ISSN:
0009-2940
Keywords:
Dimethyl[2.n]metacyclophan-1-ene
;
Bromination
;
cis Addition
;
Dehydrobromination
;
(E) and (Z) isomers
;
Chemistry
;
Inorganic Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
Bromination of dimethyl[2.3]metacyclophan-1-ene (1b) with bromine affords the cis adduct 6b resulting from the addition to the bridging double bond; a similar reaction of dimethyl[2.4]metacyclophan-1-ene (1c) gives a mixture of the cis and trans adduct formed by the addition to the bridged double bond along with the products containing a brominated internal methyl group. On the other hand, bromination of dimethy1[2.n]metacyclophan-1-enes (1) with benzyltrimethylammonium tribromide affords exclusively the product of the cis addition 6 to the bridged double bond. Treatment of [3.2]metacyclophane 6b with potassium tert1-butoxide in refluxing tBuOH for 1 h gives the dehydrobrominated product (E)-8b in 95% yield; a similar reaction of [4.2]metacyclophane 6c furnishes two isomers, (E)-8c and (Z)-8c, of 1-bromo[2.4]1-metacyclophan-1-ene along with [2.4]metacyclophan-1-one 9c in 20% yield. The characterization and the reaction pathway of these products are discussed.
Additional Material:
1 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/cber.19931260223
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