768-95-6Relevant articles and documents
Thermochemistry of Bridged-ring Substances. Enthalpies of Formation of Diamantan-1-, -3-, and -4-ol and of Diamantanone
Clark, Timothy,Knox, Trevor McO.,McKervey, M. Anthony,Mackle, Henry
, p. 1686 - 1689 (1980)
The enthalpies of combustion and of sublimation four mono-oxygenated diamantanes have been determined.The derived solid and gas-phase enthalpies of formation in kcal mol-1 at 298.15 K follow: diamantanone, -81.16+/-0.38, -56.53+/-0.41; diamantan-1-ol, -102.49+/-0.24, -74.30+/-0.28; diamantan-3-ol, -98.89+/-0.35, -71.14+/-1.10; diamantan-4-ol, -103.96+/-0.39, -75.80+/-0.39.Oxo and hydroxy group increments within the diamantane, adamantane, and cyclohexane series are discussed.Enthalpy differences betveen the isomeric diamantanols are compared with existing data from equilibration studies in solution.Comparisons are made between the experimental gas-phase enthalpies of formation and those obtained by molecular mechanics (empirical force field) calculations based on the Allinger MM1 force field model.
Nitronium mediated functionalization of adamantane and its derivatives
Duddu, Rajagopal,Damavarapu, Reddy
, p. 3495 - 3501 (1996)
Functionalization of adamantane and its derivatives using claycop and nitronium trifluoromethanesulfonate is described.
REACTION OF HALOADAMANTANES WITH SALTS OF NITRO COMPOUNDS
Luk'yanov, O. A.,Savost'yanova, I. A.,Gorelik, V. P.,Shlykova, N. I.,Tartakovskii, V. A.
, p. 1395 - 1399 (1992)
Silver and mercury salts of nitro compounds react with bromo- or chloroadamantanes with the formation of products of C- and/or O-alkylation, the ratio of which depends on the structure of the initial reactants.The direct experimental evidence of nitronic esters to be isomerized into nitro derivatives and of their role as intermediates in the formation of the nitro derivatives in the alkylation of nitro compounds has been presented for the first time.Keywords: haloadamantanes, trinitromethyladamantanes, nitronic esters,alkylation, isomerization.
Site-isolated porphyrin catalysts in imprinted polymers
Burri, Estelle,Oehm, Margarita,Daguenet, Corinne,Severin, Kay
, p. 5055 - 5061 (2005)
A meso-tetraaryl ruthenium porphyrin complex having four polymerizable vinylbenzoxy groups (2) has been synthesized by reaction of pyrrole with 4-(vinylbenzoxy)benzaldehyde and subsequent metalation with [Ru 3(CO)12]. The porphyrin complex was immobilized by copolymerization with ethylene glycol dimethacrylate. The resulting polymer P2 was found to catalyze the oxidation of alcohols and alkanes with 2,6-dichloropyridine N-oxide without activation by mineral acids. Under similar conditions, the homogeneous catalyst 2 was completely inefficient. By using diphenylaminomethane and 1-aminoadamantane as coordinatively bound templates during the polymerization procedure, the molecularly imprinted polymers P3 and P4 have been synthesized. Compared with the polymer P2, the imprinted catalysts displayed a significantly increased activity with rate enhancements of up to a factor of 16.
Foiled conjugation in α-oximino carbocations
Creary, Xavier,Jiang, Ziqi
, p. 3482 - 3489 (1996)
The 4-CHNOCH3 group is a cation-stabilizing group when placed in the para-position of a cumyl cation. The effect of this group on cumyl cations when flanked by adjacent methyl groups has now been determined. Solvolysis rates of 3,5-(CH3)2-4-(CHNOCH3)cumyl trifluoroacetates are somewhat slower than that of 3,5-dimethylcumyl trifluoroacetate. This is attributed to steric inhibition of the cation-stabilizing resonance effect of the p-oximino group. In a 1-adamantyl system, where an α-oximino group has been placed directly adjacent to a developing cationic center, solvolysis rates relative to 1-adamantyl mesylate are slowed by a factor of 108. This is attributed a cation-destabilizing inductive effect where geometric constraints prevent stabilizing orbital overlap of the cationic center with the adjacent α-oximino group. This cation-destabilizing effect fades in the homoadamantyl and the bicyclo[3.3.1]nonyl systems, where rate-retarding effects are 1.6 × 104 and 1.5 × 102, respectively. The behavior of geometrically constrained α-oximino cations parallels that of analogously constrained allylic cations. Computational studies at the HF/6-31G* level indicate that twisting the α-oximino group out of planarity with a tertiary cationic center into a perpendicular arrangement decreases stabilization by 21 kcal/mol. These studies suggest that conjugative interactions, and not ground state destabilization, are the most important factors in controlling rates of formation of α-oximino cations from mesylates and trifluoroacetates.
Preparative aerobic oxidations with basidiomycetous enzymes: CH-functionalization of adamantane
Zhuk, Tatyana S.,Goldmann, Michael,Hofmann, Julia,Pohl, Juliane C.S.,Zorn, Holger
, p. 87 - 92 (2015)
The potential of basidiomycetous enzymes for selective alkane CH-functionalizations in aqueous media has been disclosed utilizing surface and submerged cultures. A screening displayed the high catalytic activity of Dichomitus albidofuscus, Pholiota squarrosa, and Abortiporus biennis in aerobic oxidations of adamantane as a model hydrocarbon. With isopropanol as a co-solvent, the oxidation was accelerated significantly without changes of the fungal growth. 1-Adamantanol was obtained in 40% preparative yield from the oxidation of adamantane by D. albidofuscus. The CH-positional selectivity (3°/2°= 3.6) and the deuterium kinetic isotopic effect (kH/kD = 2.25) values provide evidence for the participation of fungal metalloenzymes in the CH-activation step.
Oxidation of organic compounds by ozone on a surface: 1. Ozonization of adamantane on silica gel
Avzyanova,Kabal'nova,Shereshovets
, p. 360 - 362 (1996)
Adamantanol was obtained by the ozonization of adamantane, at -78°C, adsorbed on silica gel. Ozone does not decompose on silica gel in the absence of a substrate. Ozonization of adamantane on silica gel is accompanied by chemiluminescence in the IR region. The chemiluminescence quenching is of first-order with the effective rate constant k′. In the range from 0.4 to 5 mmol, k′ depends linearly on the amount of adamantane adsorbed on the silica gel. The activation energy Ea = 9.97±1.89 kcal mol-1 and the pre-exponential factor A = (2.76±0.52)·106 were calculated from the temperature dependence of k′.
Aprotic diazotization of endo-7-aminomethylbicyclo[3,3,1]nonan-3-one
Liu, Jih-Hua,Kovacic, Peter
, p. 564a (1972)
Aprotic diazotization of endo-7-aminomethylbicyclo[3,3,1]nonan-3-one yields protoadamantan-4-one and 3-methylbicyclo[3,3,1]non-2-en-7-one; the latter was converted into adamantan-1-ol on catalytic hydrogenation with Pd-C.
Dissociative electron transfer to dihaloalkanes. electrochemical reduction of 1,3-dihaloadamantanes, 1,4-dihalobicyclo[2.2.2]octanes, and 1,3-dihalobicyclo[1.1.1]pentanes
Adcock, William,Clark, Christopher I.,Houmam, Abdelaziz,Krstic, Alexander R.,Pinson, Jean,Savéant, Jean-Michel,Taylor, Dennis K.,Taylor, Julian F.
, p. 4653 - 4659 (1994)
The electrochemical reductive cleavage of the title compounds was investigated by means of cyclic voltammetry and electrolysis. The reaction is a two-electron process that yields competitively ring closure (or fragmentation) products and the monohalide resulting from the expulsion of the best leaving halide ion. Product selection occurs at the level of the carbanion resulting from the reduction of the one-electron reductive cleavage radical. In the formation of the latter, electron transfer and bond breaking are concerted; thus, the anion radical is not involved as an intermediate. The variations in the reduction potential observed in the three series of compounds can be rationalized, by application of the dissociative electron-transfer theory, as related variations of the bond dissociation energy of the first carbon-halogen bond to be cleaved. In the adamantane and bicyclopentane series, these are mainly the result of through-space-bonded interactions in the one-electron reductive cleavage radical and, to a lesser extent, in the starting dihalide itself, while through-bond interactions appear to prevail in the bicyclooctane series.
Reverse reactivity in hydroxylation of adamantane and epoxidation of cyclohexene catalyzed by the mononuclear ruthenium-oxo complexes with 6-substituted tripodal polypyridine ligands
Jitsukawa, Koichiro,Oka, Yoshiyuki,Einaga, Hisahiko,Masuda, Hideki
, p. 3467 - 3469 (2001)
The electronic character of the ruthenium complexes with tripodal polypyridine ligands, which is controlled by the substituted groups at pyridine 6-position, gives rise to differences in the reactivity for the ruthenium catalyzed hydroxylation of adamantane and epoxidation of cyclohexene with PhIO as an oxidant; Ru complexes containing electron-withdrawing groups (1, 3, and 5) promote the epoxidation, while those containing electron-donating groups (2, 4, and 6) promote the hydroxylation.
