Synthesis of 3,5-Bis(hydroxymethyl)adamantan-1-ols and 3,5-Bis(nitrooxymethyl)adamantan-1-yl Nitrates
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hesis of 3,5-Bis(hydroxymethyl)adamantan-1-ols and 3,5-Bis(nitrooxymethyl)adamantan-1-yl Nitrates E. A. Ivlevaa,*, A. I. Kazakovaa, and Yu. N. Klimochkina a
Samara State Technical University, Samara, 443100 Russia *e-mail: [email protected]
Received April 27, 2020; revised May 1, 2020; accepted May 14, 2020
Abstract—A convenient method has been developed for the synthesis of 3,5-bis(hydroxymethyl)adamantan-1ols via successive nitroxylation of 1,3-bis(acetoxymethyl)adamantanes with fuming nitric acid, alkaline hydrolysis of intermediate 3,5-bis(acetoxymethyl)adamantane-1-yl nitrates, and reaction of the resulting 3,5-bis(hydroxymethyl)adamantan-1-yl nitrates with hydrazine hydrate. 3,5-Bis(hydroxymethyl)adamantan-1-ols have been converted to the corresponding trinitrates by treatment with fuming nitric acids in acetic anhydride. Keywords: nitroxylation, fuming nitric acid, polyhydric alcohols, adamantane, nitric acid esters, hydrolysis
DOI: 10.1134/S1070428020090109 Polyhydric alcohols of the adamantane series are used as starting compounds for the preparation of polymeric materials [1], cationic surfactants [2, 3], flame retardants for polycarbonate [4], conformationally rigid crown ethers [5, 6], biologically active substances [7], and new heat-resistant base oils [8–10]. Methods have been developed for the synthesis of adamantane polyols containing hydroxy groups in the bridgehead positions. For example, adamantane-1,3-diol was obtained by oxidation of adamantan-1-ol with various oxidants [11–14], hydrolysis of 1,3-dinitrooxy[15, 16] and 1,3-dibromoadamantanes [17], and decarboxylation of adamantane-1,3-dicarboxylic acid [18]. Oxidation and hydrolysis were also utilized in the synthesis of adamantane-1,3,5-triol [3, 5, 11, 19–22] and adamantane-1,3,5,7-tetraol [6, 7, 23–27]. Bis(hydroxymethyl)adamantanes have been obtained by reduction of adamantane-1,3-dicarboxylic acid [10, 17, 28, 29] or its esters [30, 31] and hydroxymethylation of 1,3-diiodoadamantane [32]. The reduction of trimethyl
adamantane-1,3,5-tricarboxylate afforded 2,2′,2″-(adamantane-1,3,5-triyl)tri(acetic acid) [33]. On the other hand, there are only a few published data on the synthesis of adamantane alcohols in which one hydroxy group is linked directly to the adamantane skeleton while the other is separated from the cage fragment by a spacer, e.g., methylene group, and therefore has a limited conformational mobility [2, 32, 34, 35]. Trihydric alcohols with two hydroxy groups separated from the adamantane skeleton through a spacer and one hydroxy group attached directly thereto have not been reported. However, such structures attract interest due to the possibility of using them as starting materials for the synthesis of a wide series of functional adamantane derivatives with valuable properties [36]. As starting materials we used 1,3-bis(hydroxymethyl)adamantanes 1a–1c which were prepared from the corresponding adamantane-1,3-carboxylic acids according to reported procedure [17]. Diols 1a–1c were
Scheme 1. OH
OAc
OAc
Ac2O, CHCl3,
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