Modelling of an aza-Michael reaction from crystalline naphthalene derivatives containing peri–peri interactions: very long N–C bonds?

Bristow, J.C., Naftalin, I., Cliff, S.V.A., Yang, S., Carravetta, M., Heinmaa, I., Stern, R. and Wallis, J.D. ORCID: 0000-0001-7259-8783, 2020. Modelling of an aza-Michael reaction from crystalline naphthalene derivatives containing peri–peri interactions: very long N–C bonds? CrystEngComm. ISSN 1466-8033

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Abstract

The separation between a pair of peri-located dimethylamino and ethene-2,2-dinitrile groups in a naphthalene molecule, which models the progress of a Michael reaction, can be controlled by the installation of a short ethylene bridge or the introduction of repulsive interactions at the opposite set of peri positions. Introduction of a dimethylammonium substituent produced a hydrated chloride salt in which the Me2N⋯C(H)[double bond, length as m-dash]C(CN)2 separation between reactive groups decreases, reversibly, from 2.167 Å at 200 K to 1.749 Å at 100 K, with the maximum rate of change in the range 128–140 K, which was studied by variable temperature X-ray crystallography and solid state NMR. From these and other crystallographic data a correlation between Me2N⋯C bond formation and alkene bond breaking was constructed for the first step of an aza-Michael reaction.

Item Type: Journal article
Publication Title: CrystEngComm
Creators: Bristow, J.C., Naftalin, I., Cliff, S.V.A., Yang, S., Carravetta, M., Heinmaa, I., Stern, R. and Wallis, J.D.
Publisher: Royal Society of Chemistry (RSC)
Date: 17 September 2020
ISSN: 1466-8033
Identifiers:
NumberType
10.1039/d0ce01137aDOI
1371342Other
Rights: This journal is © The Royal Society of Chemistry 2020. Open Access Article. Published on 17 September 2020. Downloaded on 9/30/2020 1:39:26 PM. This article is licensed under a Creative Commons Attribution-NonCommercial 3.0 Unported Licence.
Divisions: Schools > School of Science and Technology
Record created by: Linda Sullivan
Date Added: 02 Oct 2020 10:07
Last Modified: 02 Oct 2020 10:07
URI: http://irep.ntu.ac.uk/id/eprint/41100

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