Aspects of the 2,3-trimethylenenorbornane-adamantane rearrangement

Functionalisation of saturated hydrocarbons. Part 1. Some reactions of a ferrous chloride–chloramine-T complex with hydrocarbons

“…crude product which was purified by multiple development preparative t.1.c. using benzeneacetone (99.1 : 0.9) as eluant to give the following products: 3 P-acetoxy-5 a-chloro-6P-( toluene-p-su1phonamido)cholestane (22) The above structural assignments were confirmed by double irradiation experiments and by the following reactions and syntheses.…”

“…iminocholesrane (24).-(a) N',N"-Tetramethyl-N-t-butylguanidine 24 (8.4 mg, 0.049 mmol) was added to a solution of 5achloro-6~-(toluene-p-sulphonamido)cholestane (22) (1 7 mg, 0.026 mmol) in toluene (1 ml) and the mixture was heated a t 100 "C until the reaction was complete (t.1.c.). Removal of toluene and preparative t.1.c.…”

Synthesis of some highly brominated naphthalenes

“…Several attempts to prepare these isomers via direct bromination of 1,5-and 1,8-diamino (or dinitro)naphthalene or the 1,8-dicarboxylic acid anhydride were unsuccessful. The 1,2,3,5,6,7-hexa isomer was successfully prepared following the published procedure of Hamill et al (1971) for bromination of endo-2,3-trimethylenenorbornane. The structure assignment was established by a complete X-ray crystallographic analysis (Ferguson and Subramanian, 1977).…”

“…Another example of this was seen in our early work toward the preparation of 2,3,6,7-tetrasubstituted naphthalenes. It was not possible to conveniently prepare the 2,3,6,7tetrachloro isomer (Levy, 1978) via the known tetrakis-(trimethylsilyl)naphthalene intermediate (Hamill, et al, 1971) used for the 2,3,6,7-tetrabromo isomer. The 2,3,6,7-tetrachloro isomer is at least 18 times less toxic in the guinea pig (McKinney et al, 1980).…”