ISSN:
0009-2940
Keywords:
Imines
;
Steric acceleration
;
Substituent constants
;
Substituent effects
;
Chemistry
;
Inorganic Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
The p-substituents of 2,6-dimethyl-N-(2,2,5,5-tetramethylcyclopentylidene)anilines are modified without interfering reactions at the CN double bond. The resultant series (5 - 8, 10 - 19) shows a strong (ca. - 4.7 kcal/mol) steric acceleration of (E/Z) diastereotopomerization by front strain along the CN double bond but also the usual electronic substituent dependence, characterized by a Hammett s̰p- correlation (Q = +2.7). Conversely, the substituent constant for lithium at the p-position of 7 may be estimated. The volume of activation is 1.5(8) cm3 mol-1 for 5. The π donor quality of the imino group corresponds to ca. 55 (±8)% of Pπ character as evaluated by spectral (13C NMR of 5 and 13, IR of 13) and reactivity data (of 13).
Additional Material:
2 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/cber.19931260130
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