The University of Southampton
University of Southampton Institutional Repository

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

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

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)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. This journal is

1466-8033
6783-6795
Bristow, Jonathan C.
38d2a00e-cd93-464a-b623-53a0478a525a
Naftalin, Isaac
2b289276-75f0-43f7-860d-24bf376fe54a
Cliff, Stacey V. A.
621377b4-2310-471d-b797-f654bd6582ef
Yang, Songjie
00d7824a-8943-40f9-8f88-e9d4c800cfd0
Carravetta, Marina
1b12fa96-4a6a-4689-ab3b-ccc68f1d7691
Heinmaa, Ivo
fd7cd386-fb1b-4b8a-a46f-de54c48ef4da
Stern, Raivo
a9db816e-bdfb-4cb1-a8d6-eb4d6f66da40
Wallis, John D.
bc777046-08c0-40bf-9cfd-3a69481bb06a
Bristow, Jonathan C.
38d2a00e-cd93-464a-b623-53a0478a525a
Naftalin, Isaac
2b289276-75f0-43f7-860d-24bf376fe54a
Cliff, Stacey V. A.
621377b4-2310-471d-b797-f654bd6582ef
Yang, Songjie
00d7824a-8943-40f9-8f88-e9d4c800cfd0
Carravetta, Marina
1b12fa96-4a6a-4689-ab3b-ccc68f1d7691
Heinmaa, Ivo
fd7cd386-fb1b-4b8a-a46f-de54c48ef4da
Stern, Raivo
a9db816e-bdfb-4cb1-a8d6-eb4d6f66da40
Wallis, John D.
bc777046-08c0-40bf-9cfd-3a69481bb06a

Bristow, Jonathan C., Naftalin, Isaac, Cliff, Stacey V. A., Yang, Songjie, Carravetta, Marina, Heinmaa, Ivo, Stern, Raivo and Wallis, John D. (2020) Modelling of an aza-Michael reaction from crystalline naphthalene derivatives containing peri–peri interactions: very long N–C bonds? CrystEngComm, 22 (41), 6783-6795. (doi:10.1039/D0CE01137A).

Record type: Article

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)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. This journal is

Text
WALLIS MAIN ARTICLE FINAL MOD E_ - Accepted Manuscript
Download (907kB)
Text
Supplementary WALLIS ESI FINAL MOD A
Download (1MB)

More information

Accepted/In Press date: 16 September 2020
e-pub ahead of print date: 17 September 2020
Published date: 7 November 2020
Additional Information: Funding Information: We thank Nottingham Trent University for a studentship (JCB) and for financial support for materials. We wish to thank Dr Tõnis Pehk for additional assignment of the solution NMR resonances. I. H. and R. S. were supported by the European Regional Development Fund (Grant No. TK134), and by the Estonian Research Council (PRG4, IUT23-7). Publisher Copyright: © The Royal Society of Chemistry.

Identifiers

Local EPrints ID: 444362
URI: http://eprints.soton.ac.uk/id/eprint/444362
ISSN: 1466-8033
PURE UUID: 61cee38e-c4d7-4b21-9562-df3605b61c5f
ORCID for Marina Carravetta: ORCID iD orcid.org/0000-0002-6296-2104

Catalogue record

Date deposited: 14 Oct 2020 16:30
Last modified: 06 Jun 2024 01:41

Export record

Altmetrics

Contributors

Author: Jonathan C. Bristow
Author: Isaac Naftalin
Author: Stacey V. A. Cliff
Author: Songjie Yang
Author: Ivo Heinmaa
Author: Raivo Stern
Author: John D. Wallis

Download statistics

Downloads from ePrints over the past year. Other digital versions may also be available to download e.g. from the publisher's website.

View more statistics

Atom RSS 1.0 RSS 2.0

Contact ePrints Soton: eprints@soton.ac.uk

ePrints Soton supports OAI 2.0 with a base URL of http://eprints.soton.ac.uk/cgi/oai2

This repository has been built using EPrints software, developed at the University of Southampton, but available to everyone to use.

We use cookies to ensure that we give you the best experience on our website. If you continue without changing your settings, we will assume that you are happy to receive cookies on the University of Southampton website.

×