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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)[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.
1466-8033
1-13
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), 1-13. (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)[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.

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Accepted/In Press date: 16 September 2020
e-pub ahead of print date: 17 September 2020

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

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Date deposited: 14 Oct 2020 16:30
Last modified: 28 Apr 2022 01:50

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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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