DE3627246A1 - Novel azetidinylanilines and a process for their preparation - Google Patents

Novel azetidinylanilines and a process for their preparation

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Publication number
DE3627246A1
DE3627246A1 DE19863627246 DE3627246A DE3627246A1 DE 3627246 A1 DE3627246 A1 DE 3627246A1 DE 19863627246 DE19863627246 DE 19863627246 DE 3627246 A DE3627246 A DE 3627246A DE 3627246 A1 DE3627246 A1 DE 3627246A1
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DE
Germany
Prior art keywords
radical
alkyl radical
formula
propyleneureas
hydroxymethylated
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
DE19863627246
Other languages
German (de)
Inventor
Hans-Josef Dr Buysch
Peter Dr Mues
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Bayer AG
Original Assignee
Bayer AG
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Filing date
Publication date
Application filed by Bayer AG filed Critical Bayer AG
Priority to DE19863627246 priority Critical patent/DE3627246A1/en
Publication of DE3627246A1 publication Critical patent/DE3627246A1/en
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
    • C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
    • C07D239/06—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
    • C07D239/08—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with hetero atoms directly attached in position 2
    • C07D239/10—Oxygen or sulfur atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D205/00—Heterocyclic compounds containing four-membered rings with one nitrogen atom as the only ring hetero atom
    • C07D205/02—Heterocyclic compounds containing four-membered rings with one nitrogen atom as the only ring hetero atom not condensed with other rings
    • C07D205/04—Heterocyclic compounds containing four-membered rings with one nitrogen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members

Abstract

Novel azetidinylanilines of the formula <IMAGE> in which R<1> and R<2> can be identical or different and denote a phenyl radical or naphthyl radical which is optionally mono- or polysubstituted by a C1-4-alkyl radical, or by chlorine, bromine or nitro or a trifluoromethyl, alkoxy or carbalkoxy radical having 1-4 carbon atoms and R<3> represents an alkyl radical having 1-4 carbon atoms, are prepared by heating hydroxymethylated propyleneureas of the formula <IMAGE> in which R<1>, R<2> and R<3> have the meaning indicated above, in the presence of transition metal catalysts.

Description

Die Erfindung betrifft neue Azetidinaniline sowie ein Verfahren zu deren Herstellung.The invention relates to new azetidine anilines and a Process for their production.

Azetidine werden im allgemeinen durch klassische Ringschlußreaktion hergestellt (Heterocyclic Compounds with Three- and Fourmembered Rings, Vol. II, S. 855 ff, Interscience Publishers 1964).Azetidines are generally characterized by classic Ring closure reaction produced (heterocyclic compounds with Three- and Fourmembered Rings, Vol. II, pp. 855 ff, Interscience Publishers 1964).

Gegenstand der vorliegenden Erfindung sind neue Azetidinaniline der allgemeinen Formel IThe present invention relates to new ones Azetidine anilines of the general formula I

worin
R1 und R2 gleich oder verschieden sein können und einen gegebenenfalls durch einen C1-4-Alkylrest, durch Chlor, Brom, Nitro, einen Trifluormethyl-, Alkoxy-, oder Carbalkoxyrest mit 1-4 C-Atomen ein- oder mehrfach substituierten Phenylrest oder Naphthylrest bedeuten und
R3 einen Alkylrest mit 1-4 C-Atomen
darstellt.wherein
R 1 and R 2 may be the same or different and one or more substituted by a C 1-4 alkyl radical, by chlorine, bromine, nitro, a trifluoromethyl, alkoxy or carbalkoxy radical with 1-4 C atoms Phenyl radical or naphthyl radical mean and
R 3 is an alkyl radical with 1-4 C atoms
represents.

Ein weiterer Gegenstand der vorliegenden Erfindung ist ein Verfahren zur Herstellung der neuen Azetidinaniline der allgemeinen Formel IAnother object of the present invention is a process for the preparation of the new azetidine anilines of the general formula I

worin
R1 und R2 gleich oder verschieden sein können und einen gegebenenfalls durch einen C1-4-Alkylrest, durch Chlor, Brom, Nitro, einen Trifluormethyl-, Alkoxy- oder Carbalkoxyrest mit 1-4 C-Atomen ein- oder mehrfach substituierten Phenylrest oder Naphthylrest bedeuten und
R3 einen Alkylrest mit 1-4 C-Atomen
darstellt,
das dadurch gekennzeichnet ist, daß man hydroxymethylierte Propylenharnstoffe der allgemeinen Formel II wherein
R 1 and R 2 can be the same or different and a phenyl radical which is mono- or polysubstituted or substituted by a C 1-4 alkyl radical, by chlorine, bromine, nitro, a trifluoromethyl, alkoxy or carbalkoxy radical with 1-4 C atoms or naphthyl and
R 3 is an alkyl radical with 1-4 C atoms
represents
which is characterized in that hydroxymethylated propyleneureas of the general formula II

worin
R1, R2 und R3 die oben angegebene Bedeutung haben,
in Gegenwart von Übergangsmetallkatalysatoren erhitzt.wherein
R 1 , R 2 and R 3 have the meaning given above,
heated in the presence of transition metal catalysts.

Als Alkylreste mit 1-4, bevorzugt 1-2 Kohlenstoffatomen der Formeln I und II seien genannt: der Methyl-, Ethyl-, n-Propyl-, Isopropyl-, n-Butyl-, Isobutyl- und tert. Butyl- Rest, bevorzugt der Methyl- und Ethylrest.As alkyl radicals with 1-4, preferably 1-2 carbon atoms of the formulas I and II may be mentioned: the methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl and tert. Butyl Radical, preferably the methyl and ethyl radical.

Als Alkoxygruppen mit 1-4, bevorzugt 1-2 Kohlenstoffatomen der Formeln I und II seien genannt: der Methoxy-, Ethoxy-, n-Propyloxy-, Isopropyloxy-, n-Butyloxy-, Isobutyloxy- und tert. Butyloxy-Rest, bevorzugt der Methoxy- und Ethoxyrest und als Carbalkoxygruppen mit 1-4 bevorzugt 1-2 Kohlenstoffatomen der Formeln I und II seien genannt: Methoxycarbonyl, Ethoxycarbonyl, n-Propyloxycarbonyl, Isopropyloxycarbonyl, n-Butyloxycarbonyl, Isobutyloxycarbonyl und tert.-Butyloxycarbonyl, bevorzugt Methoxycarbonyl und Ethoxycarbonyl.As alkoxy groups with 1-4, preferably 1-2 carbon atoms of formulas I and II may be mentioned: the methoxy, Ethoxy, n-propyloxy, isopropyloxy, n-butyloxy, isobutyloxy and tert. Butyloxy radical, preferably the methoxy and ethoxy radical and as carbalkoxy groups with 1-4 preferably 1-2 carbon atoms of the formulas I and II may be mentioned: methoxycarbonyl, ethoxycarbonyl, n-propyloxycarbonyl, Isopropyloxycarbonyl, n-butyloxycarbonyl, Isobutyloxycarbonyl and tert-butyloxycarbonyl, preferably methoxycarbonyl and ethoxycarbonyl.

Zum Beispiel können solche Verbindungen der Formel II in das erfindungsgemäße Verfahren eingesetzt werden, in denen die Reste R1-R3 folgende Bedeutung haben:For example, those compounds of the formula II can be used in the process according to the invention in which the radicals R 1 -R 3 have the following meaning:

Die als Ausgangsprodukte eingesetzten 5-hydroxymethylierten Propylenharnstoffe können auf einfache Weise aus Oxetanylurethanen der allgemeinen Formel III oder aus Oxetanylharnstoffen der allgemeinen Formel IV durch Erhitzen in Gegenwart eines basischen Katalysators entsprechend den angegebenen Reaktionsgleichungen hergestellt werden:The 5-hydroxymethylated used as starting products Propyleneureas can be made out easily Oxetanyl urethanes of the general formula III or from  Oxetanyl ureas of the general formula IV by heating accordingly in the presence of a basic catalyst the specified reaction equations will:

Die Oxetanylurethane der Formel III sind wiederum auf einfache Weise durch Addition entsprechender Oxetanylalkohole mit entsprechenden aromatischen Isocyanaten in Gegenwart geeigneter inerter Lösungsmittel und Katalysatoren zu erhalten. Die Oxetanylharnstoffe der Formel IV gewinnt man auf ähnlichem Wege durch Addition von entsprechenden Oxetanylaminen an entsprechenden Isocyanate. Die Oxetanylamine wiederum werden durch Erhitzen von Urethanen cyclischer Carbonate in Gegenwart von basischen Katalysatoren erhalten, wobei die Urethane auf einfache Weise durch Additions der entsprechenden, gegebenenfalls substituierten Isocyanate an 5-Hydroxy- methyl-5-alkyl-1,3-dioxan-2-, die gemäß der US-PS 44 40 937 hergestellt werden, in Gegenwart eines inerten organischen Lösungsmittels unter Verwendung von entsprechenden Katalysatoren erhalten werden.The oxetanyl urethanes of the formula III are in turn simple way by adding appropriate oxetanyl alcohols with corresponding aromatic isocyanates in Presence of suitable inert solvents and catalysts to obtain. The oxetanyl ureas of the formula IV one wins in a similar way by adding corresponding ones Oxetanylamines on corresponding isocyanates. The oxetanylamines in turn are made by heating Urethanes of cyclic carbonates in the presence of basic Get catalysts, with the urethanes on simple way by adding the appropriate, if necessary substituted isocyanates on 5-hydroxy  methyl-5-alkyl-1,3-dioxane-2-, which according to the US-PS 44 40 937 are prepared in the presence of an inert organic solvent using corresponding catalysts can be obtained.

Nach dem erfindungsgemäßen Verfahren werden die cyclischen Harnstoffe der allgemeinen Formel II in Gegenwart von Übergangsmetallkatalysatoren auf Temperaturen im Bereich von etwa 160-260°C, vorzugsweise 180-220°C erhitzt.According to the inventive method, the cyclic Urea of the general formula II in the presence of transition metal catalysts to temperatures in the Range of about 160-260 ° C, preferably 180-220 ° C heated.

Als Übergangsmetallkatalysatoren werden vorzugsweise Sn- Verbindungen eingesetzt, wie sie zur Herstellung von Kohlensäureestern in der DE-OS 30 17 419 beschrieben sind. Beispielsweise werden genannt: Butylzinntriethylat, Ethylzinntrioctylat, Ethylzinntrilaurat, Methylzinntrimethylat, Diethylzinnoxid, Diethylzinndiethylat, Diethylzinndistearat, Dibutylzinndimethylat, Dibutylzinndilaurat, Dibutylzinnoxid, Dinonylzinndioctylat, Zinndilaurat, Zinndioctanoat, Triethylzinnoctanoat und Triethylzinnlaurat. Die Katalysatoren werden in Mengen von etwa 0,01-5 Gew.-%, bevorzugt 0,1-3 Gew.-%, bezogen auf die Menge an eingesetzter Verbindung der Formel II, eingesetzt.Sn- are preferably used as transition metal catalysts Connections used as for the production of Carbonic acid esters described in DE-OS 30 17 419 are. Examples include: butyltin triethylate, Ethyl tin trioctylate, ethyl tin trilaurate, methyl tin trimethylate, Diethyltin oxide, diethyltin diethylate, Diethyltin distearate, dibutyltin dimethylate, dibutyltin dilaurate, Dibutyltin oxide, dinonyltin dioctylate, Tin dilaurate, tin dioctanoate, triethyltin octanoate and Triethyltin laurate. The catalysts are in quantities from about 0.01-5% by weight, preferably 0.1-3% by weight, based on the amount of compound used Formula II used.

Nach dem erfindungsgemäßen Verfahren wird das Erhitzen der cyclischen Harnstoffe der allgemeinen Formel II unter vermindertem Druck von etwa 0,01-100 mbar, bevorzugt 0,01-20 mbar, durchgeführt.According to the method of the invention, the heating of cyclic ureas of the general formula II under reduced pressure of about 0.01-100 mbar, preferred 0.01-20 mbar.

Das bei der Reaktion gemäß dem allgemeinen Formelschema That in the reaction according to the general formula  

entstehende Kohlendioxyd wird zweckmäßgerweise in einer mit flüssigem Stickstoff gekühlten Falle oder in einer geeigneten Flüssigkeit, wie Ethanolamin oder Ethylendiamin, unter Carbaminatbildung aufgefangen.carbon dioxide is conveniently in a trap cooled with liquid nitrogen or in a suitable liquid, such as ethanolamine or ethylenediamine, caught with carbaminate formation.

Die erhaltenen Produkte der allgemeinen Formel I können zur weiteren Reinigung fraktioniert destilliert werden.The products of general formula I obtained can be fractionally distilled for further purification.

Die neuen Azetidine sind Vorprodukte zur Herstellung von Pflanzenschutzmitteln und Polymerisationsbeschleunigern.The new Azetidines are intermediate products for the production of Plant protection products and polymerization accelerators.

Beispielexample

50 g (0,16 Mol)50 g (0.16 mol)

werden mit 0,5 ml Ethylzinntriisooctylat während 7 Stdn. im Ölpumpenvakuum auf 220°C erhitzt. Dabei destillieren (Sdp. 0,1 bar: 170-180°C) 18 g Produktwill with 0.5 ml of ethyltin triisooctylate for 7 hours in an oil pump vacuum heated to 220 ° C. Distill (Bp 0.1 bar: 170-180 ° C) 18 g product

ab.from.

10 g Ausgangsmaterial werden durch Kristallisation aus Methylenchlorid umgesetzt zurückgewonnen.10 g of starting material are crystallized out Methylene chloride recovered converted.

52% Ausbeute (bez. auf umgesetztes Ausgangsmaterial), das 1H-NMR-Sprektrum entspricht der oben angegebenen Struktur.52% yield (based on converted starting material), the 1 H-NMR spectrum corresponds to the structure given above.

Claims (5)

1. Azetindinaniline der allgemeinen Formel worin
R1 und R2 gleich oder verschieden sein können und einen gegebenenfalls durch einen C1-4-Alkylrest, durch Chlor, Brom, Nitro, einen Trifluormethyl-, Alkoxy- oder Carbalkoxyrest mit 1-4 C-Atomen ein- oder mehrfach substituierten Phenylrest oder Napthylrest bedeuten und
R3 einen Alkylrest mit 1-4 C-Atomen
darstellt.1. Azetine dinanilines of the general formula wherein
R 1 and R 2 can be the same or different and a phenyl radical which is mono- or polysubstituted or substituted by a C 1-4 alkyl radical, by chlorine, bromine, nitro, a trifluoromethyl, alkoxy or carbalkoxy radical with 1-4 C atoms or naphthyl and
R 3 is an alkyl radical with 1-4 C atoms
represents. 2. Verfahren zur Herstellung von Azetidinanilinen der Formel worin
R1 und R2 gleich oder verschieden sein können und einen gegebenenfalls durch einen C1-4-Alkylrest, durch Chlor, Brom, Nitro, einen Trifluormethyl-, Alkoxy- oder Carbalkoxyrest mit 1-4 C-Atomen ein- oder mehrfach substituierten Phenylrest oder Napthylrest bedeuten und
R3 einen Alkylrest mit 1-4 C-Atomen
darstellt,
dadurch gekennzeichnet, daß man hydroxymethylierte Propylenharnstoffe der Formel worin
R1, R2 und R3 die oben angegebene Bedeutung haben, in Gegenwart von Übergangsmetallkatalysatoren erhitzt.2. Process for the preparation of azetidine anilines of the formula wherein
R 1 and R 2 can be the same or different and a phenyl radical which is mono- or polysubstituted or substituted by a C 1-4 alkyl radical, by chlorine, bromine, nitro, a trifluoromethyl, alkoxy or carbalkoxy radical with 1-4 C atoms or naphthyl and
R 3 is an alkyl radical with 1-4 C atoms
represents
characterized in that hydroxymethylated propyleneureas of the formula wherein
R 1 , R 2 and R 3 have the meaning given above, heated in the presence of transition metal catalysts. 3. Verfahren nach Anspruch 2, dadurch gekennzeichnet, daß man die hydroxymethylierten Propylenharnstoffe bei Temperaturen von 160-260°C erhitzt.3. The method according to claim 2, characterized in that the hydroxymethylated propyleneureas heated at temperatures of 160-260 ° C. 4. Verfahren nach Ansprüchen 2 und 3, dadurch gekennzeichnet, daß man als Übergangsmetallkatalysatoren Zinnverbindungen einsetzt.4. The method according to claims 2 and 3, characterized in that one as transition metal catalysts Tin compounds used. 5. Verfahren nach Ansprüchen 2 bis 4, dadurch gekennzeichnet, daß man die Katalysatoren in Mengen von 0,01-5 Gew.-%, bezogen auf die Menge an eingesetzten hydroxymethylierten Propylenharnstoffen, einsetzt.5. The method according to claims 2 to 4, characterized in that the catalysts in amounts of 0.01-5 wt .-%, based on the amount of used hydroxymethylated propyleneureas, starts.
DE19863627246 1986-08-12 1986-08-12 Novel azetidinylanilines and a process for their preparation Withdrawn DE3627246A1 (en)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0406112A1 (en) * 1989-06-29 1991-01-02 Laboratorios Del Dr. Esteve, S.A. 1-Benzhydrylazetidines, their preparation and their use as intermediates for the preparation of compounds with antimicrobial activity
WO2001054694A1 (en) * 2000-01-28 2001-08-02 Bristol-Myers Squibb Company Tetrahydropyrimidone inhibitors of fatty acid binding protein and method
US6670380B2 (en) 2000-11-20 2003-12-30 Bristol-Myers Squibb Co. Pyridone inhibitors of fatty acid binding protein and method
DE10356489A1 (en) * 2003-12-03 2005-06-30 Construction Research & Technology Gmbh Azetidine derivatives, processes for their preparation and their use
US6919323B2 (en) 2001-07-13 2005-07-19 Bristol-Myers Squibb Company Pyridazinone inhibitors of fatty acid binding protein and method

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0406112A1 (en) * 1989-06-29 1991-01-02 Laboratorios Del Dr. Esteve, S.A. 1-Benzhydrylazetidines, their preparation and their use as intermediates for the preparation of compounds with antimicrobial activity
FR2649100A1 (en) * 1989-06-29 1991-01-04 Esteve Labor Dr NOVEL AZETIDINES, THEIR PREPARATION AND THEIR APPLICATION AS INTERMEDIATES FOR THE PREPARATION OF COMPOUNDS WITH ANTIMICROBIAL ACTIVITY
US5073646A (en) * 1989-06-29 1991-12-17 Laboratorios Del Dr. Esteve, S.A. Substituted 1-diphenylmethyl azetidines
WO2001054694A1 (en) * 2000-01-28 2001-08-02 Bristol-Myers Squibb Company Tetrahydropyrimidone inhibitors of fatty acid binding protein and method
US6649622B2 (en) * 2000-01-28 2003-11-18 Bristol-Myers Squibb Company Tetrahydropyrimidone inhibitors of fatty acid binding protein and method
US6670380B2 (en) 2000-11-20 2003-12-30 Bristol-Myers Squibb Co. Pyridone inhibitors of fatty acid binding protein and method
US6919323B2 (en) 2001-07-13 2005-07-19 Bristol-Myers Squibb Company Pyridazinone inhibitors of fatty acid binding protein and method
DE10356489A1 (en) * 2003-12-03 2005-06-30 Construction Research & Technology Gmbh Azetidine derivatives, processes for their preparation and their use
US7745565B2 (en) 2003-12-03 2010-06-29 Construction Research & Technology Gmbh Azetidine derivatives, method for producing said derivatives and use thereof

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