50795-82-9Relevant articles and documents
Selective Nitroxylation of Adamantane Derivatives in the System Nitric Acid–Acetic Anhydride
Ivleva, E. A.,Klimochkin, Yu. N.,Moiseev, I. K.
, p. 1532 - 1539 (2020/10/22)
Abstract: A number of new nitroxyadamantanes have been synthesized by nitroxylation of the corresponding substrates with nitric acid in acetic anhydride. High electrophilicity and reduced acidity of the system HNO3–Ac2O increases the stability of nitrates and significantly decreases the probability of formation of alcohols. In some cases, nitrolysis and oxidation of functional groups in the substrate are observed.
Synthesis of (3-Hydroxyadamantan-1-yl)methanols
Ivleva,Pogulyaiko,Klimochkin, Yu. N.
, p. 1294 - 1300 (2018/11/21)
A convenient procedure has been developed for the synthesis of (3-hydroxyadamantan-1-yl)-methanols on the basis of nitroxylation of adamantan-1-ylmethanols with fuming nitring acid and subsequent reduction of intermediate nitric acid esters with hydrazine hydrate. The title diols have also been obtained by the reduction of 1-nitroxy-3-(nitroxymethyl)adamantanes. The nitroxylation process is accompanied by oxidation with the formation of substituted adamantane-1-carboxylic acids.
One-pot synthesis of cage alcohols
Klimochkin, Yu. N.,Yudashkin,Zhilkina,Ivleva,Moiseev,Oshis, Ya. F.
, p. 971 - 976 (2017/09/07)
An efficient one-pot procedure has been developed for the synthesis of cage alcohols with hydroxy groups in the bridgehead positions. The procedure includes initial nitroxylation with nitric acid or a mixture of nitric acid with acetic acid and subsequent hydrolysis in the presence of urea.
ANGIOTENSIN II RECEPTOR ANTAGONISTS
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Page/Page column 53-54, (2009/10/21)
The present invention relates to nitrooxyderivatives of angiotensin II receptor antagonist having the general formula (I): where in R is selected f rom the group consisting of (IIa) - (IIk): when R is selected from (Ilk), Y is selected from the group consisting of: 1) -C(O) (CH2) nR5; 2) -C(O)(CH2n-O-CH2-R5; 3) -C(O)-R6 wherein R6 is the following group: when R is selected from (IIa)-(IIh), Y is selected from the group consisting of: 4) -C(R1R2)OC(O)-(CH2)nR5; 5) -C(R1R2)OC(O)O-(CH2)nR5; 6) C(R1R2)OC(O)(CH2)n-O-CH2-R5; 7) C(R1R2)OC(O)O(CH2)n-O-CH2-R5; 8) -C(R1R2)OC(O)-R6 wherein R6 is as above defined; R1 and R2 are independently selected from the group consisting of hydrogen and C1-4 alkyl; R5 is -CH(ONO2)R7; R7 is CH3 or C1-4 alkyl; n is an integer from 1 to 4; or a pharmaceutically acceptable salt thereof.
Ozone-mediated nitration of adamantane and derivatives with nitrogen dioxide: Selectivity in the hydrogen abstraction by nitrogen trioxide and subsequent coupling of the resulting carbon radicals with nitrogen dioxide
Suzuki, Hitomi,Nonoyama, Nobuaki
, p. 2965 - 2971 (2007/10/03)
In the presence of ozone at -78°C, nitrogen dioxide reacts rapidly and selectively with adamantane at a bridgehead position to give the corresponding nitro derivative as the sole major product. The relative reactivity has been determined for a series of 1-substituted adamantanes, which reveals that electron-withdrawing substituents exert a considerable influence on the ease of substitution at the γ-position as well as the distribution of the N- and O-functionalized products. The results may be rationalized in terms of the initial hydrogen abstraction by nitrogen trioxide, followed by rapid trapping of the resulting adamantyl radicals with nitrogen dioxide.
Oxidative functionalization of adamantane and some of its derivatives in solution
Mella,Freccero,Soldi,Fasani,Albini
, p. 1413 - 1420 (2007/10/03)
1,2,4,5-Benzenetetracarbonitrile (TCB) is irradiated in the presence of adamantane (1) and some of its derivatives. The singlet excited state of TCB is a strong oxidant, and there is various evidence, including time-resolved spectroscopy, to prove that SET from the alkane to TCB1* takes place and yields the corresponding radical ions. The adamantane radical cation deprotonates from the bridgehead position, and the resulting radical couples with TCB-*. Deprotonation via the radical cation occurs with a number of substituted adamantanes and remains the exclusive or predominating reaction also with derivatives containing a potential electrofugal group, such as one of the following carbocations: t-Bu, CH2OMe, CH2OH (notable here is that C-H deprotonation is more efficient than O-H deprotonation). A carboxy group is lost more efficiently than a proton, however. In contrast, detaching of such cations is the main process when the radical cations of substituted adamantanes is produced anodically. This different behavior is explained on the basis of thermochemical calculation and of the different environments experienced by the radical cation in the two cases, viz reaction from the solvated radical cation in the first case and from the substrate adsorbed on the anode in the latter one. 1-Methoxyadamantane deprotonates from the methyl group, a reaction explained by the different structure of the radical cation. On the other hand, the radical NO3*, conveniently produced by photolysis of cerium(IV) ammonium nitrate, reacts by hydrogen abstraction with selective attack at the bridgehead position and little interference by substituents and thus offers a useful way for the selective oxidative functionalization of adamantanes.
SYNTHESIS AND HYDROLYTIC TRANSFORMATIONS OF NITROXY DERIVATIVES OF HOMOADAMANTANE PROTOADAMANTANE AND BICYCLONONANE
Klimochkin, Yu. N.,Zhilkina, E. O.,Abramov, O. V.,Moiseev, I. K.
, p. 1126 - 1131 (2007/10/02)
Mono- and dinitroxy derivatives of homoadamantane, protoadamantane, and bicyclononane were synthesized by nitroxylation.A study was carried out on the reactivity of these hydrocarbons relative to nitric acid and the hydrolytic transformations of the products obtained.The acid-catalyzed skeletal rearrangement of 3,6-dinitroxyhomoadamantane to 3-nitroxymethyl-1-adamantanol proceeds with retention of the substituent at the carbon atom, at which the carbenium ion is generated.
REACTION OF MONOFUNCTIONAL SUBSTITUTED ADAMANTANES WITH NITRIC ACID AND ITS MIXTURES
Moiseev, I. K.,Klimochkin, Yu. N.,Zemtsova, M. N.,Trakhtenberg, P. L.
, p. 1307 - 1309 (2007/10/02)
In the reaction of monofunctional substituted adamantanes with nitric acid and its mixtures the main reaction products are the nitrates of adamantanol, formed either as a result of substitution of the functional groups or as a result of substitution of a hydrogen atom at a tertiary carbon atom.
