No abstract

Why is the triplet state of aromatic ketones quenched by protons? The long-known but unexplained quenching process was investigated in detail for benzophenone (1). Adiabatic protonation of triplet benzophenone, 3 1, encounters a state symmetry-imposed barrier, because the electronic structure of 3 1 is n,π*, while that of its conjugate acid, 3 1H + , is π,π*. Hence, the rate of protonation of 3 1, k H + ) 6.8 × 10 8 M -1 s -1 , is well below the diffusion-controlled limit. The short-lived transient intermediate formed by protonation of 3 1 in 0.1-1 M aqueous HClO 4 (λ max ) 320 and 500 nm, τ ) 50 ns) is not 3 1H + , as was assumed in previous studies. The latter (λ max ) 385 nm) is detectable only in acidified acetonitrile or in highly concentrated aqueous acid (>5 M HClO 4 ), where water activity is low. In moderately concentrated aqueous acids, adiabatic protonation of 3 1 is the rate-limiting step preceding rapid adiabatic hydration of a phenyl ring, 3 1H + + H 2 O f 3 1‚H 2 O, k 0 ) 1.5 × 10 9 s -1 . These findings lead to a revised value for the acidity constant of protonated 3 1, pK a ( 3 1H + ) ) -0.4 ( 0.1. Acetophenone (2) and several derivatives of 1 and 2 undergo a similar reaction sequence in aqueous acid. The acid-catalyzed photohydration of parent 1 and 2 is reversible. In meta-fluorinated derivatives, the reaction results in a clean and efficient formation of the corresponding phenols, a novel aromatic photosubstitution reaction. This indicates that hydration of 3 1H + occurs predominantly at the meta position. A long-lived transient (λ max ) 315 nm, τ ) 5.4 s) left after the decay of 3 1‚H 2 O is attributed to a small amount of ortho-1‚H 2 O that regenerates 1 more slowly.

2-Diazo-1,2-naphthoquinone (1) and its derivatives are the photoactive components in Novolak photoresists. A femtosecond infrared study has established that the photoreaction of 1 proceeds largely by a concerted Wolff rearrangement yielding the ketene 1H-inden-1-ylidene-methanone (3) within 300 fs after excitation, but earlier trapping studies gave evidence for a minor reaction path via a carbene intermediate 1-oxo-2(1H)-naphthalenylidene (2) with a lifetime of about 10 ps. Here, we provide a quantitative assessment of the stepwise pathway by Stern-Volmer analysis of the trapping of 2 by methanol to yield 2-methoxy-1-naphthol (4). We conclude that the lifetime of the carbene 2 is at least 200 ps. Moreover, [3 + 2]cycloaddition of 2 and acetonitrile yielding 2-methylnaphth[2,1-d]oxazole (5) was observed. A comparison of the yields of 5 formed upon photolysis and upon thermolysis of 1 in acetonitrile provides evidence that a substantial part of the hot nascent carbene 2 formed photolytically rearranges to the ketene 3 during its vibrational relaxation (hot ground-state reaction).