14504-80-4Relevant articles and documents
THE SOLVOLYSIS OF 1- AND 3-HOMOADAMANTYL-P-NITROBENZOATES IN ACETONITRILE-WATER (70:30 by weight)
Mergelsberg, Ingrid,Ruechardt, Christoph
, p. 1809 - 1812 (1982)
The solvolysis rates of t.butyl, 1-adamantyl, 3- and 1-homoadamantyl-p-nitrobenzoates in acetonitrile-water (70:30 by weight) are reported and the relative rates are discussed.These are the first solvolysis constants for 1- or 3-homoadamantyl esters of definitely known structure.
Solvent-equilibrated ion pairs from carbene fragmentation reactions
Moss, Robert A.,Zheng, Fengmei,Fede, Jean-Marie,Johnson, Lauren A.,Sauers, Ronald R.
, p. 12421 - 12431 (2004)
[R+ OC Cl-] ion pairs were generated in methanol/dichloroethane solutions, with R+ as the 1-bicyclo[2.2.2]octyl, 1-adamantyl, or 3-homoadamantyl cation. Ion pairs were produced either by the direct fragmentation of alkoxychlorocarbenes (ROCCl), with R = 1-bicyclo[2.2.2]octyl, 1-adamantyl, or 3-homoadamantyl, or by the ring expansion-fragmentation of R′CH2OCCl, with R′ = 1-norbornyl, 3-noradamantyl, or 1-adamantyl. Correlations of the [ROMe]/[RCl] product ratios as a function of the mole fraction of MeOH in dichloroethane showed that the homoadamantyl chloride ion pairs, produced by either the direct or ring expansion-fragmentations, were identical, solvent- and anion -equilibrated, and precursor independent. Laser flash photolysis experiments gave 20-30 ps as the time required for solvent equilibration and precursor independence. Methanol/chloride selectivities of the (less-stable) 1-adamantyl chloride and 1-bicyclo[2.2.2]octyl chloride ion pairs were not independent of their ROCCl or R′CH2OCCl precursors. Computational studies provided transition states for the fragmentations and for the structures of the ion pairs.
Bridgehead Hydroxylation of Tricycloalkanes with m-Chloroperbenzoic Acid
Takaishi, Naotake,Fujikura, Yoshiaki,Inamoto, Yoshiaki
, p. 293 - 294 (1983)
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Chemoselectivity of Nitroxylation of Cage Hydrocarbons
Ivleva, E. A.,Klimochkin, Yu. N.,Leonova, M. V.
, p. 1702 - 1710 (2020/12/01)
Abstract: The composition of reaction mixtures obtained by nitroxylation of 13 cage hydrocarbons with 100% nitric acid and its mixtures with acetic acid, acetic anhydride, and methylene chloride has been studied. More reactive substrates react with lowest
SYNTHESIS AND HYDROLYTIC TRANSFORMATIONS OF NITROXY DERIVATIVES OF HOMOADAMANTANE PROTOADAMANTANE AND BICYCLONONANE
Klimochkin, Yu. N.,Zhilkina, E. O.,Abramov, O. V.,Moiseev, I. K.
, p. 1126 - 1131 (2007/10/02)
Mono- and dinitroxy derivatives of homoadamantane, protoadamantane, and bicyclononane were synthesized by nitroxylation.A study was carried out on the reactivity of these hydrocarbons relative to nitric acid and the hydrolytic transformations of the products obtained.The acid-catalyzed skeletal rearrangement of 3,6-dinitroxyhomoadamantane to 3-nitroxymethyl-1-adamantanol proceeds with retention of the substituent at the carbon atom, at which the carbenium ion is generated.