41031-51-0Relevant articles and documents
Adamantylation of polysubstituted arenes in trifluoroacetic acid
Sokolenko,Svirskaya,Kondrasenko,Peterson,Pavlenko,Rubaylo
, p. 246 - 248 (2015)
A reaction of 2,3-xylenol, 2,3-dichlorophenol, and 1,3-disubstituted benzenes with 1-adamantanol in trifluoroacetic acid leads to the corresponding monoand diadamantylated products.
Ion-exchange-resin-catalyzed adamantylation of phenol derivatives with adamantanols: Developing a clean process for synthesis of 2-(1-adamantyl)-4- bromophenol, A key intermediate of adapalene
Wang, Nan,Wang, Ronghua,Shi, Xia,Zou, Gang
experimental part, p. 227 - 233 (2012/04/10)
A clean process has been developed for the synthesis of 2-adamantylphenol derivatives through adamantylation of substituted phenols with adamantanols catalyzed by commercially available and recyclable ion-exchange sulfonic acid resin in acetic acid.The sole byproduct of the adamantylation reaction,namely water,could be converted into the solvent acetic acid by addition of a slight excess of acetic anhydride during the work-up procedure,making the process waste-free except for regeneration of the ionexchange resin,and facilitating the recycling of the resin catalyst.The ion-exchange sulfonic acid resin catalyst could be readily recycled by filtration and directly reused at least ten times without a significant loss of activity.The key intermediate of adapalene,2-(1-adamantyl)-4-bromophenol,could be produced by means of this waste-free process.
The structure, photochemical reactivity, and photophysical properties of adamantyl X-substituted aryl ethers and a comparison with the alkyl groups, methyl, tert-butyl, and allyl
Pincock,Pincock
, p. 1237 - 1252 (2007/10/03)
The structure, photophysical properties, and photochemistry of the adamantyl aryl ethers 1 in both methanol and cyclohexane have been examined. UV absorption spectra, 13C NMR chemical shifts, X-ray structures, and Gaussian calculations (B3LYP/6-31G(d)) indicate that these ethers adopt a 90° conformer in the ground state. In contrast, fluorescence spectra, excited singlet state lifetimes, and calculations (TDDFT) indicated a 0° conformer is preferred in the first excited singlet state S1. Irradiation in either solvent results in the formation of adamantane and the corresponding phenol as the major products, both derived from radical intermediates generated by homolytic cleavage of the ether bond. The 4-cyano substituted ether 1j was the only one to form the ion-derived product, 1-methoxyadamantane (16% yield), on irradiation in methanol. Rate constants of bond cleavage for these ethers from S1 were estimated by two different methods by comparison with the unreactive anisoles 2, but the effect of substituents was too small to determine structure-reactivity correlations. The temperature dependence of the quantum yields of the fluorescence of the unsubstituted, 4-methoxy and 4-cyano derivatives of 1 and 2 were also determined. These results indicated that the activated process for 1 was mainly bond cleavage for the 4-cyano substrate whereas for 2, it was internal conversion and intersystem crossing.
