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A 13 C and 1 H NMR study of the geometries of the 1,3‐dicyanoallyl anion: Thermal and photochemical interconversion
Author(s) -
Boate D. R.,
Hunter D. H.
Publication year - 1984
Publication title -
organic magnetic resonance
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.483
H-Index - 72
eISSN - 1097-458X
pISSN - 0030-4921
DOI - 10.1002/mrc.1270220307
Subject(s) - sodium hydride , chemistry , ion , tetrahydrofuran , hydride , sodium , irradiation , sodium salt , salt (chemistry) , medicinal chemistry , inorganic chemistry , organic chemistry , hydrogen , physics , nuclear physics , solvent
Glutacononitrile (1,3‐dicyanopropene) (2) was converted to its anion (1) by treatment with sodium hydride in tetrahydrofuran. Both 13 C and 1 NMR showed that the sodium salt of 1 in THF existed in three slowly interconverting geometries (U, W and S). These geometries were present in similar amounts but the relative amounts of each proved to be concentration dependent. Irradiation of a 0.01 M solution of 1 at −80°C led to the conversion of a mixture of the U, W and S forms of 1 to only the W and S forms. Upon warming to 0°C equilibrium was re‐established with a half‐life of approximately 8 h.