Aminomethyl-tetrahydro-furanes.
Abstract
Aminomethyltetrahydrofurans of the general formula (I), in which A, R¹ and R² have the meanings given in the description and their use as pesticides and some still new precursors. The new aminomethyltetrahydrofurans of the general formula (I) can be prepared by analogy processes, for example by reacting suitable substituted tetrahydrofurans with suitable amines and optionally further alkylating the compounds according to the invention which can be obtained in this way.

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11 claims: 11 independent, 0 dependent
- 1Aminoemethyltetrahydrofurans of the general formula (I), in which A represents an optionally substituted doubly linked alkylene or alkenylene chain and R¹ and R² independently of one another each represent hydrogen, alkyl, alkenyl, alkynyl, alkoxyalkyl, dialkoxyalkyl, hydroxyalkyl, hydroxyalkoxyalkyl, dioxolanyalkyl, oxolanylalkyl, dioxanylalkyl or each optionally substituted cycloalkylalkyl, cycloalkyl, aralkyl, aralkenyl or aryl or R¹ and R² together with the nitrogen atom, to which they are attached represent an optionally substituted saturated heterocycle which may optionally contain further heteroatoms, their acid addition salts, their geometric and optical isomers and / or isomer mixtures. 1. Aminoemethyltetrahydrofurane der allgemeinen Formel (I), in welcher A für eine jeweils gegebenenfalls substituierte zweifach verknüpfte Alkylen- oder Alkenylenkette steht und R¹ und R² unabhängig voneinander jeweils für Wasserstoff, Alkyl, Alkenyl, Alkinyl, Alkoxyalkyl, Dialkoxyalkyl, Hydroxyalkyl, Hydroxyalkoxyalkyl, Dioxolanyalkyl, Oxolanylalkyl, Dioxanylalkyl oder für jeweils gegebenenfalls substituiertes Cycloalkylalkyl, Cycloalkyl, Aralkyl, Aralkenyl oder Aryl stehen oder R¹ und R² gemeinsam mit dem Stickstoffatom, an welches sie gebunden sind, für einen gegebenenfalls substituierten gesättigen Heterocyclus stehen, der gegebenenfalls weitere Heteroatome enthalten kann, deren Säureadditionssalze, deren geometrische und optische Isomere und/oder Isomerengemische.
- 2Aminomethyltetrahydrofurane gemäß Anspruch 1, worin in der Formel (I) A für eine jeweils gegebenenfalls einfach bis mehrfach, gleich oder verschieden substituierte zweifach verknüpfte Alkylen- oder Alkenylenkette mit jeweils 3 bis 18 Kohlenstoffatomen steht, wobei als Substituenten genannt seien:jeweils geradkettiges oder verzweigtes Alkyl, Alkoxy, Alkylthio, Alkoxycarbonyl, Halogenalkyl, Halogenalkoxy oder Halogenalkylthio mit jeweils 1 bis 9 Kohlenstoffatom und gegebenenfalls 1 bis 9 gleichen oder verschiedenen Halogenatomen;Trialkylsilyl mit jeweils 1 bis 4 Kohlenstoffatomen in den einzelnen geradkettigen oder verzweigten Alkylteilen;jeweils gegebenenfalls einfach oder mehrfach, gleich oder verschieden durch Alkyl mit 1 bis 4 Kohlenstoffatomen und Halogen substituiertes Cycloalkylalkyl oder Cycloalkyl mit jeweils 3 bis 7 Kohlenstoffatomen im Cycloalkylteil und gegebenenfalls 1 bis 4 Kohlenstoffatomen im geradkettigen oder verzweigten Alkylteil;jeweils gegebenenfalls einfach oder mehrfach, gleich oder verschieden durch Alkyl, Halogenalkyl, Alkoxy oder Halogenalkoxy mit jeweils 1 bis 4 Kohlenstoffatomen und gegebenenfalls 1 bis 9 gleichen oder verschiedenen Halogenatomen und/oder Halogen substituiertes jeweils zweifach verknüpftes Alkylen oder Alkenylen mit jeweils biz zu 5 Kohlenstoffatomen jeweils gegebenenfalls einfach bis mehrfach, gleich oder verschieden substituiertes einfach verknüpftes Aryl oder zweifach verknüpftes Arylen mit jeweils 6 bis 10 Kohlenstoffatomen, wobei als Substituenten genannt seien: Halogen, Cyano, Nitro, jeweils geradkettiges oder verzweigtes Alkyl, Alkoxy, Alkylthio, Halogenalkyl, Halogenalkoxy, Halogenalkylthio, Alkoxycarbonyl oder Alkoximinoalkyl mit jeweils 1 bis 4 Kohlenstoffatomen in den einzelnen Alkylteilen und gegebenenfalls 1 bis 9 gleichen oder verschiedenen Halogenatomen, R¹ und R² unabhängig voneinander jeweils für Wasserstoff;für jeweils geradkettiges oder verzweigtes Alkyl mit 1 bis 12 Kohlenstoffatomen, Alkenyl mit 3 bis 8 Kohlenstoffatomen, Alkinyl mit 3 bis 8 Kohlenstoffatomen, Hydroxyalkyl mit 2 bis 6 Kohlenstoffatomen, Alkoxyalkyl oder Dialkoxyalkyl mit jeweils 1 bis 6 Kohlenstoffatomen oder Hydroxylalkoxyalkyl mit 2 bis 6 Kohlenstoffatomen in den einzelnen Alkylteilen, für jeweils geradkettiges oder verzweigtes Dioxolanylalkyl, Oxolanylalkyl oder Dioxanylalkyl mit jeweils 1 bis 4 Kohlenstoffatomen im Alkylteil oder für jeweils gegebenenfalls im Cycloalkylteil einfach bis mehrfach, gleich oder verschieden substituiertes Cycloalkyl oder Cycloalkyalkyl mit jeweils 3 bis 7 Kohlenstoffatomen im Cycloalkylteil und gegebenenfalls 1 bis 4 Kohlenstoffatomen im Alkylteil stehen, wobei als Substituenten genannt seien: Halogen, jeweils geradkettiges oder verzweigtes Alkyl, Alkoxy, Halogenalkyl oder Halogenalkoxy mit jeweils 1 bis 4 Kohlenstoffatomen und gegebenenfalls 1 bis 9 gleichen oder verschiedenen Halogenatomen;außerdem für jeweils gegebenenfalls einfach bis mehrfach, gleich oder verschieden im Arylteil substituiertes Arylalkyl, Arylalkenyl oder Aryl mit jeweils 6 bis 10 Kohlenstoffatomen im Arylteil und gegebenenfalls bis zu 6 Kohlenstoffatomen im geradkettigen oder verzweigten Alkyl- bzw. Alkenylteil stehen, wobei als Arylsubstituenten genannt seien: Halogen, Cyano, Nitro, jeweils geradkettiges oder verzweigtes Alkyl, Alkoxy, Alkythio, Halogenalkyl, Halogenalkoxy, Halogenalkylthio, Alkoxycarbonyl oder Alkoximinoalkyl mit jeweils 1 bis 4 Kohlenstoffatomen in den einzelnen Alkylteilen und gegebenenfalls 1 bis 9 gleichen oder verschiedenen Halogenatomen oder R¹ und R² gemeinsam mit dem Stickstoffatom, an welches sie gebunden sind, für einen gegebenenfalls einfach bis mehrfach, gleich oder verschieden substituierten, gesättigten 5- bis 7-gliedrigen Heterocyclus stehen, der gegebenenfalls ein weiteres Heteroatom, enthalten kann, wobei als Substituenten genannt seien: jeweils geradkettiges oder verzweigtes Alkyl oder Hydroxyalkyl mit jeweils 1 bis 4 Kohlenstoffatomen, deren Säureadditonssalze, deren geometrische und optische Isomere und/oder Isomerengemische. 2nd Aminomethyltetrahydrofurans according to claim 1, wherein in the formula (I) A represents a doubly linked alkylene or alkenylene chain, each of which is optionally mono- to polysubstituted, identical or differently substituted, each having 3 to 18 carbon atoms, the following being mentioned as substituents: each straight-chain or branched alkyl, alkoxy, alkylthio, alkoxycarbonyl, haloalkyl, haloalkoxy or haloalkylthio each having 1 to 9 carbon atoms and optionally 1 to 9 identical or different halogen atoms;Trialkylsilyl each having 1 to 4 carbon atoms in the individual straight-chain or branched alkyl parts;each optionally singly or multiply, identically or differently, by alkyl having 1 to 4 carbon atoms and halogen substituted cycloalkylalkyl or cycloalkyl each having 3 to 7 carbon atoms in the cycloalkyl part and optionally 1 to 4 carbon atoms in the straight-chain or branched alkyl part;each optionally mono- or polysubstituted, identically or differently, by alkyl, haloalkyl, alkoxy or haloalkoxy, each having 1 to 4 carbon atoms and optionally 1 to 9 identical or different halogen atoms and / or halogen, each having a doubly linked alkylene or alkenylene, each having up to 5 carbon atoms if necessary, single to multiple, Identically or differently substituted single-linked aryl or double-linked arylene each having 6 to 10 carbon atoms, the following being mentioned as substituents: Halogen, cyano, nitro, each straight-chain or branched alkyl, alkoxy, alkylthio, haloalkyl, haloalkoxy, haloalkylthio, alkoxycarbonyl or alkoximinoalkyl, each having 1 to 4 carbon atoms in the individual alkyl parts and optionally 1 to 9 identical or different halogen atoms, R¹ and R² are each independently hydrogen;for each straight-chain or branched alkyl having 1 to 12 carbon atoms, alkenyl having 3 to 8 carbon atoms, alkynyl having 3 to 8 carbon atoms, hydroxyalkyl having 2 to 6 carbon atoms, alkoxyalkyl or dialkoxyalkyl each having 1 to 6 carbon atoms or hydroxylalkoxyalkyl having 2 to 6 carbon atoms in the individual alkyl parts, each for straight-chain or branched dioxolanylalkyl, Oxolanylalkyl or dioxanylalkyl, each having 1 to 4 carbon atoms in the alkyl part or for cycloalkyl or cycloalkyl or cycloalkylalkyl with 1 to 4 carbon atoms each having 1 to 4 carbon atoms in the cycloalkyl part and optionally 1 to 4 carbon atoms in the alkyl part, optionally substituted in the cycloalkyl part, optionally with 1 to 4 carbon atoms, the substituents being mentioned be: Halogen, in each case straight-chain or branched alkyl, alkoxy, haloalkyl or haloalkoxy, each having 1 to 4 carbon atoms and optionally 1 to 9 identical or different halogen atoms;in addition for arylalkyl, arylalkenyl or aryl which are each mono- or polysubstituted in the aryl part and are each mono- or polysubstituted in the aryl part and optionally up to 6 carbon atoms in the straight-chain or branched alkyl or Alkenyl part stand, whereby the following are mentioned as aryl substituents: Halogen, cyano, nitro, each straight-chain or branched alkyl, alkoxy, alkythio, haloalkyl, haloalkoxy, haloalkylthio, alkoxycarbonyl or alkoximinoalkyl, each having 1 to 4 carbon atoms in the individual alkyl parts and optionally 1 to 9 identical or different halogen atoms or R¹ and R² together with the nitrogen atom to which they are attached for an optionally mono- to polysubstituted, identical or different, saturated 5- to 7-membered heterocycle, which may optionally contain a further heteroatom, where the following may be mentioned as substituents: in each case straight-chain or branched alkyl or hydroxyalkyl each having 1 to 4 carbon atoms, their acid addition salts, their geometric and optical isomers and / or mixtures of isomers.
- 3Aminoethyltetrahydrofurane gemäß Anspurch 1, wobei in der Formel (I) A für jeweils gegebenenfalls ein- bis fünffach, gleich oder verschieden substituiertes 1,4-Butylen, 1,5-Pentylen, 1,6-Hexylen, 1,5-Pent-1-enylen, 1,5-Pent-2-enylen oder 1,11-Undecylen steht, wobei als Substituenten jeweils genannt seien:Methyl, Ethyl, n- oder i-Propyl, n-, i-, s- oder t-Butyl, n- oder i-Pentyl, n- oder i-Hexyl, n- oder i-Heptyl n- oder i-Octyl, n- oder i-Nonyl, Methoxy, Ethoxy, n- oder i-Propoxy, n-, i-, s- oder t-Butoxy, Methylthio, Methoxycarbonyl, Ethoxycarbonyl, Trifluormethyl, Trifluormethoxy, Trifluormethylthio, Trimethylsilyl, jeweils gegebenenfalls ein- bis dreifach, gleich oder verschieden durch Fluor, Chlor, Brom, Methyl, Ethyl, n- oder i-Propyl und/oder t-Butyl substituiertes Cyclohexyl, Cyclohexylmethyl, Cyclohexylethyl oder Cyclohexylpropyl, jeweils gegebenenfalls ein- bis dreifach, gleich oder verschieden durch Methyl, Ethyl, n- oder i-Propyl, n-, i-, s- oder t-Butyl, Trifluormethyl und Trifluormethoxy substituiertes Methylen, 1,2-Ethylen, 1,3-Propylen, 1,4-Butylen oder 1,4-Butenylen, oder jeweils gegebenenfalls ein- bis dreifach, gleich oder verschieden substituiertes Phenyl oder o-Phenylen, wobei als Substituenten im Phenyl oder o-Phenylen jeweils infrage kommen: Fluor, Chlor, Brom, Cyano, Nitro, Methyl, Ethyl, n- oder i-Propyl, n-, i-, s- oder t-Butyl, Methoxy, Ethoxy, Trifluormethyl, Trifluormethoxy, Trifluormethylthio oder Methoximinomethyl und R¹ und R² unabhängig voneinander jeweils für Wasserstoff, Methyl, Ethyl, n- oder i-Propyl, n-, i-, s- oder t-Butyl, n- oder i-Pentyl, n- oder i-Hexyl, n- oder i-Heptyl, n- oder i-Octyl, Allyl, n- oder i-Butenyl, n- oder i-Pentenyl, Propargyl, n- oder i-Butinyl, Hydroxyethyl, Hydroxypropyl, Methoxyethyl, Ethoxyethyl, Propoxyethyl, Butoxyethyl, Methoxypropyl, Ethoxypropyl, Propoxypropyl, Butoxypropyl, Hydroxyethoxyethyl, Dimethoxyethyl, Dimethoxypropyl, Diethoxyethyl, Dioxolanylmethyl, Dioxolanylethyl, Oxolanylmethyl, Oxolanylethyl, Dioxanylmethyl, Dioxanylethyl, für jeweils gegebenenfalls ein- bis fünffach, gleich oder verschieden durch Fluor, Chlor, Brom, Methyl, Ethyl, n- oder i-Propyl, n-, i-, s- und/oder t-Butyl substituiertes Cyclopropyl, Cyclopropylmethyl, Cyclopropylethyl, Cyclopropylpropyl, Cyclopentyl, Cyclopentylmethyl, Cyclohexyl oder Cycloxhexylmethyl oder für jeweils gegebenenfalls ein- bis dreifach, gleich oder verschieden substituiertes Phenyl, Benzyl, oder Phenylethyl stehen, wobei als Substituenten jeweils infrage kommen: Fluor, Chlor, Brom, Cyano, Nitro, Methyl, Ethyl, n- oder i-Propyl, n-, i-, s- oder t-Butyl, Methoxy, Ethoxy, Methylthio, Trifluormethyl, Trifluormethoxy, Trifluormethylthio, Methoxycarbonyl, Ethoxycarbonyl oder Methoximinomethyl oder R¹ und R² gemeinsam mit dem Stickstoffatom, an welches sie gebunden sind, für einen gegebenenfalls ein- bis dreifach, gleich oder verschieden substituierten Heterocyclus der Formel stehen, wobei als Substituenten jeweils genannt seien: Methyl, Ethyl oder Hydroxymethyl, deren Säureadditionssalze, deren geometrische und optischen Isomeren und/oder Isomerengemische. 3rd Aminoethyltetrahydrofurans according to Claim 1, wherein in formula (I) A for 1,4-butylene, 1,5-pentylene, 1,6-hexylene, 1,5-pent-1-enylene, 1,5-pent-2-enylene which are optionally mono- to pentasubstituted or substituted differently or 1,11-undecylene, where the following are mentioned as substituents: Methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, n- or i-pentyl, n- or i-hexyl, n- or i-heptyl n- or i-octyl , n- or i-nonyl, methoxy, ethoxy, n- or i-propoxy, n-, i-, s- or t-butoxy, methylthio, methoxycarbonyl, ethoxycarbonyl, trifluoromethyl, trifluoromethoxy, trifluoromethylthio, trimethylsilyl, each optionally a up to three times, identical or different, fluorine, chlorine, bromine, methyl, ethyl, n- or i-propyl and / or t-butyl substituted cyclohexyl, Cyclohexylmethyl, cyclohexylethyl or cyclohexylpropyl, each optionally one to three times, identically or differently, by methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, trifluoromethyl and trifluoromethoxy-substituted methylene, 1,2 -Ethylene, 1,3-propylene, 1,4-butylene or 1,4-butenylene, or in each case optionally mono- to trisubstituted, identically or differently substituted, phenyl or o-phenylene, in each case as substituents in phenyl or o-phenylene come: Fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, methoxy, ethoxy, trifluoromethyl, trifluoromethoxy, trifluoromethylthio or methoximinomethyl and R¹ and R² are each independently hydrogen, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, n- or i-pentyl, n- or i-hexyl, n- or i-heptyl, n- or i-octyl, allyl, n- or i-butenyl, n- or i-pentenyl, propargyl, n- or i-butinyl, hydroxyethyl, hydroxypropyl, Methoxyethyl, ethoxyethyl, propoxyethyl, butoxyethyl, methoxypropyl, ethoxypropyl, propoxypropyl, butoxypropyl, hydroxyethoxyethyl, dimethoxyethyl, dimethoxypropyl, diethoxyethyl, dioxolanylmethyl, dioxolanylethyl, oxolanylmethyl, oxolanylethyl, dioxanylmethyl, in each case different from one to the other, by same, same as same as dioxanylmethyl, dioxanylmethyl, dioxanyl, Chlorine, bromine, methyl, ethyl, n- or i-propyl, n-, i-, s- and / or t-butyl substituted cyclopropyl, cyclopropylmethyl, Cyclopropylethyl, cyclopropylpropyl, cyclopentyl, cyclopentylmethyl, cyclohexyl or cycloxhexylmethyl or for phenyl, benzyl or phenylethyl which are monosubstituted to trisubstituted identically or differently in each case, where in each case the following are suitable as substituents: Fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, methoxy, ethoxy, methylthio, trifluoromethyl, trifluoromethoxy, trifluoromethylthio, methoxycarbonyl, ethoxycarbonyl or Methoximinomethyl or R¹ and R² together with the nitrogen atom to which they are attached, for an optionally mono- to trisubstituted, identically or differently substituted heterocycle of the formula stand, where the following may be mentioned as substituents: methyl, ethyl or hydroxymethyl, their acid addition salts, their geometric and optical isomers and / or mixtures of isomers.
- 4Aminomethyltetrahydrofurane gemäß Anspruch 1, wobei in der Formel (I) A gemeinsam mit dem Kohlenstoffatom, an welches es gebunden ist, für ein gegebenenfalls ein- bis dreifach, gleich oder verschieden substituiertes carbocyclisches Ringsystem der Formel steht, wobei als Substituenten in den cycloaliphatischen Ringen jeweils genannt seien:Methyl, Ethyl, n- oder i-Propyl, n-, i-, s- oder t-Butyl, n-oder i-Pentyl, Trifluormethyl, Trifluormethoxy, Methoxycarbonyl, Ethoxycarbonyl oder Trimethylsilyl und wobei als Substituenten in den aromatischen Ringen jeweils genannt seien: Fluor, Chlor, Brom, Methyl, Ethyl, n- oder i-Propyl, n-, i-, s- oder t-Butyl, Methoxy, Ethoxy, Trifluormethyl, Trifluormethoxy oder Trifluormethylthio und R¹ und R² unabhängig voneinander jeweils für Wasserstoff, Methyl, Ethyl, n- oder i-Propyl, n-, i-, s- oder t-Butyl, n- oder i-Pentyl, n-oder i-Hexyl, Ally, n- oder i-Butenyl, n-oder i-Pentenyl, Propargyl, n- oder i-Butinyl, Hydroxyethyl, Hydroxypropyl, Methoxyethyl, Methoxypropyl, Ethoxyethyl, Ethoxypropyl, Hydroxyethoxyethyl, Dimethoxyethyl, Diethoxyethyl, Dioxolanylmethyl, Dioxolanylethyl, Oxolanylmethyl, Oxolanylethyl, Dioxanylmethyl, Cyclopropylmethyl, Dichlorcyclopropymethyl, Dimethylcyclopropylmethyl, Dichlordimethylcyclopropylmethyl, Cyclopentyl, Cyclohexyl oder Cyclohexylmethyl stehen oder R¹ und R² gemeinsam mit dem Stickstoffatom, an welches sie gebunden sind, für einen gegebenenfalls ein- bis dreifach gleich oder verschieden substituierten Heterocyclus der Formel stehen, wobei als Substituenten jeweils genannt seien: Methyl, Ethyl, Hydroxmethyl, deren Säureadditionssalze, geometrische und optische Isomere und/oder Isomerengemische. 4th Aminomethyltetrahydrofurans according to claim 1, wherein in the formula (I) A together with the carbon atom to which it is attached, for a carbocyclic ring system of the formula which is optionally mono- to trisubstituted by identical or different substituents stands, where the following may be mentioned as substituents in the cycloaliphatic rings: methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, n- or i-pentyl, trifluoromethyl, trifluoromethoxy, methoxycarbonyl, ethoxycarbonyl or Trimethylsilyl and where the following may be mentioned as substituents in the aromatic rings: Fluorine, chlorine, bromine, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, methoxy, ethoxy, trifluoromethyl, trifluoromethoxy or trifluoromethylthio and R¹ and R² independently of one another each represent hydrogen, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, n- or i-pentyl, n- or i-hexyl, ally, n - or i-butenyl, n- or i-pentenyl, propargyl n- , n- or i-butinyl, hydroxyethyl, hydroxypropyl, methoxyethyl, methoxypropyl, ethoxyethyl, ethoxypropyl, hydroxyethoxyethyl, Are or R¹ and R² together with the nitrogen atom to which they are attached, for a heterocycle of the formula which is optionally mono- to trisubstituted by the same or different substituents stand, where the following may be mentioned as substituents: Methyl, ethyl, hydroxmethyl, their acid addition salts, geometric and optical isomers and / or mixtures of isomers.
- 5Process for the preparation of aminomethyltetrahydrofurans of the general formula (I), in which A represents an optionally substituted doubly linked alkylene or alkenylene chain and R¹ and R² independently of one another each represent hydrogen, alkyl, alkenyl, alkynyl, alkoxyalkyl, dialkoxyalkyl, hydroxyalkyl, hydroxyalkoxyalkyl, dioxolanyalkyl, oxolanylalkyl, dioxanylalkyl or each optionally substituted cycloalkylalkyl, cycloalkyl, aralkyl, aralkenyl or aryl or R¹ and R² together with the nitrogen atom, to which they are attached represent an optionally substituted saturated heterocycle which may optionally contain further heteroatoms, as well as their acid addition salts, their geometric or optical isomers and their isomer mixtures, characterized in that (a) substituted tetrahydrofurans of the formula (II), in which A has the meaning given above and X¹ represents an electron-withdrawing leaving group, with amines of the formula (III), in which R¹ and R² have the meaning given above, optionally in the presence of a diluent and optionally in the presence of an acid binder, or that (b) the aminomethyltetrahydrofurans of the formula (Ia) obtainable by process (a), in which R¹ and A have the meaning given above, with alkylating agents of the formula (V), R²⁻¹-X² (V) in which R²⁻¹ represents alkyl, alkenyl, alkynyl, alkoxyalkyl, dialkoxyalkyl, hydroxyalkyl, hydroxyalkoxyalkyl, dioxolanyalkyl, oxolanylalkyl, dioxanylalkyl or for optionally substituted cycloalkylalkyl, cycloalkyl, aralkyl or aralkenyl and X² represents an electron-withdrawing leaving group, if appropriate in the presence of a diluent and if appropriate in the presence of an acid binder and if appropriate subsequently adding an acid. 5. Verfahren zur Herstellung von Aminomethyltetrahydrofuranen der allgemeinen Formel (I), in welcher A für eine jeweils gegebenenfalls substituierte zweifach verknüpfte Alkylen- oder Alkenylenkette steht und R¹ und R² unabhängig voneinander jeweils für Wasserstoff, Alkyl, Alkenyl, Alkinyl, Alkoxyalkyl, Dialkoxyalkyl, Hydroxyalkyl, Hydroxyalkoxyalkyl, Dioxolanyalkyl, Oxolanylalkyl, Dioxanylalkyl oder für jeweils gegebenenfalls substituiertes Cycloalkylalkyl, Cycloalkyl, Aralkyl, Aralkenyl oder Aryl stehen oder R¹ und R² gemeinsam mit dem Stickstoffatom, an welches sie gebunden sind, für einen gegebenenfalls substituierten gesättigen Heterocyclus stehen, der gegebenenfalls weitere Heteroatome enthalten kann, sowie deren Säureadditionssalze, deren geometrische oder optische Isomere und deren Isomerengemische, dadurch gekennzeichnet, daß man (a) substituierte Tetrahydrofurane der Formel (II), in welcher A die oben angegebene Bedeutung hat und X¹ für eine elektronenanziehende Abgangsgruppe steht, mit Aminen der Formel (III), in welcher R¹ und R² die oben angegebene Bedeutung haben, gegebenenfalls in Gegenwart eines Verdünnungsmittel und gegebenenfalls in Gegenwart eines Säurebindemittels umsetzt, oder daß man (b) die nach Verfahren (a) erhältlichen Aminomethyltetrahydrofurane der Formel (Ia), in welcher R¹ und A die oben angegebene Bedeutung haben, mit Alkylierungsmitteln der Formel (V), R²⁻¹-X² (V) in welcher R²⁻¹ für Alkyl, Alkenyl, Alkinyl, Alkoxyalkyl, Dialkoxyalkyl, Hydroxyalkyl, Hydroxyalkoxyalkyl, Dioxolanyalkyl, Oxolanylalkyl, Dioxanylalkyl oder für jeweils gegebenenfalls substituiertes Cycloalkylalkyl, Cycloalkyl, Aralkyl oder Aralkenyl steht und X² für eine elektronenanziehende Abgangs gruppe steht, gegebenenfalls in Gegenwart eines Verdünnungsmittels und gegebenenfalls in Gegenwart eines Säurebindemittels umsetzt und gegebenenfalls anschließend eine Säure addiert.
- 8Verfahren zur Herstellung von Schädlingsbekämpfungsmitteln, dadurch gekennzeichnet, daß man Aminomethyltetrahydrofurane der Formel (I) nach den Ansprüchen 1 und 5 auf Schädlinge und/oder ihren Lebensraum einwirken läßt. 8th. Process for the preparation of pesticides, characterized in that aminomethyltetrahydrofurans of the formula (I) according to Claims 1 and 5 are allowed to act on pests and / or their habitat.
- 9Process for the preparation of pesticides, characterized in that aminomethyltetrahydrofurans of the formula (I) according to Claims 1 and 5 are mixed with extenders and / or surface-active agents. 9. Verfahren zur Herstellung von Schädlingsbekämpfungsmitteln, dadurch gekennzeichnet, daß man Aminomethyltetrahydrofurane der Formel (I) nach den Ansprüchen 1 und 5 mit Streckmitteln und/oder oberflächenaktiven Mitteln vermischt.
- 10Substituierte Tetrahydrofurane der Formel (IIa), in welcher A¹ für eine jeweils gegebenenfalls substituierte zweifach verknüpfte Alkylen- oder Alkenylenkette steht und Y für Halogen oder für jeweils gegebenenfalls substituiertes Alkylsulfonyloxy oder Arylsulfonyloxy steht, mit Ausnahme der Verbindungen, bei welchen A¹ für eine 1,4-Butandiylkette steht und Y glieichzeitig für Brom oder Iod steht. 10th Substituted tetrahydrofurans of the formula (IIa), in which A¹ represents an optionally substituted doubly linked alkylene or alkenylene chain and Y stands for halogen or for optionally substituted alkylsulfonyloxy or arylsulfonyloxy, with the exception of the compounds in which A¹ is a 1,4-butanediyl chain and Y is simultaneously bromine or iodine.
- 11Process for the preparation of substituted tetrahydrofurans of the formula (IIa), in which A¹ represents an optionally substituted doubly linked alkylene or alkenylene chain and Y stands for halogen or for optionally substituted alkylsulfonyloxy or arylsulfonyloxy, with the exception of the compounds in which A1 is a 1,4-butanediyl chain and Y is simultaneously bromine or iodine, characterized in that the cyclic ketones of the formula (VI), in which A¹ has the meaning given above, initially in a first stage with buten-1-yl-4-magnesium bromide of the formula (VII) CH₂ = CH-CH₂-CH₂-Mg-Br (VII) in the presence of a diluent, at temperatures between - 20 ° C and + 50 ° C and the carbinols of the formula (VIII) obtainable in this way, in which A¹ has the meaning given above, with a halogenating agent, in the presence of quinoline or with N-bromosuccinimide, optionally in the presence of a diluent, at temperatures between -20 ° C and + 80 ° C, or trihydroxy compounds of the formula IX) in which A¹ has the meaning given above, cyclized with acids in a conventional manner and the hydroxmethyltetrahydrofurans of the formula (X) thus obtainable, in which A¹ has the meaning given above, in a second stage with sulfonic acid halides of the formula (XI), R³-SO₂-Hal (XI) in which R³ represents in each case optionally substituted alkyl or aryl and Hal stands for halogen, if appropriate in the presence of a diluent and if appropriate in the presence of an acid binder at temperatures between 0 ° and 120 ° C. 11. Verfahren zur Herstellung von substituierten Tetrahydrofuranen der Formel (IIa), in welcher A¹ für eine jeweils gegebenenfalls substituierte zweifach verknüpfte Alkylen- oder Alkenylenkette steht und Y für Halogen oder für jeweils gegebenenfalls substituiertes Alkylsulfonyloxy oder Arylsulfonyloxy steht, mit Ausnahme der Verbindungen, bei welchen A¹ für eine 1,4-Butandiylkette steht und Y glieichzeitig für Brom oder Iod steht, dadurch gekennzeichnet, daß man die cyclischen Ketone der Formel (VI), in welcher A¹ die oben angegebene Bedeutung hat, zunächst in einer ersten Stufe mit Buten-1-yl-4-magnesiumbromid der Formel (VII) CH₂=CH-CH₂-CH₂-Mg-Br (VII) in Gegenwart eines Verdünnungsmittels, bei Temperaturen zwischen - 20 °C und + 50 °C umsetzt und die so erhältlichen Carbinole der Formel (VIII), in welcher A¹ die oben angegebene Bedeutung hat, mit einem Halogenierungsmittel, in Gegenwart von Chinolin oder mit N-Bromsuccinimid, gegebenenfalls in Gegenwart eines Verdünnungsmittels, bei Temperaturen zwischen -20°C und + 80°C umsetzt, oder Trihydroxyverbindungen der Formel IX) in welcher A¹ die oben angegebene Bedeutung hat, mit Säuren, in üblicher Weise cyclisiert und die so erhältlichen Hydroxmethyltetrahydrofurane der Formel (X), in welcher A¹ die oben angegebene Bedeutung hat, in einer 2. Stufe mit Sulfonsäurehalogeniden der Formel (XI), R³-SO₂-Hal (XI) in welcher R³ für jeweils gegebenenfalls substituiertes Alkyl oder Aryl steht und Hal für Halogen steht, gegebenenfalls in Gegenwart eines Verdünnungsmittels und gegebenenfalls in Gegenwart eines Säurebindemittels bei Temperaturen zwischen 0° und 120°C umsetzt.
Independent claims11
82 paragraphs, as filed
The invention relates to new aminomethyltetrahydrofurans, several processes for their preparation and their use as pesticides.
It is already known that certain aminomethyltetrahydrofurans, such as 2- (4-chlorophenyl) -5- (3,5-dimethylpiperidin-1-ylmethyl) tetrahydrofuran, have fungicidal properties (cf. DE-OS 34 13 996).
However, the effectiveness of these previously known compounds is not entirely satisfactory in all areas of application, in particular at low application rates and concentrations.
There were new aminomethyltetrahydrofurans of the general formula (I)<chemistry id="chem0001" num="0001"><img file="EP0278352A2_D0001.tif" /></chemistry> in which A represents an optionally substituted doubly linked alkylene or alkenylene chain and R¹ and R² independently of one another each represent hydrogen, alkyl, alkenyl, alkynyl, alkoxyalkyl, dialkoxyalkyl, hydroxyalkyl, hydroxyalkoxyalkyl, dioxolanyalkyl, oxolanylalkyl, dioxanylalkyl or each optionally substituted cycloalkylalkyl, cycloalkyl, aralkyl, aralkenyl or aryl or R¹ and R² together with the nitrogen atom, to which they are attached represent an optionally substituted saturated heterocycle, which may optionally contain further heteroatoms, and the plant-compatible acid addition salts found.
The compounds of formula (I) can exist as geometric and / or optical isomers or mixtures of isomers with different compositions. Both the pure isomers and the isomer mixtures are claimed according to the invention.
Furthermore, it was found that the new aminomethyltetrahydrofurans of the general formula (II)<chemistry id="chem0002" num="0002"><img file="EP0278352A2_D0002.tif" /></chemistry> in which A represents an optionally substituted doubly linked alkylene or alkenylene chain and R¹ and R² independently of one another each represent hydrogen, alkyl, alkenyl, alkynyl, alkoxyalkyl, dialkoxyalkyl, hydroxyalkyl, hydroxyalkoxyalkyl, dioxolanyalkyl, oxolanylalkyl, dioxanylalkyl or each optionally substituted cycloalkylalkyl, cycloalkyl, aralkyl, aralkenyl or aryl or R¹ and R² together with the nitrogen atom, to which they are attached represent an optionally substituted saturated heterocycle which may optionally contain further heteroatoms, as well as the plant-compatible acid addition salts, if one<ul id="ul0001" list-style="none"><li>(a) substituted tetrahydrofurans of the formula (II),<chemistry id="chem0003" num="0003"><img file="EP0278352A2_D0003.tif" /></chemistry> in which A has the meaning given above and X¹ represents an electron-withdrawing leaving group, with amines of the formula (III),<chemistry id="chem0004" num="0004"><img file="EP0278352A2_D0004.tif" /></chemistry> in which R¹ and R² have the meaning given above, if appropriate in the presence of a diluent and if appropriate in the presence of an acid binder, or if</li><li>(b) the aminomethyltetrahydrofurans of the formula (Ia) obtainable by process (a),<chemistry id="chem0005" num="0005"><img file="EP0278352A2_D0005.tif" /></chemistry> in which R¹ and A have the meaning given above, with alkylating agents of the formula (V), R²⁻¹-X² (V) in which R²⁻¹ represents alkyl, alkenyl, alkynyl, alkoxyalkyl, dialkoxyalkyl, hydroxyalkyl, hydroxyalkoxyalkyl, dioxolanyalkyl, oxolanylalkyl, dioxanylalkyl or for optionally substituted cycloalkylalkyl, cycloalkyl, aralkyl, or aralkenyl and X² represents an electron-withdrawing leaving group, if appropriate in the presence of a diluent and if appropriate in the presence of an acid binder and if appropriate subsequently adding an acid.</li></ul>
Finally, it was found that the new aminomethyltetrahydrofurans of the general formula (I) have an action against pests, in particular against fungal pests.
Surprisingly, the aminomethyltetrahydrofurans of the general formula (I) according to the invention show a better fungicidal activity than the aminoethyltetrahydrofurans known from the prior art, such as, for example, 2- (4-chlorophenyl) -5- (3,5-dimethylpiperidin-1-yl-methyl) ) -tetrahydrofuran, which are chemically and functionally obvious compounds.
The aminomethyltetrahydrofurans according to the invention are generally defined by the formula (I). Compounds of the formula (I) in which A stands for a doubly linked alkylene or alkenylene chain, each optionally monosubstituted to polysubstituted, identically or differently, each having 3 to 18 carbon atoms, the following being suitable as substituents: each straight-chain or branched alkyl, alkoxy, alkylthio, alkoxycarbonyl, haloalkyl, haloalkoxy or haloalkylthio each having 1 to 9 carbon atoms and optionally 1 to 9 identical or different halogen atoms; Trialkylsilyl each having 1 to 4 carbon atoms in the individual straight-chain or branched alkyl parts; each optionally singly or multiply, identically or differently, by alkyl having 1 to 4 carbon atoms and / or halogen-substituted cycloalkylalkyl or cycloalkyl each having 3 to 7 carbon atoms in the cycloalkyl part and optionally 1 to 4 carbon atoms in the straight-chain or branched alkyl part; each optionally mono- or polysubstituted, identically or differently, by alkyl, haloalkyl, alkoxy or haloalkoxy, each having 1 to 4 carbon atoms and optionally 1 to 9 identical or different halogen atoms and / or halogen, in each case doubly linked alkylene or alkenylene, each having up to 5 carbon atoms, and each one or more times, if necessary, Identically or differently substituted single-linked aryl or double-linked arylene each having 6 to 10 carbon atoms, the following being suitable as substituents: Halogen, cyano, nitro, each straight-chain or branched alkyl, alkoxy, alkylthio, haloalkyl, haloalkoxy, haloalkylthio, alkoxycarbonyl or alkoximinoalkyl each having 1 to 4 carbon atoms in the individual alkyl parts and optionally 1 to 9 identical or different halogen atoms and R¹ and R² are each independently hydrogen; for each straight-chain or branched alkyl having 1 to 12 carbon atoms, alkenyl having 3 to 8 carbon atoms, alkynyl having 3 to 8 carbon atoms, hydroxyalkyl having 2 to 6 carbon atoms, alkoxyalkyl or dialkoxyalkyl each having 1 to 6 carbon atoms or hydroxylalkoxyalkyl having 2 to 6 carbon atoms in the individual alkyl parts, each for straight-chain or branched dioxolanylalkyl, Oxolanylalkyl or dioxanylalkyl, each with 1 to 4 carbon atoms in the alkyl part or for cycloalkyl, in each case optionally in the cycloalkyl part, mono- or polysubstituted, identically or differently, cycloalkyl or cycloalkyalkyl, each with 3 to 7 carbon atoms in the cycloalkyl part and optionally 1 to 4 carbon atoms in the alkyl part, with substituents in each case come into question: Halogen and in each case straight-chain or branched alkyl, alkoxy, haloalkyl or haloalkoxy each having 1 to 4 carbon atoms and optionally 1 to 9 identical or different halogen atoms; in addition for arylalkyl, arylalkenyl or aryl which are each mono- or polysubstituted in the aryl part and are each mono- or polysubstituted in the aryl part and optionally up to 6 carbon atoms in the straight-chain or branched alkyl or Are alkenyl part, the following being suitable as aryl substituents: Halogen, cyano, nitro, each straight-chain or branched alkyl, alkoxy, alkythio, haloalkyl, haloalkoxy, haloalkylthio, alkoxycarbonyl or alkoximinoalkyl, each having 1 to 4 carbon atoms in the individual alkyl parts and optionally 1 to 9 identical or different halogen atoms or R¹ and R² together with the nitrogen atom to which they are attached for an optionally mono- to polysubstituted, identical or different, saturated 5- to 7-membered heterocycle, which may optionally contain a further heteroatom, in particular nitrogen, oxygen or sulfur, the following being suitable as substituents: straight-chain or branched alkyl or hydroxyalkyl each having 1 to 4 carbon atoms.
Compounds of the formula (I) in which A for 1,4-butylene, 1,5-pentylene, 1,6-hexylene, 1,5-pent-1-enylene, 1,5-pent-2-enylene which are optionally mono- to pentasubstituted or substituted differently or 1,11-undecylene, where the following are suitable as substituents: Methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, n- or i-pentyl, n- or i-hexyl, n- or i-heptyl n- or i-ocytl , n- or i-nonyl, methoxy, ethoxy, n- or i-propoxy, n-, i-, s- or t-butoxy, methylthio, methoxycarbonyl, ethoxycarbonyl, trifluoromethyl, trifluoromethoxy, trifluoromethylthio, trimethylsilyl, each optionally a up to three times, identical or different, fluorine, chlorine, bromine, methyl, ethyl, n- or i-propyl and / or t-butyl substituted cyclohexyl, Cyclohexylmethyl, cyclohexylethyl or cyclohexylpropyl, each optionally one to three times, identically or differently, by methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, trifluoromethyl and / or trifluoromethoxy-substituted methylene, 1 , 2-ethylene, 1,3-propylene, 1,4-butylene or 1,4-butylene, or in each case optionally mono- to trisubstituted, identically or differently substituted, phenyl or o-phenylene, where the following are in each case possible as substituents: Fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, methoxy, ethoxy, trifluoromethyl, trifluoromethoxy, trifluoromethylthio or methoximinomethyl and R¹ and R² are each independently hydrogen, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, n- or i-pentyl, n- or i-hexyl, n- or i-heptyl, n- or i-octyl, allyl, n- or i-butenyl, n- or i-pentenyl, propargyl, n- or i-butinyl, hydroxyethyl, hydroxypropyl, methoxyethyl, Ethoxyethyl, propoxyethyl, butoxyethyl, methoxypropyl, ethoxypropyl, propoxypropyl, butoxypropyl, hydroxyethoxyethyl, dimethoxyethyl, dimethoxypropyl, diethoxyethyl, dioxolanylmethyl, dioxolanylethyl, oxolanylmethyl, oxolanylethyl, dioxioxlmethyl, dioxanylethyl, fluorine, each, optionally, same or same, bisanyl different, for, in each case, same or similar, Bromine, methyl, ethyl, n- or i-propyl, n-, i-, s- and / or t-butyl substituted cyclopropyl, cyclopropylmethyl, cyclopropylethyl, Cyclopropylpropyl, cyclopentyl, cyclopentylmethyl, cyclohexyl or cycloxhexylmethyl or for phenyl, benzyl or phenylethyl which are monosubstituted to trisubstituted identically or differently in each case, where in each case the following are suitable as substituents: Fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, methoxy, ethoxy, methylthio, trifluoromethyl, trifluoromethoxy, trifluoromethylthio, methoxycarbonyl, ethoxycarbonyl or Methoximinomethyl or R¹ and R² together with the nitrogen atom to which they are attached, for an optionally mono- to trisubstituted, identically or differently substituted heterocycle of the formula<chemistry id="chem0006" num="0006"><img file="EP0278352A2_D0006.tif" /></chemistry> are available, the following being suitable as substituents: methyl, ethyl or hydroxymethyl.
Compounds of the formula (I) in which A together with the carbon atom to which it is attached, for a carbocyclic ring system of the formula which is optionally mono- to trisubstituted by identical or different substituents<chemistry id="chem0007" num="0007"><img file="EP0278352A2_D0007.tif" /></chemistry> stands, where the substituents in the cycloaliphatic rings are in each case: methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, n- or i-pentyl, trifluoromethyl, trifluoromethoxy, methoxycarbonyl, ethoxycarbonyl or Trimethylsilyl and the substituents in the aromatic rings are: Fluorine, chlorine, bromine, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, methoxy, ethoxy, trifluoromethyl, trifluoromethoxy or trifluoromethylthio and R¹ and R² independently of one another each represent hydrogen, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, n- or i-pentyl, n- or i-hexyl, allyl, n - or i-butenyl, n- or i-pentenyl, propargyl, n- or i-butinyl, hydroxyethyl, hydroxypropyl, methoxyethyl, methoxypropyl, ethoxyethyl, ethoxypropyl, hydroxyethoxyethyl, Are or R¹ and R² together with the nitrogen atom to which they are attached, for a heterocycle of the formula which is optionally mono- to trisubstituted by the same or different substituents<chemistry id="chem0008" num="0008"><img file="EP0278352A2_D0008.tif" /></chemistry> stand, where the following can be used as substituents: Methyl, ethyl, hydroxymethyl.
Preferred compounds according to the invention are also addition products of acids and those aminomethyltetrahydrofurans of the formula (I) in which the substituents A, R 1 and R 2 have the meanings which have already been mentioned for these substituents.
The acids that can be added preferably include hydrohalic acids, such as hydrochloric acid and hydrobromic acid, especially hydrochloric acid, furthermore phosphoric acid, nitric acid, mono-, bi- and trifunctional carboxylic acids and hydroxycarboxylic acids, such as Acetic acid, maleic acid, succinic acid, fumaric acid, tartaric acid, citric acid, salicylic acid, sorbic acid and lactic acid, and also sulfonic acids, such as p-toluenesulfonic acid and 1,5-naphthalenedisulfonic acid and saccharin.
In addition to the compounds mentioned in the preparation examples, the following aminomethyltetrahydrofurans of the general formula (I) may be mentioned individually:<tables id="tabl0001" num="0001"><img file="EP0278352A2_D0009.tif" /></tables><tables id="tabl0002" num="0002"><img file="EP0278352A2_D0010.tif" /></tables><tables id="tabl0003" num="0003"><img file="EP0278352A2_D0011.tif" /></tables><tables id="tabl0004" num="0004"><img file="EP0278352A2_D0012.tif" /></tables><tables id="tabl0005" num="0005"><img file="EP0278352A2_D0013.tif" /></tables><tables id="tabl0006" num="0006"><img file="EP0278352A2_D0014.tif" /></tables><tables id="tabl0007" num="0007"><img file="EP0278352A2_D0015.tif" /></tables><tables id="tabl0008" num="0008"><img file="EP0278352A2_D0016.tif" /></tables><tables id="tabl0009" num="0009"><img file="EP0278352A2_D0017.tif" /></tables>
If, for example, 2-bromomethyl-1-oxaspiro [4,5] decane and piperidine are used as starting materials, the course of the reaction of process (a) according to the invention can be represented by the following formula:<chemistry id="chem0009" num="0009"><img file="EP0278352A2_D0018.tif" /></chemistry>
If, for example, 8-t-butyl-2- (N-cyclohexylaminomethyl) -1-oxaspiro [4,5] decane and allyl bromide are used as starting materials, the reaction sequence of process (b) according to the invention can be represented by the following formula:<chemistry id="chem0010" num="0010"><img file="EP0278352A2_D0019.tif" /></chemistry>
Formula (III) provides a general definition of the substituted tetrahydrofurans required as starting materials for carrying out process (a) according to the invention. In this formula (II) A preferably represents those radicals which have already been mentioned as preferred for these substituents in connection with the description of the substances of the formula (I) according to the invention.
X¹ preferably represents halogen, in particular chlorine or bromine or optionally substituted alkylsulfonyloxy having 1 to 4 carbon atoms or optionally one to more times substituted by alkyl having 1 to 4 carbon atoms arylsulfonyloxy, such as methanesulfonyloxy or p-toluenesulfonyloxy.
Some of the substituted tetrahydrofurans of the formula (II) are known (cf., for example, heterocycles <u style="single">23</u> 2035 - 2039 [1985]).
Substituted tetrahydrofurans of the formula (IIa) are not yet known,<chemistry id="chem0011" num="0011"><img file="EP0278352A2_D0020.tif" /></chemistry> in which A¹ represents an optionally substituted doubly linked alkylene or alkenylene chain and Y stands for halogen or for optionally substituted alkylsulfonyloxy or arylsulfonyloxy, with the exception of the compounds in which A¹ is a 1,4-butanediy chain and at the same time Y is bromine or iodine.
The alkylsulfonyloxy radical may contain 1 to 4 alcohol atoms and may be mono- to polysubstituted by halogen and the arylsulfonyloxy radical preferably represents a phenylsulfonyloxy radical optionally substituted by alkyl having 1 to 4 carbon atoms.
The as yet unknown substituted tetrahydrofurans of the formula (IIa) are obtained in analogy to known processes, cf. eg DE-OS 34 13 996) for example by using the generally known cyclic ketones of the formula (VI),<chemistry id="chem0012" num="0012"><img file="EP0278352A2_D0021.tif" /></chemistry> in which A¹ has the meaning given above, initially in a first stage with butene 1-yl-4-magnesium bromide of the formula (VII) CH₂ = CH-CH₂-CH₂-Mg-Br (VII) in the presence of a diluent, such as diethyl ether or tetrahydrofuran, at temperatures between - 20 ° C and + 50 ° C (see also Tetrahedron Lett. <u style="single">26</u>, 127-130 [1985]; Bull. Soc. Chim, Fr.<u style="single">12</u>, Pt. 2, 3377-3381 [1973] or the preparation examples) and the carbinols of the formula (VIII) obtainable in this way,<chemistry id="chem0013" num="0013"><img file="EP0278352A2_D0022.tif" /></chemistry> in which A¹ has the meaning given above, with a halogenating agent, such as elemental bromine, in the presence of quinoline or with N-bromosuccinimide, optionally in the presence of a diluent, such as chloroform, at temperatures between -20 ° C and + 80 ° C (see also DE-OS 34 13 996), or if you use trihydroxy compounds of the formula IX)<chemistry id="chem0014" num="0014"><img file="EP0278352A2_D0023.tif" /></chemistry> in which A¹ has the meaning given above, cyclized with acids, such as sulfuric acid or phosphoric acid, in a conventional manner (see, for example, Houben-Weyl "Methods of Organic Chemistry" Volume VI / 3 p. 528; 4th edition, Thieme Verlag Stuttgart or Khim Geterotsikl. Soedin. Sb. No. 2, 15-17, [1970] and CA. <u style="single">77</u>, 48144 g) and the hydroxymethyltetrahydrofurans of the formula (X) thus obtainable,<chemistry id="chem0015" num="0015"><img file="EP0278352A2_D0024.tif" /></chemistry> in which A¹ has the meaning given above, in a 2nd Step with sulfonic acid halides of the formula (XI), R³ = SO₂-Hal (XI) in which R³ represents alkyl optionally substituted by halogen or optionally substituted by alkyl having 1 to 4 carbon atoms, in particular methyl, trifluoromethyl or p-tolyl and Hal represents halogen, in particular chlorine, bromine or iodine, optionally in the presence of a diluent, such as dichloromethane, and optionally in the presence of an acid binder, such as pyridine, at temperatures between 0 ° and 120 ° C.
The carbinols of the formula (VIII) can alternatively also be obtained if the ketones of the formula (VI) are epoxidized in a manner known in principle, for example with trimethylsulfonium ylide, and then reacted with allyl magnesium bromide (cf., for example, J. Am. Chem. Soc. <u style="single">87</u>, 1363-1364 [1965] or Heterocycles 8, 397 [1977]).
The sulfonic acid halides of the formula (XI) are generally known compounds of organic chemistry.
The trihydroxy compounds of the formula (IX) are known or can be obtained in analogy to known processes (cf., for example, Bull. Soc. Chim. France <u style="single">1964</u> 564-569; Belg. Pat. 631,243, Nov. 4, 1963; Belg. Pat. 631,242, Nov. 4, 1963; GB 1.036.087 from July 13th, 1966 or FR 1.334.968 from August 16th, 1963).
Formula (III) provides a general definition of the amines which are further required as starting materials for carrying out process (a) according to the invention. In this formula (III), R 1 and R 2 preferably represent those radicals which have already been mentioned as preferred for these substituents in connection with the description of the substances of the formula (I) according to the invention.
The amines of the formula (III) are generally known compounds of organic chemistry.
Formula (Ia) provides a general definition of the aminomethyltetrahydrofurans required as starting materials for carrying out process (b) according to the invention. In this formula (Ia), A and R 1 preferably represent those radicals which have already been mentioned as preferred for these substituents in connection with the description of the substances of the formula (I) according to the invention.
The aminomethyltetrahydrofurans of the formula (Ia) are compounds according to the invention and can be obtained with the aid of process (a) according to the invention.
Formula (V) provides a general definition of the alkylating agents which are furthermore required as starting materials for carrying out process (b) according to the invention. In this formula (V) R²⁻¹ is preferably straight-chain or branched alkyl having 1 to 12 carbon atoms, alkenyl having 3 to 8 carbon atoms, alkynyl having 3 to 8 carbon atoms, hydroxyalkyl having 2 to 6 carbon atoms, alkoxyalkyl or dialkoxyalkyl having 1 to 6 carbon atoms or hydroxyalkoxyalkyl with 2 to 6 carbon atoms in the individual alkyl parts; for straight-chain or branched dioxolanylalkyl, oxolanylalkyl or dioxanylalkyl, each having 1 to 4 carbon atoms in the alkyl part; for cycloalkyl or cycloalkyalkyl, each of which is monosubstituted or polysubstituted in the cycloalkyl part, in each case with 3 to 7 carbon atoms in the cycloalkyl part and optionally 1 to 4 carbon atoms in the alkyl part, the substituents being in each case: Halogen, in each case straight-chain or branched alkyl, alkoxy, haloalkyl or haloalkoxy, each having 1 to 4 carbon atoms and optionally 1 to 9 identical or different halogen atoms; in addition for arylalkyl or arylalkenyl which are each mono- or polysubstituted in the aryl part and are each mono- or polysubstituted in the aryl part and up to 6 carbon atoms in the straight-chain or branched alkyl or Alkenyl part, the aryl substituents in each case being suitable: halogen, cyano, nitro, in each case straight-chain or branched alkyl, alkoxy, alkylthio, haloalkyl, haloalkoxy, haloalkylthio, alkoxycarbonyl or alkoximinoalkyl each having 1 to 4 carbon atoms in the individual alkyl parts and optionally 1 to 9 same or different halogen atoms.
R<sup>2-1</sup> particularly preferably represents methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, n- or i-pentyl, n- or i-hexyl, n- or i-heptyl, n - or i-octyl, allyl, n- or i-butenyl, n- or i-pentenyl, propargyl, n- or i-butinyl, hydroxyethyl, hydroxypropyl, methoxyethyl, ethoxyethyl, propoxyethyl, butoxyethyl, methoxypropyl, ethoxypropyl, propoxypropyl, butoxypropyl , Hydroxyethoxyethyl, dimethoxyethyl, dimethoxypropyl, diethoxyethyl, dioxolanylmethyl, dioxolanylethyl, Oxolanylmethyl, oxolanylethyl, dioxanylmethyl, dioxanylethyl, each optionally one to five times, the same or different by fluorine, chlorine, bromine, methyl, ethyl, n- or i-propyl, n-, i-, s- and / or t- Butyl-substituted cyclopropyl, cyclopropylmethyl, cyclopropylethyl, cyclopropylpropyl, cyclopentyl, cyclopentylmethyl, cyclohexyl or cycloxhexylmethyl or for benzyl or phenylethyl which is monosubstituted to trisubstituted identically or differently, or where in each case the following are suitable as substituents: fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, methoxy, ethoxy, methylthio, trifluoromethyl, trifluoromethoxy , Trifluoromethylthio, methoxycarbonyl, ethoxycarbonyl or methoximinomethyl.
R<sup>2-1</sup> very particularly preferably represents methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, n- or i-pentyl, n- or i-hexyl, n- or i-butenyl, n- or i-pentenyl, propargyl, n- or i-butynyl, hydroxyethyl, hydroxypropyl, methoxyethyl, methoxypropyl, ethoxyethyl, ethoxypropyl, hydroxyethoxyethyl, dimethoxyethyl, diethoxyethyl, dioxolanylmethyl, dioxolanylethyl, oxolanylmethyl, oxolanylethyl, cyclopropylmethylmethyl, dichloromethylmethyl, dichloromethylmethyl, dichloromethylmethyl Dichlorodimethylcyclopropylmethyl, cyclopentyl, cyclohexyl or cycloxhexylmethyl.
X² preferably stands for halogen, in particular for chlorine, bromine or iodine or for alkylsulfonyloxy or alkoxysulfonyloxy each optionally substituted by halogen, each having 1 to 4 carbon atoms and optionally 1 to 9 halogen atoms or arylsulfonyloxy optionally substituted by alkyl having 1 to 4 carbon atoms, such as, for example, methanesulfonyloxy , Methoxysulfonyloxy or p-toluenesulfonyloxy.
The alkylating agents of the formula (V) are likewise generally known compounds of organic chemistry or can be obtained in analogy to generally known processes.
Suitable diluents for carrying out processes (a) and (b) according to the invention are inert organic solvents or aqueous systems. These include in particular aliphatic or aromatic, optionally halogenated hydrocarbons, such as, for example, gasoline, benzene, toluene, xylene, chlorobenzene, petroleum ether, hexane, cyclohexane, dichloromethane, chloroform, carbon tetrachloride; Ethers such as diethyl ether, dioxane, tetrahydrofuran or ethylene glycol dimethyl or diethyl ether; Ketones such as acetone or butanone; Nitriles such as acetonitrile or propionitrile; Amides such as dimethylformamide, dimethylacetamide, N-methylformanilide, N-methylpyrrolidone or hexamethylphosphoric triamide; Esters such as ethyl acetate or sulfoxides such as dimethyl sulfoxide.
Processes (a) and (b) according to the invention can optionally also be carried out in a two-phase system, such as water / toluene or water / dichloromethane, if appropriate in the presence of a phase transfer catalyst. Examples of such catalysts are: tetrabutylammonium iodide, tetrabutylammonium bromide, tributyl-methylphosphonium bromide, trimethyl-C₁₃ / C₁₅-alkylammonium chloride, dibenzyldimethyl-ammonium-methyl-sulfate, dimethyl-C₁₂ / C₁ T-alkyl-benzium-hydroxiumammonium, crown, 5-benzyl-ammonium-chloride, crown-15-benzyl-ammonium-chloride, crown-15-benzyl-ammonium-chloride, crown-15-benzyl-ammonium-chloride, crown-15-benzyl-ammonium-chloride, crown-5-ammonium chloride, 6, triethylbenzylammonium chloride, trimethylbenzylammonium chloride. It is also possible to carry out processes (a) and (b) according to the invention without adding a solvent.
All commonly used inorganic and organic bases are suitable as acid binders for carrying out processes (a) and (b) according to the invention. Alkali metal hydroxides, carbonates or bicarbonates, such as, for example, sodium hydroxide, sodium carbonate or sodium bicarbonate, or else tertiary amines, such as, for example, triethylamine, N, N-dimethylaniline, pyridine, 4- (N, N-dimethylamino) pyridine, diazabicyclooctane (DABCO ), Diazabicyclonones (DBN) or diazabicycloundecene (DBU).
It is also possible to use the amines of the formulas (III) and (Ia) used as reactants in a corresponding excess at the same time as acid binders.
The reaction temperatures can be varied within a substantial range when carrying out processes (a) and (b) according to the invention. In general, temperatures between - 20 ° C and + 180 ° C, preferably at temperatures between 20 ° C and + 150 ° C.
To carry out process (a) according to the invention, 1.0 to 3.0 mol, preferably 1.0 to 1.5 mol, of amine of the formula (III) and, if appropriate, 1, are generally employed per mol of substituted tetrahydrofuran of the formula (II) , 0 to 3.0 mol, preferably 1.0 to 1.5 mol of acid binder, and optionally 0.1 to 1.0 mol of phase transfer catalyst.
To carry out process (b) according to the invention, 1.0 to 5.0 mol, preferably 1.0 to 2.0 mol, of alkylating agent of the formula (V) and 1.0 are generally employed per mol of aminomethyltetrahydrofuran of the formula (Ia) up to 5.0 mol, preferably 1.0 to 2.0 mol of acid binder, and optionally 0.1 to 1.0 mol of phase transfer catalyst.
The reaction, working up and isolation of the reaction products of the formula (I) are carried out in both cases by customary methods.
The following acids are preferably suitable for the preparation of acid addition salts of the compounds of the formula (I): hydrohalic acids, such as, for example, hydrochloric acid and hydrobromic acid, in particular hydrochloric acid, furthermore phosphoric acid, nitric acid, sulfuric acid, mono-, bi- and trifunctional carboxylic acids and hydroxycarboxylic acids, such as, for example Acetic acid, maleic acid, succinic acid, fumaric acid, tartaric acid, citric acid, salicylic acid, sorbic acid, lactic acid, and sulfonic acid, such as p-toluenesulfonic acid and 1,5-naphthalenedisulfonic acid and saccharin.
The acid addition salts of the compounds of the formula (I) can be obtained in a simple manner by customary salt formation methods, for example by dissolving a compound of the formula (I) in a suitable inert solvent and adding the acid, for example hydrochloric acid, and in a known manner, for example by filtering, iosliert and optionally cleaned by washing with an inert organic solvent.
The active compounds according to the invention have a strong action against pests and can be used in practice to combat unwanted harmful organisms. The active ingredients are suitable for use, inter alia, as crop protection agents, in particular as fungicides.
Fungicidal agents in crop protection are used to control Plasmodiophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes, Deuteromycetes.
Some pathogens of fungal diseases that fall under the generic names listed above may be mentioned as examples, but not by way of limitation: Pythium species, such as, for example, Pythium ultimum; Phytophthora species, such as, for example, Phytophthora infestans; Pseudoperonospora species, such as, for example, Pseudoperonospora humuli or Pseudoperonospora cubensis; Plasmopara species, such as, for example, Plasmopara viticola; Peronospora species, such as, for example, Peronospora pisi or P. brassicae; Erysiphe species, such as, for example, Erysiphe graminis; Sphaerotheca species, such as, for example, Sphaerotheca fuliginea; Podosphaera species, such as, for example, Podosphaera leucotricha; Venturia species, such as, for example, Venturia inaequalis; Pyrenophora species, such as, for example, Pyrenophora teres or P. graminea (conidial form: Drechslera, Syn: Helminthosporium); Cochliobolus species such as, for example, Cochliobolus sativus (conidial form: Drechslera, Syn: Helminthosporium); Uromyces species, such as, for example, Uromyces appendiculatus; Puccinia species, such as, for example, Puccinia recondita; Tilletia species, such as, for example, Tilletia caries; Ustilago species, such as, for example, Ustilago nuda or Ustilago avenae; Pellicularia species, such as, for example, Pellicularia sasakii; Pyricularia species, such as, for example, Pyricularia oryzae; Fusarium species, such as, for example, Fusarium culmorum; Botrytis species, such as, for example, Botrytis cinerea; Septoria species, such as, for example, Septoria nodorum; Leptosphaeria species, such as, for example, Leptosphaeria nodorum; Cercospora species such as, for example, Cercospora canescens; Alternaria species, such as, for example, Alternaria brassicae; Pseudocercosporella species, such as, for example, Pseudocercosporella herpotrichoides.
The fact that the active compounds are well tolerated by plants in the concentrations required to combat plant diseases allows treatment of above-ground parts of plants, of propagation stock and seeds, and of the soil.
The active compounds according to the invention can be used with particularly good results in combating cereal diseases, such as, for example, against the causative agent of powdery mildew of barley (Erysiphe graminis) or against the causative agent of wheat staining (Leptosphaeria nodorum), to combat rice diseases such as, for example, against the pathogen of leaf blotch on rice (Pyricularia oryzae) or to combat diseases in fruit and vegetable cultivation, for example against the pathogen of apple scab (Venturia inaequalis).
Depending on their respective physical and / or chemical properties, the active substances can be converted into customary formulations, such as solutions, emulsions, suspensions, powders, foams, pastes, granules, aerosols, active substance-impregnated natural and synthetic substances, very fine encapsulations in polymeric substances and in coating compositions for seeds, as well as ULV cold and warm mist formulations.
These formulations were prepared in a known manner, for example by mixing the active ingredients with extenders, that is to say liquid solvents, pressurized liquefied gases and / or solid carriers, if appropriate using surface-active agents, that is to say emulsifiers and / or dispersants and / or foam-generating agents. In the case of the use of water as an extender, for example organic solvents can also be used as auxiliary solvents. The following are essentially suitable as liquid solvents: aromatics, such as xylene, toluene, or alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chlorethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, for example Petroleum fractions, alcohols, such as butanol or glycol, and their ethers and esters, ketones, such as acetones, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents, such as dimethylformamide and dimethyl sulfoxide, and water; Liquefied gaseous extenders or carriers mean liquids which are gaseous at normal temperature and under normal pressure, for example Aerosol propellants, such as halogenated hydrocarbons and butane, propane, nitrogen and carbon dioxide; Possible solid carriers are: for example natural rock powders such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic rock powders such as highly disperse silica, aluminum oxide and silicates; as solid carriers for granules come into question: for example 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 stalks; suitable emulsifiers and / or foam-generating agents are: for example nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example Alkylaryl polyglycol ethers, alkyl sulfonates, alkysulfates, aryl sulfonates and protein hydrolyzates; Possible dispersing agents are, for example, lignin sulfite waste liquor and methyl cellulose.
Adhesives such as carboxymethyl cellulose, natural and synthetic polymers in the form of powders, granules or latices, such as gum arabic, polyvinyl alcohol, polyvinyl acetate, and also 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, for example 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 percent by weight of active compound, preferably between 0.5 and 90%.
The active compounds according to the invention can be present in the formulations in a mixture with other known active compounds, such as fungicides, insecticides, acaricides and herbicides, and also in mixtures with fertilizers and growth regulators.
The active ingredient can be used as such, in the form of its formulations or the use forms prepared therefrom, such as ready-to-use solutions, suspensions, wettable powders, pastes, soluble powders, dusts and granules. They are used in the usual way, e.g. by pouring, spraying, atomizing, scattering, dusting, foaming, brushing, etc. It is also possible to apply the active ingredients by the ultra-low-volume process or to inject the active ingredient preparation or the active ingredient into the soil itself. The seeds of the plants can also be treated.
When treating parts of plants, the active compound concentrations in the use forms can be varied within a substantial range. They are generally between 1 and 0.0001% by weight, preferably between 0.05 and 0.001%.
In the case of seed treatment, generally active compound amounts of 0.001 to 50 g per kilogram of seed, preferably 0.01 to 10 g, are required.
When treating the soil, active ingredient concentrations of 0.00001 to 0.1% by weight, preferably 0.0001 to 0.02%, are required at the site of action.
Manufacturing examples:
Example 1:
<chemistry id="chem0016" num="0016"><img file="EP0278352A2_D0025.tif" /></chemistry>
A mixture of 15 g (0.05 mol) of 2-bromomethyl-8-t-butyl-1-oxaspiro [4,5] decane and 13 g (0.11 mol) of 3,5-dimethylpiperidine is 16 hours at 140 ° C bath temperature stirred, cooled and taken up in a mixture of diethyl ether and water; the organic phase is separated off, dried over sodium sulfate, concentrated in vacuo and the residue is subjected to bulb tube distillation (jacket temperature 170 ° C. to 200 ° C. at 0.13 mbar).
9.5 g (57% of theory) of 8-t-butyl-2- (3,5-dimethylpiperidin-1-ylmethyl) -1-oxaspiro [4,5] decane of refractive index n are obtained<img file="EP0278352A2_D0026.tif" /> 1.4869.
Preparation of the starting compound:
<chemistry id="chem0017" num="0017"><img file="EP0278352A2_D0027.tif" /></chemistry>
40 g (0.2 mol) of N-bromosuccinimide are added in portions to a solution of 42 g (0.2 mol) of 1- (3-butenyl) -4-t-butylcyclohexanol in 600 ml of absolute chloroform with stirring and cooling so that the temperature of the reaction mixture does not exceed 40 ° C. After the addition has ended, the mixture is stirred for a further 16 hours at room temperature, washed twice with water, dried over sodium sulfate and the solvent is removed in vacuo.
43 g (74% of theory) of 2-bromomethyl-8-t-butyl-1-oxaspiro [4,5] decane of refractive index n are obtained<img file="EP0278352A2_D0028.tif" /> = 1,4921. <chemistry id="chem0018" num="0018"><img file="EP0278352A2_D0029.tif" /></chemistry>
To a solution of 7.2 g (0.3 mol) of magnesium and 40.5 g (0.3 mol) of 4-bromo-1-butene in 200 ml of absolute diethyl ether, a solution of 45 g ( 0.3 mol) of 4-t-butylcyclohexanone in 100 ml of absolute tetrahydrofuran. When the addition is complete, the mixture is stirred at reflux temperature for 4 hours and then hydrolyzed with a mixture of 2 normal hydrochloric acid and ice. The organic phase is separated off, dried over sodium sulfate and freed from solvent in vacuo.
After distillation in vacuo, 47 g (75% of theory) of 1- (3-butenyl) -4-t-butyl-cyclohexanol with a boiling point of 89 ° -91 ° C. at 0.1 mbar are obtained.
The following aminomethyltetrahydrofurans of the general formula (I) are obtained in a corresponding manner and in accordance with the general information on the preparation:<tables id="tabl0010" num="0010"><img file="EP0278352A2_D0030.tif" /></tables><tables id="tabl0011" num="0011"><img file="EP0278352A2_D0031.tif" /></tables><tables id="tabl0012" num="0012"><img file="EP0278352A2_D0032.tif" /></tables><tables id="tabl0013" num="0013"><img file="EP0278352A2_D0033.tif" /></tables><tables id="tabl0014" num="0014"><img file="EP0278352A2_D0034.tif" /></tables><tables id="tabl0015" num="0015"><img file="EP0278352A2_D0035.tif" /></tables>
*) The ¹H-NMR spectra were recorded in CDCl₃ with tetramethylsilane (TMS) as the internal standard. The chemical shift is given as a δ value in ppm.
Examples of use
In the following application example, the compound listed below was used as a comparison substance:<chemistry id="chem0019" num="0019"><img file="EP0278352A2_D0036.tif" /></chemistry>
Example A
Erysiphe test (barley) / protective
Solvent: 100 parts by weight of dimethylformamide Emulsifier: 0.25 parts by weight of alkylaryl polyglycol ether
To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier and the concentrate is diluted with water to the desired concentration.
To test for protective efficacy, young plants are sprayed with the preparation of active compound as dewy. After the spray coating has dried on, the plants are dusted with spores from Erysiphe graminis f.sp.hordei.
The plants are placed in a greenhouse at a temperature of approx. 20 ° C and a relative humidity of approx. 80% in order to promote the development of mildew pustules.
7 Evaluation is carried out days after the inoculation.
In this test, for example, the compounds according to the preparation examples: 1, 2, 3, 4, 7, 8, 9, 10 show a clear superiority in effectiveness over the prior art.
51 sheets
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| US8158992B2 | Cited by | United States of America | Applicant |
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Priority claims8
| Document | Office | Kind | Date |
|---|---|---|---|
| 3703972 | Germany | A | |
| 3703972 | Germany | – | |
| 3730499 | Germany | A | |
| 3730499 | Germany | – | |
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| DE3730499A1 | Germany | A1 | |
| BR8800530A | Brazil | A | |
| EP0278352A3 | European Patent Office (EPO) | A3 | |
| US4800202A | United States of America | A | |
| EP0278352B1 | European Patent Office (EPO) | B1 | |
| DE3862309D1 | Germany | D1 |
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Numbers
- Publication
- 0278352
- Publication, DOCDB
- 0278352
- Publication, EPODOC
- EP0278352
- Application
- 88101375
- Application, DOCDB
- 88101375
- Application, EPODOC
- EP19880101375
Titles6
- German
- Aminomethyltetrahydrofurane
- English
- Aminomethyl-tetrahydro-furanes
- French
- Aminométhyl-tétrahydro-furans
- German
- Aminomethyltetrahydrofurane.
- English
- Aminomethyl-tetrahydro-furanes.
- French
- Aminométhyl-tétrahydro-furans.
Classification
- CPC, 6
- C07D307/94
- A01N43/12
- A01N43/28
- A01N43/40
- A01N43/80
- A01N43/84
- IPC, 9
- A01N43 12
- A01N43 28
- A01N43 40
- A01N43 80
- A01N43 84
- C07D307 94
- C07D405 06
- C07D413 06
- C07D417 06
Designated states8
- Contracting states, 8
- Belgium
- Switzerland
- Germany
- France
- United Kingdom
- Italy
- Liechtenstein
- Netherlands (Kingdom of the)