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Preparation of ring labelled adamantane derivatives II. 2‐adamantanone‐2− 14 C, adamantane‐2− 14 C and 1‐methyladamantane‐2 or 4− 14 C
Author(s) -
Liggero Samuel H.,
Majerski Zdenko,
von R. Schleyer Paul,
Wolf A. P.,
Redvanly C. S.,
Wynberg Hans,
Boerma J. A.,
Strating J.
Publication year - 1971
Publication title -
journal of labelled compounds
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.432
H-Index - 47
eISSN - 1099-1344
pISSN - 0022-2135
DOI - 10.1002/jlcr.2590070102
Subject(s) - adamantane , chemistry , diazomethane , yield (engineering) , bromide , ring (chemistry) , benzyl bromide , stereochemistry , medicinal chemistry , organic chemistry , catalysis , materials science , metallurgy
A high‐yield, relatively simple synthetic route leading to incorporation of 14 C into the secondary position of the adamantane nucleus is described. The synthesis was achieved by the sequence shown in Figure 2. The key steps involved the introduction of a 14 C label by diazomethane‐ 14 C ring expansion of adamantanone to give 4‐homoadamantanone‐4− 14 C (I). Benzylic acid rearrangement of the corresponding homoadamantane diketone (II) gave hydroxy acid (III) which was converted by a novel reaction (SOCl 2 /benzene) to 2‐adamantanone‐2− 14 C (IV). The overall yield of labelled 2‐adamantanone was 66%. Wolff‐Kishner reduction of (IV) gave adamantane‐2− 14 C (V). This was converted to the l‐methyl derivative (VII) by treatment of the corresponding bromide (VI) with methylmagnesium bromide.