53329-08-1Relevant academic research and scientific papers
Charge-Transfer Band of 7-Norbornenone. Circular Dichroism of (1R)-2-Deuteriobicyclohept-2-en-7-one and (1R)-2-Methylbicyclohept-2-en-7-one
Lightner, David A.,Gawronski, Jacek K.,Hansen, Aage E.,Bouman, Thomas D.
, p. 4291 - 4297 (1981)
(1R)-2H>Bicyclohept-2-en-7-one (1), bicyclohept-2-en-7-one (7-norbornenone) (2), and (1R)-2-methylbicyclohept-2-en-7-one (3) were prepared from (1R)-7,7-dimethoxybicycloheptan-2-one p-toluenesulfonylhydrazone of known absolute configuration and optical purity.Circular dichroism spectra of deuterio ketone 1 (Δε273max-0.033, δε224max-0.028, and Δε213max+0.029) and methyl ketone 3 (Δε275max-0.62, Δε226max+2.10, and Δε208max-3.0) confirm the existence of a new low-lying electronic transition near 225 nm whose existence and origin have been questioned during the past 20 years.The partial charge-transfer nature of this band is supported by preliminary calculations in the localized orbital random phase approximation.
The Octant Rule. 7. Deuterium as an Octant Pertuber
Lightner, David A.,Gawronski, Jacek K.,Bouman, Thomas D.
, p. 1983 - 1990 (2007/10/02)
(1S)-exo-2-Deuteriobicycloheptan-7-one (1) and (1S)-endo-2-deuteriobicycloheptan-7-one (2) were synthesized, and their circular dichroism spectra were measured and analyzed.Both ketones show dissignate Cotton effects near 295 nm corresponding to their n-?* electronic transitions: 1 (Δε296 = +0.033) and 2 (Δε292 = +0.132).The nature of the isotopic perturbation on the n-?* transitions of 1 and 2, related β-deuterioadamantanones and cyclohexanones, and α-deuteriocyclohexanones is treated theoretically.The net contribution to the sign of the rotatory strength is determined by the relatively more consignate contribution on the C-H bond that is located in an oppositely signed octant relative to the C-D bond.
