Reactions of 1,3-dehydroadamantane with inorganic oxygen-free acids

Abstract

A convenient and efficient procedure has been developed for the synthesis of 1-azidoadamantane, 1-adamantyl isocyanate, and 1-adamantyl isothiocyanate by reaction of 1,3-dehydroadamantane with hydrazoic, isocyanic, and isothiocyanic acids, respectively, under mild conditions. The reaction of 1,3-dehydroadamantane with hydrogen cyanide under analogous conditions gives adamantane-1-carbonitrile in a poor yield which may be improved using hexane as solvent.

Effects of adamantane alterations on soluble epoxide hydrolase inhibition potency, physical properties and metabolic stability

“…Introduction of spacers between adamantane and functional groups also decreases melting points. For example, 1-isocyanatoadamantane melting point is 143–144 °C 27 while 1-isocyanatomethyladamantane is a liquid compound. As predicted, compounds 1–7 appear as liquids and compound 9 has very low melting point of 29–30 °C.…”

1,3-Disubstituted and 1,3,3-trisubstituted adamantyl-ureas with isoxazole as soluble epoxide hydrolase inhibitors

“…23 For example, ureas synthesized with amino-pyridazines, pyridines, pyrimidines, triazines, oxazoles and thiazoles containing amino groups showed high potency against epoxide hydrolases from Mycobacterium tuberculosis . 24 Thus, here as a continuation of previous work 25,26 we report the testing of adamantyl-ureas containing isoxazoles, however we also tested the hypothesis that nodal substitution on the adamantane will help solubilize and stabilize the resulting compounds because for adamantane containing urea inhibitors hydroxylation of nodal carbon is important metabolic pathway leading to a decrease of inhibitory potency.…”

N-Substituted S-Alkyl Carbamothioates in the Synthesis of Nitrogen-containing Functional Derivatives of the Adamantane Series

“…Most of the methods for the preparation of adamantan-1-yl isocyanate include the aforementioned treatment of 1-aminoadamantane hydrochloride with phosgene [ 26 , 27 ] or triphosgene [ 28 ] and the implementation of Curtius rearrangement [ 29 ], including with the preliminary preparation of 1-azidoadamantane from adamantane-1-carboxylic acid [ 13 , 30 ] or its acid chloride [ 31 – 35 ]. Alternative synthetic approaches to adamantan-1-yl isocyanate involve the cleavage of 1,3-dehydroadamantane in sulfuric acid in the presence of sodium cyanate [ 36 ], the reaction of 1-bromoadamantane with the silver salt of nitrocyanamide [ 37 ], and thermolysis of 2-(adamantan-1-yl)-5-methyl-1,3-oxothiolane [ 38 ].…”