Photolytic Addition of Formamide to Olefins

Free radical additions to mono-olefins are quite common and can frequently be employed to advantage on a synthetic scale. Formamide, for example, on exposure to sunlight or UV radiation adds to olefins in an anti-Markovnikov sense giving 1 1 adducts that are readily isolated and crystallized. Moreover, since alkyl formamides may be conveniently converted to carboxylic acids by conventional means, the reaction represents a general method of chain extension. 

Alkyl Formamides from Olefins Catalysis by Ultraviolet Light or Sunlight (7) 

Formamide is distilled under vacuum before use. /-Butyl alcohol may be dried by distillation from sodium or calcium hydride (3 g/100 ml). All other reagents should be dry. 

A mixture of olefin (0.005 mole), formamide (40 g), /-butyl alcohol (35 ml), and acetone (5 ml) is irradiated for 45 minutes. A solution of olefin (0.045 mole), /-butyl alcohol (10 ml), and acetone (7 ml) is then added in ten equal portions at 45-minute intervals. The irradiation is continued for an additional 6 hours. At the conclusion of 

CARBON-CARBON BOND FORMATION BY MISCELLANEOUS REACTIONS 

---