The photocycloaddition of naphthoates with acetylacetone; dramatic acid promotions of product quantum yields

Abstract

In acetonitrile and methanol, methyl 1- and methyl 2-naphthoate (1- and 2-NpCO2CH3) underwent [2 + 2] photocycloaddition with acetylacetone (acacH) from a reactive species derived from the lowest spectroscopic singlet excited state to give cyclobutane derivatives such as 9 that ring-opened to afford addition products of acetyl and acetonyl moieties at the 7,8-position for 1-NpCO2CH3 (2 and 3) and the 1,2-position for 2-NpCO2CH3 (7). Further irradiation of 3 and 7 caused a deep-seated rearrangement of 3 to give 4 and an intramolecular addition of 7 to give the caged product 8. The photocycloaddition quantum yields were increased remarkably in the presence of a trace amount (< 0.001 M) of protic acids. For example, the limiting quantum yield of 2 and 3 with Фadducts = 0.033 (in the absence) increased to Фadducts > 0.5 under comparable conditions in the presence of [H2SO4] = 0.001 M, approaching the maximum asymptotically at about this concentration; the increases of the quantum yield could not be correlated with H2SO4 concentrations. The acid promotion of the product formation elevated the photocycloaddition to a significantly useful preparative reaction. The photocycloaddition of 2-NpCO2CH3 was quenched by tributylamine, dimethylaniline, and methyl iodide, and could not be initiated by typical triplet sensitization. Strong fluorescence of 2-NpCO2CH3 at 358 nm in CH3CN was quenched by acetylacetone, tributylamine, dimethylaniline, and methyl iodide, the last of which concurrently enhanced the phosphorescence intensity of 2-NpCO2CH3. In the presence of [H2SO4] > 0.005 M the fluorescence intensity at 358 nm was quenched and a new fluorescence at 470 nm corresponding to protonated 12-NpCO2CH3 appeared. However, in the [H2SO4] < 0.002 M region, the new fluorescence was not observed, indicating that the protonation scarcely occurred. The Stern–Volmer constant, obtained by the quantum yield monitor, of the 2-NpCO2CH3 photocycloaddition with acacH was more than an order of magnitude smaller than that obtained by the quenching of 2-NpCO2CH3 fluorescence by acacH. The discrepancies outlined above clearly demonstrate that the reactive intermediate of the photocycloaddition is not the exciplex of the spectroscopic singlet excited species of 12-NpCO2CH3 and acacH, but one that is derived from the exciplex. It is speculated that this unknown reactive intermediate interacts with a proton to promote the photocycloaddition. Key words: photocycloaddition of naphthoates, photorearrangement of styryl ketones, acid catalysis of quantum yields, fluorescence of protonated naphthoates, acid enhancement of singlet quenching.