ISSN:
0030-4921
Keywords:
Chemistry
;
Analytical Chemistry and Spectroscopy
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
Carbon-13 n.m.r. data have been determined for a series of 26 aromatic carbonyl compounds including benzoyl, naphthoyl and pyrenoyl derivatives 13C labelled in the carbonyl group. Doubly labelled anthraquinone has also been included. The compounds investigated comprise non-hindered molecules and molecules in which the carbonyl substituent is subject to ortho- or peri-interactions affecting conjugation of the carbonyl group with the aromatic ring. The dependence of long range 13C,13C coupling constants involving the carbonyl carbon, in particular 2J and 3J, on steric conditions is discussed, as is the possibility of deciding on the orientation of the carbonyl bond. The following results have emerged. 2J(s-t)〉2J(s-c) for ketones and aldehydes, and the reverse is valid for acids and acid derivatives. (s-t and s-c refer to the orientation of the C=O group relative to the aromatic bond in question with respect to the connecting single bond). For ketones 3J(t,s-c)〈3J(t,s-t), and both of these 3J(t) values decrease with increasing angle of twist, θ, about the single bond, whereas 3J(c,s-c) increases with θ. For acids and acid derivatives no similar regularity was found. (The initial t and c refer to the geometry of the three-bond coupling path). Generally it is found that 3J(t)〉3J(c) and 3J(t)〉2J, confirming earlier results. Theoretical calculations on a few model compounds are qualitatively in accordance with the experimental results. Some sign determinations for coupling constants are presented. A short discussion is given of substituent effects on chemical shifts. Observed trends are consistent with earlier results.
Additional Material:
1 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/mrc.1270091109
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