Synthesis 2016; 48(24): 4431-4442
DOI: 10.1055/s-0035-1562626
paper
© Georg Thieme Verlag Stuttgart · New York

Structural Aspects of Thermally Cleavable Adducts Derived from the Reaction of Imidazolines with Isocyanates

Andreas Laue
a  Technische Universität Chemnitz, Institute of Chemistry, Polymer Chemistry, 09107 Chemnitz, Germany   Email: stefan.spange@chemie.tu-chemnitz.de
,
Andrea Preuß
a  Technische Universität Chemnitz, Institute of Chemistry, Polymer Chemistry, 09107 Chemnitz, Germany   Email: stefan.spange@chemie.tu-chemnitz.de
,
Manuel Heck
a  Technische Universität Chemnitz, Institute of Chemistry, Polymer Chemistry, 09107 Chemnitz, Germany   Email: stefan.spange@chemie.tu-chemnitz.de
,
Mandy Martin
a  Technische Universität Chemnitz, Institute of Chemistry, Polymer Chemistry, 09107 Chemnitz, Germany   Email: stefan.spange@chemie.tu-chemnitz.de
,
Marcus Binner
b  Leibniz Institute of Polymer Research Dresden, Hohe Strasse 6, 01069 Dresden, Germany
,
Tobias Rüffer
c  Technische Universität Chemnitz, Institute of Chemistry, Inorganic Chemistry, 09107 Chemnitz, Germany
,
Susann Anders
d  Technische Universität Chemnitz, Faculty of Mechanical Engineering, Department of Lightweight Structures and Polymer Technology, 09107 Chemnitz, Germany
,
Carsten Werner
b  Leibniz Institute of Polymer Research Dresden, Hohe Strasse 6, 01069 Dresden, Germany
,
Lothar Kroll
d  Technische Universität Chemnitz, Faculty of Mechanical Engineering, Department of Lightweight Structures and Polymer Technology, 09107 Chemnitz, Germany
,
Heinrich Lang
c  Technische Universität Chemnitz, Institute of Chemistry, Inorganic Chemistry, 09107 Chemnitz, Germany
,
Stefan Spange*
a  Technische Universität Chemnitz, Institute of Chemistry, Polymer Chemistry, 09107 Chemnitz, Germany   Email: stefan.spange@chemie.tu-chemnitz.de
› Author Affiliations
Further Information

Publication History

Received: 03 May 2016

Accepted after revision: 22 July 2016

Publication Date:
09 September 2016 (online)


Abstract

The reaction of isocyanates with substituted imidazolines and the thermally induced cleavage of the resulting adducts are presented. For this purpose, reactions of various isocyanates [ethyl isocyanate, p-methylphenyl isocyanate, phenyl isocyanate, p-(trifluoromethyl)phenyl isocyanate] with 1-alkylimidazoline derivatives have been studied as a function of the substituent at the 2-position of the imidazoline ring. Three equivalents of isocyanate react with one equivalent of 1-ethylimidazoline to give a stoichiometric well-defined adduct. However, 1-ethyl-2-isopropylimidazoline reacts with isocyanates at 0 °C in another way, with formation of 2:1 adducts which belong to the family of 1,3-diphenyltetrahydroimidazo[1,2-a][1,3,5]triazine-2,4(1H,3H)-diones. The reaction of 1-ethyl-2-methylimidazoline with aromatic isocyanates at 0 °C also leads to 2:1 adducts, in this case of a malonamide type, which can react at 60 °C with an additional isocyanate equivalent to give the known pyrimidinediones. Thermal analysis (TG-MS/DSC) and trapping reactions with nucleophilic reagents, such as diphenylamine, show the release of isocyanate during the thermally induced cleavage reaction. Thus, blocked isocyanates are available by the reaction of isocyanates with 1-ethylimidazoline or 1-ethyl-2-isopropylimidazoline.

Supporting Information

 
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