Secondary deuterium isotope effects for addition of nitrogen nucleophiles to substituted benzaldehydes
β Scribed by Do Amaral, Luciano.; Bastos, M. P.; Bull, H. G.; Cordes, E. H.
- Book ID
- 126324890
- Publisher
- American Chemical Society
- Year
- 1973
- Tongue
- English
- Weight
- 812 KB
- Volume
- 95
- Category
- Article
- ISSN
- 0002-7863
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π SIMILAR VOLUMES
Electrophilic additions to allene interestingly proceed with orientations for addition which are very much dependent upon the nature of the electrophile. 2 Additions involving a proton as the reactive electrophile, for example, proceed with almost exclusive attack at the
## Abstract Deuteriumβinduced isotope effects on ^13^C chemical shifts and ^1^__J__(^13^CβΞ±, ^1^H) coupling constants in benzaldehyde were measured. Over 30 different effects on ^13^C chemical shifts were revealed. The effects through one (^1^Ξ) and two bonds (^2^Ξ) have mean values of 282.1 Β± 9.6
Sumnary: Addition of phenyl radical to benzyl isocyanides gives benzonitrile and benzyl radicals, exhibiting positive Hamnett p=O.26 and notable secondary a-deuterium kinetic isotope effects. These can be rationalized by concerted bond formation/cleavage occurring with polar transition states(TS).