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Ringerweiterungen und Ringverengungen bei der Umsetzung von 1,3- Oxazolidin-2,4-dionen und 1,3-Thiazolidin-2,4-dion mit 3-Amino-2H-azirinen


Ametamey, Simon M; Heimgartner, Heinz (1990). Ringerweiterungen und Ringverengungen bei der Umsetzung von 1,3- Oxazolidin-2,4-dionen und 1,3-Thiazolidin-2,4-dion mit 3-Amino-2H-azirinen. Helvetica Chimica Acta, 73(5):1314-1328.

Abstract

The reaction of 3-amino-2H-azirines 1 and 1,3-oxazolidine-2,4-diones 2 in MeCN at room temperature leads to 3,4-dihydro-3-(2-hydroxyacetyl)-2H-imidazol-2-ones 3 in good yield (Scheme 2, Table I). A reaction mechanism proceeding via ring enlargement of the bicyclic zwitterion A to give B, followed by transannular ring contraction to C, is proposed for the formation of 3. This mechanism is in accordance with the result of the reaction of 2a and the 15N-labelled 1a*: in the isolated product 3a*, only N(3) is labelled (Scheme 2). The analogous reaction of 1 and 1,3-thiazolidine-2,4-dione (5) is more complex (Schemes 4 and 5,Table 2). Besides the expected 3,4-dihydro-3-(2-mercaptoacetyl)-2H-imidazol-2-ones 7, 5-amino-3,4-dihydro-2H-imidazol-2-ones of type 8 and/or N-(1,4-thiazin-2-ylidene)ureas 9 are formed. In the case of 2-(dimethylamino)-1- azaspiro[2.3]hex-1-ene (1d), the postulated eight-membered intermediate 6d could be isolated. Its structure as well as that of 9f has been determined by X-ray structure analysis. A reaction mechanism for the formation of
the 1,4-thiazine derivatives of type 9 is proposed in Scheme 6.

Abstract

The reaction of 3-amino-2H-azirines 1 and 1,3-oxazolidine-2,4-diones 2 in MeCN at room temperature leads to 3,4-dihydro-3-(2-hydroxyacetyl)-2H-imidazol-2-ones 3 in good yield (Scheme 2, Table I). A reaction mechanism proceeding via ring enlargement of the bicyclic zwitterion A to give B, followed by transannular ring contraction to C, is proposed for the formation of 3. This mechanism is in accordance with the result of the reaction of 2a and the 15N-labelled 1a*: in the isolated product 3a*, only N(3) is labelled (Scheme 2). The analogous reaction of 1 and 1,3-thiazolidine-2,4-dione (5) is more complex (Schemes 4 and 5,Table 2). Besides the expected 3,4-dihydro-3-(2-mercaptoacetyl)-2H-imidazol-2-ones 7, 5-amino-3,4-dihydro-2H-imidazol-2-ones of type 8 and/or N-(1,4-thiazin-2-ylidene)ureas 9 are formed. In the case of 2-(dimethylamino)-1- azaspiro[2.3]hex-1-ene (1d), the postulated eight-membered intermediate 6d could be isolated. Its structure as well as that of 9f has been determined by X-ray structure analysis. A reaction mechanism for the formation of
the 1,4-thiazine derivatives of type 9 is proposed in Scheme 6.

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Additional indexing

Other titles:Ring Enlargements and Ring Contractions in the Reaction of 1,3-Oxazolidine-2,4-diones and 1,3-Thiazolidine-2,4-dione with 3-Amino-2H-azirines
Item Type:Journal Article, refereed, original work
Communities & Collections:07 Faculty of Science > Department of Chemistry
Dewey Decimal Classification:540 Chemistry
Language:German
Date:1990
Deposited On:27 Mar 2014 15:30
Last Modified:05 Apr 2016 17:46
Publisher:Wiley-Blackwell
ISSN:0018-019X
Funders:Schweizerischer Nationalfonds zur Förderung der wissenschaftlichen Forschung, F. Hoffmann-La Roche AG, Basel, Prof. Hans-E.-Schmid-Stiftung
Publisher DOI:https://doi.org/10.1002/hlca.19900730520

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