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Dihaloadamantanes: Ring Closure versus Rearrangement or Halogen‐Displacement Reactions
Author(s) -
MlinarićMajerski Kata,
Veljković Jelena,
Kaselj Mira,
Marchand Alan P.
Publication year - 2004
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/ejoc.200400121
Subject(s) - chemistry , adamantane , ring (chemistry) , halogen , reagent , toluene , medicinal chemistry , diamondoid , metal , organic chemistry , molecule , alkyl
Abstract Three dihaloadamantanes [i.e., 2‐bromo‐1‐(chloromethyl)adamantane ( 1 ), 1‐(bromomethyl)‐2‐chloroadamantane ( 2 ) and 2‐bromo‐1‐(bromomethyl)adamantane ( 3 )] were synthesized, and their corresponding ring‐closing reactions, performed by using Na metal or alkyllithium reagents, were studied. Compound 1 reacted with Na in toluene or in tetraglyme to afford 1,2‐methanoadamantane ( 4 ) as the major product. However, the corresponding reactions, when performed by using 2 and 3 as substrates, produced methyladamantane ( 5 ) or 4‐methyleneprotoadamantane ( 6 ) as the major reaction products. The corresponding reactions of 1 and 2 with t BuLi or n BuLi afforded small quantities of 4 , 5 and 6 along with the corresponding monohalides, that is, 1‐(chloromethyl)adamantane ( 7 ) and 2‐chloro‐1‐methyladamantane ( 8 ), which constituted the major products of these reactions. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)