WO1997017847A1 - Ethers esters de polysaccharide liberant un principe actif - Google Patents

Ethers esters de polysaccharide liberant un principe actif Download PDF

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Publication number
WO1997017847A1
WO1997017847A1 PCT/EP1996/004823 EP9604823W WO9717847A1 WO 1997017847 A1 WO1997017847 A1 WO 1997017847A1 EP 9604823 W EP9604823 W EP 9604823W WO 9717847 A1 WO9717847 A1 WO 9717847A1
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WIPO (PCT)
Prior art keywords
methyl
dimethyl
polysaccharide
active ingredients
ether esters
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PCT/EP1996/004823
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German (de)
English (en)
Inventor
Jochen Kalbe
Rainhard Koch
Hanns-Peter Müller
Uwe Priesnitz
Gunther Penners
Bodo Rehbold
Wolfram Andersch
Klaus Stenzel
Jürgen Engelhardt
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Bayer Aktiengesellschaft
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Priority to EP96938092A priority Critical patent/EP0861024A1/fr
Priority to AU75652/96A priority patent/AU7565296A/en
Priority to JP9518549A priority patent/JP2000500148A/ja
Publication of WO1997017847A1 publication Critical patent/WO1997017847A1/fr

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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
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/08—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing solids as carriers or diluents
    • A01N25/10—Macromolecular compounds

Definitions

  • the present invention relates to biodegradable active ingredient-releasing systems made from thermoplastically processable polysaccharide ether esters and agrochemical active ingredients and their use for plant treatment.
  • thermoplastically processable polymers The incorporation of active ingredients into thermoplastically processable polymers is known. However, it cannot be predicted from the outset whether an active substance-polymer system will release the active substance to a sufficient extent and over a sufficiently long time. In addition, after the end of the treatment, the polymer carrier with residual active ingredient remains on the plants or in the soil and has to be disposed of in a complex manner (see US Pat. No. 4,743,448, US Pat. No. 4,666,767, US Pat. No. 5,201,925).
  • Biodegradable carrier systems which release agrochemical active substances have also become known (see WO 91/3940, EP-A 344 1 18, EP-A 404 727,
  • the present invention therefore relates to systems composed of polysaccharide ether esters and agrochemical active substances, which may contain customary additives.
  • Polysaccharide OR where Polysaccharide-O represent the substituted OH groups of a polymeric saccharide unit
  • R is either a mono- and / or polymeric substituent of structure X:
  • a and A ' represent a linear polyether chain of the following structures:
  • D represents a linear aliphatic or aromatic branched or unbranched chain having 2 to 11 carbon atoms and n is an integer equal to or greater than 0, m is an integer equal to or greater than 1, and
  • B is a dicarboxylic acid of the following structure: in which E is an aromatic or aliphatic carbon skeleton which may optionally be provided with further substituents, the ratio of A 'to B being equal to or greater than 0.1, or R corresponding to the degree of substitution per saccharide unit with X being H (hydrogen) and / or alkyl with 1 to 4, preferably 1 to 2 carbon atoms.
  • These polysaccharide ether esters are prepared by first activating the polysaccharide with an alkali metal hydroxide solution.
  • This activation can take place by the synthesis and isolation of an alkali polysaccharide or alternatively by producing a water-moist alkali polysaccharide or a suspension of the polysaccharide in water-miscible solvents and then adding an aqueous alkali solution.
  • the water and / or solvent-moist alkali polysaccharide is subjected to a solvent wash, as a result of which a defined alkali content can be set.
  • the activation can also be carried out by spraying on an aqueous alkali lye.
  • the epoxide is grafted onto the cellulose activated in this way and the water present in the reaction mixture is preferably distilled off before the reaction with the dicarboxylic acid anhydride.
  • the reaction with the dicarboxylic acid anhydrides is carried out in suspension media. It is surprising that the dicarboxylic acid anhydride reacts in a two-phase reaction (liquid-solid) with the polysaccharide in standard organic solvents, since comparable reactions could only be carried out in activating and strongly swelling solvents such as acetic acid and pyridine.
  • the reaction of the polysaccharide with the dicarboxylic acid anhydride can also be carried out with organic amines.
  • the polysaccharide or the alkali-free cellulose ether is stirred in the suspension medium with the amine as catalyst and the dicarboxylic acid anhydride is added to this suspension or solution. This creates the dicarboxylic acid monoester of the polysaccharide or the polysaccharide ether.
  • the product goes into solution during the reaction with the dicarboxylic acid anhydride.
  • the still free carboxyl group of the resulting dicarboxylic acid monoester is reacted with alkylene oxides.
  • the proportions can be chosen so that the free carboxylic acids are fully or only partially reacted with alkylene oxide.
  • the free acid groups can also serve as starters for a polymeric ether structure.
  • amine was used for activation, it also serves as a catalyst in this reaction step. Accordingly, small amounts of amine can be added at this point when alkali is activated.
  • cellulose such as. B. wood pulp and cotton sinters of any molecular weight or other cellulose-containing products such as Sawdust, suitable.
  • native and soluble starches of any provenance and pretreatment as well as amylose, amylopectin, alginate, glycogen, carraghenate, chitin, chitosan, guar as splits or flour, locust bean gum, pectin, xylan, xanthan, pullulan, dextran and laevan are suitable.
  • cellulose ethers are suitable as methyl cellulose or ethyl cellulose, or benzyl cellulose with average degrees of substitution less than / equal to 2.5, hydroxyethyl cellulose, hydroxypropyl cellulose, dihydroxypropyl cellulose, hydroxybutylcellulose, methylhydroxyethylcellulose, methylhydroxypropylcellulose, methylhydroxybutyl, Ethylhydroxypropylcellulose, ethyl, carboxyalkyl, sulfoalkyl cellulose, cyanoethyl cellulose and their mixed ethers.
  • Suitable dicarboxylic acid anhydrides are anhydrides such as phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, maleic anhydride, succinic anhydride, trimellitic anhydride and isatoic anhydride.
  • Preferred epoxides are monoepoxides such as ethylene oxide, propylene oxide,
  • Insecticides, fungicides and herbicides may be mentioned as active agrochemicals.
  • organic phosphorus compounds such as phosphoric acid esters, carbamates, pyrethroids, urea derivatives such as benzoylureas, triazines, agonists or antagonists of the nicotinogenic acetylcholine receptors of insects.
  • the pyrethroids include:
  • Allethrin 2,2-dimethyl-3- (2-methyl-1-propenyll) cyclopropane carboxylate of 2-methyl-4-oxo-3- (2-propenyl) -2-cyclopenten-1-yl.
  • Barthrin 2,2-dimethyl-3- (2-methyl-1-propenyl) cyclopropane carboxylate of (6-chloro-1,3-benzodioxol-5-yl) methyl.
  • Bioresmethrin 2,2,3- (2-methyl-l-propenyl) carboxylate of [5- (phenyl-methyl) -3-furanyl] methyl.
  • Bromethrin 2- (2,2-dibromovinyl) -3,3-dimethylcyclopropane carboxylate of (5-benzyl-3-furyl) methyl.
  • Cycloethrin 2,2-dimethyl-3- (2-methyl-propenyl) -cyclopropane-carboxylate of 3- (2-cyclopenten-1-yl) -2-methyl-4-oxo-2-cyclopenten-1-yl.
  • Dimethrin 2,2,3- (2-methyl-1-propenyl) carboxylate of 2,4-dimethylbenzyl.
  • Tetramethrin 2,2,3- (2-methyl-1-propenyl) carboxylate of (1,3,4,5,6,7-hexahydro-1,3-di-oxo-2H-isoindol-2-yl ) methyl.
  • K-othrin 2,2-dimethylcyclopropane carboxylate of (5-benzyl-3-furyl) methyl trans - (+) - 3-cyclopentylidene-methyl.
  • FMC 33297 2,2-dimethylcyclopropane carboxylate of m-phenoxybenzyl-cis-trans - (+) - 3- (2,2-dichlorovinyl).
  • Cinerin I 2,2,3- (2-methyl-1-propenyl) carboxylate of 2- (2-butenyl) -4-hydroxy-3-methyl-2-cyclopenten-1-one.
  • Pyrethrin I 2,2,3- (2-methyl-1-propenyl) carboxylate of 4-hydroxy-3-methyl-2- (2,4-pentadienyl) -2-cyclopenten-1-one.
  • Cinerin II 2,2,3- (2-methyl-1-propenyl) carboxylate of 2- (2-butenyl) -4-hydroxy-3-methyl-2-cyclopenten-1-one.
  • Pyrethrin II 2,2,3- (2-methyl-1-propenyl) carboxylate of 4-hydroxy-3-methyl-2- (2,4-pentadienyl) -2-cyclopenten-1-one.
  • Jasmohn I 4 ', 5'-dihydropyrethrin-I.
  • Jasmolin II 4 ', 5'-dihydropyrethrin-II.
  • Biothanometrin 2,2-dimethyl-3- (2-cyclopentylvinyl) -cyclopropane-carboxylate of (5-benzyl-3-furyl) methyl.
  • Bioethanomethrin 2- (2,2-dichlorovinyl) -3,3-dimethyl-cyclopropane-carboxylate of (3-diphenyl ether) methyl.
  • Cypermethrin 2- (2,2-dichlorovmyl) -3,3-dimethyl-cyclopropane-carboxylate of (3-diphenyl ether) -cynomethyl.
  • Decamethrin 2- (2,2-dibromovinyl) -3,3-dimethyl-cyclopropane-carboxylate of (3-diphenyl ether) -cyanomethyl.
  • ES-56 2,2,3- (2-methyl-1-propenyl) carboxylate of 2,3-dihydrofuran.
  • Fenpropanate (S-3206) 2,2-dimethyl-3,3-dimethyl-cyclopropane-carboxylate of (3-diphenyl ether) cyanomethyl.
  • Fenvalerate (S-5602) [(p-chlorophenyl) - (isopropyl)] acetate of (3-diphenyl ether) cyanomethyl.
  • Cyfluthrin 2- (2,2-dichlorovinyl) -3,3-dimethylcyclopropane carboxylate of 4-fluoro-3-diphenylether-cyanomethylol.
  • the carbamates include:
  • Aldicarb 2-methyl-2- (methylthio) propanol-O - [(methylamino) carbonyi] oxime.
  • Aldoxycarb 2-methyl-2- (methylsulfonyl) propanol-O- [methylamino) carbonyl] oxime.
  • Aminocarb methyl carbamate of 4-dimethylamino-3-methylphenyl.
  • Bendiocarb N-methyl carbamate of 2,2-dimethyl-benzo-1,3-dioxol-4-yl.
  • Bufencarb methyl carbamate of 3- (1-methylbutyl) phenyl and methyl carbamate of 3- (1-ethylpropyI) phenyl (3: 1).
  • Butacarb methyl carbamate of 3,5-bis (1,1-dimethylethyl) phenyl.
  • Butocarboxime 3-methylthio-2-butane-O - [(methylamino) carbonyl] oxime.
  • Butoxycarboxime 3-methylthio-2-butanone-O - [(methylamino) carbonyl] oxime.
  • 2-sec-butylphenylmethyl carbamate methyl carbamate of 2- (1-methylpropyl) phenyl.
  • Carbanolates methyl carbamates of 2-chloro-4,5-dimethylphenyl.
  • Carbaryl methyl carbamate of 1-naphthalenyI.
  • Carbofuran methyl carbamate of 2,3-dihydro-2,2-dimethyl-7-benzofuranyl.
  • Cartap carbamothicate of S, S '- [2- (dimethylamino) -1,3-propanediyl].
  • Decarbofuran methyl carbamate of 2,3-dihydro-2-methylbenzofuran-7-yl.
  • Dimetilan dimethyl carbamate des - [(dimethylamino) carbonyl] -5-methyl-1H-pyrazol-3-yl.
  • Dioxocarb methyl carbamate of 2- (1,3-dioxolan-2-yl) phenyl.
  • Ethiofencarb methyl carbamate of 2-ethylthiomethylphenyl
  • Formparanate methyl carbamate of 3-methyl-4-dimethylamino-methylenaminophenyl
  • Isoprocarb methyl carbamate of 2-isopropylphenyl.
  • Methiocarb methyl carbamate of 3,5-dimethyl-4-methylthiophenyl.
  • Methomyl methyl N - [[(methylamino) carbonyl] oxy] ethane imidothioate.
  • Mexacarbate methyl carbamate of 4-dimethylamino-3,5-dimethylphenyl.
  • Nabam 1,2-ethanediylbis (carbamodithioate) disodique.
  • Nitrile acarb to Cl 2 , (4,4-dimethyl-5-methylamino-carbonyloximino) pentanenitrile.
  • Oxamil Memyl 2- (dimethylamino) -N - [[(methylamino) carbonyl] oxy] -2-oxoethaniminothioate.
  • Pirimicarb dimethyl carbamate of 2- (dimethylamino) -5,6-dimethyl-4-pyrimidinyl.
  • Promecarb methyl carbamate of 3-methyl-5- (1-methylethyl) phenyl.
  • Propoxur methyl carbamate of 2- (1-methylethoxy) phenyl.
  • Thiofanox 3,3-dimethyl- (methylthio) -2-butanone-O - [(methylamino) carbonyl] oxime
  • Thiocarboxime carbamate of 1- (2-cyanoethylthio) ethylene aminomethyl.
  • Trimethylphenylmethyl carbamate methyl carbamate of 3,4,5-trimethylphenyl.
  • 4-xylylmethyl carbamate methyl carbamate of 3,4-dimethylphenyl.
  • 3,5-xylylmethyl carbamate methyl carbamate of 3,5-dimethylphenyl.
  • Amidithione S- (N-2-methoxyethylcarbamoylmethyl) dimethylphosphorodithioate.
  • Amiton S- [2- (diethylamino) ethyl] diethylphosphorothioate.
  • Athidation O, O-Diethyl-S-5-methoxy-2-oxo-1,3,4-thiadiazol-3-yl-methylphosphorodithioate.
  • Azinphos-ethyl O, O-Diethyl-S - [(4-oxo-1,2,3-benzotriazin-3 (4H) -yl) methyl] phosphorodithioate.
  • Azinphos-methyl O, O-Dimethyl-S - [(4-oxo-1,2,3-benzotriazin-3 (4H) -yl) methyl] phosphorodithioate.
  • Azothioate O, O-Dimethyl-O- [p- (p-chlorophenylazo) phenyl] phosphorothioate.
  • Carbophenothione S - [[(4-chlorophenyl) thio] methyl] -O, O-diuethylphosphorodithioate.
  • Chlorfenvinphos 2-chloro-1- (2,4-dichlorophenyl) ethenyl phosphate of diethyl.
  • Chlorprazophos O, O-Diethyl-O-3-chloro-7-methyl-pyrazolo [1,5-a] pyrimidin-2-yl-phosphorothioate.
  • Chlorpyrifos O, O-Diethyl-0,3,5,6, -trichloro-2-pyridylphosphorothioat.
  • Chlorpyrifos-methyl O, O-dimethyl-O, 3,5,6-trichloro-2-pyridylphosphorothioate.
  • Chlorothiophos O-2,5-dichloro-4- (methylthio) phenyl-O, O-diethylphosphorothioate
  • Coumaphos O-3-chloro-4-methylcoumarin-7-yl-O, O-diethylphosphorothioate.
  • Coumithoate O, O-diethyl-O- (7,8,9,10-tetrahydro-6-oxo-6H-dibenzo [b, d] pyran-3-yl-phosphorothioate.
  • Cortoxyphos 1-phenylethyl (E) -3 - [(dimethoxyphosphonyl) oxy] -2-butenoate.
  • Cyanophos O-4-cyanophenyl-O, O-dimethylphosphorothioate.
  • Cyanthoate O, O-Diethyl-S- [N- (1-cyano-1-methylethyl)] carbamoylmethylphosphorothioate.
  • Demephion O, O-Dimethyl-O-2-methylthioethylphosphorothioat and the OkO-Dimethyl-S-2-methylthioethylphosphorothioat.
  • Demeton O, O-Diethyl-O-2-ethylthioethylphosphorothioat and O, O-Diethyl-S-2-ethylthioethylphosphorothioat
  • Demeton-S-methyl O, O-Dimethyl-S-2-ethylthioethylphosphorothioat.
  • Demetone S-methylsulfone S-2-ethylsulfonylethyl-O, O-dimethylphosphorothioate.
  • Demeton-S O, O-Diethyl-S- [2- (ethylthio) ethyl] phosphorothioate.
  • Demetone-O O, O-diethyl-O- [2- (ethylthio) ethyl] phosphorothioate.
  • Demetone-O-methyl O, O-dimethyl-O- [2- (ethylthio) ethyl] phosphorothioate.
  • Dichlorofenthion O, O-diethyl-O- (2,4-dichlorophenyl) phosphorothioate. O-2,4-dichlorophenyl-O-ethylphenylphosphonothioate.
  • Dicrotophos dimethyl-3- (dimethylamino) -1-methyl-3-oxo-1-propenyl phosphate.
  • Dimethoate O, O-Dimethyl-S- [2- (methylamino) -2-oxo-ethyl] phosphorodithioate.
  • 1,3-Di- (methoxycarbonyl) -1-propen-2-yl dimethyl phosphate dimethyl 3 - [(dimethoxyphosphinyl) oxy] -2-pentene dioate.
  • Dioxathione S, S'-1,4-dioxane-2,3-diyl-O, O ', O'-tetraethyl-di- (phosphorodithioate).
  • Disulfoton O, O-Diethyl-S-2-ethylthioethylphosphorodithioat.
  • EPN O-ethyl-O-4-nitrophenylphenylphosphonothioate.
  • Endothion O, O-dimethyl-S- (5-methoxy-4-pyron-2-yl-methyl) phosphorothioate.
  • Ethion O, O, O ", O” -Tetraehyl-S, S'-methylene-di (phosphorodithioate).
  • Ethoat-methyl O, O-dimethyl-S- (N-ethylcarbamoyl-methyl) phosphorodithioate.
  • Ethoprophos O-ethyl-S, S-dipropylphosphorodothioat.
  • Etrimfos O- (6-ethoxy-2-ethyl-4-pyrimidinyl) -O, O-dimethylphosphorothioate.
  • Famphur O, O-dimethyl-O-p- (dimethylsulfamoyl) phenyl phosphorothioate.
  • Fenchlorphos O, O-DimethyI-O- (2,4,5-trichlorophenyl) phosphorothioate.
  • Fensulfothione O, O-diethyl-O-4- (methylsulfinyl) phenyl phosphorothioate.
  • Fenthion O, O-dimethyl-O- [3-methyl-4- (methylthio) phenyl] phosphorothioate.
  • Fonophos O-ethyl-S-phenylethylphosphonodithioate.
  • Formothion S- [2- (formylmethylamino) -2-oxoethyl] -O, O-dimethylphosphorodithioate.
  • Fospirate dimethyl-3,5,6-trichloro-2-pyridyl phosphate.
  • Fosthietan diethyl-1,3-dithietan-2-yl-idene-phosphoramidate.
  • Heptenophos 7-chlorobicyclo [3, 2.0] hepta-2,6-dien-6-yl dimethyl phosphate.
  • Iodofenphos O-2,5-dichloro-4-iodophenyl-O, O-dimethyl-phosphorothioate.
  • Isofenphos 1-methylethyl-2 - [[ethoxy] - (1-methylethyl) amino [phosphmothioyl] -oxyjbenzoate.
  • Leptophos O-4-bromo-2,5-dichlorophenyl-O-methylphenylphosphonothioate.
  • Lythidathione O, O-Dimethyl-S- (5-ethoxy-2,3-dihydro-2-oxo-1,3,4-thiadiazol-3-yl-methyl) phosphotodithioate.
  • Malathion diethyl (dimethoxyphosphinothioyl) thiobutene dioate.
  • Mecarbam methyl ethyl [[(diethoxyphosphinothioyl) thio] acetal] carbamate.
  • Mecarphone N-methylcarbonyl-N-methyl-carbamoyl-methyl-O-methylmethylphosphonodithioate.
  • Menazon S - [(4,6-diamino-1,3,5-triazin-2-yl) methyl] -O, O-dimethylphosphorodithioate.
  • Mephosfolan diethyl-4-methyl-1,3-dithiolan-2-yl-dinen-phosphoroamidate.
  • Methamidophos O, S-dimethylphosphoramidothioate.
  • Methidation S - [[5-methoxy-2-oxo-1,3,4-thiadiazol-3 (2H) -yI] methyl] -O, O-dimethylphosphorodithioate.
  • Methocrotophos dimethyl-cis-2- (N-methoxy-N-methyl) carbamoyl) -1-methyl vinyl phosphate.
  • Methyl carbophenotion S - [[(4-chlorophenyl) thio] methyl] -O, O-dimethylphosphorodithioate.
  • Mevinphos methyl 3 - [(dimethoxyphosphinyl) oxy] -2-buenoate.
  • Monocrotophos dimethyl-1-methyl-3- (methylamino) -3-oxo-1-propenyl phosphate.
  • Morphotion O, O-Dimethyl-S- (morpholino-carbonylmethyl) -phosphorodithioate.
  • Naled dimethyl-1,2-dibromo-2,2-dichloroethyl phosphate.
  • Omethoate O, O-Dimethyl-S- [2- (methylamino) -2-oxoethyl] phosphorothioate.
  • Oxydimetone-methyl S- [2- (ethylsulfinyl) ethyl] -O, O-dimethylphosphorothioate.
  • Oxydisulfoton O, O-Diethyl-S- [2- (ethyl-sulfinyl) -ethyl] -phosphorodithioate.
  • Parathion O, O-diethyl-O-4-nitrophenyl phosphorothioate.
  • Parathion-methyl O, O-dimethyl-O-4-nitrophenyl-phosphorothioate.
  • Phenkapton O, O-Diethyl-S- (2,5-dichloro-phenylthiomethyl) phosphorodithioate.
  • Phenthoate ethyl ⁇ [(dimethoxyphosphinothioyl) thio] benzene acetate.
  • Phorate O, O-Diethyl-S-ethylthiomethyl-phosphorodithioate.
  • Phosalone S - [[(6-chloro-2-oxo-3) (2H) -benzoxazolyl] - (methyl)] - O-diethylphosphorodithioate.
  • Phosfolan diethyl-1,3-dithiolan-2-ylidene phosphoramidate.
  • Phosmet S - [(1,3-dihydro-1,3-dioxo-2H-isoindol-2-yl) methyl] -O, O-dimethylphosphorodithioate.
  • Phosnichlor O, O-Dimethyl-O-4-chloro-3-nitrophenyl-phosphorothioate.
  • Phosphamidon 2-chloro-3- (diethylamino) -1-methyl-3-oxo-l-propenyl phosphate of dimethyl.
  • Phoxim - [[Diethoxyphosphinothioyl) oxy] imino) -benzenacetonitriI.
  • Pirimiphos-ethyl O- [2- (diethylamino) -6-methyl-4-pyrimidinyl)] - O, O-diethylphosphorothioate.
  • Pirimiphos-methyl O- [2- (diethylamino) -6-methyl-4-pyrimidinyl)] - O, O-dimethylphosphorothioate.
  • Profenofos O- (4-bromo-2-chlorophenyl) -O-ethyl-S-propylphosphorothioate.
  • Propetamphos (E) -1-methylethyl-3 - [[(ethylamino) methoxyphosphinothioyl] oxy] 2-butenoate.
  • Prothidathione O, O-Diethyl-S- (2,3-dihydro-5-isopropyl-2-oxo-1,3,4-thiadiazol-3-yl-methyl) -phosphorodithioate.
  • Prostoate O, O-Diethyl-S- [2- (1-methylethyl) amino-2-oxoethyl] phosphorodithioate.
  • Quinothione O, O-Diethyl-2-methylquinolin-4-yl-phosphorothioate. Quintiofos - O-ethyl-O-8-quinolylphenyl phosphorothioate.
  • Sophamide O, O-dimethyl-S- (N-methoxy-methyl) carbamoyl-methylphosphorodithioate
  • Sulfotepp thiodiphosphate of tetraethyl.
  • Sulfprofos O-ethyl-O- (4-methylthiophenyl) -S-propylphosphorodithioate.
  • Temephos O, O '- (Thiodi-4, 1-phenylene) -O, O, O', O'-tetramethyl-di (phosphorodithioate).
  • Tepp diphosphate of tetraethyl.
  • Terbufos S - [(1,1-dimethylethyl) thiomethyl] -O, O-diethylphosphorodithioate.
  • Tetrachlorvinphos trans-2-chloro-1- (2,4,5-trichlorophenyl) vinyl phosphate des
  • O, O, O ', O'-tetrapropyl dithiopyrophosphate thiodiphosphate of tetrapropyl.
  • Thiometone O, O-Dimethyl-S- [2- (ethylthio) ethyl] phosphorodithioate.
  • Thionazine O, O-diethyl-O-pyrazinyl phosphorothioate.
  • Triazophos O, O-Diethyl-O- (phenyl-1H-1,2,4-triazol-3-yl) phosphorothioate.
  • Trichloronate O-ethyl-O-2,4,5-trichlorophenyl-ethylphosphonothioate.
  • Trichlorphone dimethyl (1-hydroxy-2,2,2-trichloro-ethyl) phosphonate.
  • Vamidothione O, O-Dimethyl-S- [2- (1-methylcarbamoyl) ethyleneethyl] phosphorothioate.
  • Benzoylureas include compounds of the formula (V): - 17th
  • R 1 represents halogen
  • R 2 represents hydrogen or halogen
  • R 3 represents hydrogen, halogen or C 1-4 alkyl
  • R 4 is halogen, 1-5 haloC 1-4 alkyl, C 1-4 alkoxy, 1-5 haloC 1-4 alkoxy, C 1-4 alkylthio, 1-5 halogen -C 1-4 alkylthio, phenoxy or pyridyloxy, which may optionally be substituted by halogen, C 1-4 alkyl, 1-5 haloC 1-4 alkyl, C 1-4 alkoxy, 1-5 -Halogen C 1-4 alkoxy, C 1-4 alkylthio, 1-5 halogen C 1-4 alkylthio.
  • Benzoylureas of the formula may be mentioned in particular:
  • the triazines include compounds of the formula
  • the agonists or antanogists of the nicotinogenic acetylcholine receptors of insects include the known compounds from, for example, European Offenlegungsschrift No. 464 830, 428 941, 425 978, 386 565, 383 091, 375 907, 364 844, 315 826, 259 738, 254 859, 235 725, 212 600, 192 060, 163 855, 154 178, 136 636, 303 570, 302 833, 306 696, 189 972, 455 000, 135 956, 471 372, 302 389, German Offenlegungsschriften No. 3,639,877, 3,712,307; Japanese Laid-Open No.
  • R represents hydrogen, optionally substituted radicals from the group acyl, alkyl,
  • A represents a monofunctional group from the series hydrogen, acyl, alkyl, aryl or represents a bifunctional group which is linked to the radical Z,
  • E represents an electron-withdrawing radical such as NO 2 or CN
  • H atom can be linked to the radical Z;
  • R represents hydrogen and also optionally substituted radicals from the series acyl, alkyl, aryl, aralkyl, heteroaryl, heteroaryl alkyl.
  • Formyl, alkylcarbonyl, arylcarbonyl, alkylsulfonyl, arylsulfonyl, (alkyl-) - (aryl-) - phosphoryl, which in turn can be substituted, may be mentioned as acyl radicals.
  • alkyl examples include C 1-10 -alkyl, in particular C 1-4 -alkyl, in particular methyl, ethyl, i-propyl, sec.- or t.-butyl, which in turn may be substituted.
  • Phenyl, naphthyl, especially phenyl, may be mentioned as aryl.
  • Phenylmethyl and phenethyl may be mentioned as aralkyl.
  • Heteroaryl with up to 10 ring atoms and N, O, S in particular N as heteroatoms may be mentioned as heteroaryl.
  • Thienyl, furyl, thiazolyl, imidazolyl, pyridyl, benzothiazolyl may be mentioned in particular.
  • Heteroarylalkyl which may be mentioned are heteroarylmethyl, heteroarylethyl having up to 6 ring atoms and N, O, S, in particular N, as heteroatoms.
  • Optionally substituted alkylene with 1-4, in particular 1-2, C atoms may be mentioned, the substituents listed above being mentioned as substituents and the alkylene groups being interrupted by heteroatoms from the series N, O, S. could be.
  • a and Z together with the atoms to which they are attached can form a saturated or unsaturated heterocyclic ring.
  • the heterocyclic ring can contain a further 1 or 2 identical or different heteroatoms and / or hetero groups.
  • the heteroatoms are preferably oxygen, sulfur or nitrogen and the hetero groups are N-alkyl, alkyl of the N-alkyl group preferably containing 1 to 4, in particular 1 or 2, carbon atoms.
  • the alkyls are methyl, ethyl, n- and i-propyl and n -, i- and t-Butyl called.
  • the heterocyclic ring contains 5 to 7, preferably 5 or 6, ring members.
  • heteroeyclic ring examples include pyrrolidine, piperidine, piperazine, hexamethyleneimine, hexahydro-1,3,5-triazine and morpholine, which may optionally be substituted by methyl.
  • E stands for an electron-withdrawing radical, in particular NO 2 , CN,
  • Haloalkylcarbonyl such as 1,5-halo-C 1-4 -carbonyl, in particular COCF 3 may be mentioned.
  • Z stands for optionally substituted radicals alkyl, -OR, -SR, -NRR, where
  • R and the substituents preferably have the meaning given above.
  • Z can together with the atom to which it is attached and the rest form a saturated or unsaturated heterocyclic ring at the position of X.
  • the heterocyclic ring can contain a further 1 or 2 identical or different heteroatoms and / or hetero groups.
  • the heteroatoms are preferably oxygen, sulfur or nitrogen and the hetero groups are N-alkyl, the alkyl or N-alkyl group preferably containing 1 to 4, in particular 1 or 2, carbon atoms.
  • the alkyls are methyl, ethyl, n- and i-propyl and n-, i- and t-butyl called
  • the heterocyclic ring contains 5 to 7, preferably 5 or 6 ring members.
  • heterocyclic ring examples include pyrrolidine, piperidine, piperazine, hexamethyleneimine, morpholine and N-methylpiperazine.
  • n 1 or 2
  • Sulfenanude such as dichlorofluoride (Euparen), tolylfluanid (Methyl euparen), Folpet, Fluorfolpet;
  • Benzimidazoles such as Carbendazim (MBC), Benomyl, Fuberidazole, Thiabendazole or their salts;
  • Thiocyanates such as thiocyanatomethylthiobenzothiazole (TCMTB), methylene bisthiocyanate (MBT); quaternary ammonium compounds such as benzyldimethyltetradecylammonium chloride,
  • Azoles such as tridimefon, triadimenol, bitertanol, tebuconazole, propiconazole, azaconazole, hexaconazole, prochloraz, cyproconazole, 1- (2-chlorophenyl) -2- (1-chlorocyclopropyl) -3- (1,2,4-triazol-1-yl ) -propan-2-ol, 1- (2-chlorophenyl) -2- (1,2,4-triazol-1-yl-methyl) -3,3-dimethyl-butan-2-ol.
  • Iodopropargyl derivatives such as iodopropargyl butyl carbamate (IPBC), chlorophenyl formal, phenyl carbamate, hexyl carbamate, cyclohexyl carbamate, iodopropargyloxyethylphenyl carbamate;
  • IPBC iodopropargyl butyl carbamate
  • chlorophenyl formal phenyl carbamate
  • hexyl carbamate hexyl carbamate
  • cyclohexyl carbamate iodopropargyloxyethylphenyl carbamate
  • Iodine derivatives such as diiodomethyl-p-arylsulfones e.g. Diiodomethyl p-tolyl sulfone; Bromine derivatives such as bromopol;
  • Isothiazolines such as N-methylisothioazolin-3-one, 5-chloro-N-methylisothiazolin-3-one, 4,5-dichloro-N-octylisothiazolin-3-one, N-octylisothiazolin-3-one (octilinones);
  • Pyridines such as 1-hydroxy-2-pyridinthione, tetrachlor-4-methylsulphonylpyridine; Nitriles such as 2,4,5,6-tetrachloroisophthalonitrile (chlorothalonil) and others microbicides with activated halogen group such as CI-Ac, MCA, tectamer, bromopol, bromidox;
  • Benzothiazoles such as 2-mercaptobenzothiazoles, see above or Dazomet;
  • Particularly preferred insecticides are; Phosphoric acid esters such as azinphos-eteyl, azinphos-methyl, 1- (4-chlorophenyl) -4- (O-ethyl, S-propyl) phosphoryloxypyrazole (TIA-230), chlorpyrifos, Coumaphos, Demeton, Demeton-S-methyl, diazinon, Dichlorvos, Dimethoate, Ethoprophos, Etrimfos, Fenitrothion, Fention, Heptenophos, Parathion, Parathion-methyl, Phosalone, Phoxion, Pirimiphos-ethyl, Pirimiphos-methyl, Profenofos, Prothiofos, Sulprofos, Triazophos and Trichlorphon.
  • Phosphoric acid esters such as azinphos-eteyl, azinphos-methyl, 1- (4-chlorophenyl) -4- (O-
  • Carbamates such as aldicarb, bendiocarb, BPMC (2- (1-methylpropyl) phenylmethylcarbamate), butocarboxime, butoxycarboxim, carbaryl, carbofuran, carbosulfan, cloethocarb, isoprocarb, methomyl, oxamyl, pirimicarb, promecarb, propoxur and thiodicarbox.
  • Pyrethroids such as allethrin, alphamethrin, bioresmethrin, byfenthrin (FMC 54 800), cycloprothrin, cyfluthrin, decamethrione, cyhalothrin, cypermethrin, deltamethrin, alpha-cyano-3-phenyl-2-methylbenzyl-2,2-dimethyl-3- ( chloro-2-trifluoromethylvinyl) cyclopropane carboxylate, fenpropathrin, fenfluthrin, fenvalerate, flucythrinate, flumethrin, fluvalinate, permethrin and resmethrin; Nitroimino and
  • Nitroimides such as 1 - [(6-chloro-3-pyridinyl) methyl] -4,5-dihydro-N-nitro-1H-imidazol2-amine (imidacloprid).
  • herbicides are anilides, such as diflufenican and propanil, aryl carboxylic acids, such as, for example, dichloropicolinic acid, dicamba and picloram, aryloxyalkanoic acids, such as, for example, 2,4-D, 2,4-DB, 2,4-DP, fluroxypyr , MCPA, MCPP and triclopyr, aryloxy-phenoxy-alkanoic acid esters, such as Diclofop-methyl, fenoxaprop-ethyl, fluazifop-butyl, haloxyfop-methyl and quizalofop-ethyl, azinones such as e.g.
  • chloridazone and norflurazon carbamates such as e.g. Chlorpropham, desmedipham, phenmedipham and propham, chloroacetanilides such as e.g. Alachlor, Acetochlor, Butachlor, Metazachlor, Metolachlor, Pretilachlor and
  • diphenyl ether such as e.g. Acifluorfen, bifenox, fluoroglycofen, fomesafen, halosafen, lactofen and oxyfluorfen
  • ureas such as e.g. Chlorotoluron,
  • Imidazohnones e.g. Imazethapyr, imazamethabenz, imazapyr and imazaquin, nitriles such as e.g. Bromoxynil, dichlorobile and ioxynil, oxacetamides, e.g. Mefenacet, sulfonylureas, e.g.
  • Atrazin Cyanazin, Simazm, Simetryne, Terbutryne and Terbutylazin, Triazinone, e.g. Hexazinone, metamitron and metribuzin, others such as e.g. Aminotriazole, benfuresate, bentazone, cinmethylin, clomazone, clopyralid,
  • Difenzoquat Dithiopyr, Ethofumesate, Fluorochloride, Glufosinate, Glyphosate, Isoxaben, Pyridate, Quinchlorac, Quinmerac, Sulphosate and Tridiphane.
  • the systems according to the invention contain 0.1 to 30% by weight of active ingredient, preferably 1 to 20% by weight of active ingredient and particularly preferably 5 to 20% by weight of active ingredient.
  • active ingredient preferably 1 to 20% by weight of active ingredient and particularly preferably 5 to 20% by weight of active ingredient.
  • carrier polymer preferably 1 to 20% by weight of active ingredient and particularly preferably 5 to 20% by weight of active ingredient.
  • they can also contain other customary additives.
  • Such additives are fillers such as Table salt, carbonates such as calcium carbonate, hydrogen carbonate, aluminum oxides, silicas, clays, precipitated or colloidal silicon dioxide, phosphates.
  • Suitable additives are lubricants and lubricants such as Magnesium stearate, stearic acid, talc, bentonite.
  • Suitable additives are the plasticizers which are usually used to plasticize solid vinyl resins.
  • Suitable plasticizers are, for example, esters of phosphoric acid, such as esters of phthalic acid, such as
  • esters of adipic acid such as diisobutyl adipate.
  • Other esters such as the esters of azelaic acid, maleic acid, ricinoleic acid, myristic acid, palmitic acid, oleic acid, sebacic acid, stearic acid and trimellitic acid, as well as complexed linear polyester epoxy polymers, plasticizers, and plasticizers.
  • Plasticizer is up to about 50%, preferably about 10 to 30% by weight of the total composition.
  • additives are stabilizing agents and coloring materials. Suitable stabilizing agents are antioxidants and agents which protect the polymers from undesired degradation during processing. Some stabilizing agents, such as epoxidized soybean ols, also serve as secondary plasticizers.
  • the additives can be used in a concentration of up to about 50% by weight. preferably up to about 20% by weight of the total composition can be used.
  • Components are dry mixed according to known mixing methods and compression molded according to known extrusion or injection molding methods.
  • the solution is preferably introduced into a nozzle Precipitation bath pressed, the resulting coagulating material drawn off as threads (wet spinning process).
  • the precipitation is preferably carried out by means of the known dry and wet spinning processes.
  • the choice of the processing method for producing the shaped bodies according to the invention is fundamentally based on the theological properties of the shaped body material and the shape of the desired structure.
  • the processing methods can be adjusted according to the processing technology or the type of shaping.
  • the processes can be subdivided according to the theological conditions they run through. Then pouring, pressing, spraying and applying for viscous molded body materials and injection molding, extrusion (extrusion), calendering, rolling and, if necessary, kneading are considered for the type of shaping divided, the shaped bodies according to the invention can be produced by casting, dipping, pressing, injection molding, extruding, calendering, embossing, bending, deep drawing, spinning, etc.
  • the systems according to the invention are suitable, for example, for introducing crop protection agents such as fungicides or insecticides into the soil near the roots. There they are biodegraded as a depot preparation with controlled release of active ingredients and are completely degraded at the end of their effectiveness.
  • the systems according to the invention can also be used for the treatment of individual plants, such as trees.
  • they are preferably in the form of suitable shaped bodies such as rods, tablets, plates, foils, tiles, fabrics, strips, rivets, nails, clips, pins, needles, Hollow nailing, wires inserted into the sap flow of the plants.
  • the shaped bodies are either inserted into the cavities made in the plant or simply into the plant Plant tissue pressed, pressed, beaten. They can also be pushed under carefully loosened bark or parts of plants, the bark or parts of plants then serving again for covering.
  • the systems according to the invention can also be used for the production of transcuticular agents.
  • transcuticular agents are in the form of paints, film-forming pastes,
  • Solid-state NMR determined degree of substitution is 1.7 moles of phthalic acid and 2.75 moles of propyl groups per glucose unit.
  • a glucose release of 85, 19 ⁇ g glucose / ml-h of the sample preincubated at 60 ° C. was found.
  • the composting test the sample is completely degraded after four weeks.
  • the degree of substitution determined by solid-state NMR is 3.0 mol of hexahydrophthalic acid and 3.0 mol of propyl groups per glucose unit.
  • the enzyme test a release of 70.6 ⁇ g of glucose / ml-h of the sample preincubated at 60 ° C. is found.
  • the composting test the sample is completely degraded after four weeks.
  • Example 6 a were used to produce active substance-containing molded articles according to the invention
  • OH groups per glucose unit 1.80 metered separately into a twin-screw extruder using differential scales. Furthermore, c) 100 parts by weight of the plasticizer triethylene glycol were metered into the screw by means of a pump.
  • the components were homogenized in the extruder at 140 ° C. to 150 ° C. within 4 minutes and the melt was extruded at a throughput of 3.8 kg / h, cooled with air and granulated.
  • the molding compound containing the active ingredient is shaped into bars, pins, strips and plates using an injection molding machine at 160 ° C.
  • the melt strand was drawn off at a speed of 35 m / min, so that a cable with a diameter of approximately 1 mm was formed, and after cooling with air, it was wound onto a spool. By subsequently cutting the cable, pins with a length of 2 cm were produced.
  • the melt was pressed at 155 ° C. through a 75 mm wide slot nozzle with a gap height of 0.5 mm, cooled by air blowing and drawn off by means of a Teflon conveyor belt at a speed of 5 / min. In this way, films with a thickness of approximately 50 ⁇ m were obtained.
  • the resulting active substance-containing mass was shaped in a press at 200 bar pressure and 120 ° C. into sheets with an area of 10 cm 2 and a thickness of 2 mm.

Abstract

L'invention concerne des systèmes comprenant des éthers esters de polysaccharide et des principes actifs agrochimiques, qui contiennent éventuellement des additifs classiques et sont biodégradables.
PCT/EP1996/004823 1995-11-15 1996-11-05 Ethers esters de polysaccharide liberant un principe actif WO1997017847A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
EP96938092A EP0861024A1 (fr) 1995-11-15 1996-11-05 Ethers esters de polysaccharide liberant un principe actif
AU75652/96A AU7565296A (en) 1995-11-15 1996-11-05 Polysaccharide ether esters which release active ingredients
JP9518549A JP2000500148A (ja) 1995-11-15 1996-11-05 有効化合物を放出する多糖エーテル−エステル類

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19542500A DE19542500A1 (de) 1995-11-15 1995-11-15 Wirkstofffreisetzende Polysaccharidetherester
DE19542500.6 1995-11-15

Publications (1)

Publication Number Publication Date
WO1997017847A1 true WO1997017847A1 (fr) 1997-05-22

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JP (1) JP2000500148A (fr)
AU (1) AU7565296A (fr)
DE (1) DE19542500A1 (fr)
WO (1) WO1997017847A1 (fr)
ZA (1) ZA969562B (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0896791A2 (fr) * 1997-08-11 1999-02-17 Bayer Ag Composition contre les insectes détruisant le bois
AU2004200975B2 (en) * 1997-08-11 2007-04-19 Bayer Intellectual Property Gmbh Compositions against wood-destroying insects

Citations (5)

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Publication number Priority date Publication date Assignee Title
US3824085A (en) * 1972-02-01 1974-07-16 Anheuser Busch Esters of polymeric hydroxypropyl carbohydrates and method of using same as gelling agent for organic solvents
US3940384A (en) * 1973-08-13 1976-02-24 Anheuser-Busch, Incorporated Methyl hydroxypropyl cellulose acetate and process
WO1991003940A1 (fr) * 1989-09-15 1991-04-04 Goodman Fielder Wattie Australia Limited Matrices biodegradables de liberation regulee
EP0511541A1 (fr) * 1991-04-27 1992-11-04 Nihon Bayer Agrochem K.K. Agent de préservation du bois ou de matériaux à base de bois contre les insectes
DE4404840A1 (de) * 1994-02-16 1995-08-17 Wolff Walsrode Ag Thermoplastische biologisch abbaubare Polysaccharidderivate, Verfahren zu ihrer Herstellung und ihre Verwendung

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3824085A (en) * 1972-02-01 1974-07-16 Anheuser Busch Esters of polymeric hydroxypropyl carbohydrates and method of using same as gelling agent for organic solvents
US3940384A (en) * 1973-08-13 1976-02-24 Anheuser-Busch, Incorporated Methyl hydroxypropyl cellulose acetate and process
WO1991003940A1 (fr) * 1989-09-15 1991-04-04 Goodman Fielder Wattie Australia Limited Matrices biodegradables de liberation regulee
EP0511541A1 (fr) * 1991-04-27 1992-11-04 Nihon Bayer Agrochem K.K. Agent de préservation du bois ou de matériaux à base de bois contre les insectes
DE4404840A1 (de) * 1994-02-16 1995-08-17 Wolff Walsrode Ag Thermoplastische biologisch abbaubare Polysaccharidderivate, Verfahren zu ihrer Herstellung und ihre Verwendung

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Title
J. ENGELHARDT: "Biologisch abbaubare thermoplastische Polymere aus Cellulose", DAS PAPIER, vol. 50, no. 12, December 1996 (1996-12-01), pages 701-2,707-11, XP000646864 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0896791A2 (fr) * 1997-08-11 1999-02-17 Bayer Ag Composition contre les insectes détruisant le bois
EP0896791A3 (fr) * 1997-08-11 2000-01-12 Bayer Ag Composition contre les insectes détruisant le bois
US6264968B1 (en) 1997-08-11 2001-07-24 Bayer Aktiengesellschaft Compositions against wood-destroying insects
AU2004200975B2 (en) * 1997-08-11 2007-04-19 Bayer Intellectual Property Gmbh Compositions against wood-destroying insects

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ZA969562B (en) 1997-06-25
DE19542500A1 (de) 1997-05-22
JP2000500148A (ja) 2000-01-11
EP0861024A1 (fr) 1998-09-02

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