Issue 41, 2020
From the journal:

CrystEngComm

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

Jonathan C. Bristow,a   Isaac Naftalin,a   Stacey V. A. Cliff,a   Songjie Yang,a   Marina Carravetta, ORCID logo b   Ivo Heinmaa,c   Raivo Stern ORCID logo c  and  John D. Wallis ORCID logo *a  

* Corresponding authors

a School of Science and Technology, Nottingham Trent University, Clifton Lane, Nottingham NG11 8NS, UK
E-mail: john.wallis@ntu.ac.uk

b School of Chemistry, University of Southampton, Highfield, Southampton, UK

c Laboratory of Chemical Physics, National Institute of Chemical Physics and Biophysics, Tallinn, Estonia

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.

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

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Article information

DOI
https://doi.org/10.1039/D0CE01137A
Article type
Paper
Submitted
04 Aug 2020
Accepted
16 Sep 2020
First published
17 Sep 2020
This article is Open Access
Creative Commons BY-NC license

CrystEngComm, 2020,22, 6783-6795

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

J. C. Bristow, I. Naftalin, S. V. A. Cliff, S. Yang, M. Carravetta, I. Heinmaa, R. Stern and J. D. Wallis, CrystEngComm, 2020, 22, 6783 DOI: 10.1039/D0CE01137A

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