ChemInform Abstract: PHOTOLYSE VON P‐CHLOR‐BENZOYLAZID IN 1‐AETHOXY‐2‐METHYL‐PROPEN‐(1) UND 2‐METHYL‐BUTEN‐(2)

Photochemistry of Azides: The Azide/Nitrene Interface

“…117,118 Similar results were obtained for 2 -naphthoyl azide ( 35 ). 122 Irradiation of 35 in cyclohexane at room temperature produces isocyanate (36 , ∼ 45%), N -cyclohexyl -2 -naphthamide -the product of 2 -naphthoylnitrene ( 37 ) insertion ( ∼ 50%), and a trace ( < 1%) of 2 -naphthamide ( 38 ).…”

“…108 -110,119 -133 It has been shown that the yield of isocyanates, formed upon photolysis of a series of carbonyl azides (R -CO -N 3 , R = t -Butyl, Aryl), remains constant in the presence and in the absence of nitrene traps. 111,112,117,118 For example, the yield of isocyanate 33a produced on photolysis of pivaloyl azide (R = tr -Butyl, 31a ) in methylene chloride (an inert solvent) is 40%. Photolysis of 31a in cyclohexene leads to a 45% yield of aziridine adduct 34a and a 41% yield of isocyanate 33a .…”

Theoretical investigation of the decomposition of acyl azides: Molecular orbital treatment

“…Additional evidence for the singlet multiplicity of benzoylnitrene is obtained from by the fact that the rate of decay of its absorption band at 1,700 cm −1 is completely unaffected by oxygen in an electron spin resonance study. The formation of phenylisocyanate, along with products derived from singlet benzoylnitrene, is well known to occur upon photolysis of benzoyl azide at room temperature 40–44.…”

Study of photochemical transformations of organic azides by matrix isolation techniques and quantum chemistry

“…100,101 The photolysis of benzoyl azide and a series of its derivatives in both inert solvents and solvents giving adducts with acylnitrenes affords isocyanates in similar yields (40% ± 50%). 102,103 Based on these facts, it was concluded that isocyanates and acylnitrenes are independently formed in the photolysis of acyl azides and that acylnitrenes do not undergo isomerisation to isocyanates. 98, 100 ± 103…”