WO1998006710A1 - Derives substitues de la 4-nitro-imino-perhydro-1,3,5-oxadiazine, leur utilisation comme pesticides, et intermediaires pour leur preparation - Google Patents

Derives substitues de la 4-nitro-imino-perhydro-1,3,5-oxadiazine, leur utilisation comme pesticides, et intermediaires pour leur preparation Download PDF

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WO1998006710A1
WO1998006710A1 PCT/EP1997/004137 EP9704137W WO9806710A1 WO 1998006710 A1 WO1998006710 A1 WO 1998006710A1 EP 9704137 W EP9704137 W EP 9704137W WO 9806710 A1 WO9806710 A1 WO 9806710A1
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formula
tautomer
compound
group
salt
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PCT/EP1997/004137
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English (en)
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Peter Maienfisch
Laurenz Gsell
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Novartis Ag
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Priority to AU42971/97A priority Critical patent/AU4297197A/en
Publication of WO1998006710A1 publication Critical patent/WO1998006710A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
    • C07D413/06—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms
    • 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
    • A01N51/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds having the sequences of atoms O—N—S, X—O—S, N—N—S, O—N—N or O-halogen, regardless of the number of bonds each atom has and with no atom of these sequences forming part of a heterocyclic ring
    • 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
    • C07D273/02—Heterocyclic compounds containing rings having nitrogen and oxygen atoms as the only ring hetero atoms, not provided for by groups C07D261/00 - C07D271/00 having two nitrogen atoms and only one oxygen atom
    • C07D273/04—Six-membered rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
    • C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
    • C07D417/06—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
    • C07D417/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing three or more hetero rings

Definitions

  • the invention relates to compounds of the formula
  • A is a substituted or unsubstituted heterocyclyl group
  • R is hydrogen or a substituted or unsubstituted alkyl, alkenyl, alkynyl, cycloalkyl, aryl or heteroaryl group;
  • R is hydrogen or a substituted or unsubstituted alkyl, alkenyl, alkynyl, cycloalkyl, aryl or heteroaryl group, in free form or in salt form, where appropriate to tautomers, in free form or in salt form, of these compounds, to a process for the preparation and to the use of these compounds and tautomers, to pesticidal compositions whose active ingredient is selected from amongst these compounds and tautomers, in each case in free form or in agrochemically utiiizable salt form, to a process for the preparation and to the use of these compositions, to plant propagation material treated with these compositions, to a method of controlling pests, to intermediates, in free form or in salt form, for the preparation of these compounds, where appropriate to tautomers, in free form or in salt form, of these intermediates, and to a process for the preparation and to the use of these intermediates.
  • the compounds I can exist as tautomers
  • the compounds I hereinabove and hereinbelow are to be understood as including such tautomers, where appropriate, even though the latter are not mentioned specifically in each individual case.
  • Compounds I which have at least one basic centre can form, for example, acid addition salts, for example with strong inorganic acids such as mineral acids, for example perchloric acid, sulfunc acid, nitric acid, nitrose acid, a phosphorus acid or a hydrohalic acid, with strong organic carboxyiic acids, such as CrC4alkanecarboxylic acids which are unsubstituted or substituted, for example by halogen, for example acetic acid, such as saturated or unsaturated dicarboxylic acids, for example oxalic acid, malonic acid, succinic acid, maleic acid, fumaric acid or phthalic acid, such as hydroxycarboxylic acids, for example ascorbic acid, lactic acid, malic acid, tartaric acid or citric acid, or such as benzoic acid, or with organic sulfonic acids, such as C ⁇ -C 4 alkane- or arylsulfonic acids which are unsubstituted or substituted, for
  • Compounds I which have at least one acidic group can form, for example, salts with bases, for example mineral salts such as alkali metal or alkaline earth metal salts, for example sodium, potassium or magnesium salts, or salts with ammonia or an organic amine, such as mor- pholine, pipendine, pyrrolidine, a mono-, di- or tri-lower-alkylamine, for example ethyl-, die- thyl-, t ⁇ ethyl- or dimethylpropylamine, or a mono-, di- or trihydroxy-lower-alkyiamine, for example mono-, di- or t ⁇ ethanolamine.
  • the corresponding internal salts can furthermore be formed.
  • agrochemically advantageous salts Preferred within the scope of the invention are agrochemically advantageous salts; however, the invention also encompasses salts which have disadvantage for agrochemical use, for example salts which are toxic to bees or fish, and which are employed, for example, for the isolation or purification of free compounds I or agrochemically horrbie salts thereof.
  • the free compounds I or their salts hereinabove and hereinbelow are respectively to be understood as including, where appropriate, the corresponding salts or the free compounds I.
  • the free form is preferred in each case.
  • Suitable as ring heteroatom(s) in the ring skeleton of the heterocyclyl group A which is, for example, bicyclic or, preferably, monocyclic, are all elements of the Periodic System which can form at least two covalent bonds (where a ring nitrogen atom is also to be understood as meaning the N-oxide form thereof) where, if the ring skeleton of A consists of more than one ring, (a) ring heteroatom(s) may be present either only in one ring or else in more than one ring of the ring skeleton of A.
  • carbon-containing groups and compounds comprise for example in each case 1 up to and including 15, preferably 1 up to and including 10, especially 1 up to and including 8, in particular 1 up to and including 5, especially 1 or 2, carbon atom(s).
  • Cycloalkyl - as a group per se and as a structural element of other groups and compounds such as halocycloalkyl, cycloalkoxy, halocycloalkoxy, cycloalkylthio and halocycloalkylthio - is, in each case with due consideration of the number of carbon atoms contained in each case in the relevant group or compound, for example cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyi or cycloheptyl.
  • Alkyl - as a group per se and as a structural element of other groups and compounds such as haloalkyi, tnalkylsilyl, alkoxy, haloalkoxy, alkylthio, haloalkylthio, alkyisulfinyl, haloalkylsul- finyl, alkylsulfinyloxy, haloalkylsulfmyloxy, alkylsulfonyl, haloalkylsulfonyl, alkylsulfonyloxy, haloalkylsulfonyloxy, alkylcarbonyl, alkylcarbonyloxy, alkoxycarbonyl, alkoxycarbonyloxy, alkoxyalkoxy, alkylamino, dialkylamino, N-alkylarylamino, N-alkylcarbonylarylamino, N-alkyl- heteroarylamino and N-alkylcarbonylhe
  • Alkenyl - as a group per se and as a structural element of other groups and compounds such as haloalkenyl, alkenyloxy, haloalkenyloxy, alkenylthio and haloalkenylthio - is, in each case with due consideration of the number of carbon atoms contained in each case in the relevant group or compound, either straight-chain or branched and comprises in each case 2 or more than 2 or preferably 1 carbon-carbon double bond(s), the double bonds of these substituents being separated from the remaining moiety of the compound I by preferably at least one saturated carbon atom, and is, for example, ally!, propen-2-yl, methallyl, but-2-en- 1-yl, but-3-en-1 -yl, pent-4-en-1-yl or undec-10-en-1-yl.
  • Alkynyl - as a group per se and as a structural element of other groups and compounds such as haloalkynyl, alkynyloxy, haloalkynyloxy, alkynylthio and haloalkynylthio - is, in each case with due consideration of the number of carbon atoms contained in each case in the relevant group or compound, either straight-chain or branched and comprises in each case 2 or more than 2 or preferably 1 carbon-carbon triple bond(s), the triple bonds of these substituents being separated from the remaining moiety of the compound I by preferably at least one saturated carbon atom, and is, for example, propargyl, but-2-ynyl or but-3-yn-2-yl
  • Heteroaryl - as a group per se and as a structural element of other groups and compounds such as heteroarylcarbonyl, heteroarylcarbonyloxy, heteroaryloxy, heteroarylthio, heteroa- rylsulfinyl, heteroarylsulfinyioxy, heteroarylsulfonyl, heteroarylsulfonyloxy, heteroarylamino, N-alkyl-heteroarylamino, N-formyl-heteroarylamino and N-alkylcarbonyl-heteroarylamino - has, for example, an aromatic ring skeleton composed of a ring having 5 or 6 ring members or of a combination of at least two rings having in each case independently of one another 5 or 6 ring members, where for example 1 up to and including 4 of the ring members is (are) (a) heteroatom(s) selected from the group consisting of nitrogen, oxygen and sulfur, and is, for example, pyridyl, thieny
  • Non-aromatic heterocyclyl - as a group per se and as a structural element of other groups and compounds such as non-aromatic heterocyclyloxy and non-aromatic heterocyclylthio - has, for example, a non-aromatic ring skeleton composed of a ring having 5 or 6 ring members or of a combination of at least two rings having in each case independently of one another 5 or 6 ring members, where for example 1 up to and including 4 of the ring members is (are) (a) heteroatom(s) selected from the group consisting of nitrogen, oxygen and sulfur and is, for example, piperidyl, pyrrolinyl, tetrahydrofuryl or chromanyl.
  • alkoxyalkoxy an alkoxy group which is bonded to the remaining moiety of the compound I is substituted by, for example, 2 or 3 or, preferably, 1 alkoxy group(s).
  • N-alkyl-arylamino an arylamino group which is bonded to the remaining moiety of the compound I is substituted on its nitrogen atom by one alkyl group.
  • N-formyl-arylamino an arylamino group which is bonded to the remaining moiety of the compound I is substituted on its nitrogen atom by one formyl group.
  • N-alkylcarbonyl-arylamino an arylamino group which is bonded to the remaining moiety of the compound I is substituted on its nitrogen atom by one alkylcarbonyl group.
  • N-alkyl-heteroarylamino a heteroarylammo group which is bonded to the remaining moiety of the compound I is substituted on its ammo nitrogen atom by one alkyl group.
  • N-formyl-heteroarylamino a heteroarylammo group which is bonded to the remaining moiety of the compound I is substituted on its amino nitrogen atom by one formyl group.
  • N-alkylcarbonyl-heteroarylamino a heteroarylammo group which is bonded to the remaining moiety of the compound I is substituted on its ammo nitrogen atom by one alkylcarbonyl group.
  • a compound of the formula I in which A is a substituted or unsubstituted heterocyclyl group;
  • a compound of the formula I in which the ring skeleton of A is saturated or unsaturated, in particular the ring skeleton of A comprises no, or 2 to 4, preferably conjugated, double bond(s), preferably comprises no, or 2 or 3, preferably conjugated, double bonds, especially comprises 2 or 3, preferably conjugated, double bonds, in particular the ring skeleton of A has aromatic character;
  • a compound of the formula I in which the ring skeleton of A comprises 1 up to and including 4, in particular 1 up to and including 3, especially 1 or 2, ring heteroatom(s) (where a ring nitrogen atom is also to be understood as meaning the N-oxide form thereof); (5) A compound of the formula I, in which the ring skeleton of A comprises 1 , 2 or 3 ring he- tero atom(s) selected from the group consisting of oxygen, sulfur and nitrogen (where a ring nitrogen atom is also to be understood as meaning the N-oxide form thereof), where the ring skeleton comprises not more than one ring oxygen atom and where the ring skeleton comprises not more than one nng sulfur atom, in particular comprises 1 , 2 or 3 ring heteroatom(s) selected from the group consisting of oxygen, sulfur and nitrogen (where a ring nitrogen atom is also to be understood as meaning the N-oxide form thereof), where the ring skeleton comprises not more than one ring oxygen atom or one ring sulfur
  • a compound of the formula I in which A is unsubstituted or mono- to tetrasubstituted, where up to two of the substituents of A are selected from the group consisting of halogen, cycloalkyl, halocycloalkyl, alkyl, haloalkyi, alkenyl, haloalkenyl, alkynyl, haloalkynyl, alkoxy, haloalkoxy, alkylthio, haloalkylthio, alkenyloxy, haloalkenyloxy, alkynyloxy, haloalkynyloxy, alkenylthio, haloalkenylthio, alkynylthio, haloalkynylthio, cyano and nitro, and where, if A is t ⁇ - or tetrasubstituted, each substituent of A, which differs from the two substituents, which lead to the di
  • 2-haloth ⁇ azol-5-yl group preferably A is a py ⁇ d-3-yl, 2-chloropyr ⁇ d-5-yl, 2-chloro-1 -oxido-5-pyr ⁇ d ⁇ n ⁇ o or 2-chloroth ⁇ - azol-5-yl group, in particular A is a 2-chloropyrid-5-yl or 2-chloroth ⁇ azol-5-yl group;
  • R is hydrogen or a substituted or unsubstituted alkyl, alkenyl, alkynyl, cycloalkyl, aryl or heteroaryl group
  • R is hydrogen or an alkyl, alkenyl, alkynyl, cycloalkyl, aryl or heteroaryl group which is unsubstituted or mono- to tnsubstituted by substituents selected from the group consisting of halogen, cyano, nitro, tnalkylsilyl, ammo, alkylamino, dialkylamino, alkyl, haloalkyi, hydroxy, alkoxy, haloalkoxy, alkoxyalkoxy, mercapto, alkylthio, haloalkylthio, alkyisulfinyl, haloalkylsulfinyl, alkylsulfinyloxy, haloalkylsulfulfinylsulfiny
  • R is a C ⁇ -C ⁇ alkyl group which is unsubstituted or mono- to trisubstituted by substituents selected from the group consisting of halogen, C ⁇ -C 5 alkylcarbonyloxy, C 3 -C 8 cycloal- kyl, unsubstituted phenyl and phenyl which is mono- to trisubstituted by substituents selected from the group consisting of C C 5 alkyl and nitro; an unsubstituted C 2 -C 6 alkenyl or C 3 - C ⁇ cycloalkyl group; or a phenyl group which is unsubstituted or mono- to trisubstituted by substituents selected from the group consisting of halogen, cyano, nitro, C ⁇ -C 5 alkyl, halo- C ⁇ -C 5 alkyl, CrC 5 alkoxy and C ⁇
  • the process for the preparation of the compounds of the formula I or, where appropriate, a tautomer thereof, in each case in free form or in salt form comprises, for example, a) reacting a compound of the formula
  • the reactions described hereinabove and hereinbelow are carried out in a manner known per se, for example in the absence or, normally, in the presence of a suitable solvent or diluent or of a mixture of these, the process being carried out, as required, with cooling, at room temperature or with heating, for example in a temperature range of from approximately -80°C to the boiling point of the reaction mixture, preferably from approximately -20°C to approximately +150 C C, and, if required, in a sealed vessel, under pressure, in an inert gas atmosphere and/or under anhydrous conditions.
  • a suitable solvent or diluent or of a mixture of these the process being carried out, as required, with cooling, at room temperature or with heating, for example in a temperature range of from approximately -80°C to the boiling point of the reaction mixture, preferably from approximately -20°C to approximately +150 C C, and, if required, in a sealed vessel, under pressure, in an inert gas atmosphere and/or under anhydrous conditions.
  • Examples of suitable leaving groups Y in the compounds III are hydroxy, d-C ⁇ alkoxy, halo- C ⁇ -C ⁇ alkoxy, d-C 8 alkanoyloxy, mercapto, d-C 8 alkylthio, halo-d-C 8 alkylthio, d-C 8 alkylsul- fonyloxy, halo-d-C 8 alkylsulfonyloxy, benzenesulfonyloxy, toluenesulfonyloxy and preferably halogen, such as chlorine.
  • suitable bases for facilitating the detachment of HY are alkali metal or alkaline earth metal hydroxides, alkali metal or alkaline earth metal hydrides, alkali metal or alkaline earth metal amides, alkali metal or alkaline earth metal alkoxides, alkali metal or alkaline earth metal acetates, alkali metal or alkaline earth metal carbonates, alkali metal or alkaline earth metal dialkylamides or alkali metal or alkaline earth metal alkylsilylamides, alkyla- mines, alkylenediamines, free or N-alkylated saturated or unsaturated cycloalkylamines, basic heterocycles, ammonium hydroxides and carbocyciic amines.
  • Examples which may be mentioned are sodium hydroxide, sodium hydride, sodium amide, sodium methoxide, sodium acetate, sodium carbonate, potassium tert-butoxide, potassium hydroxide, potassium carbonate, potassium hydride, lithium diisopropylamide, potassium bis(trimethylsilyl)amide, calcium hydride, triethyiamine, diisopropylethylamine, triethylenediamine, cyclohexylamine, N-cyclohexyl-N.N-dimethylamine, N,N-diethylaniline, pyridine, 4-(N,N-dimethylamino)pyri- dine, quinuclidine, N-methylmorpholine, benzyltrimethylammonium hydroxide and 1 ,8-diaza- bicyclo[5.4.0]undec-7-ene (DBU).
  • DBU benzyltrimethylammonium hydroxide
  • the reactants can be reacted with each other as such, i.e. without addition of a solvent or diluent, for example in the melt. In most cases, however, it is advantageous to add an inert solvent or diluent or a mixture of these.
  • solvents or diluents which may be mentioned are: aromatic, aliphatic and alicyclic hydrocarbons and halohydrocarbons such as benzene, toluene, xylene, mesitylene, tetralin, chlorobenzene, dichlorobenzene, bromo- benzene, petroleum ether, hexane, cyclohexane, dichloromethane, trichloromethane, tetra- chloromethane, dichloroethane, trichloroethene or tetrachloroethene; esters such as ethyl acetate; ethers such as diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, tert-bu- tyl methyl ether, ethyleneglycol monomethyl ether, ethylene glycol monoethyl ether, ethyle- n
  • bases which are employed in excess such as triethyiamine, pyridine, N-methylmorpholine or N,N- diethylaniline, may also act as solvents or diluents.
  • the reaction is advantageously carried out in a temperature range from approximately -80°C to approximately +140°C, preferably from approximately -30°C to approximately +100°C, in many cases from approximately -10°C to approximately +80°C.
  • a compound II is reacted with a compound III in an amide such as N.N-dimethylformamide, in the presence of a base such as NaH, in a temperature range from approximately 0°C to approximately +70°C.
  • Examples of suitable leaving groups Y in the compounds V are of the type given under variant a).
  • Examples of suitable bases for facilitating the detachment of HY are of the type given under variant a).
  • the reactants can be reacted with each other as such, i.e. without adding a solvent or diluent, for example in the melt. In most cases, however, it is advantageous to add an inert solvent or diluent or a mixture of these. Examples of suitable diluents or solvents are of the type described under variant a).
  • the reaction is advantageously carried out in a temperature range from approximately -80°C to approximately +140°C, preferably from approximately -20°C to approximately +100°C, in many cases from approximately 0°C to approximately +80°C.
  • a compound IV is reacted with a compound V in a halogenated or unhalogenated hydrocarbon, such as dichloromethane, an amide such as N.N-dimethylformamide or a nitrile such as acetonitrile, in the presence of a base such as pyridine or NaH in a temperature range from approximately +10°C to approximately +50°C.
  • a halogenated or unhalogenated hydrocarbon such as dichloromethane
  • an amide such as N.N-dimethylformamide or a nitrile such as acetonitrile
  • the reactants can be reacted with each other as such, i.e. without adding a solvent or diluent, for example in the melt. In most cases, however, it is advantageous to add an inert solvent or diluent or a mixture of these. Examples of suitable diluents or solvents are of the type described under variant a).
  • the reaction is advantageously carried out in a temperature range from approximately -80°C to approximately +140°C, preferably from approximately -20°C to approximately +100 C C, in many cases in the range between room temperature and the reflux temperature of the reaction mixture.
  • Another subject of the invention is the process for the preparation of the compounds of the formula II or the tautomers thereof, in each case in free form or in salt form, which comprises, for example, d) reacting the compound of the formula
  • a compound I or II, respectively, can be converted in a manner known per se into another compound I or II, respectively, by replacing one or more substituents of the starting compound I or II, respectively, in the customary manner by (an)other subst ⁇ tuent(s) according to the invention.
  • radical A in compounds I which have a substituted radical A, substituents of the radical A can be replaced by other substituents.
  • Salts of compounds I or II, respectively can be prepared in a manner known per se.
  • acid addition salts of compounds I or II, respectively are obtained by treatment with a suitable acid or a suitable ion exchanger reagent and salts with bases are obtained by treatment with a suitable base or with a suitable ion exchanger reagent.
  • Salts of compounds I or II, respectively can be converted in the customary manner into the free compounds I or II, respectively, acid addition salts, for example, by treatment with a suitable basic compound or with a suitable ion exchanger reagent and salts with bases, for example, by treatment with a suitable acid or with a suitable ion exchanger reagent.
  • Salts of compounds I or II, respectively can be converted in a manner known per se into other salts of compounds I or II, respectively, acid addition salts, for example, into other acid addition salts, for example by treatment of a salt of inorganic acid such as hydrochloride with a suitable metal salt such as a sodium, barium or silver salt, of an acid, for example with silver acetate, in a suitable solvent in which an inorganic salt which forms, for example silver chloride, is insoluble and thus precipitates from the reaction mixture.
  • a salt of inorganic acid such as hydrochloride
  • a suitable metal salt such as a sodium, barium or silver salt
  • the compounds I or II, respectively, which have salt-forming properties can be obtained in free form or in the form of salts.
  • the compounds I and II, respectively, and, where appropriate, in each case the tautomers thereof, in each case in free form or in salt form, can be present in the form of one of the isomers which are possible or as a mixture of these, for example in the form of pure iso- mers, such as antipodes and/or diastereomers, or as isomer mixtures, such as enantiomer mixtures, for example racemates, diastereomer mixtures or racemate mixtures, depending on the number, absolute and relative configuration of asymmetric carbon atoms which occur in the molecule and/or depending on the configuration of non-aromatic double bonds which occur in the molecule; the invention relates to the pure isomers and also to all isomer mixtures which are possible and is to be understood in each case in this sense hereinabove and hereinbelow, even when stereochemical details are not mentioned specifically in each case.
  • Diastereomer mixtures or racemate mixtures of compounds I or II, respectively, in free form or in salt form, which can be obtained depending on which starting materials and procedures have been chosen can be separated in a known manner into the pure diasteromers or racemates on the basis of the physicochemical differences of the components, for example by fractional crystallization, distillation and or chromatography.
  • Enantiomer mixtures such as racemates, which can be obtained in a similar manner can be resolved into the optical antipodes by known methods, for example by recrystallization from an optically active solvent, by chromatography on chiral adsorbents, for example high- performance liquid chromatography (HPLC) on acetyl celulose, with the aid of suitable microorganisms, by cleavage with specific, immobilized enzymes, via the formation of inclusion compounds, for example using chiral crown ethers, where only one enantiomer is com- plexed, or by conversion into diastereomeric salts, for example by reacting a basic end-product racemate with an optically active acid, such as a carboxyiic acid, for example camphor, tartaric or malic acid, or sulfonic acid, for example camphorsulfonic acid, and separating the diastereomer mixture which can be obtained in this manner, for example by fractional crystallization based on their differing solubil
  • Pure diastereomers or enantiomers can be obtained according to the invention not only by separating suitable isomer mixtures, but also by generally known methods of diastereose- lective or enantioselective synthesis, for example by carrying out the process according to the invention with starting materials of a suitable stereochemistry.
  • the compounds I and II, respectively, in free form or in salt form, can, if appropriate, also be obtained in the form of hydrates and/or include other solvents, for example those which may have been used for the crystallization of compounds which are present in solid form.
  • the invention relates to all those embodiments of the process by which, starting from a compound obtainable at any level of the process as starting material or intermediate, all or some of the missing steps are carried out or a starting material is used in the form of a derivative and/or salt and/or racemates or antipodes thereof or, in particular, is formed under the reaction conditions.
  • the invention relates to the preparation processes described in Examples H1 to
  • the compounds I according to the invention are preventively and/or curatively valuable active ingredients in the field of pest control, even at low rates of application, which have a very favorable biocidal spectrum and are well tolerated by warm-blooded species, fish and plants.
  • the active ingredients according to the invention act against all or individual developmental stages of normally sensitive, but also resistant, animal pests, such as insects or representatives of the order Acarina.
  • the insecticidal or acaricidal activity of the active ingredients according to the invention can manifest itself directly, i. e.
  • Examples of the abovementioned animal pests are: from the order Acarina, for example,
  • Haematopinus spp. Linognathus spp., Pediculus spp., Pemphigus spp. and Phylloxera spp.; from the order Coleoptera, for example,
  • Sitophilus spp. Sitotroga spp., Tenebno spp., Tribohum spp. and Trogoderma spp.; from the order Diptera, for example,
  • Cimex spp. Distantiella theobroma, Dysdercus spp., Euchistus spp., Eurygaster spp., Lep- tocorisa spp., Nezara spp., Piesma spp., Rhodnius spp., Sahlbergella singularis, Scotino- phara spp. and Triatoma spp.; from the order Homopt ⁇ ra, for example,
  • Atta spp. Cephus spp., Diprion spp., Diprionidae, Gilpinia polytoma, Hoplo- campa spp., Lasius spp., Monomorium pharaonis, Neodiprion spp., Solenopsis spp. and Vespa spp.; from the order Isoptera, for example, Reticulitermes spp.; from the order Lepidopt ⁇ ra, for example,
  • Ostrinia nubilalis Pammene spp., Pandemis spp., Panolis flammea, Pectinophora gossypi- ela, Phthorimaea operculella, Pieris rapae, Pieris spp., Plutella xylostella, Prays spp., Scir- pophaga spp., Sesamia spp., Sparganothis spp., Spodoptera spp., Synanthedon spp.,
  • Thaumetopoea spp. Tortrix spp., Trichoplusia ni and Yponomeuta spp.; from the order Mallophaga, for example,
  • Blatta spp. Blattella spp., Gryllotalpa spp., Leucophaea maderae, Locusta spp., Periplaneta spp. and Schistocerca spp.; from the order Psocoptera, for example,
  • Liposcelis spp. from the order Siphonaptera, for example,
  • the active ingredients according to the invention can be used for controlling, i. e. containing or destroying, pests of the abovementioned type which occur in particular on plants, especially on useful plants and ornamentals in agriculture, in horticulture and in forests, or on organs, such as fruits, flowers, foliage, stalks, tubers or roots, of such plants, and in some cases even plant organs which are formed at a later point in time remain protected against these pests.
  • Suitable target crops are, in particular, cereals, such as wheat, barley, rye, oats, rice, maize or sorghum; beet, such as sugar or fodder beet; fruit, for example pomaceous fruit, stone fruit or soft fruit, such as apples, pears, plums, peaches, almonds, cherries or berries, for example strawberries, raspberries or blackberries; leguminous crops, such as beans, lentils, peas or soya; oil crops, such as oilseed rape, mustard, poppies, olives, sunflowers, coconut, castor, cocoa or ground nuts; cucurbits, such as pumpkins, cucumbers or melons; fibre plants, such as cotton, flax, hemp or jute; citrus fruit, such as oranges, lemons, grapefruit or tangerines; vegetables, such as spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes or bell peppers; Lauraceae, such as avocado, Cinnamonium or camphor; and also tobacco, nuts,
  • the active ingredients according to the invention are especially suitable for controlling Aphis craccivora, Diabrotica balteata, Myzus persicae and Nilaparvata lugens in vegetable, maize and rice crops.
  • the invention therefore also relates to pesticidal compositions such as emulsifiable concentrates, suspension concentrates, directly sprayable or dilutable solutions, spreadable pastes, dilute emulsions, soluble powders, dispersible powders, wettable powders, dusts, granules or encapsulations in polymeric substances, which comprise - at least - one of the active ingredients according to the invention and which are to be selected to suit the intended aims and the prevailing circumstances.
  • pesticidal compositions such as emulsifiable concentrates, suspension concentrates, directly sprayable or dilutable solutions, spreadable pastes, dilute emulsions, soluble powders, dispersible powders, wettable powders, dusts, granules or encapsulations in polymeric substances, which comprise - at least - one of the active ingredients according to the invention and which are to be selected to suit the intended aims and the prevailing circumstances.
  • the active ingredient is employed in pure form, a solid active ingredient for example in a specific particle size, or, preferably, together with - at least - one of the auxiliaries conventionally used in the art of formulation, such as extenders, for example solvents or solid carriers, or such as surface-active compounds (surfactants).
  • auxiliaries conventionally used in the art of formulation, such as extenders, for example solvents or solid carriers, or such as surface-active compounds (surfactants).
  • suitable solvents are: unhydrogenated or partially hydrogenated aromatic hydrocarbons, preferably the fractions C 8 to C, 2 of alkylbenzenes, such as xylene mixtures, al- kylated naphthalenes or tetrahydronaphthalene, aliphatic or cycloaliphatic hydrocarbons, such as paraffins or cyclohexane, alcohols such as ethanol, propanol or butanol, glycols and their ethers and esters such as propylene glycol, dipropylene glycol ether, ethylene gly- col or ethylene glycol monomethyl ether or ethylene glycol monoethyl ether, ketones, such as cyclohexanone, isophorone or diacetone alcohol, strongly polar solvents, such as N-me- thylpyrrolid-2-one, dimethyl sulfoxide or N.N-dimethylformamide, water, unepoxidized or epoxidized vegetable
  • Solid carriers which are used for example for dusts and dispersible powders are, as a rule, ground natural minerals such as calcite, talc, kaolin, montmorillonite or attapulgite.
  • ground natural minerals such as calcite, talc, kaolin, montmorillonite or attapulgite.
  • highly disperse silicas or highly disperse absorbtive polymers are also possible to add highly disperse silicas or highly disperse absorbtive polymers.
  • Suitable particulate adsorptive carriers for granules are porous types, such as pumice, brick grit, sepiolite or bentonite, and suitable non-sorptive carrier materials are calcite or sand.
  • a large number of granulated materials of inorganic or organic nature can be used, in particular dolomite or comminuted plant residues.
  • Suitable surface-active compounds are, depending on the type of the active ingredient to be formulated, non-ionic, cationic and/or anionic surfactants or surfactant mixtures which have good emulsifying, dispersing and wetting properties.
  • the surfactants mentioned below are only to be considered as examples; a large number of further surfactants which are conventionally used in the art of formulation and suitable according to the invention are described in the relevant literature.
  • Suitable non-ionic surfactants are, especially, polyglycol ether derivatives of aliphatic or cyc- loaliphatic alcohols, of saturated or unsaturated fatty acids or of alkyl phenols which may contain approximately 3 to approximately 30 glycol ether groups and approximately 8 to approximately 20 carbon atoms in the (cyclo)aliphatic hydrocarbon radical or approximately 6 to approximately 18 carbon atoms in the alkyl moiety of the alkyl phenols.
  • water-soluble polyethylene oxide adducts with polypropylene glycol, ethylenediaminopo- lypropylene glycol or alkyl polypropylene glycol having 1 to approximately 10 carbon atoms in the alkyl chain and approximately 20 to approximately 250 ethylene glycol ether groups and approximately 10 to approximately 100 propylene glycol ether groups.
  • the abovementioned compounds contain 1 to approximately 5 ethylene glycol units per propylene glycol unit.
  • nonylphenoxypolyethoxyethanol examples which may be mentioned are nonylphenoxypolyethoxyethanol, castor oil polyglycol ether, polypropylene glycol/polyethylene oxide adducts, tributylpheno- xypolyethoxyethanol, polyethylene glycol or octylphenoxypolyethoxyethanol.
  • fatty acid esters of polyoxyethylene sorbitan such as polyoxyethylene sorbitan trioleate.
  • the cationic surfactants are, especially, quarternary ammonium salts which generally have at least one alkyl radical of approximately 8 to approximately 22 C atoms as substituents and as further substituents (unhalogenated or halogenated) lower alkyl or hydroxyalkyl or benzyl radicals.
  • the salts are preferably in the form of halides, methylsulfates or ethylsul- fates. Examples are stearyltrimethylammonium chloride and benzylbis(2-chloroethyl)ethyl- ammonium bromide.
  • Suitable anionic surfactants are water-soluble soaps or water-soluble synthetic surface-active compounds.
  • suitable soaps are the alkali, alkaline earth or (unsubstituted or substituted) ammonium salts of fatty acids having approximately 10 to approximately 22 C atoms, such as the sodium or potassium salts of oleic or stearic acid, or of natural fatty acid mixtures which are obtainable for example from coconut or tall oil; mention must also be made of the fatty acid methyl taurates.
  • synthetic surfactants are used more frequently, in particular fatty sulfonates, fatty sulfates, sulfonated benzimidazole derivatives or alkylaryl sulfonates.
  • the fatty sulfonates and fatty sulfates are present as alkali, alkaline earth or (substituted or unsubstituted) ammonium salts and they generally have an alkyl radical of approximately 8 to approximately 22 C atoms, alkyl also to be understood as including the alkyl moiety of acyl radicals; examples which may be mentioned are the sodium or calcium salts of lignosulfonic acid, of the dodecylsulfuric ester or of a fatty alcohol sulfate mixture prepared from natural fatty acids. This group also includes the salts of the sulfuric esters and sulfonic acids of fatty alcohol/ethylene oxide adducts.
  • the sulfonated benzimidazole derivatives preferably contain 2 sulfonyl groups and a fatty acid radical of approximately 8 to approximately 22 C atoms.
  • alkylarylsulfonates are the sodium, calcium or triethanolammonium salts of decylbenzenesulfonic acid, of dibutyl- naphthalenesulfonic acid or of a naphthalenesuifonic acid/formaldehyde condensate.
  • suitable phosphates such as salts of the phosphoric ester of a p- nonylphenol/(4-14)ethylene oxide adduct, or phospholipids.
  • the compositions comprise from 0.0001 to 99.9999 %, in particular 0.1 to 95 %, of active ingredient, and 0.0001 to 99.9999 %, in particular 5 to 99.9 %, of - at least - one solid or liquid auxiliary, it being possible, as a rule, for 0 to 25 %, in particular 0.1 to 20 %, of the compositions to be surfactants (% in each case is per cent by weight). While concentrated compositions are more preferred as commercially available goods, the end user uses, as a rule, dilute compositions which have considerably lower concentrations of active ingredient.
  • compositions according to the invention can be broadened considerably, and adapted to prevailing circumstances, by adding other insecticidally or acaricidally active ingredients.
  • Suitable additions to active ingredients are, for example, representatives of the following class of active ingredients: organophosphorus compounds, nitrophenol derivatives, thioureas, juvenile hormones, formamidines, benzophenone derivatives, ureas, pyrrole derivatives, carbamates, pyrethroids, chlorinated hydrocarbons, acylureas, pyridyl- methyleneamino derivatives and Bacillus thuringiensis preparations.
  • compositions can also comprise further solid or liquid auxiliaries, such as stabilizers, for example unepoxidi- zed or epoxidized vegetable oils (for example epoxidized coconut oil, rapeseed oil or soya oil), antifoams, for example silicone oil, preservatives, viscosity regulators, binders and/or tackifiers, fertilizers or other active ingredients for achieving specific effects, for example bactericides, fungicides, nematocides, plant activators, molluscicides or herbicides.
  • auxiliaries such as stabilizers, for example unepoxidi- zed or epoxidized vegetable oils (for example epoxidized coconut oil, rapeseed oil or soya oil), antifoams, for example silicone oil, preservatives, viscosity regulators, binders and/or tackifiers, fertilizers or other active ingredients for achieving specific effects, for example bactericides, fungicides, nem
  • compositions according to the invention are prepared in a manner known per se, in the absence of auxiliaries for example by grinding, screening and/or compressing a solid active ingredient and in the presence of at least one auxiliary for example by intimately mixing and/or grinding the active ingredient with the auxiliary (auxiliaries).
  • auxiliaries for example by grinding, screening and/or compressing a solid active ingredient and in the presence of at least one auxiliary for example by intimately mixing and/or grinding the active ingredient with the auxiliary (auxiliaries).
  • compositions that is the methods of controlling pests of the abovementioned type, such as spraying, atomizing, dusting, brushing on, dressing, scattering or pouring - which are to be selected to suit the intended aims of the prevailing circumstances - and the use of the compositions for controlling pests of the abovementioned type are other subjects of the invention.
  • Typical rates of concentration are between 0.1 and 1000 ppm, preferably between 0.1 and 500 ppm, of active ingredient.
  • the rate of application per hectare is generally 1 to 2000 g of active ingredient per hectare, in particular 10 to 1000 g/ha, preferably 10 to 600 g/ha.
  • a preferred method of application in the field of crop protection is application to the foliage of the plants (foliar application), it being possible to select frequency and rate of application to match the danger of infestation with the pest in question.
  • the active ingredient can reach the plants via the root system (systemic action), by drenching the locus of the plants with a liquid composition or by incorporating the active ingredient in solid form into the locus of the plants, for example into the soil, for example in the form of granules (soil application).
  • systemic action systemic action
  • the active ingredient in solid form into the locus of the plants for example into the soil, for example in the form of granules (soil application).
  • paddy rice crops such granules can be metered into the flooded paddy-field
  • compositions according to the invention are also suitable for the protection of plant propagation material, for example seeds, such as fruit, tubers or kernels, or nursery plants, against pests of the abovementioned type.
  • the propagation mate ⁇ al can be treated with the compositions prior to planting, for example seed can be treated prior to sowing.
  • the compositions can be applied to seed kernels (coating), either by soaking the kernels in a liquid composition or by applying a layer of a solid composition. It is also possible to apply the compositions when the propagation material is planted to the site of application, for example into the seed furrow during drilling.
  • Example H2 The other compounds listed in Table 1 and the tautomers thereof can also be prepared analogously to the procedure described in Example H1.
  • a mixture of 1.8 g of 4-nitroimino-perhydro-1 ,3,5-oxadiaz ⁇ ne and 20 ml of dry N,N-d ⁇ methyl- formamide (DMF) is treated, at 0°, with 0.34 g of sodium hydnde (80% in oil), and the mixture is stirred for one hour at 0-5°. Then, a solution of 2 g of 2-chloro-5-chloromethyl-pyr ⁇ - dine in 20 ml of dry DMF is added dropwise in the course of 20 minutes at 0-5°. The reaction mixture is stirred for 2 hours at the same temperature, ice-water is added, and the mixture is extracted with ethyl acetate.
  • DMF dry N,N-d ⁇ methyl- formamide
  • Example H5 3-Acetyl-5-(2-chloroth ⁇ azol-5-ylmethyl)-4-n ⁇ troim ⁇ no-perhydro-1 ,3,5-oxad ⁇ az ⁇ ne
  • the reaction mixture ⁇ s stirred for 15 minutes at room temperature, a solution of 1.1 ml of phenylacetyl chloride in 10 ml of dry DMF is added, and the mixture is stirred for 16 hours at room temperature, poured into 50 ml of hydrochloric acid (1N) and extracted with 100 ml of ethyl acetate.
  • Example F1 Emulsion concentrates a) b) c)
  • Tributylphenoxypolyethylene glycol ether (30 mol of EO) - 12 % 4 % ⁇
  • Emulsions of any desired concentration can be prepared from such concentrates by dilution with water.
  • Petroleum ether (boiling range: 160-190°)
  • the solutions are suitable for use in the form of microdrops.
  • Example F3 Granules a) b) c) d)
  • Example F4 Dusts Active ingredient Highly disperse silica Talc Kaolin
  • Ready-to-use dusts are obtained by intimately mixing carriers and active ingredient.
  • the active ingredient is mixed with the additives and the mixture is ground thoroughly in a suitable mill This gives wettable powders which can be diluted with water to give suspensions of any desired concentration.
  • Example F6 Emulsion concentrate
  • Emulsions of any desired concentration can be prepared from this concentrate by dilution with water.
  • Ready-to-use dusts are obtained by mixing the active ingredient with the carrier and thoroughly grinding the mixture in a suitable mill.
  • Example F8 Extruder granules
  • the active ingredient is mixed with the additives, and the mixture is ground, moistened with water, extruded, granulated and dried in a stream of air.
  • the finely ground active ingredient is applied uniformly to tne kaolin which has been moistened with polyethylene glycol. This gives dust-free coated granules.
  • Nonylphenoxypolyethylene glycol ether (15 mol of EO) 6 %
  • the finely ground active ingredient is mixed intimately with the additives.
  • Suspensions of any desired concentration can be prepared from the thus resulting suspension concentrate by dilution with water.
  • Example B1 Activity against Anthonomus grandis
  • the percentage reduction in population and in feeding damage are determined by comparing the number of dead beetles and the feeding damage between the treated and untreated plants.
  • Example B2 Activity against Aphis craccivora
  • Pea seedlings are infected with Aphis craccivora, subsequently sprayed with a spray mixture which comprises 400 ppm of active ingredient and then incubated at 20°. 3 and 6 days later, the test is evaluated.
  • the percentage reduction in population is determined by comparing the number of dead aphids on the treated and on untreated plants.
  • compounds of Tables 2 to 4 show good activity.
  • compounds nos. 2.1 , 2.2 and 2.20 have an efficacy of over 80 %.
  • Dwarf bean plants are placed into gauze cages and populated with adult Bemisia tabaci. After oviposition has taken place, all the adults are removed. 10 days later, the plants with the nymphs thereon are sprayed with an aqueous emulsion spray mixture which comprises 400 ppm of active ingredient. After a further 14 days, the percentage hatching rate of the eggs is evaluated in comparison with untreated control batches. In this test, compounds of Tables 2 to 4 show good activity.
  • Example B4 Activity against Blattella oermanica
  • the amount of a solution (0.1%) of the active ingredient in acetone which is introduced into a Petri dish corresponds to a rate of application of 1 g/m 2 .
  • 10 nymphs of Blattella germanica (last nymphal stage) are introduced into the dish, exposed to the action of the test substance for 2 hours, then anaesthetized with CO 2l transferred into a fresh Petri dish and kept in the dark at 25° and an atmospheric humidity of approximately 70 %. After 48 hours, the insecticidal activity is determined by determining the mortality. In this test, compounds of Tables 2 to 4 show good activity.
  • Example B5 Activity aoainst Ctenocephalides felis
  • Maize seedlings are sprayed with an aqueous emulsion spray mixture which comprises 400 ppm of active ingredient, and, after the spray coating has dried on, populated with 10 larvae (2nd instar) of Diabrotica balteata and introduced into a plastic container. 6 days later, the test is evaluated. The percentage reduction in population (% activity) is determined by comparing the number of dead larvae between the treated and untreated plants. In this test, compounds of Tables 2 to 4 show good activity. In particular, compounds nos.
  • Example B7 Activity aoainst Heliothis virescens (foliar application)
  • Young soya plants are sprayed with an aqueous emulsion spray mixture which comprises
  • % activity are determined by comparing the number of dead caterpillars and the feeding damage between the treated and untreated plants.
  • Example B8 Activity against Heliothis virescens (application to e ⁇ osl Heliothis virescens eggs which have been deposited on cotton are sprayed with an aqueous emulsion spray mixture which comprises 400 ppm of active ingredient. After 8 days, the percentage hatching rate of the eggs and the survival rate of the caterpillars are evaluated in comparison with untreated control batches (% reduction in population). In this test, compounds of Tables 2 to 4 show good activity.
  • Example B10 Activity against Musca domestica
  • Pea seedlings are infected with Myzus persicae, subsequently sprayed with a spray mixture which comprises 400 ppm of active ingredient and then incubated at 20°. 3 and 6 days later, the test is evaluated.
  • the percentage reduction in population is determined by comparing the number of dead aphids on the treated and on untreated plants.
  • compounds of Tables 2 to 4 show good activity.
  • the compounds nos. 2.1 , 2.2 and 2.20 have an efficacy of over 80 %.
  • Example B12 Activity aoainst Mvzus persicae (systemic application! Pea seedlings are infected with Myzus persicae, and the roots are subsequently placed into a spray mixture which comprises 400 ppm of active ingredient, whereupon the seedlings are incubated at 20°. 3 and 6 days later, the test is evaluated. The percentage reduction in population (% activity) is determined by comparing the number of dead aphids on the treated and on untreated plants.
  • Example B13 Activity against Nephotettix cincticeps (foliar application) Rice plants are sprayed with an aqueous emulsion spray mixture which comprises 400 ppm of active ingredient and, after the spray coating has dried on, populated with larvae (2nd and 3rd instar) of Nephotettix cincticeps. 21 days later, the test is evaluated. The percentage reduction in population (% activity) is determined by comparing the number of surviving leaf hoppers on the treated and on untreated plants. In this test, compounds of Tables 2 to 4 show good activity.
  • Example B14 Activity against Nephotettix cincticeps (systemic application) Rice plants in pots are placed into an aqueous emulsion spray mixture which comprises 400 ppm of active ingredient. The plants are subsequently populated with larvae (2nd and 3rd instar) of Nephotettix cincticeps. 6 days later, the test is evaluated. The percentage reduction in population (% activity) is determined by comparing the number of surviving leaf hop pers on the treated and on untreated plants.
  • Example B15 Activity against Nilaparvata luoens (foliar application)
  • Rice plants are sprayed with an aqueous emulsion spray mixture which comprises 400 ppm of active ingredient and, after the spray coating has dried on, populated with larvae (2nd and 3rd instar) of Nilaparvata lugens. 21 days later, the test is evaluated. The percentage reduction in population (% activity) is determined by comparing the number of surviving leaf hoppers on the treated and on untreated plants.
  • Example B16 Activity against Nilaparvata lugens (systemic application)
  • Rice plants in pots are placed into an aqueous emulsion spray mixture which comprises 400 ppm of active ingredient.
  • the plants are subsequently populated with larvae (2nd and 3rd instar) of Nilaparvata lugens. 6 days later, the test is evaluated.
  • the percentage reduction in population (% activity) is determined by comparing the number of surviving leaf hoppers on the treated and on untreated plants.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
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  • Plural Heterocyclic Compounds (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

L'invention concerne des composés de formule (I), dans laquelle A est un groupe hétérocyclyle substitué ou non substitué; E-R est C(=O)-R, C(=O)O-R, C(=O)N(R1)-R, C(=O)C(=O)-R, C(=O)C(=O)O-R, C(=O)C(=O)N(R1)-R ou C(=S)N(R1)-R; R est hydrogène ou un groupe alkyle, alcényle, alkynyle, cycloalkyle, aryle ou hétéro-aryle, substitué ou non substitué; et R1 est hydrogène ou un groupe alkyle, alcényle, alkynyle, cycloalkyle, aryle ou hétéro-aryle, substitué ou non substitué; ainsi que, quand cela est approprié, des tautomères desdits composés, toujours sous forme libre ou sous forme de sels. Ces composés et leurs tautomères peuvent être utilisés comme principes actifs agrochimiques et préparés d'une manière connue en soi.
PCT/EP1997/004137 1996-08-08 1997-07-30 Derives substitues de la 4-nitro-imino-perhydro-1,3,5-oxadiazine, leur utilisation comme pesticides, et intermediaires pour leur preparation WO1998006710A1 (fr)

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AU42971/97A AU4297197A (en) 1996-08-08 1997-07-30 Substituted 4-nitroimino-perhydro-1,3,5-oxadiazine derivatives, their use as pesticides and intermediates for their preparation

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CH194796 1996-08-08
CH1947/96 1996-08-08

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WO1998055448A2 (fr) * 1997-06-03 1998-12-10 Novartis Ag Derives d'acides fluoralcenecarboxyliques, procede de production de ces derives, et agents insecticides contenant ces derives
WO2000029378A2 (fr) * 1998-11-17 2000-05-25 Novartis Ag Pesticides
WO2000040582A1 (fr) * 1999-01-08 2000-07-13 Bayer Aktiengesellschaft Derives de guanidine cycliques et leur utilisation comme pesticides
CN1328264C (zh) * 2004-12-13 2007-07-25 中国农业大学 含噁二嗪环的[反]－β－法尼烯类似物及其制备方法与应用
CN102241643A (zh) * 2011-05-16 2011-11-16 中国农业大学 1-杂环-5-取代苯基-1-戊酮类化合物及其制备方法与应用
CN103880832A (zh) * 2014-04-04 2014-06-25 连云港市金囤农化有限公司 一种噻虫嗪的制备方法
CN105330661A (zh) * 2015-10-30 2016-02-17 青岛科技大学 一种n-芳甲基取代的噁二嗪硝基亚胺衍生物及其用途
CN107245060A (zh) * 2017-06-29 2017-10-13 南通天泽化工有限公司 一种3‑乙酰基‑4‑硝基亚氨基‑1,3,5‑恶二嗪的合成方法
CN114605347A (zh) * 2020-12-09 2022-06-10 南通天泽化工有限公司 一种3-乙酰基-4-硝基亚氨基-1,3,5-噁二嗪的合成方法

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Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998055448A3 (fr) * 1997-06-03 1999-05-06 Novartis Ag Derives d'acides fluoralcenecarboxyliques, procede de production de ces derives, et agents insecticides contenant ces derives
WO1998055448A2 (fr) * 1997-06-03 1998-12-10 Novartis Ag Derives d'acides fluoralcenecarboxyliques, procede de production de ces derives, et agents insecticides contenant ces derives
US7271184B2 (en) 1998-11-17 2007-09-18 Novartis Animal Health Us, Inc. Acyclic and cyclic guanidine- and acetamidine derivatives, their preparation and their use as pesticides, esp. as parasiticides
WO2000029378A2 (fr) * 1998-11-17 2000-05-25 Novartis Ag Pesticides
WO2000029378A3 (fr) * 1998-11-17 2000-12-14 Novartis Ag Pesticides
US6538013B2 (en) 1998-11-17 2003-03-25 Novartis Animal Health Us, Inc. Acyclic and cyclic guanidine-and acetamidine derivatives, their preparation and their use as pesticides, esp. as parasiticides
US6759407B2 (en) 1998-11-17 2004-07-06 Novartis Animal Health Us, Inc. Acyclic and cyclic guanidine- and acetamidine derivatives, their preparation and their use as pesticides, ESP as parasiticides
WO2000040582A1 (fr) * 1999-01-08 2000-07-13 Bayer Aktiengesellschaft Derives de guanidine cycliques et leur utilisation comme pesticides
US6683028B1 (en) 1999-01-08 2004-01-27 Bayer Aktiengesellschaft Cyclic guanidine derivatives and their use as pesticides
CN1328264C (zh) * 2004-12-13 2007-07-25 中国农业大学 含噁二嗪环的[反]－β－法尼烯类似物及其制备方法与应用
CN102241643A (zh) * 2011-05-16 2011-11-16 中国农业大学 1-杂环-5-取代苯基-1-戊酮类化合物及其制备方法与应用
CN103880832A (zh) * 2014-04-04 2014-06-25 连云港市金囤农化有限公司 一种噻虫嗪的制备方法
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