The pKa of 2-, 3-and 4-substituted quinuclidinium perchlorates and the solvolysis rates of the corresponding bicyclo[2.2.2loctyl-l-pnitrobenzenesulfonates reveal the dispersal of charge in ammonium ions and carbocations. Recent studies1 have shown that the solvolysis rates (log k) of several substi
Charge dispersal in 1- and 2-adamantyl cations
β Scribed by Cyril A. Grob; Guangyi Wang; Chengxi Yang
- Publisher
- Elsevier Science
- Year
- 1987
- Tongue
- French
- Weight
- 212 KB
- Volume
- 28
- Category
- Article
- ISSN
- 0040-4039
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β¦ Synopsis
Substituents at the remoter 5-position of 2-adamantyl arylsulfonates control solvolysis rates more strongly than substituents at the 4-position.
π SIMILAR VOLUMES
Standard deviations of the pK,, upon which n? values are based, and of the conductometric rate measurements, as well uncertainties regarding the orientation of dipolar substituents, contribute to this limitation, as in most Hammett treatments. The I3C-NMR signals for the a-, /3-, and r-C-atoms in th
When both diastereomers of [5-D]-2-methyl-2-adamantyl 2-01s (19a, b) were obtained. The stereoselectivity of secon-2,4-dinitrophenolate (18a) and [5-D]-2-phenyl-2-adamantyl dary 2-adamantyl cations, attributed to cr participation, is ef-2,4-&nitrophenolate (18b) were solvolyzed in 40% aqueous fectiv
The persistence of alkyl substituted cyclobutadiene radical cations strongly depends on the method of generation and the size of the alkyl substituents used. Hindered rotation, the consequence of bulky substituents, is observed in the title compounds. Cyclobutadiene radical cations are transient spe