WO1997001546A1 - 1,3-oxa(thia)zin-derivate - Google Patents
1,3-oxa(thia)zin-derivate Download PDFInfo
- Publication number
- WO1997001546A1 WO1997001546A1 PCT/EP1996/002552 EP9602552W WO9701546A1 WO 1997001546 A1 WO1997001546 A1 WO 1997001546A1 EP 9602552 W EP9602552 W EP 9602552W WO 9701546 A1 WO9701546 A1 WO 9701546A1
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- Prior art keywords
- alkyl
- substituted
- alkoxy
- optionally
- phenyl
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- RQNQDQDZBRUMIK-UHFFFAOYSA-N CC1(C)COC(c(c(Cl)ccc2)c2F)=NC1 Chemical compound CC1(C)COC(c(c(Cl)ccc2)c2F)=NC1 RQNQDQDZBRUMIK-UHFFFAOYSA-N 0.000 description 1
Classifications
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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
- C07D413/04—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 directly linked by a ring-member-to-ring-member bond
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D265/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom and one oxygen atom as the only ring hetero atoms
- C07D265/04—1,3-Oxazines; Hydrogenated 1,3-oxazines
- C07D265/12—1,3-Oxazines; Hydrogenated 1,3-oxazines condensed with carbocyclic rings or ring systems
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/72—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
- A01N43/86—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 one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D265/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom and one oxygen atom as the only ring hetero atoms
- C07D265/04—1,3-Oxazines; Hydrogenated 1,3-oxazines
- C07D265/12—1,3-Oxazines; Hydrogenated 1,3-oxazines condensed with carbocyclic rings or ring systems
- C07D265/14—1,3-Oxazines; Hydrogenated 1,3-oxazines condensed with carbocyclic rings or ring systems condensed with one six-membered ring
- C07D265/16—1,3-Oxazines; Hydrogenated 1,3-oxazines condensed with carbocyclic rings or ring systems condensed with one six-membered ring with only hydrogen or carbon atoms directly attached in positions 2 and 4
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D279/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom and one sulfur atom as the only ring hetero atoms
- C07D279/04—1,3-Thiazines; Hydrogenated 1,3-thiazines
- C07D279/08—1,3-Thiazines; Hydrogenated 1,3-thiazines condensed with carbocyclic rings or ring systems
-
- 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
-
- 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
- C07D417/12—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 chain containing hetero atoms as chain links
Definitions
- the invention relates to new 1,3-oxa (thia) zin derivatives, several processes for their preparation and their use for controlling animal pests.
- A represents substituted phenyl or optionally substituted naphthyl, pyridyl, thienyl, phenylalkyl or phenylalkenyl,
- D stands for hydrogen, alkyl, haloalkyl, alkoxyalkyl, alkylthioalkyl, optionally substituted cycloalkyl or for optionally substituted phenyl, naphthyl or pyridyl,
- E represents hydrogen or alkyl
- G represents hydrogen or alkyl
- X represents oxygen or sulfur and Y together with the two carbon atoms to which it is attached represents an optionally substituted, mono- or bicyclic, saturated or unsaturated cycle.
- the compounds of the formula (I) are also present as geometric and / or optical isomers or isomer mixtures of different compositions.
- the invention relates to both the pure isomers and the isomer mixtures.
- R 1 and R 2 are the same or different and represent alkyl, or
- E, G and Y have the meaning given above, if appropriate in the presence of a catalyst and if appropriate in the presence of a diluent; or c) 1,3-oxa (thia) tin derivatives of the formulas (Ia) or (Ib)
- Ar represents in each case optionally substituted phenyl or pyridyl, in the presence of a base, optionally in the presence of a catalyst and in the presence of a diluent; or d) 1,3-oxazine derivatives of the formula (Ic)
- A, D, E, G and Y have the meaning given above, with a sulfurizing agent, optionally in the presence of a diluent.
- the new 1,3-oxa (thia) zin derivatives of the formula (I) are very good for controlling animal pests, in particular insects, arachnids and nematodes, which are used in agriculture, in forests, in the protection of stocks and materials as well as in the hygiene sector are suitable.
- the 1,3-oxa (thia) zin derivatives of the formula (I) according to the invention show a considerably better activity against animal pests than the constitutionally similar previously known compounds.
- A preferably (preferably) represents phenyl which is mono- to pentas, identical or differently substituted, or in each case optionally in the phenyl part monosubstituted to pentasily, identical or differently substituted by phenyl-C 1 -C 8 -alkyl or phenyl-C 2 -C 6 -alkenyl, where are suitable as substituents in each case
- halogen C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 -C 4 alkoxy, C 1 -C 4 haloalkoxy, C 1 -C 4 -Alkylthio or C 1 -C 4 -Halogenalkylthio substituted phenyl, benzyl, benzyloxy, phenethyl, phenethenyl, phenethinyl, phenoxy or phenylthio, for optionally single to triple, identical or different by halogen, C 1 -C 8 alkyl, C 1 - C 6 -alkoxy or C 1 -C 8 -haloalkoxy substituted naphthyl, for optionally mono- to triple, identical or different by halogen, C 1 -C 6 -alkyl, C 1 -C 6 -alkoxy, C 1 -C 6 -alkoxy, C 1 -C 6
- D is preferably (preferably) hydrogen, C 1 -C 6 alkyl, C 1 -C 6 - haloalkyl, C 1 -C 6 alkoxy-C 1 -C 6 alkyl, C 1 -C 6 -alkylthio-C 1 -C 6 alkyl, optionally optionally up to five times, the same or different by halogen, C 1 -C 6 alkyl, C 1 -C 6 alkoxy, C 1 -C 6 haloalkyl or C 1 -C 6 - haloalkoxy substituted C 3 -C 7 cycloalkyl, for optionally single to triple, identical or different by halogen, C 1 -C 6 alkyl, C 1 -C 6 alkoxy, C 1 -C 6 haloalkyl, C 1 -C 6 Haloalkoxy or cyano substituted pyridyl, or for pheny
- pyridyloxy optionally substituted once or twice, identically or differently by halogen, C 1 -C 4 alkyl or C 1 -C 4 haloalkyl, in each case optionally by up to five times, identically or differently by
- E is preferably (preferably) hydrogen or methyl.
- G is preferably (preferably) hydrogen or methyl.
- X is preferably (preferably) oxygen or sulfur.
- Y preferably (preferably) with the two carbon atoms to which it is attached represents an optionally mono- to pentasubstituted, identically or differently substituted, mono- or bicyclic, saturated or unsaturated C 5 -C 18 cycle, the substituents being suitable come
- E particularly preferably represents hydrogen or methyl.
- G particularly preferably represents hydrogen or methyl.
- X particularly preferably represents oxygen or sulfur.
- Y particularly preferably, with the two carbon atoms to which it is attached, represents a single to fivefold, the same or, if appropriate differently substituted, mono- or bicyclic, saturated or unsaturated C 5 -C 12 cycle, where substituents are suitable
- a very particularly preferably represents phenyl monosubstituted to trisubstituted identically or differently or in each case optionally in the phenyl part monosubstituted to trisubstituted identically or differently by phenyl-C 1 -C 4 -alkyl or styryl, phenyl substituents in each case being suitable
- D very particularly preferably represents hydrogen, C 1 -C 4 alkyl, for one to five times, identically or differently by F or Cl-substituted C 1 -C 2 - alkyl, C 1 -C 2 alkoxy-C 1 -C 4- alkyl, C 1 -C 2 -alkylthio-C 1 -C 4 -alkyl, each in each case optionally up to triple, identical or different by CH 3 , C 2 H 5 , tC 4 H 9 , OCH 3 , OtC 4 H 9 , CF 3 or OCF 3 substituted cyclopropyl, cyclopentyl or cyclohexyl, for optionally single or double, identical or different by F,
- each cyclohexyl or cyclohexyloxy optionally substituted by C 1 -C 4 alkyl, C 1 -C 4 alkoxy, cyclohexyl or phenyl, optionally mono- or disubstituted, identically or differently substituted by F, Cl or CF 3, pyridyloxy, in each case optionally mono- to triple , same or different through
- E very particularly preferably represents hydrogen or methyl.
- G very particularly preferably represents hydrogen or methyl.
- X very particularly preferably represents oxygen or sulfur.
- Y very particularly preferably, with the two carbon atoms to which it is bonded, represents a one to five times, optionally, the same or differently substituted, mono- or bicyclic, saturated or unsaturated C 5 -C 12 cycle, where substituents are suitable
- A is particularly emphasized for phenyl, styryl or phenyl-C 1 -C 4 -alkyl, which in the phenyl part in each case one to three times, identically or differently by fluorine, chlorine, bromine, hydroxyl, C 1 -C 4 -alkyl, once to five times , C 1 -C 2 alkyl, identical or different substituted by fluorine or chlorine, optionally single to five times, identical or different C 1 -C 2 alkoxy substituted by fluorine or chlorine, optionally single to fivefold, identical or different by fluorine or chlorine substituted
- D is particularly emphasized for hydrogen, in each case optionally substituted by methyl, ethyl, methoxy, trifluoromethyl or trifluoromethoxy, cyclopentyl or cyclohexyl or for phenyl, which is optionally monosubstituted to trisubstituted, identically or differently, by fluorine, chlorine, bromine, C 1 -C 4 -Alkyl, optionally single to six times, identically or differently substituted by fluorine or chlorine, C 1 -C 4 -alkoxy or optionally single to triple, identical or different by fluorine, chlorine, bromine, each optionally once to six times, identical or different by fluorine or chlorine substituted
- E is particularly highlighted for hydrogen or methyl.
- G is particularly highlighted for hydrogen or methyl.
- X is particularly highlighted for oxygen or sulfur.
- Y is particularly emphasized with the two carbon atoms to which it is attached, for a mono- or optionally substituted to mono- or trisubstituted, identically or differently by C 1 -C 3 -alkyl, C 1 -C 3 -alkoxy, trifluoromethyl or phenyl bicyclic, saturated or unsaturated C 5 - C 8 cycle.
- hydrocarbon radicals mentioned above in the definition of the compounds according to the invention can also be straight-chain or branched as far as possible, even in conjunction with heteroatoms such as alkoxy.
- Preferred compounds according to the invention are substances of the formula (IA)
- a and Y stand for the abovementioned general, preferred, particularly preferred, very particularly preferred and particularly emphasized meanings and
- D represents phenyl which is mono- to pentasubstituted by identical or different substituents, the substituents mentioned above under D being preferred, particularly preferred, very particularly preferred and particularly emphasized for the phenyl radical.
- process (a) uses N- [morpholin-4-yl- (4-bromophenyl) methyl] -2,6-difluorobenzamide and cyclopentene as starting materials in the presence of titanium tetrachloride as catalyst, the course of the process according to the invention can be determined by the following reaction scheme can be reproduced:
- Formula (II) provides a general definition of the amide derivatives required as starting materials for carrying out process (a) according to the invention.
- a and D preferably or particularly preferably have those meanings which are preferred or particularly preferred for these in connection with the description of the compounds of formula (I)
- R 1 and R 2 are the same or different and are preferably C 1 -C 4 alkyl, in particular methyl, ethyl, n- or i-propyl or preferably together with the N atom to which they are attached optionally one to five times, the same or differently substituted
- Formula (III) provides a general definition of the olefins also required as starting materials for carrying out processes (a) and (b) according to the invention.
- E, G and Y preferably or particularly preferably have those meanings which have already been mentioned above in connection with the description of the compounds of the formula (I) as preferred or particularly preferred for these substituents.
- the olefins of the formula (III) are generally known or can be obtained in a generally customary and known manner.
- Formula (IV) provides a general definition of the amide derivatives required as starting materials for carrying out process (b) according to the invention.
- a and X preferably or particularly preferably have those meanings which have already been mentioned above in connection with the description of Compounds of formula (I) have been mentioned as preferred or particularly preferred for these substituents.
- Formula (V) provides a general definition of the aldehydes also required as starting materials for carrying out process (b) according to the invention.
- D preferably or particularly preferably has those meanings which have already been mentioned above in connection with the description of the compounds of the formula (I) or are particularly preferred for these substituents.
- the amide derivatives of the formula (IV) and the aldehydes of the formula (V) are generally known or can be obtained in a generally known manner.
- the 1,3-oxa (thia) tin derivatives required as starting materials for carrying out process (c) according to the invention are generally defined by the formulas (Ia) and (Ib).
- A, D, E, G, X and Y preferably or particularly preferably have those meanings which have already been mentioned as preferred or particularly preferred for these substituents in connection with the description of the compounds of the formula (I).
- 1,3-oxa (thia) tin derivatives of the formulas (Ia) and (Ib) are compounds according to the invention and can be obtained according to processes (a), (b) or (d) according to the invention.
- Formula (VI) provides a general definition of the boronic acids which are also required as starting materials for carrying out process (c) according to the invention.
- Ar represents in each case optionally one to three times, identical or different, by C 1 -C 4 alkyl, halogen, C 1 -C 4 haloalkyl, C 1 -C 4 alkoxy, C 1 -C 4 -Halogenalkoxy, C 1 -C 4 alkylthio and C 1 -C 4 -haloalkylthio substituted phenyl or pyridyl, preferably for optionally single to triple, identical or different by C 1 -C 4 alkyl, F, Cl, Br, simple to C 1 -C 4 alkyl, C 1 -C 4 alkoxy substituted six times by F and / or Cl, alkoxy simple to six times substituted by F and / or Cl, C 1 -C 4 alkylthio as well as simply up to six times by F and / or Cl substituted C 1 -C 4 alkylthio-substituted phenyl and preferably for optionally mono- to trisub
- the boronic acids of the formula (VI) are generally known compounds of organic chemistry or can be obtained by generally known methods.
- Formula (Ic) provides a general definition of the 1,3-oxazine derivatives required as starting materials for carrying out process (d) according to the invention.
- A, D, E, G and Y preferably or particularly preferably have those meanings which have already been mentioned as preferred or particularly preferred for these substituents in connection with the description of the compounds of the formula (I).
- the 1,3-oxazine derivatives of the formula (Ic) are compounds according to the invention and can be obtained according to processes (a) to (c) according to the invention.
- Process (a) according to the invention is optionally carried out in the presence of hydrogen chloride gas and in the presence of a catalyst.
- Suitable catalysts are Lewis acids, such as preferably transition metal halides, such as, in particular, titanium tetrachloride, tin tetrachloride and zinc dichloride.
- organic solvents are suitable as diluents for carrying out process (a) according to the invention.
- organic solvents include, for example, chlorobenzene, dichlorobenzene, petroleum ether, hexane, cyclohexane, dichloromethane,
- reaction temperatures can be varied within a substantial range when carrying out process (a) according to the invention. In general, temperatures between 0 ° C and 120 ° C, preferably at temperatures between 0 ° C and 100 ° C.
- process (a) generally between 1 and 5 mol, preferably between 1 and 3 mol of olefin of the formula (III) and between 1 and 5 mol, preferably between 1 and 1 mol, are employed per mol of amide derivative of the formula (II) up to 4 moles of catalyst and optionally between 1 and 5 moles, preferably between 1 to 3 moles of hydrogen chloride gas.
- the workup can be carried out in the usual way; the reaction mixture is preferably made alkaline with cooling between 0 ° C. and 10 ° C. and the end product is isolated in a generally customary manner.
- Process (b) according to the invention is optionally carried out in the presence of a catalyst.
- inorganic or organic acids can be used.
- sulfuric acid, hydrogen fluoride, methanesulfonic acid, trifluoromethanesulfonic acid, benzene sulfonic acid or p-toluenesulfonic acid are preferably used.
- Suitable diluents for carrying out process (b) according to the invention are preferably acetic acid and dichloromethane.
- reaction temperatures can be varied within a substantial range when carrying out process (b) according to the invention. In general, temperatures between 0 ° C and 100 ° C, preferably at temperatures between 10 ° C and 80 ° C.
- process (b) according to the invention is carried out per mole
- Amide derivative of the formula (IV) in general between 1 and 1.5 mol, preferably between 1 and 1.2 mol of aldehyde of the formula (V) and between 1 and 2 mol, preferably between 1 and 1.5 mol of the olefin of the formula (III) and optionally between 1 and 5 mol, preferably between 1 and 3 mol, of a catalyst.
- reaction mixture is preferably made alkaline with cooling between 0 ° C. and 10 ° C. and the end product is isolated in a generally customary manner.
- Suitable diluents for carrying out process (c) according to the invention are all organic solvents which are inert under the given reaction conditions. If necessary, they can be used in a mixture with water. Hydrocarbons such as toluene, xylene, tetralin, hexane, cyclohexane, halogenated hydrocarbons such as methylene chloride, chloroform, chlorobenzene, o-dichlorobenzene, alcohols such as methanol, ethanol, glycol, the isomeric propanols, butanols, pentanols, ethers, such as diethyl ether, are preferably used.
- Hydrocarbons such as toluene, xylene, tetralin, hexane, cyclohexane, halogenated hydrocarbons such as methylene chloride, chloroform, chlorobenzene, o-dichlorobenzene, alcohols such as
- Diisopropyl ether dimethoxyethane, tetrahydrofuran, dioxane, nitriles such as acetonitrile or butyronitrile, amides such as dimethylformamide, sulfoxides such as dimethyl sulfide, and also sulfolane.
- Suitable bases for carrying out process (c) according to the invention are all customary acid acceptors. Tertiary are preferably used
- Amines such as triethylamine, pyridine, diazabicyclooctane (DABCO), diazabicycloundecene (DBU), diazabicyclonones (DBN), N, N-dimethylaniline, furthermore alkaline earth metal oxides such as magnesium or carcium oxide, furthermore alkali metal and alkaline earth metal carbonate, and alkali metal carbonate, as well as alkali metal carbonate and sodium carbonate, as well as alkali metal carbonate and carbonate Sodium bicarbonate, alkali hydroxides such as sodium or potassium hydroxide, and also alcoholates such as sodium ethanolate or potassium tert-butoxide.
- DABCO diazabicyclooctane
- DBU diazabicycloundecene
- DBN diazabicyclonones
- N N-dimethylaniline
- alkaline earth metal oxides such as magnesium or carcium oxide
- Process (c) according to the invention is optionally carried out in the presence of a catalyst.
- a catalyst examples include: tetrakis (triphenylphosphine) palladium; Palladium II acetate / tri (o-tolyl) phosphine; Palladium-II-chloride, -II-acetate / triphenylphosphine; Bis (triphenylphosphine) palladium II chloride; and Pd / C / triphenylphosphine.
- reaction temperatures can be varied within a substantial range when carrying out process (c) according to the invention. In general, temperatures between 0 ° C and 150 ° C, preferably between 0 ° C and
- catalyst preferably being introduced and the 1,3-oxa (thia) zin derivative under an inert gas stream, such as e.g. an argon stream.
- an inert gas stream such as e.g. an argon stream.
- Possible sulfurizing agents in carrying out process (d) according to the invention are: phosphorus pentasulfide or Lawesson's reagent [2,4-bis (4-methoxyphenyl) -1,3,2,4-dithiadiphosphetane-2,4-dithione].
- Suitable diluents for carrying out process (d) according to the invention are preferably hydrocarbons, such as toluene, xylene, tetralin, hexane or cyclohexane.
- reaction temperatures can be varied within a substantial range when carrying out process (d) according to the invention. In general, temperatures between 0 ° C and 200 ° C, preferably between 20 ° C and 150 ° C.
- the active substances are suitable for controlling animal pests, in particular insects, arachnids and nematodes, which occur in agriculture, in forests, in the protection of stored products and materials, and in the hygiene sector. They can preferably be used as pesticides. They are effective against normally sensitive and resistant species as well as against all or individual stages of development.
- the pests mentioned above include:
- Isopoda e.g. Oniscus asellus, Armadillidium vulgare, Porcellio scaber.
- Thysanura for example Lepisma saccharina.
- Collembola for example Onychiurus armatus.
- Orthoptera for example Blatta orientalis, Periplaneta americana, Leucophaea maderae, Blattella germanica, Acheta domesticus, Gryllotalpa spp., Locusta migratoria migratorioides, Melanoplus differentialis, Schistocerca gregaria.
- Thysanoptera e.g. Hercinothrips femoralis, Thrips tabaci.
- Heteroptera e.g. Eurygaster spp., Dysdercus intermedius
- Homoptera e.g. Aleurodes brassicae, Bemisia tabaci, Trialeurodes vaporariorum, Aphis gossypii, Brevicoryne brassicae, Cryptomyzus ribis, Doralis fabae, Doralis pomi, Eriosoma lanigerum, Hyalopterus arundinis, Macrosiphum avenae, Myzus spp., Rhoralosobusumumisis, pad.
- Homoptera e.g. Aleurodes brassicae, Bemisia tabaci, Trialeurodes vaporariorum, Aphis gossypii, Brevicoryne brassicae, Cryptomyzus ribis, Doralis fabae, Doralis pomi, Eriosoma lanigerum, Hyalopterus arundinis, Macrosiphum avenae, Myzus spp., Rhoralosobusumumisis,
- Nephotettix cincticeps Lecanium corni, Saissetia oleae, Laodelphax striatellus, Nilaparvata lugens, Aonidiella aurantii, Aspidiotus hederae, Pseudococcus spp., Psylla spp.
- Hymenoptera e.g. Diprion spp., Hoplocampa spp., Lasius spp., Monomorium pharaonis, Vespa spp.
- Siphonaptera e.g. Xenopsylla cheopis, Ceratophyllus spp .. From the order of the Arachnida e.g. Scorpio maurus, Latrodectus mactans.
- Acarina e.g. Acarus siro, Argas spp., Ornithodoros spp., Dermanyssus gallinae, Eriophyes ribis, Phyllocoptruta oleivora, Boophilus spp., Rhipicephalus spp., Amblyomma spp., Hyalomma spp., Ixodes spp., Psoroptes spp.,. Chori ., Tarsonemus spp., Bryobia praetiosa, Panonychus spp., Tetranychus spp ..
- Plant-parasitic nematodes include, for example, Pratylenchus spp., Radopholus similis, Ditylenchus dipsaci, Tylenchulus semipenetrans, Heterodera spp., Globodera spp., Meloidogyne spp., Aphelenchoides spp., Longidorus spp., Tripichichus spp., Xiphinema spp.
- the compounds of the formula (I) according to the invention are notable in particular for outstanding insecticidal and acaricidal activity. They can be used with particularly good success to control plant-damaging insects and mites.
- the active compounds according to the invention show not only protective, but also leaf-systemic and root-systemic properties.
- the active compounds of the formula (I) according to the invention also have a fungicidal action, for example against Pyricularia oryzea on rice.
- the active compounds can be converted into the customary formulations, such as solutions, emulsions, wettable powders, suspensions, powders, dusts, pastes, soluble powders, granules, suspension emulsion concentrates, active substance-impregnated natural and synthetic substances and very fine encapsulations in polymeric substances.
- formulations are made in a known manner, e.g. by mixing the active ingredients with extenders, that is to say liquid solvents and / or solid carriers, optionally using surface-active agents
- Agents ie emulsifiers and / or dispersants and / or foam-generating agents.
- organic solvents can, for example, also be used as auxiliary solvents.
- liquid solvents aromatics, such as xylene, toluene, or alkylnaphthalenes, chlorinated aromatics and chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chlorethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, for example petroleum fractions, mineral and vegetable oils, alcohols , such as butanol or glycol and their ethers and esters, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents such as dimethyl form amide and dimethyl sulfoxide, and water.
- solid carriers such as solid carriers:
- Ammonium salts and natural rock powders such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic rock powders, such as highly disperse silicic acid, aluminum oxide and silicates, are suitable as solid carriers for granules: e.g. broken and fractionated natural rocks such as calcite, marble, pumice, sepiolite, dolomite and synthetic granules from inorganic and organic flours and granules from organic material such as sawdust, coconut shells, corn cobs and tobacco stems; as emulsifying and / or foaming agents are possible: e.g.
- nonionic and anionic emulsifiers such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, e.g. Alkylaryl polyglycol ethers, alkyl sulfonates, alkyl sulfates, aryl sulfonates and protein hydrolyzates;
- Possible dispersants are: e.g. Lignin sulfite liquor and methyl cellulose.
- Adhesives such as carboxymethyl cellulose, natural and synthetic powdery, granular or latex-shaped polymers, such as gum arabic, polyvinyl alcohol, polyvinyl acetate, and natural phospholipids such as cephalins and lecithins and synthetic phospholipids can be used in the formulations.
- Other additives can be mineral and vegetable oils.
- Dyes such as inorganic pigments, e.g. Iron oxide, titanium oxide, ferrocyan blue and organic dyes such as alizarin, azo and metal phthalocyanine dyes and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc can be used.
- the formulations generally contain between 0.1 and 95% by weight of active compound, preferably between 0.5 and 90%.
- the active substance according to the invention can be present in its commercially available formulations and in the use forms prepared from these formulations in a mixture with other active substances, such as insecticides, attractants, sterilants, bactericides, acaricides, nematicides, fungicides, growth-regulating substances or herbicides.
- Insecticides include, for example, phosphoric acid esters, carbamates, carboxylic acid esters, chlorinated hydrocarbons, phenyl ureas, substances produced by microorganisms, and others The following are particularly favorable mixed partners:
- Difenoconazole dimethirimol, dimethomorph, diniconazole, dinocap, diphenylamine, dipyrithione, ditalimfos, dithianon, dodine, drazoxolone,
- Fenarimol Fenbuconazole, Fenfuram, Fenitropan, Fenpiclonil, Fenpropidin, Fenpropimorph, Fentinacetat, Fentinhydroxyd, Ferbam, Ferimzone, Fluazinam,
- Fludioxonil fluoromide, fluquinconazole, flusilazole, flusulfamide, flutolanil, flutriafol, folpet, fosetyl aluminum, fthalides, fuberidazole, furalaxyl, furmecyclox,
- Mancopper Mancozeb, Maneb, Mepanipyrim, Mepronil, Metalaxyl, Metconazol,
- Tebuconazole Tebuconazole, tecloftalam, tecnazene, tetraconazole, thiabendazole, Thicyofen, thiophanate-methyl, thiram, Tolclophos-methyl, tolylfluanid, triadimefon, triadimenol, triazoxide, Trichlamid, tricyclazole, tridemorph, triflumizole, triforine, triticonazole,
- Bacillus thuringiensis Bendiocarb, Benfuracarb, Bensultap, Betacyfluthrin, Bifenthrin, BPMC, Brofenprox, Bromophos A, Bufencarb, Buprofezin, Butocarboxin, Butylpyridaben,
- Fenamiphos fenazaquin, fenbutatin oxide, fenitrothion, fenobucarb, fenothiocarb,
- Fenoxycarb Fenpropathrin, Fenpyrad, Fenpyroximat, Fenthion, Fenvalerate, Fipronil, Fluazinam, Flucycloxuron, Flucythrinat, Flufenoxuron, Flufenprox, Fluvalinate, Fonophos, Formothion, Fosthiazat, Fubfenprox, Furathiocarb,
- HCH HCH
- heptenophos hexaflumuron
- hexythiazox Imidacloprid
- Iprobefos Isazophos, Isofenphos, Isoprocarb, Isoxathion, Ivermectin, Lambda-cyhalothrin, Lufenuron,
- Methamidophos Methidathion, Methiocarb, Methomyl, Metolcarb, Milbemectin, Monocrotophos, Moxidectin,
- Parathion A Parathion M, Permethrin, Phenthoat, Phorat, Phosalon, Phosmet,
- Tebufenozid Tebufenpyrad
- Tebupirimphos Teflubenzuron
- Tefluthrin Temephos
- the active compounds according to the invention can furthermore be present in their commercially available formulations and in the use forms prepared from these formulations in a mixture with synergists.
- Synergists are compounds through which the action of the active ingredients is increased without the added synergist itself having to be active.
- the active substance content of the use forms prepared from the commercially available formulations can vary within wide ranges.
- the active substance concentration of the use forms can be from 0.0000001 to 95% by weight of active substance, preferably between 0.0001 and 1% by weight.
- the application takes place in a customary manner adapted to the application forms.
- the active ingredient is distinguished by an excellent residual action on wood and clay and by a good alkali stability on limed substrates.
- the active compounds according to the invention act not only against plant, hygiene and stored-product pests, but also in the veterinary sector against animal parasites (ectoparasites) such as tick ticks, leather ticks, mites, running mites, flies (stinging and licking), parasitic fly larvae, lice, hair lice, Featherlings and fleas. For example, they show an excellent development-inhibiting effect against fly larvae from Lucilia cuprina.
- animal parasites ectoparasites
- ectoparasites such as tick ticks, leather ticks, mites, running mites, flies (stinging and licking), parasitic fly larvae, lice, hair lice, Featherlings and fleas.
- the active compounds of the formula (I) according to the invention are also suitable for combating arthropods which are farm animals, such as, for example, cattle, sheep, goats, horses, pigs, donkeys, camels, buffalo, rabbits, chickens, turkeys, ducks, geese, bees, other pets such as dogs, cats, house birds, aquarium fish and so-called experimental animals such as hamsters, guinea pigs, rats and mice.
- arthropods are farm animals, such as, for example, cattle, sheep, goats, horses, pigs, donkeys, camels, buffalo, rabbits, chickens, turkeys, ducks, geese, bees, other pets such as dogs, cats, house birds, aquarium fish and so-called experimental animals such as hamsters, guinea pigs, rats and mice.
- the active compounds according to the invention are used in the veterinary sector in a known manner by enteral administration in the form of, for example, tablets, capsules, drinkers, drenches, granules, pastes, boluses, the feed-through method, suppositories, by parenteral administration, for example by Injections (intramuscular, subcutaneous, intravenous, intraperitonal, etc.), implants, by nasal application, by dermal application in the form of, for example, diving or bathing (dipping), spraying (spray), pouring on (pour-on and spot-on), washing , powdering and with the aid of shaped articles containing active ingredients, such as collars, ear tags, tail tags, limb tapes, halters, marking devices, etc.
- enteral administration in the form of, for example, tablets, capsules, drinkers, drenches, granules, pastes, boluses, the feed-through method, suppositories
- parenteral administration for example by In
- the active ingredients of the formula (I) can be used as formulations (for example powders, Emulsions, flowable agents), which contain the active ingredients in an amount of 1 to 80 wt .-%, directly or after 100 to 10,000-fold dilution or use it as a chemical bath.
- formulations for example powders, Emulsions, flowable agents
- insects may be mentioned by way of example and preferably, but without limitation:
- Kalotermes flavicollis Cryptotermes brevis, Heterotermes indicola, Reticulitermes flavipes, Reticulitermes santonensis, Reticulitermes lucifugus, Mastotermes darwiniensis, Zootermopsis nevadensis, Coptotermes formosanus.
- Bristle tails such as Lepisma saccarina.
- technical materials are understood to mean non-living materials, such as preferably plastics, adhesives, glues, papers and cartons, leather, wood and wood processing products and paints.
- the material to be protected against insect infestation is very particularly preferably wood and wood processing products.
- wood and wood processing products which can be protected by the agent according to the invention or mixtures containing it are exemplary to understand: timber, wooden beams, railway sleepers, bridge parts, jetties, wooden vehicles, boxes, pallets, containers, telephone poles, wooden cladding, wooden windows and doors, plywood, chipboard, carpentry or wood products that are used in general in house construction or in joinery.
- the active substances can be used as such, in the form of concentrates or generally customary formulations such as powders, granules, solutions, suspensions, emulsions or pastes.
- the formulations mentioned can be prepared in a manner known per se, e.g. by mixing the active ingredients with at least one solution or. Diluent, emulsifier, dispersant and / or binder or fixative, water repellent, optionally siccatives and UV stabilizers and optionally dyes and pigments and other processing aids.
- the insecticidal compositions or concentrates used to protect wood and wood-based materials contain the active compound according to the invention in a concentration of 0.0001 to 95% by weight, in particular 0.001 to 60% by weight.
- the amount of the agents or concentrates used depends on the type and occurrence of the insects and on the medium. The optimal amount can be determined in each case by test series. In general, however, it is sufficient to use 0.0001 to 20% by weight, preferably 0.001 to 10% by weight, of the active compound, based on the material to be protected.
- the organic chemical solvents used are preferably oily or oily solvents with an evaporation number above 35 and a flash point above 30 ° C., preferably above 45 ° C.
- Corresponding minerals are used as such low-volatility, water-insoluble, oily and oily solvents oils or their aromatic fractions or mineral oil-containing solvent mixtures, preferably white spirit, petroleum and / or alkylbenzene.
- Mineral oils with a boiling range of 170 to 220 ° C, white spirit with a boiling range of 170 to 220 ° C, spindle oil with a boiling range of 250 to 350 ° C, petroleum or aromatics with a boiling range of 160 to 280 ° C, turpentine oil are advantageous and the like.
- liquid aliphatic hydrocarbons with a boiling range from 180 to 210 ° C or high-boiling mixtures of aromatic and aliphatic hydrocarbons with a boiling range from 180 to 220 ° C and / or locker oil and / or monochloronaphthalene, preferably monochloronaphthalene, are used.
- the organic semi-volatile oily or oily solvents with an evaporation number above 35 and a flash point above 30 ° C, preferably above 45 ° C, can be partially replaced by slightly or medium-volatile organic chemical solvents, with the proviso that the solvent mixture also has an evaporation number 35 and a flash point above 30 ° C, preferably above 45 ° C, and that the insecticide-fungicide mixture is soluble or emulsifiable in this solvent mixture.
- part of the organic chemical solvent or solvent mixture is replaced by an aliphatic polar organic chemical solvent or solvent mixture.
- Aliphatic organic chemical solvents containing hydroxyl and / or ester and / or ether groups, such as, for example, glycol ethers, esters or the like, are preferably used.
- the known organic-chemical binders are the water-thinnable and / or synthetic resins which are soluble or dispersible or emulsifiable in the organic-chemical solvents used and / or binding drying oils, in particular binders consisting of or containing an acrylate resin, a vinyl resin, for example polyvinyl acetate, polyester resin, polycondensation or polyaddition resin, polyurethane resin, alkyd resin or modified alkyd resin, phenolic resin, hydrocarbon resin such as indene-coumarone resin, silicone resin, drying vegetable and / or drying oils and / or physically drying binders based on a natural and / or synthetic resin.
- binders consisting of or containing an acrylate resin, a vinyl resin, for example polyvinyl acetate, polyester resin, polycondensation or polyaddition resin, polyurethane resin, alkyd resin or modified alkyd resin, phenolic resin, hydrocarbon resin such as indene-coumarone resin,
- the synthetic resin used as a binder can be used in the form of an emulsion, dispersion or solution. Bitumen or bituminous substances up to 10% by weight can also be used as binders. In addition, known dyes, pigments, water-repellants, odor correctors and inhibitors or anticorrosive agents and the like can be used.
- At least one alkyd resin or modified alkyd resin and / or a drying vegetable oil is preferably contained in the agent or in the concentrate as the organic chemical binder.
- Alkyd resins with an oil content of more than 45% by weight, preferably 50 to 68% by weight, are preferably used according to the invention.
- binder mentioned can be replaced by a fixative (mixture) or a plasticizer (mixture).
- fixative mixture
- plasticizer mixture
- additives are intended to prevent volatilization of the active ingredients and crystallization or precipitation. They preferably replace 0.01 to 30% of the binder (based on 100% of the binder used).
- the plasticizers come from the chemical classes of phthalic acid esters such as dibutyl, dioctyl or benzyl butyl phthalate, phosphoric acid esters such as tributyl phosphate, adipic acid esters such as di- (2-ethylhexyl) adipate, stearates such as butyl stearate or amyl stearate, oleates such as butyl oleate, higher glyceryl glycol or glycerol ether and p-toluenesulfonic acid ester.
- phthalic acid esters such as dibutyl, dioctyl or benzyl butyl phthalate
- phosphoric acid esters such as tributyl phosphate
- adipic acid esters such as di- (2-ethylhexyl) adipate
- stearates such as butyl stearate or amyl
- Fixing agents are chemically based on polyvinyl alkyl ethers such as e.g. Polyvinyl methyl ether or ketones such as benzophenone, ethylene benzophenone. Water is also particularly suitable as a solvent or diluent, optionally in a mixture with one or more of the above-mentioned organic chemical solvents or diluents, emulsifiers and dispersants.
- polyvinyl alkyl ethers such as e.g. Polyvinyl methyl ether or ketones such as benzophenone, ethylene benzophenone.
- Water is also particularly suitable as a solvent or diluent, optionally in a mixture with one or more of the above-mentioned organic chemical solvents or diluents, emulsifiers and dispersants.
- a particularly effective wood protection is achieved by industrial impregnation processes, e.g. vacuum, double vacuum or pressure processes.
- the ready-to-use compositions can optionally contain further insecticides and, if appropriate, one or more fungicides.
- the insecticides and fungicides mentioned in Wo 94/29 268 are particularly suitable as additional mixing partners.
- the compounds mentioned in this document are an integral part of the present application.
- Insecticides such as chlorpyriphos, phoxime, silafluofin, alphamethrin, cyfluthrin, cypermethrin, deltamethrin, permethrin, imidacloprid, NI-25, flufenoxuron, hexaflumuron and triflumazole, epoxazole, as well as fungonazole, epoxazole, as well as fungonazole, as well as Fungazazole, as well as Fungazazole, as well as Fungazazole, as well as Fungazazole, as well as Fungazazole, as well as Fungazazole, as well as Fungazazole, as well as Fungazazole, as well as Fungazazole, as well as Fungazazole, as well as Fungazazole, as well as Fungazazole, as well as Fungazazole, such as, Fungazazole, such as, Fungazazone, such as, Fungazazole, such as,
- a solution of 8.2 is added dropwise with ice-cooling to a solution of 5 g (0.026 mol) of 4-tert-butylthiobenzamide, 5 g (0.027 mol) of 4-bromobenzaldehyde and 3.6 g (0.053 mol) of cyclopentene in 40 ml of acetic acid g (0.081 mol) of concentrated sulfuric acid in 30 ml of acetic acid within 10 minutes.
- the reaction mixture is then stirred at room temperature for 18 hours. After the acetic acid has been removed by distillation, 70 ml of ice water are added to the reaction mixture, the mixture is made alkaline at 0 ° C. with sodium hydroxide solution and extracted with dichloromethane. The organic phase is dried over magnesium sulfate and concentrated in vacuo.
- reaction mixture is stirred under reflux for 3 hours, then cooled, poured into water and extracted three times with 20 ml of diethyl ether each time.
- the combined organic phases are washed with saturated sodium chloride solution, dried over magnesium sulfate and concentrated in vacuo.
- the residue is chromatographed on silica gel using methylene chloride as the eluent.
- Emulsifier 1 part by weight of alkylaryl polyglycol ether
- active compound 1 part by weight of active compound is mixed with the stated amount of solvent and the stated amount of emulsifier, and the concentrate is diluted with water to the desired concentration.
- Cabbage leaves (Brassica oleracea) are treated by being dipped into the preparation of active compound of the desired concentration and populated with horseradish leaf beetle larvae Phaedon cochleariae while the leaves are still moist.
- the kill is determined in%. 100% means that all beetle larvae have been killed; 0% means that no beetle larvae have been killed.
- the compounds according to Preparation Examples 4a, 10 and 37, with an exemplary active compound concentration of 0.1% caused at least 80% to be killed after 7 days, while the compounds (A), (B) known from the prior art and (C) did not cause kill.
- Emulsifier 1 part by weight of alkylaryl polyglycol ether
- active compound 1 part by weight of active compound is mixed with the stated amount of solvent and the stated amount of emulsifier, and the concentrate is diluted with water to the desired concentration.
- Cabbage leaves (Brassica oleracea) are treated by being dipped into the preparation of active compound of the desired concentration and populated with caterpillars of the Plutella maculipennis cockroach while the leaves are still moist.
- the kill is determined in%. 100% means that all caterpillars have been killed; 0% means that no caterpillars have been killed.
- the compounds according to Preparation Examples 4a, 32, 43, 46, 55, 62, 63 and 64 at an exemplary active ingredient concentration of 0.1% caused at least 80% to be killed after 3 days, while those from the prior art Compounds (A), (B), (D) and (G) known in the art caused a maximum kill of 5%.
- Emulsifier 1 part by weight of alkylaryl polyglycol ether
- active compound 1 part by weight of active compound is mixed with the stated amount of solvent and the stated amount of emulsifier, and the concentrate is diluted with water to the desired concentration.
- Cabbage leaves (Brassica oleracea) are treated by dipping into the active ingredient preparation of the desired concentration and with caterpillars of the owl butterfly
- the effect is determined in%. 100% means that all caterpillars have been killed; 0% means that no caterpillars have been killed.
- the compound according to Preparation Example 4a with an exemplary active compound concentration of 0.1%, caused 100% killing after 7 days, while the compounds (A), (E) and (F) known from the prior art did not kill caused.
- Emulsifier 1 part by weight of alkyl aryl polyglycol ether
- active compound 1 part by weight of active compound is mixed with the stated amount of solvent and the stated amount of emulsifier, and the concentrate is diluted with water to the desired concentration.
- Rice seedlings (Oryza sativa) are treated by dipping into the active ingredient preparation of the desired concentration and populated with larvae of the green rice leafhopper Nephotettix cincticeps while the seedlings are still moist.
- the kill is determined in%. 100% means that all cicadas have been killed; 0% means that no cicadas have been killed.
- the compounds according to Preparation Examples 9, 10, 24, 25, 26, 36, 41 and 43 caused a kill of 100% after 6 days at an exemplary active compound concentration of 0.1%, while those from the prior art known compounds (A), (B), (C) and (G) did not cause any kill.
- Emulsifier 1 part by weight of alkylaryl polyglycol ether
- active compound 1 part by weight of active compound is mixed with the stated amount of solvent and the stated amount of emulsifier, and the concentrate is diluted to the desired concentrations with water containing emulsifier.
- Bean plants Phaseolus vulgaris
- Tetranychus urticae which are heavily affected by all stages of development of the common spider mite Tetranychus urticae, are immersed in an active ingredient preparation of the desired concentration.
- the effect is determined in%. 100% means that all spider mites have been killed; 0% means that no spider mites have been killed.
- the compounds according to Preparation Examples 2, 21, 38 and 71, with an exemplary active compound concentration of 0.1% caused a kill of at least 95% after 13 days, while the compounds (B) known from the prior art ( G) and (H) caused a maximum kill of 45%.
- Example F Test with fly larvae / development-inhibiting effect
- Test animals All larval stages of Lucilia cuprina (OP-resistant)
- Solvent 35 parts by weight of ethylene glycol monomethyl ether
- Larvae after 48 hours (larvicidal effect), or the inhibition of adult hatching from the pupa or the inhibition of pupa formation.
- the criterion for the in vitro effect of a substance is the inhibition of flea development or a development standstill before the adult stage. 100% larvicidal activity means that all larvae have died after 48 hours. 100% development-inhibitory effect means that no adult flies have hatched.
- the compounds according to the invention according to preparation examples 10 and 55 have a 100% action at an exemplary active ingredient concentration of 1000 ppm.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Dentistry (AREA)
- Wood Science & Technology (AREA)
- Plant Pathology (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Agronomy & Crop Science (AREA)
- General Health & Medical Sciences (AREA)
- Pest Control & Pesticides (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Plural Heterocyclic Compounds (AREA)
- Thiazole And Isothizaole Compounds (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
- Nitrogen- Or Sulfur-Containing Heterocyclic Ring Compounds With Rings Of Six Or More Members (AREA)
Abstract
Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AU63028/96A AU6302896A (en) | 1995-06-26 | 1996-06-13 | 1,3-oxa(thia)zine derivatives |
BR9609310A BR9609310A (pt) | 1995-06-26 | 1996-06-13 | Derivados de 1,3-OXA(TIA)ZINA |
EP96921979A EP0842162A1 (de) | 1995-06-26 | 1996-06-13 | 1,3-oxa(thia)zin-derivate |
JP9504127A JP2000502319A (ja) | 1995-06-26 | 1996-06-13 | 1,3−オキサ(チア)ジン誘導体 |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19523087.6 | 1995-06-26 | ||
DE19523087A DE19523087A1 (de) | 1995-06-26 | 1995-06-26 | 1,3-Oxa(thia)zin-Derivate |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1997001546A1 true WO1997001546A1 (de) | 1997-01-16 |
Family
ID=7765227
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP1996/002552 WO1997001546A1 (de) | 1995-06-26 | 1996-06-13 | 1,3-oxa(thia)zin-derivate |
Country Status (9)
Country | Link |
---|---|
EP (1) | EP0842162A1 (de) |
JP (1) | JP2000502319A (de) |
KR (1) | KR19990028393A (de) |
CN (1) | CN1193320A (de) |
AU (1) | AU6302896A (de) |
BR (1) | BR9609310A (de) |
DE (1) | DE19523087A1 (de) |
TW (1) | TW336229B (de) |
WO (1) | WO1997001546A1 (de) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8710043B2 (en) | 2011-06-24 | 2014-04-29 | Amgen Inc. | TRPM8 antagonists and their use in treatments |
US8778941B2 (en) | 2011-06-24 | 2014-07-15 | Amgen Inc. | TRPM8 antagonists and their use in treatments |
US8952009B2 (en) | 2012-08-06 | 2015-02-10 | Amgen Inc. | Chroman derivatives as TRPM8 inhibitors |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
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CN112789278A (zh) * | 2018-10-06 | 2021-05-11 | 先正达参股股份有限公司 | 杀微生物的喹啉二氢-(噻嗪)噁嗪衍生物 |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE1545671A1 (de) * | 1965-05-05 | 1969-08-07 | Huels Chemische Werke Ag | Verfahren zur Herstellung von 4H-5,6-Dihydro-1,3-oxazinen |
WO1994014783A1 (en) * | 1992-12-25 | 1994-07-07 | Nippon Soda Co., Ltd. | Heterocyclic derivative and pest control agent |
EP0635500A1 (de) * | 1993-07-21 | 1995-01-25 | Yashima Chemical Industry Co., Ltd. | 5,6-Dihydro-(4H)1,3-Oxazin und - Thiazin-Derivate als Insektizide |
-
1995
- 1995-06-26 DE DE19523087A patent/DE19523087A1/de not_active Withdrawn
-
1996
- 1996-06-12 TW TW085107036A patent/TW336229B/zh active
- 1996-06-13 CN CN96196351A patent/CN1193320A/zh active Pending
- 1996-06-13 JP JP9504127A patent/JP2000502319A/ja active Pending
- 1996-06-13 EP EP96921979A patent/EP0842162A1/de not_active Withdrawn
- 1996-06-13 WO PCT/EP1996/002552 patent/WO1997001546A1/de not_active Application Discontinuation
- 1996-06-13 KR KR1019970709709A patent/KR19990028393A/ko not_active Application Discontinuation
- 1996-06-13 BR BR9609310A patent/BR9609310A/pt not_active Application Discontinuation
- 1996-06-13 AU AU63028/96A patent/AU6302896A/en not_active Abandoned
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE1545671A1 (de) * | 1965-05-05 | 1969-08-07 | Huels Chemische Werke Ag | Verfahren zur Herstellung von 4H-5,6-Dihydro-1,3-oxazinen |
WO1994014783A1 (en) * | 1992-12-25 | 1994-07-07 | Nippon Soda Co., Ltd. | Heterocyclic derivative and pest control agent |
EP0635500A1 (de) * | 1993-07-21 | 1995-01-25 | Yashima Chemical Industry Co., Ltd. | 5,6-Dihydro-(4H)1,3-Oxazin und - Thiazin-Derivate als Insektizide |
Non-Patent Citations (2)
Title |
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A.R. KATRITZKY ET AL.: "Synthesis and some transformations of substituted 5,6-dihydro- 4H-1,3-oxazines", TETRAHEDRON, (INCL TETRAHEDRON REPORTS), vol. 49, no. 19, 1993, OXFORD GB, pages 3907 - 3918, XP002014654 * |
G. STAJER ET AL.: "Phenyl-substituted cyclopentane- and cyclohexane-cis-fused-1,3-oxazines and -1,4-oxazepinones. Preparation and stereochemical study", TETRAHEDRON, (INCL TETRAHEDRON REPORTS), vol. 46, no. 19, 1990, OXFORD GB, pages 6859 - 6868, XP002014653 * |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8710043B2 (en) | 2011-06-24 | 2014-04-29 | Amgen Inc. | TRPM8 antagonists and their use in treatments |
US8778941B2 (en) | 2011-06-24 | 2014-07-15 | Amgen Inc. | TRPM8 antagonists and their use in treatments |
US9096527B2 (en) | 2011-06-24 | 2015-08-04 | Amgen Inc. | TRPM8 antagonists and their use in treatments |
US8952009B2 (en) | 2012-08-06 | 2015-02-10 | Amgen Inc. | Chroman derivatives as TRPM8 inhibitors |
Also Published As
Publication number | Publication date |
---|---|
JP2000502319A (ja) | 2000-02-29 |
DE19523087A1 (de) | 1997-01-02 |
AU6302896A (en) | 1997-01-30 |
TW336229B (en) | 1998-07-11 |
BR9609310A (pt) | 1999-07-06 |
EP0842162A1 (de) | 1998-05-20 |
KR19990028393A (ko) | 1999-04-15 |
MX9710358A (es) | 1998-07-31 |
CN1193320A (zh) | 1998-09-16 |
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