Theory and Practice of the Preparation of Adamantylarenes

Таразанов, С. В.; Shakun, V. A.; Nesterova, T. N.; Sarkisova, V. S.; Naumkin, P. V.; Nesterov, I. A.; Repina, O. V.

doi:10.1134/s0965544118100171

Cited by 3 publications

(1 citation statement)

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“…Due to the great importance of both carbocyclic and heterocyclic systems functionalized with the adamantyl group [27], different types of adamantylation reactions ( C -, N -, or O -adamantylation) attract attention, and typically 1,3-dehydroadamantane [28] or 1-haloadamantanes [29] are applied as alkylating reagents. Adamantan-1-yl carboxylates are also known as efficient adamantylating reagents [30].…”

Section: Resultsmentioning

confidence: 99%

Synthesis and selected transformations of 2-unsubstituted 1-(adamantyloxy)imidazole 3-oxides: straightforward access to non-symmetric 1,3-dialkoxyimidazolium salts

Mlostoń¹,

Celeda²,

Urbaniak³

et al. 2019

Beilstein J. Org. Chem.

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Adamantyloxyamine reacts with formaldehyde to give N-(adamantyloxy)formaldimine as a room-temperature-stable compound that exists in solution in monomeric form. This product was used for reactions with α-hydroxyiminoketones leading to a new class of 2-unsubstituted imidazole 3-oxides bearing the adamantyloxy substituent at N(1). Their reactions with 2,2,4,4-tetramethylcyclobutane-1,3-dithione or with acetic acid anhydride occurred analogously to those of 1-alkylimidazole 3-oxides to give imidazol-2-thiones and imidazol-2-ones, respectively. Treatment of 1-(adamantyloxy)imidazole 3-oxides with Raney-Ni afforded the corresponding imidazole derivatives without cleavage of the N(1)–O bond. Finally, the O-alkylation reactions of the new imidazole N-oxides with 1-bromopentane or 1-bromododecane open access to diversely substituted, non-symmetric 1,3-dialkoxyimidazolium salts. Adamantyloxyamine reacts with glyoxal and formaldehyde in the presence of hydrobromic acid yielding symmetric 1,3-di(adamantyloxy)-1H-imidazolium bromide in good yield. Deprotonation of the latter with triethylamine in the presence of elemental sulfur allows the in situ generation of the corresponding imidazol-2-ylidene, which traps elemental sulfur yielding a 1,3-dihydro-2H-imidazole-2-thione as the final product.

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Section: Resultsmentioning

confidence: 99%