Carol W. Mosher

Chiral 1-deuterio azides

Abstract Five chiral primary 1-deuterio alcohols (R-CHDOH, R = methyl, n -propyl, tert -butyl, 1-adamantyl, phenyl) were converted (via their tosylate or mesylate) into the corresponding chiral primary 1-deuterio azides (RCHDN3 of opposite configuration. Three of the four non-aromatic, primary, (R)-1-deuterio azides have a positive sodium D-line rotation, and a positive circular dichroism (CD) Cotton effect at 286–288 nm attributable to the azide chromophore. However, the first member of the series, (R)-(+)-ethyl-1-d azide, has a negative CD (287 nm, [θ]=12.5) and does not conform to the other three which show a positive CD. The chiral azides, RCHDN3, which have an R group possessing C3v symmetry (methyl, tert -butyl and adamantyl), constitute a simple conformational situation for application of the azide octant rule. Since one of these three (methyl) has a CD of opposite sign to the other two, these results cannot be reconciled with the azide octant rule, per se. Ethyl azide detonated upon attempted sealing in a vial.