Radical addition of tert-butyl hypochlorite to 1-buten-3-yne (15) proceeds by competitive olefinic attack to give 1, 2 and 1, 4 adducts (16 and 17) and acetylenic attack to give a 4, 3 adduct (19) which suffers rapid secondary electrophilic chlorination to form aldehyde 18; the former pathway is preferred by a factor of 4 at 25'. Products from the four monomethyl homologs (6, 12, 21, and 29) have also been determined and correlated with the ...
