702-79-4Relevant articles and documents
The standard molar enthalpies of formation of some alkyladamantanes
Melkhanova,Pimenova,Kolesov,Pimerzin,Sarkisova
, p. 1311 - 1317 (2000)
The standard massic energies of combustion of three alkyl-derivative of adamantane were measured at T = 298.15 K by static-bomb combustion calorimetry. The standard molar enthal pi es of formation in the liquid and gaseous states were obtained from these data. The enthalpies of some reactions of isomerization were calculated from the equilibrium study and compared with the results of calorimetric measurements.
Synthesis of 1,3-dimethyladamantane by skeletal rearrangement of C 12H18 and C12H20 hydrocarbons over Na/H-Y-zeolite
Khusnutdinov,Kislitsina,Khazipova,Kutepov
, p. 1273 - 1278 (2013)
Granular binder-free Y-zeolite with a degree of Na+/H + ion exchange of 0.97 efficiently catalyzed isomerization of tetracyclo[6.2.1.13,6.02,7]dodecane and (2aR,5aα,8aR,8bα)-dodecahydroacenaphthene (perhydroacenaphthene) to 1,3-dimethyladamantane.
Exhaustive One-Step Bridgehead Methylation of Adamantane Derivatives with Tetramethylsilane
Bonsir, Maxime,Davila, Christian,Geerts, Yves,Kennedy, Alan R.
supporting information, p. 5227 - 5237 (2021/10/19)
A methylation protocol of adamantane derivatives was investigated and optimized using AlCl3 and tetramethylsilane as the methylation agent. Substrates underwent exhaustive methylation of all available bridgehead positions with yields ranging from 62 to 86 %, and up to six methyl groups introduced in one step. Scaling-up of the reaction was demonstrated by performing the >40 gram-scale synthesis of 1,3,5,7-tetramethyladamantane with 62 % yield. For several substrates, rearrangements were observed, as well as cleavage of functional groups or Csp3?Csp2 bonds or even cyclohexyl-adamantyl bonds. Based on mechanistic studies, it is suggested that a reactive methylation complex is formed from tetramethylsilane and AlCl3. X-ray diffraction structures of hexamethylated bis-adamantyls reveal elongation or widening of sp3 carbon bonds between adamantyl moieties to 1.585(3) ? and 125.26(9)° due to repulsive H???H contacts.
Dehydroxymethylation of alcohols enabled by cerium photocatalysis
Zhang, Kaining,Chang, Liang,An, Qing,Wang, Xin,Zuo, Zhiwei
supporting information, p. 10556 - 10564 (2019/08/20)
Dehydroxymethylation, the direct conversion of alcohol feedstocks as alkyl synthons containing one less carbon atom, is an unconventional and underexplored strategy to exploit the ubiquity and robustness of alcohol materials. Under mild and redox-neutral reaction conditions, utilizing inexpensive cerium catalyst, the photocatalytic dehydroxymethylation platform has been furnished. Enabled by ligand-to-metal charge transfer catalysis, an alcohol functionality has been reliably transferred into nucleophilic radicals with the loss of one molecule of formaldehyde. Intriguingly, we found that the dehydroxymethylation process can be significantly promoted by the cerium catalyst, and the stabilization effect of the fragmented radicals also plays a significant role. This operationally simple protocol has enabled the direct utilization of primary alcohols as unconventional alkyl nucleophiles for radical-mediated 1,4-conjugate additions with Michael acceptors. A broad range of alcohols, from simple ethanol to complex nucleosides and steroids, have been successfully applied to this fragment coupling transformation. Furthermore, the modularity of this catalytic system has been demonstrated in diversified radical-mediated transformations including hydrogenation, amination, alkenylation, and oxidation.
A 1,3-dimethyladamantane method for the preparation of
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Paragraph 0008-0010, (2017/03/08)
The invention relates to the field of chemistry, and in particular to a preparation method of 1,3-dimethyladamantane. The preparation method comprises the following steps of: A, by taking perhydroacenaphthene as a raw material, adding aluminum chloride anhydrous as a catalyst, continuously dropping a small amount of water at 80-100 DEG C, and carrying out rearrangement reaction to obtain 1,3-dimethyladamantane reaction liquid; B, removing the aluminum trichloride catalyst to obtain crude 1,3-dimethyladamantane; C, rectifying the crude 1,3-dimethyladamantane obtained in the step B through a rectifying tower to obtain 1,3-dimethyladamantane. The preparation method of 1,3-dimethyladamantane has the advantages of being simple in operation, clean, environment-friendly, high in yield and low in equipment investment.
