123033-33-0Relevant academic research and scientific papers
Synthesis of Bridgehead Halides by Barton Halodecarboxylation
Della, Ernest W.,Tsanaktsidis, John
, p. 61 - 69 (2007/10/02)
Bridgehead carboxylic acids can be converted into their corresponding chlorides very efficiently under Barton halodecarboxylation conditions.Addition of the acid chloride to a suspension of the sodium salt of 1-hydroxypyridine-2(1H)-thione in boiling carbon tetrachloride under irradiation leads to excellent yields of the bridgehead chloride via the derived thiohydroxamic ester.In a useful modification for the synthesis of volatile halides, either 1,1,1-trichloro-2,2,2-trifluoroethane or trichlorofluoromethane can be employed as substitute solvents.It is found that the Barton procedure is applicable to the synthesis of labile bromides such as 1-bromobicycloheptane for which the usual Hunsdiecker reaction fails.For these, and other brominations, 2-bromo-2-chloro-1,1,1-trifluoroethane ('Halothane') is shown to function as an efficient solvent/bromine atom donor.
Coupling to sp-Hybridized Carbon: 13C-13C Coupling Constants in Some Polycycloalkanecarbonitriles
Della, Ernest W.,Gangodawila, Hemakanthi
, p. 1485 - 1492 (2007/10/02)
Comparison of the effect of sp-hybridized carbon on the magnitude of directly bonded and vicinal coupling constants in the labelled nitriles (1)-(7) with that of sp2 and sp3 carbon reveals some interesting, though not major, differences.As noted previously, three-bond coupling involving the labelled carbon and the bridgehead carbon in the bicycloalkanes has an important through-space component.
