁇ -C 6 -Halogenalk ⁇ xy-C ⁇ -C 4 -alkyl for: C ⁇ -C 6 -Halogenalkoxy substituted C vorierd-C 4 alkyl as mentioned above, for example for 2- (OCHF 2 ) ethyl, 2- (0CF 3 ) ethyl or 2- (OC 2 F 5 ) ethyl;
  • C 3 -C 6 alkenyloxy-C ⁇ -C 4 alkyl for: by C 3 -C 6 alkenyloxy such as allyloxy, but-l-en-3-yloxy, but-l-en-4-yloxy, but- 2-en-l-yloxy, l-methylprop-2-enyloxy or 2-methylprop-2-enyloxy substituted C ⁇ -C 4 -alkyl, for example for allyloxymethyl, 2-allyloxyethyl or but-l-en-4-yloxymethyl, in particular for 2-allyloxyethyl;
  • C 3 -C 6 -alkynyloxy-C ⁇ -C 4 -alkyl for: by C 3 -C 6 -alkynyloxy such as propargyloxy, but-l-in-3-yloxy, but-l-in-4-yloxy, but- 2-in-1-yloxy, 1-methylprop-2-inyloxy or 2-methylprop-2-inyloxy, preferably propargyloxy, substituted C ⁇ -C 4 -alkyl, that is to say, for example, for propargyloxymethyl or 2-propargyloxyethyl, in particular for 2-propargyloxyethyl;
  • cycloalkyl for: cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl;
  • - aryl for phenyl, ⁇ -naphthyl or ⁇ -naphthyl;
  • - aryloxy for phenoxy, ⁇ -naphthyloxy or ⁇ -naphthyloxy;
  • Aryl-C ⁇ -C 4 alkyl for C ⁇ -C 4 alkyl which is substituted with phenyl, ⁇ -naphthyl or ß-naphthyl, for example for benzyl, 1- or 2-phenylethyl, 1-, 2- or 3 phenylpropyl;
  • Aryloxy-C ⁇ -C-alkyl for C ⁇ -C 4 alkyl, which is substituted with phenoxy, ⁇ -naphthyloxy or ß-naphthyloxy, for example for phenoxy ethyl, 1- or 2-phenoxyethyl, 1-, 2- or 3 -Phenoxy-propyl;
  • Aryl-C 2 -C 4 alkenyl for C 2 -C 4 alkenyl which is substituted with phenyl, ⁇ -naphthyl or ⁇ -naphthyl, for example for 1- or 2-phenylethenyl, l-phenylprop-2-ene -l-yl, 3-phenyl-l-pro- pen-l-yl, 3-phenyl-2-propen-l-yl, 4-phenyl-l-buten-l-yl or 4-phenyl-2-buten-l-yl;
  • Aryl-C 2 -C 4 -alkynyl for C 2 -C 4 -alkynyl which is substituted with phenyl, ⁇ -naphthyl or ⁇ -naphthyl, for example for 1-phenyl-prop-2-yn-l-yl, 3-phenyl-l-propyne-l-yl, 3-phenyl-2-propyne-l-yl, 4-phenyl-l-butyne-l-yl or 4-phenyl-2-butyne-l-yl;
  • Heterocyclyl for saturated, partially saturated or unsaturated (aromatic) heterocyclyl, which has 5 to 8 ring atoms and 1, 2, 3 or 4 heteroatoms selected from nitrogen, oxygen and sulfur, also have one or two carbonyl or thiocarbonyl ring members and can also be benzo-condensed.
  • saturated or partially unsaturated heterocyclyl examples include: 2-tetrahydrofuranyl, oxiranyl, 3-tetrahydrofuranyl, 2-tetrahydrothienyl, 3-tetrahydrothienyl, 2-pyrrolidinyl, 3-pyrrolidinyl, 3-isoxazoldinyl, 4-isoxazolidinyl, 5-isoxazolidinyl -Isothiazolidinyl, 4-isothiazolidinyl, 5-isothiazolidinyl, 3-pyrazolidinyl, 4-pyrazolidinyl, 5-pyrazolidinyl, 2-oxazolidinyl, 4-oxazolidinyl, 5-0xazolidinyl, 2-thiazolidinyl, 4-thiazolidinyl, 5-thiazolidinyl , 2-imidazolidinyl, 4-imidazolidinyl, l, 2,4-oxadiazolidin-3-yl, 1,2,4-o
  • heteroaryl examples include:
  • 5-ring heteroaryl containing one to four nitrogen atoms as ring members; or one to three nitrogen atoms and one sulfur or oxygen atom; or an oxygen atom; or a sulfur atom: e.g. 2-furyl, 3-furyl, 2-thienyl, 3-thienyl, 2-pyrrolyl, 3-pyrrolyl, 3-isoxazolyl, 4-isoxazolyl, 5-isoxazolyl, 3-isothiazolyl, 4-isothiazolyl, 5-isothiazolyl, 3- Pyrazolyl, 4-pyrazolyl, 5-pyrazolyl, 2-0xazolyl, 4-0xazolyl, 5-oxazolyl, 2-thiazolyl, 4-thiazolyl, 5-thiazolyl, 2-imidazolyl, 4-imidazolyl, 1, 2, 4-oxadiazole 3-yl, l, 2,4-oxadiazol-5-yl, 1,2,4-thiadiazol -3-yl, 1,2,4-thiadiazol
  • Benzocondensed 5-Rin ⁇ heteroaryl 5-ring heteroaryl with 1, 2 or 3 nitrogen atoms; or a heteroatom selected from oxygen and sulfur and optionally one or two nitrogen atoms; wherein two adjacent carbon ring members are bridged by a buta-1,3-diene-1,4-diyl group: e.g. Indolyl, benzofuranyl, benzothienyl, benzoxazolyl, benzopyrazolyl or benzothiazolyl;
  • 6-ring heteroaryl which in addition to carbon atoms can contain one to three or one to four nitrogen atoms as ring members: for example 2-pyridinyl, 3-pyridinyl, 4-pyridinyl, 3-pyridazinyl, 4-pyridazinyl, 2-pyrimidinyl, 4-pyrimidinyl , 5-pyrimidinyl, 2-pyrazinyl, 1, 3, 5-triazin-2-yl, 1,2,4-triazin-3-yl and 1,2, 4, 5-tetrazinyl;
  • - Benzo-condensed 6-ring heteroaryl 6-ring heteroaryl, in which two adjacent carbon ring members can be bridged by a buta-1,3-diene-1,4-diyl group: for example quinoline, isoquinoline, quinazoline and quinoxaline.
  • n denotes 0 or 1 and in particular 0.
  • R 1 represents chlorine or bromine and especially chlorine.
  • R 2 stands for methyl, ethyl, n-propyl, isopropyl, allyl or propargyl and in particular for methyl or ethyl.
  • W represents an ethylene substituted by R 7 , where R 7 preferably denotes methyl, ethyl or trifluoromethyl.
  • R 7 preferably denotes methyl, ethyl or trifluoromethyl.
  • W stands for unsubstituted ethylene (-CH 2 -CH 2 -).
  • R 5 is a radical substituted by R 5
  • R 5 preferably represents halogen, cyano, nitro, C ⁇ -C 6 -alkyl, Ci-C ß -haloalkyl, C ⁇ -C 6 -alkoxy, C ⁇ -C 6 -haloalkoxy, Ci-C ⁇ -alkylcarbonyl, C ⁇ -C 6 -haloalkylcarbonyl, C ⁇ -C 6 -alkoxycarbonyl, C ⁇ -C 6 -haloalkoxycarbonyl, C ⁇ -C 6 -alkylamino, bis-C ⁇ -C 6 -alkylamino, C ⁇ -C 6 -haloalkyl- mino, bis-C ⁇ -C 6 -haloalkylamino, Cx-Ce-haloalkylaminocarbonyl, bis-Cx-Cg-haloalkylaminocarbonyl and C ⁇ -C 6 -alkoxyiminomethyl, C ⁇ -Cg-hal
  • substituents R 5 are fluorine, chlorine, bromine, nitro, cyano, amino, hydroxy, methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, methoxy, ethoxy, n- Propoxy, iso-propoxy, n-butoxy, tert-butoxy, fluoromethyl, difluoromethyl, trifluoromethyl, 2,2,2-trifluoroethyl, fluoromethoxy, difluoromethoxy, trifluoromethoxy, 2,2,2-trifluoroethoxy, 1,1 , 2, 2-tetrafluoroethoxy, vinyl, allyl, 2-propen-1-yloxy, propargyloxy, methylthio, methylsulfonyl, methoxyiminomethyl, ethoxyiminomethyl, 1-methoxyimino-1-ethyl, acetyl, propionyl, but
  • R 5 examples of two radicals R 5 forming bridges are methylene-dioxy (-O-CH 2 -O-), dimethylmethylene dioxy (-0-C (CH 3 ) 2 -0-), difluoromethylene-dioxy (-0-CF 2 - 0-) and ethylenedioxy (-0-CH 2 -CH 2 -0-).
  • radicals R 3 are those mentioned in Table A, lines 71-267 residues R 3, in particular phenyl, 4-fluorophenyl, 4-chlorophenyl, 4-methylphenyl, 4-methoxyphenyl, 3-trifluoromethylphenyl and 2, 4-dichlorophenyl.
  • azadioxacycloalkenes of the formula Ia are particularly preferred.
  • R 1 is chlorine and R 2 is methyl and R3 has one of the meanings given in Table A.
  • R 3 is n-propyl and R 3 has one of the meanings given in Table A.
  • R 1 is chlorine and R 2 is methyl and R3 has one of the meanings given in Table A.
  • R 1 is chlorine and R 2 is methyl and R3 has one of the meanings given in Table A.
  • Table 26 Compounds of the general formula IC where R 1 is chlorine and R 2 is ethyl and R 3 has one of the meanings given in Table A.
  • R 1 is chlorine and R 3 has one of the meanings given in Table A.
  • R 1 is chlorine and R 3 has one of the meanings given in Table A.
  • the compounds I can be obtained in various ways, it being irrelevant for the synthesis whether the group X # or the bisoximether side chain E # is first built up,
  • Compounds I can be prepared, for example, by first converting a carboxylic acid ester II with hydroxylamine into the corresponding hydroxamic acid III (step 1), then reacting it with a benzyl compound IV to give the corresponding hydroxamic acid ester V (step 2) and V with a halogenating agent transferred to the corresponding target compound I (step 3) [cf. DE-A 197 08 940].
  • R x in formula II represents the rest of a usual leaving group.
  • customary leaving groups are to be understood in particular as the following groups: C ⁇ -C 4 -alkyl (especially methyl or ethyl) or phenyl.
  • L in formula IV stands for a nucleofugic leaving group.
  • halogen or alkyl or aryl sulfonate especially chlorine, bromine, iodine, mesylate, tosylate and triflate.
  • the reaction of the carboxylic acid ester II with hydroxylamine is usually carried out at from -20 ° C. to 50 ° C., preferably 0 ° C. to 20 ° C., in an inert organic solvent, preferably in the presence of a base (cf. Houben-Weyl, 4th edition, vol.E5, p. 1141 ff.).
  • Suitable solvents are aliphatic hydrocarbons such as pentane, hexane, cyclohexane and petroleum ether, aromatic hydrocarbons such as toluene, o-, m- and p-xylene, halogenated hydrocarbons such as methylene chloride, chloroform and chlorobenzene, ethers such as diethyl ether, diisopropyl ether, tert-butyl methyl ether , Dioxane, anisole and tetrahydrofuran, nitriles such as acetonitrile and propionitrile, alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol and tert-butanol, as well as dimethyl sulfoxide, dimethylformamide and dimethyl acetamide, particularly preferably alcohols such as methanol and ethanol. Mixtures of the solvents mentioned can also be used.
  • the bases generally include inorganic compounds such as alkali metal and alkaline earth metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide and calcium hydroxide, alkali metal and alkaline earth metal oxides such as lithium oxide, sodium oxide, calcium oxide and magnesium oxide, alkali metal and alkaline earth metal carbonates such as lithium carbonate and alkaline earth metal carbonate and sodium alkali metal calcium carbonate and sodium alkali metal and calcium alkali metal carbonate and alkaline earth metal carbonate and alkaline earth metal carbonate and alkaline earth metal carbonate - Ummethanolat, sodium ethanolate, potassium ethanolate, potassium tert-butanolate and dimethoxymagnesium, also organic bases, for example tertiary amines such as trimethylamine, triethylamine, tri-isopropylethylamine and N-methylpiperidine, pyridine, substituted pyridines such as collidine, lutidine and 4-dimethylaminopyridine,
  • the starting materials are generally reacted with one another in equimolar amounts. It may be advantageous for the yield to use hydroxylamine in an excess based on II.
  • the carboxylic acid esters II required for the preparation of the compounds I are known in the literature [DE-A 28 08 317; DE-A 22 65 234; J. Chem. Soc. PT 1, 2340 ff. (1975); Chem. Ber. 16, 2987 ff. (1883); J. Org. Chem. 37, 139 (1972)] or can be prepared according to the literature cited.
  • the reaction of the hydroxamic acid III with the benzyl compound IV is usually carried out at temperatures from 0 ° C. to 130 ° C., preferably 10 ° C. to 60 ° C., in an inert organic solvent in the presence of a base [cf. Liebigs Ann. Chem. 10, 997 ff. (1992); Synth. Commun. 19, 339 ff. (1989)].
  • L represents halogen, in particular chlorine or bromine
  • Suitable solvents are aliphatic hydrocarbons such as pentane, hexane, cyclohexane and petroleum ether, aromatic hydrocarbons such as toluene, o-, m- and p-xylene, halogenated hydrocarbons such as methylene chloride, chloroform and chlorobenzene, ethers such as diethyl ether, diisopropyl ether, tert-butyl methyl ether , Dioxane, anisole and tetrahydrofuran, nitriles such as acetonitrile and propionitrile, ketones such as acetone, methyl ethyl ketone, diethyl ketone and tert-butyl methyl ketone, alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol and tert-butanol and dimethyl sulfoxide , Dimethyl
  • Bases generally include inorganic compounds such as alkali metal and alkaline earth metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide and calcium hydroxide, alkali metal and alkaline earth metal oxides such as lithium oxide, sodium oxide, calcium oxide and magnesium oxide, alkali metal and alkaline earth metal hydrides such as lithium hydride, calcium hydride, sodium hydride Alkali metal amides such as lithium amide, sodium amide and potassium amide, alkali metal and alkaline earth metal carbonates such as lithium carbonate, potassium carbonate and calcium carbonate as well as alkali metal hydrogen carbonates such as sodium hydrogen carbonate, organometallic compounds, in particular alkali metal alkyls such as methyl lithium, butyllithium and phenomagnesium magnesium chloride, and methyl lithium magnesium chloride Alkaline earth metal alcoholates such as sodium methoxide, sodium ethanolate, potassium ethanolate, potassium tert-butoxide and dimethoxy magnesium, and also organic bases, for
  • the starting materials are generally reacted with one another in equimolar amounts. It may be advantageous for the yield to use III in an excess based on IV. Of course, one can also use the compound IV in excess if this is expedient.
  • the halogenation of the hydroxamic acid V is usually carried out at temperatures from -20 ° C to 100 ° C, preferably -10 ° C to 80 ° C, in an inert organic solvent [cf. Houben-Weyl, 4th ed., Vol. E5, p. 631 ff .; J. Org. Chem. 36, 233 (1971); Synthesis 9, 750 ff. (1991); Tetrahedron 52 (1), 233 ff. (1996)].
  • Suitable halogenating agents in this reaction are the customary inorganic and organic halogenating agents, for example thionyl chloride, oxalyl chloride, phosphorus tribromide, phosphorus trichloride, phosphorus pentachloride, phosphorus oxychloride, phosphorus triiodide, triphenylphosphine / CCl 4 , triphenylphosphine / CBr, triphenylphosphine / iodine, preferably called thorophenyl chloride, preferably thorophenylchloride, preferably thorophenyl chloride - reagents.
  • Suitable solvents are aliphatic hydrocarbons such as pentane, hexane, cyclohexane and petroleum ether, aromatic hydrocarbons such as toluene, o-, m- and p-xylene, halogenated hydrocarbons such as methylene chloride, chloroform and chlorobenzene, ethers such as diethyl ether, diisopropyl ether, tert-butyl methyl ether , Dioxane, anisole and tetrahydrofuran, nitriles such as acetonitrile and propionitrile, ketones such as acetone, methyl ethyl ketone, diethyl ketone and tert-butyl methyl ketone, and
  • the halogenating agents are generally used at least in equimolar amounts. It can be advantageous for the yield to use it in an excess of up to 10 mol based on 1 mol of compound V, preferably up to 5 mol, in particular up to 3 mol.
  • the benzyl compounds IV required for the preparation of the compounds I are known from the literature [cf. WO-A 95/04728; WO-A 98/17653]. For example, they can be obtained by the following synthetic route:
  • L a stands for an oxygen atom protected by a protective group
  • R for halogen, alkylcarbonyloxy, OH, C ⁇ -C 4 -alkoxy or an active ester such as optionally substituted phenoxy (such as, for example, p-nitrophenoxy or pentafluorophenoxy), Succinimidoxy or isourea.
  • W has the meaning given above.
  • L 1 , L 2 each represent a nucleophilically interchangeable group such as halide, C ⁇ -C 4 alkyl sulfonate, C ⁇ -C ⁇ 2 alkylphenyl sulfonate or mono-C ⁇ - C alkyl sulfate or L 1 and L 2 can also be a bridge together - Represent O-. Steps 1) to 3) of this implementation are explained in more detail below.
  • Benzyl compounds of the formula VI are reacted with hydroxylamine or its acid addition salt, optionally in the presence of a base or a dehydrating agent, such as N, N'-dicyclohexylcarbodiimide, or in the presence of a coupling reagent, such as 2-ethoxy-l-ethoxycarbonyl-l, 2-dihydroquinoline (EEDQ), 1-isobutyloxycarbonyl 2-isobutyloxy-l, 2-dihydroquinoline (IIDQ) or benzotriazol-l-yl-oxy-tris (dimethylamino) phosphonium hexafluorophosphate (BOP), converted to the hydroxamic acids of formula VII.
  • a base or a dehydrating agent such as N, N'-dicyclohexylcarbodiimide
  • a coupling reagent such as 2-ethoxy-l-ethoxycarbonyl-l, 2-dihydroquinoline
  • reaction sequence VI ⁇ VII ⁇ IVa can be carried out in two stages or preferably in one stage, ie without isolation of the hydroxamic acid VII formed in the first process step the.
  • the implementation can be carried out analogously to the methods described in WO 95/04728, WO 97/00866 and EP-A 846 691, to which reference is hereby made.
  • the protective group can first be split off from compound IVa and then the OH function in the benzyl alcohol derivative formed can be converted into a reactive group L.
  • L halogen
  • conventional halogenating agents such as S0C1, BBR 4 / SnCl, CCl / triphenylphosphine or HBr
  • Benzyl compounds of the formula VI are also known from the literature or can be prepared by known methods [cf. EP-A 178 826; EP-A 253 213; WO-A 95/04728].
  • the compounds of the formula IV with L halogen, for example chlorine or bromine, can alternatively also be prepared from compounds of the formula IVa in which L a is hydrogen by side chain halogenation, for example with N-bromosuccinimide [cf. WO 95/04728].
  • Another advantageous way of preparing the compounds I is based on ⁇ -bisoxime (mono) benzyl ethers of the formula VIII, in which R 1 to R 4 and X have the meaning given in claim 1 and Y is halogen, alkylcarbonyloxy, OH, NH 2 , C ⁇ -C 4 alkoxy, optionally substituted phenoxy (such as p-nitrophe- noxy or pentafluorophenoxy), C ⁇ -C-alkylamino, di-C ⁇ -C 4 -alkylamino or an active ester such as succinimidoxy or isourea.
  • R 1 to R 4 and X have the meaning given in claim 1 and Y is halogen, alkylcarbonyloxy, OH, NH 2 , C ⁇ -C 4 alkoxy, optionally substituted phenoxy (such as p-nitrophe- noxy or pentafluorophenoxy), C ⁇ -C-alkylamino, di-C ⁇ -C
  • the compounds VIII are in a first step 1) with hydroxylamine or its acid addition salt optionally in the presence of a base or a dehydrating compound such as N, N'-dicyclohexylcarbodiimide and then in a second step 2) with a compound L 1 -WL 2 in which W has the abovementioned meaning and L 1 , L 2 each represent a nucleophilically exchangeable group such as halide, C 1 -C 4 -alkyl sulfonate, C ⁇ -C ⁇ 2 - alkylphenyl sulfonate or mono-C ⁇ -C 4 -alkyl sulfate or L 1 and L 2 together represent a bridge -O-, implemented.
  • Process steps 1) and 2) listed in Scheme 2 can be two-stage or preferably one-stage, i.e. without isolating the hydroxamic acid IVa formed in the first process step.
  • the procedure can be carried out analogously to the methods described in WO 95/04728, WO 97/00866 and EP-A 846 691.
  • reaction mixtures are worked up in a customary manner, for example by mixing with water, separating the phases and, if appropriate, purifying the crude products by chromatography.
  • Some of the intermediate and end products are in the form of colorless or slightly brownish, viscous oils, which are freed from volatile components or purified under reduced pressure and at a moderately elevated temperature. If the intermediate and end products are obtained as solids, they can also be purified by recrystallization or digesting.
  • the ⁇ -bisoxime (mono) benzyl ethers of the formula VIII can be obtained by syntheses known from the literature [cf. WO 97/15552].
  • Another access to the compounds I consists in reacting a carboxylic acid ester of the formula II under the conditions described above for the reaction of II with hydroxylamine to III with the benzylhydroxylamine IX to give the compound X and then first building up the azadioxacycloalkene unit by cyclization and then converted the carbonyl group of the side chain into the radical R 1 by halogenation or carried out these steps in the reverse order.
  • the compounds I are advantageously obtained by converting an amidoxime IIb with a benzyl compound XI into the corresponding compound of the formula Xa (step 1), exchanging the amino group of Xa for halogen by diazotization (step 2) and then performs the cyclization in the manner described above (step 3).
  • step 2) and step 3) can also be carried out in the reverse order.
  • the reaction of the amidoxime IIb with the benzyl compound XI usually takes place at temperatures from 0 ° C. to 130 ° C., preferably 10 ° C. to 60 ° C., in an inert organic solvent in the presence of a base [cf. Lit. Heterocycles 36, 1027 ff. (1993)].
  • Suitable solvents are aliphatic hydrocarbons such as pentane, hexane, cyclohexane and petroleum ether, aromatic hydrocarbons such as toluene, o-, m- and p-xylene, halogenated hydrocarbon substances such as methylene chloride, chloroform and chlorobenzene, ethers such as diethyl ether, diisopropyl ether, tert-butyl methyl ether, dioxane, anisole and tetrahydrofuran, nitriles such as acetonitrile and propionitrile, ketones such as acetone, methyl ethyl ketone, diethyl ketone and tert-butyl methyl ketone, alcohols such as methanol Ethanol, n-propanol, isopropanol, n-butanol and tert-butanol, and also dimethyl sulfoxide, di
  • Suitable bases are, generally, inorganic compounds such as alkali and alkaline earth metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide and calcium hydroxide, alkali metal and alkaline earth metal oxides such as lithium oxide, sodium oxide, calcium oxide and magnesium oxide, alkali metal and alkaline earth metal hydrides such as lithium hydride, sodium hydride, potassium hydride and calcium hydride, such as Al kalimetallamide Lithium amide, sodium amide and potassium amide, alkali metal and alkaline earth metal carbonates such as lithium carbonate,.
  • alkali and alkaline earth metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide and calcium hydroxide
  • alkali metal and alkaline earth metal oxides such as lithium oxide, sodium oxide, calcium oxide and magnesium oxide
  • alkali metal and alkaline earth metal hydrides such as lithium hydride, sodium hydride, potassium hydride and calcium hydride
  • alkali metal bicarbonates such as sodium bicarbonate, organometallic compounds, in particular alkali metal alkyls such as methyl lithium, butyllithium and phenyllithium, alkyl magnesium halides such as methyl magnesium chloride and alkali metal and alkaline earth metal alcoholates such as sodium methanolate, potassium methoxide, sodium ethane, sodium ethanolate, sodium methoxide, sodium ethane and sodium methoxide, sodium methoxide, sodium methoxide, sodium methoxide, sodium methoxide, sodium ethoxide and sodium methoxide, sodium ethoxide and sodium methoxide, Bases, e.g.
  • Tertiary amines such as trimethylamine, triethylamine, triisopropylethylamine and N-methylpiperidine, pyridine, substituted pyridines such as collidine, lutidine and 4-dimethylaminopyridine and bicyclic amines.
  • Sodium methoxide, potassium carbonate and sodium hydride are particularly preferred.
  • the bases are generally used in equimolar amounts or in excess.
  • the starting materials are generally reacted with one another in equimolar amounts. It may be advantageous for the yield to use Ilb in an excess based on XI.
  • amidoximes IIb required for this preparation of the compounds I are known in the literature [DE-A 44 42 732; Gazz. Chim. Ital. 55, 327 (1925)] or can be prepared according to the literature cited.
  • the diazotization and halogenation of Xa usually takes place at temperatures from -20 ° C. to 50 ° C., preferably 0 ° C. to 20 ° C.
  • hydrogen fluoride, hydrogen chloride, hydrogen bromide and hydrogen iodide, in particular hydrogen chloride serve as halogenating agents.
  • the halogenating agents are generally used in excess or, if appropriate, as a solvent.
  • Suitable solvents for diazotization and halogenation are aliphatic hydrocarbons such as pentane, hexane, cyclohexane and petroleum ether, aromatic hydrocarbons such as toluene, o-, m- and p-xylene, halogenated hydrocarbons such as methylene chloride, chloroform and chlorobenzene, ethers such as diethyl ether, diisopropyl ether , tert-butyl methyl ether, dioxane, anisole and tetrahydrofuran, nitriles such as acetonitrile and propionitrile, ketones such as acetone, methyl ethyl ketone, diethyl ketone and tert-butyl methyl ketone, alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol and tert.- Butanol,
  • the compounds I are suitable as fungicides. They are characterized by excellent activity against a broad spectrum of phytopathogenic fungi, in particular from the class of the Ascomycetes, Deuteromycetes, Phycomycetes and Basidiomycetes. Some of them are systemically effective and can be used in plant protection as leaf and soil fungicides.
  • Botrytis cinerea (gray mold) on strawberries, vegetables, ornamental plants and vines
  • the compounds I are also suitable for combating harmful fungi such as Paecilomyces variotii in the protection of materials (e.g. wood, paper, dispersions for painting, fibers or fabrics) and in the protection of stored products.
  • harmful fungi such as Paecilomyces variotii in the protection of materials (e.g. wood, paper, dispersions for painting, fibers or fabrics) and in the protection of stored products.
  • the compounds I are used by treating the fungi or the plants, seeds, materials or the soil to be protected against fungal attack with a fungicidally active amount of the active compounds.
  • the application can take place both before and after the infection of the materials, plants or seeds by the fungi.
  • the fungicidal compositions generally contain between 0.1 and 95, preferably between 0.5 and 90% by weight of active ingredient.
  • the application rates in crop protection are between 0.01 and 2.0 kg of active ingredient per ha.
  • active ingredient 0.001 to 0.1 g, preferably 0.01 to 0.05 g, per kg of seed are generally required.
  • the amount of active ingredient applied depends on the type of application and the desired effect. Usual application rates in material protection are, for example, 0.001 g to 2 kg, preferably 0.005 g to 1 kg of active ingredient per cubic meter of treated material.
  • the compounds of the formula I are also suitable for effectively combating animal pests from the class of the insects, arachnids and nematodes. They can be used in crop protection as well as in the hygiene, storage protection and veterinary sectors to control animal pests. They are particularly suitable for controlling the following animal pests:
  • Beetles (Coleoptera), e.g. Agrilus sinuatus, Agriotes lineatus, Agriotes obscurus, Amphimallus solstitialis, Anisandrus dispar,
  • Crioceris asparagi Diabrotica longicornis, Diabrotica 12-puncata, Diabrotica virgifera, Epilachna varivestis, Epitrix hir- tipennis, Eutinobothrus brasiliensis, Hylobius abietis, Hypera brunneipennis, Hypera postica, Ips typineaopa, lemaanotinus, lemaanotanus, lema - cus, Lissorhoptrus oryzophilus, Melanotus communis, Meligethes aeneus, Melolontha hippocastani, Melolontha melolontha, Oulema oryzae, Ortiorrhynchus sulcatus, Otiorrhynchus ovatus, Phaedon cochleariae, Phyllotreta chrysocephala, Phyllophaga sp.,
  • Two-winged e.g. Aedes aegypti, Aedes vexans, Anas- trepha ludens, Anopheles maculipennis, Ceratitis capitata, Chrysomya bezziana, Chrysomya hominivorax, Chrysomya macella- ria, Contarinia sorghicola, Cordylobia anthropophaga, Culex pi piens, Dacus cucurbitae, Dacus oleae, Dasineura brassicae, fan- nia canicularis, Gasterophilus intestinalis, Glossina morsitans, Haematobia irritans, Haplodiplosis equestris, Hylemyia platura, Hypoderma lineata, Liriomyza sativae, Liriomyza trifolii, Lucilia caprina, Lucilia cuprina, Lucilia cuprina, Luc
  • Thrips e.g. Frankliniella fusca, Frankliniella occidentalis, Frankliniella tritici, Scirtothrips citri, Thrips oryzae, Thrips palmi and Thrips tabaci,
  • Dermatoptera e.g. Athalia rosae, Atta cephalotes, Atta sexdens, Atta texana, Hoplocampa minuta, Hoplocampa testudinea, Monomorium pharaonis, Solenopsis geminata and Solenopsis invicta,
  • Heteroptera e.g. Acrosternum hilare, Blissus leucopterus, Cyrtopeltis notatus, Dysdercus cingulatus, Dysdercus intermedius, Eurygaster integriceps, Euschistus impictiventris, Leptoglossus phyllopus, Lygus lineolaris, Lygus pratensis, Nezara quadrantulais, Pyanma viridula, Pies
  • Plant suckers e.g. Acyrthosiphon onobrychis, Adelges laricis, Aphidula nasturtii, Aphis fabae, Aphis pomi, Aphis sambuci, Brachycaudus cardui, Brevicoryne brassicae, Ceosipha gossypii, Dreyfusia nordmannianae, Dreyfusia piceae
  • Termites e.g. Calotermes flavicollis, Leucotermes flavipes, Reticulitermes lucifugus and Termes natalensis,
  • Straight wing aircraft e.g. Acheta domestica, Blatta orien- talis, Blattella germanica, Forficula auricularia, Gryllotalpa gryllotalpa, Locusta migratoria, Melanoplus bivittatus, Melano- plus femur-rubrum, Melanoplus mexicanus, Melanoplus sanguini- pes, Melanoplus spretus, Nomadascocata americanana, Pericascacerana america, Schistocerca peregrina, Stauronotus maroccanus and Tachycines asynamorus,
  • Orthoptera e.g. Acheta domestica, Blatta orien- talis, Blattella germanica, Forficula auricularia, Gryllotalpa gryllotalpa, Locusta migratoria, Melanoplus bivittatus, Melano- plus femur-rubrum, Melanoplus mexi
  • Arachnoid such as arachnids (Acarina), e.g. Amblyomma america- num, Amblyomma variegatum, Argas persicus, Boophilus annulatus, Boophilus decoloratus, Boophilus microplus, Brevipalpus phoeni- cis, Bryobia praetiosa, Dermacentor silvarum, Eotetranychus carpini, Eriophyes sheldoni, Hyalommxnodinus rodoni, Hyalommxnodinus me- gnini, Paratetranychus pilosus, Dermanyssus gallinae, Phyllo- coptruta oleivora, Polyphagotarsonemus latus, Psoroptes ovis, Rhipicephalus appendiculatus, Rhipicephalus evertsi, Sarcoptes scabieus, Tetranychus cinnabarin
  • Nematodes such as root gall nematodes, e.g. Meloidogyne hapla, Meloidogyne incognita, Meloidogyne javanica, cyst-forming nematodes, e.g. Globodera rostochiensis, Heterodera avenae, Heterodera glycines, Heterodera schachtii, Heterodera trifolii, stick and leaf wholes, e.g.
  • Belonolaimus longicaudatus Ditylenchus destructor, Ditylenchus dipsaci, Heliocotylenchus multi- ticinctus, Longidorus elongatus, Radopholus similis, Rotylen- chus robustus, Trichodorus primitivus, Tylenchorhynchus clay- toni, Tylenchorhynchus dubius, Pratylenchus neglectus, Pratylenchus penetrans, Pratylenchus curvitatus and Pratylenchus goodeyi.
  • the application rate of active ingredient for controlling animal pests is 0.1 to 2.0, preferably 0.2 to 1.0 kg / ha under field conditions.
  • the compounds I can be converted into the customary formulations, for example solutions, emulsions, suspensions, dusts, powders, pastes and granules.
  • the form of application depends on the respective purpose; in any case, it should be ensure fine and uniform distribution of the compound of the invention.
  • the formulations are prepared in a known manner, e.g. by stretching the active ingredient with solvents and / or carriers, if desired using emulsifiers and dispersants, and in the case of water as diluent other organic solvents can also be used as auxiliary solvents.
  • auxiliaries solvents such as aromatics (e.g. xylene), chlorinated aromatics (e.g. chlorobenzenes), paraffins (e.g. petroleum fractions), alcohols (e.g. methanol, butanol), ketones (e.g. cyclohexanone), amines (e.g. B. ethanolamine, dimethylformamide) and water;
  • Carriers such as natural stone powder (e.g.
  • Emulsifiers such as non-ionic and anionic emulsifiers (e.g. polyoxyethylene fatty alcohol ethers, alkyl sulfonates and aryl sulfonates) and dispersants such as lignin sulfite liquors and methyl cellulose.
  • non-ionic and anionic emulsifiers e.g. polyoxyethylene fatty alcohol ethers, alkyl sulfonates and aryl sulfonates
  • dispersants such as lignin sulfite liquors and methyl cellulose.
  • Mineral oil fractions of medium to high boiling point such as kerosene or diesel oil, furthermore coal tar oils as well as oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, e.g. benzene, toluene, xylene, paraffin, are used for the production of directly sprayable solutions, emulsions, pastes or oil dispersions.
  • Powders, materials for broadcasting and dusts can be prepared by mixing or grinding the active substances together with a solid carrier.
  • Granules e.g. Coating, impregnation and homogeneous granules can be produced by binding the active ingredients to solid carriers.
  • Solid carriers are e.g. Mineral soils, such as silica gel, silicas, silica gels, silicates, talc, kaolin, Attaclay, limestone, lime, chalk, bolus, loess, clay, dolomite, diatomaceous earth, calcium and magnesium sulfate, magnesium oxide, ground plastics, fertilizers such as e.g. Ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas and vegetable products such as cereal flour, tree bark, wood and nutshell flour, cellulose powder and other solid carriers.
  • Mineral soils such as silica gel, silicas, silica gels, silicates, talc, kaolin, Attaclay, limestone, lime, chalk, bolus, loess, clay, dolomi
  • the formulations generally contain between 0.01 and 95% by weight, preferably between 0.1 and 90% by weight, of the active ingredient.
  • the active ingredients are used in a purity of 90% to 100%, preferably 95% to 100% (according to the NMR spectrum).
  • V 80 parts by weight of a compound according to the invention are with
  • VIII.20 parts by weight of a compound according to the invention are mixed well with 3 parts by weight of the sodium salt of diisobutylnaphthalene- ⁇ -sulfonic acid, 17 parts by weight of the sodium salt of lignosulfonic acid from a sulfite waste liquor and 60 parts by weight of powdered silica gel and milled in a hammer mill.
  • a spray liquor is obtained which contains 0.1% by weight of the active ingredient.
  • the active ingredients as such in the form of their formulations or the use forms prepared therefrom, e.g. in the form of directly sprayable solutions, powders, suspensions or dispersions, emulsions, oil dispersions, pastes, dusts, sprinkling agents, granules by spraying, atomizing, dusting, scattering or pouring.
  • the application forms depend entirely on the intended use; in any case, they should ensure the finest possible distribution of the active compounds according to the invention.
  • Aqueous use forms can be prepared from emulsion concentrates, pastes or wettable powders (wettable powders, oil dispersions) by adding water.
  • emulsions, pastes or oil dispersions the substances as such or dissolved in an oil or solvent can be homogenized in water by means of wetting agents, adhesives, dispersants or emulsifiers.
  • wetting, adhesive wetting, adhesive,
  • Dispersants or emulsifiers and possibly solvents or oil existing concentrates are prepared which are suitable for dilution with water.
  • the active substance concentrations in the ready-to-use preparations can be varied over a wide range. Generally they are between 0.0001 and 10%. Small amounts of active compound I are often sufficient in the ready-to-use preparation, e.g. 2 to 200 ppm. Ready-to-use preparations with active ingredient concentrations in the range from 0.01 to 1% are also preferred.
  • the active ingredients can also be used with great success in the ultra-low-volume process (ULV), it being possible to apply formulations with more than 95% by weight of active ingredient or even the active ingredient without additives.
  • UUV ultra-low-volume process
  • Oils of various types, herbicides, fungicides, other pesticides, bactericides can be added to the active ingredients, if appropriate also only immediately before use (tank mix). These agents can be added to the agents according to the invention in a weight ratio of 1:10 to 10: 1.
  • compositions according to the invention can also be present together with other active compounds, for example with herbicides, insecticides, growth regulators, fungicides or else with fertilizers.
  • other active compounds for example with herbicides, insecticides, growth regulators, fungicides or else with fertilizers.
  • Sulfur, dithiocarbamates and their derivatives such as ferridimethyldithiocarbamate, zinc dimethyldithiocarbamate, zinc ethylene bisdithiocarbamate, manganese ethylene bisdithiocarbamate, manganese zinc ethylenediamine bis dithiocarbamate, tetramethylthiurondarbamethyne damidulfide, , Ammonia complex of zinc (N, N '-propylene-bis-dithiocarbamate), zinc (N, N' -propylene-bis-dithiocarbamate), N, N'-polypropylene-bis- (thiocarbamoyl) disulfide;
  • Nitroderivate such as dinitro- (1-methylheptyl) phenylcrotonate, 2-sec-butyl-4, 6-dinitrophenyl-3, 3-dimethylacrylate, 2-sec-butyl-4, 6-dinitrophenyl-isopropyl carbonate, 5- Nitro-isophthalic acid-di-isopropyl ester;
  • Heterocyclic substances such as 2-heptadecyl-2-imidazoline acetate, 2,4-dichloro-6- (o-chloroanilino) -s-triazine, 0.0-diethyl-phthalimidophosphonothioate, 5-amino-l- [ bis- (dimethylamino) phosphinyl] -3-phenyl-l, 2,4-triazole, 2,3-dicyano-l, 4-di-thioanthraquinone, 2-thio-l, 3-dithiolo [4,5 -b] Quinoxaline, 1- (butylcarbamoyl) -2-benzimidazole-carbamic acid methyl ester, 2-methoxycarbonylamino-benzimidazole, 2- (furyl- (2)) -benzimidazole, 2- (thiazolyl- (4)) -benzimidazole, N. - (1, 1,2,2-tetrach
  • Strobilurins such as methyl-E-methoxyimino- [ ⁇ - (o-tolyloxy) -o-tolyl] acetate, methyl-E-2- ⁇ 2- [6- (2-cyanophenoxy) pyrimidin-4-yl- oxy] -phenyl ⁇ -3-methoxyacrylate, methyl1-E-methoxyimino- [ ⁇ - (2-phenoxyphenyl)] acetamide, methyl-E-methoxyimino- [ ⁇ - (2,5-dimethylphenoxy) -o-toly1 ] acetamide,
  • Anilinopyrimidines such as N- (4,6-dimethylpyrimidin-2-yl) aniline, N- [4-methyl-6- (1-propynyl) pyrimidin-2-yl] aniline, N- [4-Me- thyl-6-cyclopropyl-pyrimidin-2-yl] aniline,
  • Phenylpyrroles such as 4- (2,2-difluoro-1,3-benzodioxol-4-yl) pyrrole-3-carbonitrile,
  • Cinnamic acid amides such as 3- (4-chlorophenyl) -3- (3, 4-dimethoxyphenyl) acrylic morpholide,
  • fungicides such as dodecylguanidine acetate, 3- [3- (3, 5-dimethyl-2-oxycyclohexyl) -2-hydroxyethyl] glutarimide, hexachlorobenzene, DL-methyl-N- (2, 6-dimethyl-phenyl) - N-furoyl (2) alaninate, DL-N- (2,6-dimethylphenyl) -N- (2'-methoxyacetyl) alanine methyl ester, N- (2,6-dimethylphenyl) ) -N-chloroacetyl1-D, L-2-aminobutyrolactone, DL-N- (2,6-dimethylphenyl) -N- (phenylacetyl) -alanine methyl ester, 5-methyl-5-vinyl-3- (3rd , 5-dichlorophenyl) -2, 4-dioxo-l, 3-oxo-
  • the plants were again placed in a moist chamber for 16 hours to accelerate the sporangia outbreak. The extent of the development of the infestation on the undersides of the leaves was then determined visually.
  • test plants which contained 4 ppm of active ingredient and which had been prepared from a stock solution consisting of 10% active ingredient, 63% cyclohexanone and 27% emulsifier, until dripping wet. After the spray coating had dried on, the test plants were grown in the greenhouse at temperatures between 20 and 22 ° C. and 65 to 70%
  • Example 2 Compound No. 2
  • Example 3 Compound No. 3
  • the compounds VI and V2 had the following formulas:
  • Leaves of potted vines of the "Müller-Thurgau" variety were inoculated with an aqueous suspension of zoospores from Plasmopara viticola.
  • the vines were then placed in a steam-saturated chamber at 22 to 24 ° C. for 48 h. They were then removed from the chambers and, after drying, were sprayed to runoff point with aqueous active compound preparation which was made up with a stock solution of 10% active compound, 63% cyclohexanone and 27% emulsifier. After the spray coating had dried on, the plants were further cultivated for 5 days in a greenhouse at temperatures between 20 and 30 ° C. After this time, the plants were again placed in a humid climatic chamber for 16 h to accelerate the sporangium carrier outbreak. The extent of the development of the infestation on the undersides of the leaves was then determined.
  • Leaves of potted rice seedlings of the "Tai-Nong 67" variety were sprayed to runoff point with aqueous active substance preparation which was prepared with a stock solution of 10% active substance, 63% cyclohexanone and 27% emulsifier. The following day, the plants were inoculated with an aqueous spore suspension of Pyricularia oryzae. The test plants in climatic chambers at 22 to 24 ° C and 95 to 99% were then more relative Humidity set up for 6 days. The extent of the development of the infestation on the leaves was then determined visually.
  • Experiment 8 was carried out like experiment 6, but with a lower concentration of the active ingredient in the aqueous preparation.

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Abstract

La présente invention concerne des azadioxacycloalcènes de formule générale (I) dans laquelle les substituants R?1, R2, R3, R4¿ et X, l'indice n et l'élément de pont W correspondent aux éléments indiqués dans la revendication 1. Cette invention concerne également des substances permettant de lutter contre les parasites animaux et les champignons nocifs, comprenant au moins un azadioxacycloalcène de formule générale (I) ou un sel de (I) utilisable en agriculture.
EP00972907A 1999-11-12 2000-11-10 Azadioxacycloalcenes Withdrawn EP1228050A1 (fr)

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DE19954620 1999-11-12
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BR112012033095B1 (pt) 2010-06-24 2018-10-30 Ihara Chemical Ind Co derivado de alcoxiimino, agente e método de controle de peste

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