KNORR, R and HOANG, TP and MEHLSTAUBL, J and HINTERMEYERHILPERT, M and LUDEMANN, HD and LANG, E and SEXTL, G and RATTAY, W and BOHRER, P (1993) STERICALLY CONGESTED MOLECULES .6. LONE ELECTRON PAIR DONOR QUALITY OF THE IMINO FUNCTION - INCREASED FRONT STRAIN AND ELECTRONIC SUBSTITUENT EFFECTS ON STERICALLY ACCELERATED NITROGEN INVERSION IN IMINOCYCLOPENTANES. CHEMISCHE BERICHTE-RECUEIL, 126 (1). pp. 217-224. ISSN 0009-2940,
Full text not available from this repository.Abstract
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 sigma(p)- correlation (rho = +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 pi donor quality of the imino group corresponds to ca. 55 (+/- 8) % of p(pi) character as evaluated by spectral (C-13 NMR of 5 and 13, IR of 13) and reactivity data (of 13).
| Item Type: | Article |
|---|---|
| Uncontrolled Keywords: | C-13 CHEMICAL-SHIFTS; COUPLING-CONSTANTS; RESONANCE; CONFIGURATION; ISOMERIZATION; SPECTROSCOPY; ANIONS; SALTS; N-15; IMINES; STERIC ACCELERATION; SUBSTITUENT CONSTANTS; SUBSTITUENT EFFECTS |
| Depositing User: | Dr. Gernot Deinzer |
| Last Modified: | 19 Oct 2022 08:43 |
| URI: | https://pred.uni-regensburg.de/id/eprint/54173 |
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