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
6783-6795
Bristow, Jonathan C.
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Naftalin, Isaac
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Cliff, Stacey V. A.
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Yang, Songjie
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Carravetta, Marina
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Heinmaa, Ivo
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Stern, Raivo
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Wallis, John D.
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7 November 2020
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), .
(doi:10.1039/D0CE01137A).
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
Text
Supplementary WALLIS ESI FINAL MOD A
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
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Date deposited: 14 Oct 2020 16:30
Last modified: 06 Jun 2024 01:41
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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
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