shown by nmr and ir spectra. Purification of this product other than by glpc proved difficult. endo,exo-Tricyclo[3.2.2.02 •4]nonan-6-ol (10). A solution of 7.2 g of olefin 9 in 100 ml of tetrahydrofuran at 0°was treated with a stream of diborane generated from a solution of 4.75 g of NaBHU in diglyme and 25 ml of BF3-Et20 in 30 ml of diglyme according to the procedure previously used.28 This led to 7.31 g (87%) of a solid which upon crystallization from pentane had mp 165-168°. Glpc (B) of the original mixture indicated greater than 90% of a single alcohol, 10, nmr r 6.4 (1) m, 6.95 (1) 5, 8.15 (3) m, 8.5 (3) m, 8.88 (1) m, 8.18 (2) m, 9.8 (2) m.
The stereochemistry of high energy chlorine-for-chlorine substitution was studied in gaseous and condensed phase 2(S)-chloropropionyl chloride and 2(/ü)-chloropropionyl chloride. Greater than 80% inversion of configuration was observed at the chiral center for both high energy 38C1 and 34mCl substitution. Net retention is observed in gaseous 2 (S) -chloro-4-methylvaleryl chloride where steric hindrance to backside attack is enhanced relative to 2 (S)-chloropropionyl chloride. Condensed state data suggest caged radical recombination reactions.
Mit hochenergetischen 38Cl‐ und 34mCl‐Atomen tritt bei Cl‐C1‐Substitution an (2S)‐ und (2R)‐Chlor‐propionylchlorid in kondensierter und Gasphase zu über 80% Inversion ein.
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