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Additionsreaktionen von 3-Dimethylamino-2,2-dimethyl-2H-azirin an Phenylisocyanat und Diphenylketen


Mukherjee-Müller, Gabriele; Heimgartner, Heinz; Schmid, Hans (1979). Additionsreaktionen von 3-Dimethylamino-2,2-dimethyl-2H-azirin an Phenylisocyanat und Diphenylketen. Helvetica Chimica Acta, 62(5):1429-1441.

Abstract

Addition Reaction of 3-Dimethylamino-2,2-dimethyl-2H-azirine with Phenylisocyanate and Diphenylketene : 3-Dimethylamino-2,2-dimethyl-2H-azirine (1a) reacts with carbon disulfide and isothiocyanates with splitting of the azirine N(1),C(3)-double bond to give dipolar, fivemembered heterocyclic 1:1 adducts. In some cases, these products can undergo secondary reactions to yield 1:2 and 1:3 adducts. In this paper it is shown that the reaction of 1a with phenylisocyanate also takes place by cleavage of the N(1),C(3)-bond, whereas with diphenylketene N(1),C(2)-splitting is observed.
The reaction of 1a and phenylisocyanate in hexane at room temperature yields the 1:3 adduct 2 in addition to the trimeric isocyanate 3 (Scheme 1). A mechanism for the formation of 2 is given in Scheme 5. Hydrolysis experiments with the 1:3 adduct 2, yielding the hydantoins 4-6 and the ureas 7 and 8 (Schemes 3 and 5),show that the formation of this adduct via the intermediates d, e and f is a reversible reaction.
The aminoazirines 1a and 1b undergo an addition reaction with diphenylketene to give the 3-oxazolines 14 (Scheme 8), the structure of which has been established by spectral data and oxidative degradation of 14a to the 3-oxazolin-2-one 15 (R1 = R2 = CH3, Scheme 9).

Abstract

Addition Reaction of 3-Dimethylamino-2,2-dimethyl-2H-azirine with Phenylisocyanate and Diphenylketene : 3-Dimethylamino-2,2-dimethyl-2H-azirine (1a) reacts with carbon disulfide and isothiocyanates with splitting of the azirine N(1),C(3)-double bond to give dipolar, fivemembered heterocyclic 1:1 adducts. In some cases, these products can undergo secondary reactions to yield 1:2 and 1:3 adducts. In this paper it is shown that the reaction of 1a with phenylisocyanate also takes place by cleavage of the N(1),C(3)-bond, whereas with diphenylketene N(1),C(2)-splitting is observed.
The reaction of 1a and phenylisocyanate in hexane at room temperature yields the 1:3 adduct 2 in addition to the trimeric isocyanate 3 (Scheme 1). A mechanism for the formation of 2 is given in Scheme 5. Hydrolysis experiments with the 1:3 adduct 2, yielding the hydantoins 4-6 and the ureas 7 and 8 (Schemes 3 and 5),show that the formation of this adduct via the intermediates d, e and f is a reversible reaction.
The aminoazirines 1a and 1b undergo an addition reaction with diphenylketene to give the 3-oxazolines 14 (Scheme 8), the structure of which has been established by spectral data and oxidative degradation of 14a to the 3-oxazolin-2-one 15 (R1 = R2 = CH3, Scheme 9).

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Additional indexing

Item Type:Journal Article, refereed, original work
Communities & Collections:07 Faculty of Science > Department of Chemistry
Dewey Decimal Classification:540 Chemistry
Language:German
Date:1979
Deposited On:12 Aug 2014 16:00
Last Modified:05 Apr 2016 18:00
Publisher:Wiley-Blackwell
ISSN:0018-019X
Funders:Schweizerischer Nationalfonds zur Förderung der wissenschaftlichen Forschung

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