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DE1025878B - Process for the preparation of N, N-AEthylenureidoalkylvinylaethers - Google Patents

Process for the preparation of N, N-AEthylenureidoalkylvinylaethers

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Publication number
DE1025878B
DE1025878B DER13959A DER0013959A DE1025878B DE 1025878 B DE1025878 B DE 1025878B DE R13959 A DER13959 A DE R13959A DE R0013959 A DER0013959 A DE R0013959A DE 1025878 B DE1025878 B DE 1025878B
Authority
DE
Germany
Prior art keywords
carbon atoms
ethyleneimine
vinyl ether
isocyanate
parts
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.)
Pending
Application number
DER13959A
Other languages
German (de)
Inventor
Sidney Melamed
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.)
Rohm and Haas Co
Original Assignee
Rohm and Haas Co
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Rohm and Haas Co filed Critical Rohm and Haas Co
Publication of DE1025878B publication Critical patent/DE1025878B/en
Pending legal-status Critical Current

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Classifications

    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D203/00Heterocyclic compounds containing three-membered rings with one nitrogen atom as the only ring hetero atom
    • C07D203/04Heterocyclic compounds containing three-membered rings with one nitrogen atom as the only ring hetero atom not condensed with other rings
    • C07D203/06Heterocyclic compounds containing three-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
    • C07D203/16Heterocyclic compounds containing three-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 with acylated ring nitrogen atoms
    • C07D203/20Heterocyclic compounds containing three-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 with acylated ring nitrogen atoms by carbonic acid, or by sulfur or nitrogen analogues thereof, e.g. carbamates

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Description

Verfahren zur Herstellung von N,N-Äthylenureidoalkylvinyläthern Die Erfindung betrifft ein Verfahren zur Herstellung von N,N-Äthylenureidoalkyl-#dnyläthern der allgemeinen Formel in der Z eine Alkylengruppe mit 1 bis 7 Kohlenstoffatomen und R1 sowie R2 Alkylgruppen mit 1 bis 4 Kohlenstoffatomen oder auch Wasserstoffatome -bedeuten, wenn Z eine Alkylengruppe mit 3 bis 7 Kohlenstoffatomen darstellt, und gegebenenfalls der Äthyleniminring an den Kohlenstoffatomen substituiert ist. In den bevorzugten Verfahrensprodukten bedeuten R1 und R2 Alkylgruppen, vorzugsweise Methylgruppen.Process for the production of N, N-Äthylenureidoalkylvinyläthern The invention relates to a process for the production of N, N-Äthylenureidoalkyl- #dnyläthern of the general formula in which Z is an alkylene group with 1 to 7 carbon atoms and R1 and R2 are alkyl groups with 1 to 4 carbon atoms or hydrogen atoms when Z is an alkylene group with 3 to 7 carbon atoms and the ethyleneimine ring is optionally substituted on the carbon atoms. In the preferred products of the process, R1 and R2 are alkyl groups, preferably methyl groups.

Diese Äthylenureidoalkylvinyläther werden erfindungsgemäß durch Umsetzung von gegebenenfalls an den Kohlenstoffatomen substituiertem Äthylenimin mit Isocyanatalkylvinyläthern der allgemeinen Formel hergestellt. Die Reaktion wird bei Temperaturen zwischen 0 und 100°C, vorzugsweise in Gegenwart eines inerten organischen Lösungsmittels, z. B. Benzol oder Toluol, durchgeführt. Theoretisch erfolgt die Reaktion zwischen j e 1 Mol der Reaktionsteilnehmer; genaue Mengenverhältnisse brauchen aber nicht eingehalten zu werden. Es ist am zweckmäßigsten, Äthylenimin im Überschuß anzuwenden und den nicht umgesetzten Teil durch Erhitzen unter vermindertem Druck aus dem Reaktionsgemisch zu entfernen, wobei als Rückstand das Reaktionsprodukt verbleibt.According to the invention, these Äthylenureidoalkylvinyläther are prepared by reacting ethyleneimine, which may be substituted on the carbon atoms, with isocyanate alkyl vinyl ethers of the general formula manufactured. The reaction is carried out at temperatures between 0 and 100 ° C, preferably in the presence of an inert organic solvent, e.g. B. benzene or toluene performed. Theoretically, the reaction takes place between 1 mole of the reactants; however, exact proportions do not need to be adhered to. It is most expedient to use ethyleneimine in excess and to remove the unreacted part from the reaction mixture by heating under reduced pressure, the reaction product remaining as the residue.

Die Herstellung der als Ausgangsmaterial verwendeten Isocyanatalkylvinyläther erfolgt in an sich bekannter Weise durch Erhitzen der entsprechenden Vinyloxyalkylcarbamate in Gegenwart starker Basen.The production of the isocyanate alkyl vinyl ethers used as starting material takes place in a manner known per se by heating the corresponding vinyloxyalkyl carbamates in the presence of strong bases.

Verfahrensgemäß werden als Isocyanatalkylvinyläther z. B. 2-Isocyanatisobutylvinyläther, 2-Isocyanat-2-methylbutylvinyläther, 2-Isocyanat-2-methylhexylvinyläther, 2-Isocyanat-2-äthylbutylvinyläther, 3-Isocyanat-3-methylbutylvinyläther, 4-Isocyanat-4-methylpentyl-(1)-vinyläther oder 7-Isocyanat-3,7-dimethyloctyl-(1)-vinyläther verwendet. An Stelle von Äthylenimin können auch an den Kohlenstoffatomen substituierte Äthylenimine, z. B. 2,2-Dimethyläthylenimin oder 2,3-Dimethvläthylenimin, verwendet werden. Der Reaktionsverlauf des erfindungsgemäßen Verfahrens war nicht vorauszusehen.According to the method, as isocyanate alkyl vinyl ethers, for. B. 2-isocyanate isobutyl vinyl ether, 2-isocyanate-2-methylbutyl vinyl ether, 2-isocyanate-2-methylhexyl vinyl ether, 2-isocyanate-2-ethylbutyl vinyl ether, 3-isocyanate-3-methylbutyl vinyl ether, 4-isocyanate-4-methylpentyl (1) vinyl ether or 7-isocyanate-3,7-dimethyloctyl (1) vinyl ether is used. Instead of ethyleneimine can also ethylenimines substituted on the carbon atoms, z. B. 2,2-dimethylethyleneimine or 2,3-dimethylethyleneimine can be used. The course of the reaction of the invention Procedure was not foreseen.

Es war zwar bekannt, Monoisocyanate mit Äthylenimin umzusetzen, wobei Äthylenharnstoffe erhalten werden, die zu einer Polymerisation unfähig sind. Es war aber nicht zu erwarten, daß beim Einwirken von Äthylenimin auf Isocyanatalkylvinyläther die Reaktion an der Isocyanatgruppe stattfinden, während die Vinylgruppe unverändert bleiben würde, so daß auf diese Weise polymerisationsfähige Monomere gewonnen werden können.It was known to implement monoisocyanates with ethyleneimine, with Ethylenureas are obtained, which are incapable of polymerization. It but it was not to be expected that when ethyleneimine acted on isocyanate alkyl vinyl ethers the reaction take place at the isocyanate group, while the vinyl group remains unchanged would remain so that polymerizable monomers are obtained in this way can.

Die Verfahrensprodukte dienen als insektizide Kontaktgifte und als Wachstumsregler für Pflanzen. Sie können in Spritzölen verwendet werden. Auch sind sie als Finish für Wolle und Seide geeignet.The products of the process serve as insecticidal contact poisons and as Growth regulators for plants. They can be used in spray oils. Also are they are suitable as a finish for wool and silk.

In den folgenden Beispielen sind Teile Gewichtsteile. Beispiel 1 13 Teile 2-Isocyanatisobutvlvinyläther werden in 20 Teilen Benzol und 5 Teile VÄthylenimin in 5 Teilen Benzol gelöst und beide Lösungen miteinander vermischt. Unter vermindertem Druck wird das Gemisch abgedampft und der verbleibende Rückstand bei niedrigem Druck erwärmt. Erhalten wird ein bewegliches hellgelbes Öl, das laut Analyse 58,7°i, Kohlenstoff, 8,70,/o Wasserstoff und 15,0 °/o Stickstoff enthält und in der Zusammensetzung dem 2-N,N-Äthylenureidoisobutylvinyläther entspricht, der theoretisch 58,7 °/o Kohlenstoff, 8,7 °/o Wasserstoff und 15,2 °/o Stickstoff enthält. Die Ausbeute ist fast quantitativ. Kp. 120 bis 130° C/lmm.In the following examples, parts are parts by weight. EXAMPLE 1 13 parts of 2-isocyanate isobutyl vinyl ether are dissolved in 20 parts of benzene and 5 parts of ethyleneimine in 5 parts of benzene and the two solutions are mixed with one another. The mixture is evaporated under reduced pressure and the remaining residue is heated under low pressure. A mobile, pale yellow oil is obtained which, according to analysis, contains 58.7% carbon, 8.70% hydrogen and 15.0% nitrogen and has 2-N, N-ethylenureidoisobutyl vinyl ether in its composition which theoretically contains 58.7% carbon, 8.7% hydrogen and 15.2% nitrogen. The yield is almost quantitative. Bp. 120 to 130 ° C / lmm.

Beispiel 2 Wie im Beispiel 1 werden 16 Teile 4-Isocyanat-4-methylpentyl-(2)-vinyläther und 5 Teile Äthylenimin in benzolischer Lösung zusammengebracht. Lösungsmittel und überschüssiges Äthylenimin werden durch Erhitzen auf dem Dampfbad unter vermindertem Druck entfernt. Example 2 As in Example 1, 16 parts of 4-isocyanate-4-methylpentyl (2) vinyl ether and 5 parts of ethyleneimine are combined in a benzene solution. The solvent and excess ethyleneimine are removed by heating on the steam bath under reduced pressure.

Claims (2)

PATENTANSPRÜCHE: 1. Verfahren zur Herstellung von N,N-Äthylenureidoalkylvinyläthern der allgemeinen Formel in der Z eine Alkylengruppe mit 1 bis 7 Kohlenstoffatomen und R1 sowie R= Alkylgruppen mit 1 bis 4 Kohlenstoffatomen oder auch Wasserstoffatome bedeuten, wenn Z eine Alkylengruppe mit 3 bis 7 Kohlenstoffatomen darstellt, und gegebenenfalls der Äthyleniminring an den Kohlenstoffatomen substituiert ist, dadurch gekennzeichnet, daß man gegebenen-Das verbleibende gelbe Öl entspricht in der Zusammensetzung dem 4-N,N-Äthylenureido-4-methylpentyl-(2)-vinyläther. Die Ausbeute ist fast quantitativ. Kp. 130 bis 140°C/ 0,5 mm. Beispiel 3 In gleicher Weise werden in Toluollösung 21 Teile 7-Isocyanat-3,7-dimethyloctyl-(1)-vinyläther und 5 Teile Äthylenimin umgesetzt. Das als Rückstand erhaltene Produkt entspricht in der Zusammensetzung der Verbindung falls an den Kohlenstoffatomen substituiertes Äthylenimin mit Isocyanatalkylvinyläthem der allgemeinen Formel vorzugsweise in Gegenwart eines organischen L ösungsmittels umsetzt. PATENT CLAIMS: 1. Process for the preparation of N, N-Äthylenureidoalkylvinyläthern of the general formula in which Z is an alkylene group with 1 to 7 carbon atoms and R1 and R = alkyl groups with 1 to 4 carbon atoms or hydrogen atoms, when Z is an alkylene group with 3 to 7 carbon atoms, and the ethyleneimine ring is optionally substituted on the carbon atoms, characterized in that that given-The remaining yellow oil corresponds in composition to 4-N, N-Äthylenureido-4-methylpentyl (2) vinyl ether. The yield is almost quantitative. Bp. 130 to 140 ° C / 0.5 mm. EXAMPLE 3 In the same way, 21 parts of 7-isocyanate-3,7-dimethyloctyl (1) vinyl ether and 5 parts of ethyleneimine are reacted in toluene solution. The composition of the product obtained as residue corresponds to the composition of the compound if ethyleneimine with isocyanate alkyl vinyl ether substituted on the carbon atoms of the general formula preferably reacted in the presence of an organic solvent. 2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß das Äthylenimin mit Isocyanatisobutylvinyläther umgesetzt wird. In Betracht gezogene Druckschriften: Liebigs Annalen der Chemie, Bd. 566 (1950), S.218.2. Procedure according to claim 1, characterized in that the ethyleneimine with isocyanate isobutyl vinyl ether is implemented. Considered publications: Liebig's Annalen der Chemie, Vol. 566 (1950), p.218.
DER13959A 1953-04-10 1954-04-09 Process for the preparation of N, N-AEthylenureidoalkylvinylaethers Pending DE1025878B (en)

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US1025878XA 1953-04-10 1953-04-10

Publications (1)

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DE1025878B true DE1025878B (en) 1958-03-13

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Non-Patent Citations (1)

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