Photochemistry of .alpha.,.beta.-unsaturated thiones. Cycloaddition to electron-deficient olefins from higher excited states

Electron-deficient olefins add to thioenone 1 upon m* excitation. Cycloaddition occurs to the thiocarbonyl chromophore preferentially from the less-hindered side to yield thietanes. Thietane formation is stereospecific and regioselective. This addition has been inferred to originate from the second excited singlet, S2(?rx*), state. The exciplex intermediacy has been inferred from the dependence of the fluorescence quenching rate constant on the electron-acceptor properties of the olefin. The observed site specificity and regioselectivity are rationalized on the basis of PMO theory. The observed photochemical behavior of thioenone is different from that of enones

Photochemistry of .alpha.,.beta.-unsaturated thiones: addition to electron-rich olefins from T1

1,1,3-Trimethyl-2-thioxo-1,2-dihydronaphthale(1n)e adds to electron-rich olefins upon excitation to either Sz (PP*) or Sl (ns*) states. Excitation to S2 level resulted in the same mixture of products, namely thietane and 1,4-dithiane, as on excitation to S1 level. Addition occurs to the thiocarbonyl function and not to the carbon-carbon double bond. The addition is site-specific, and the formation of thietane is regiospecific. The ratio of thietane to 1,4-dithiane in the product mixture is dependent on the concentration of the thioenone. The addition is suggested to originate from the lowest triplet state (Tl) and involves diradical intermediates

Mechanism of oxidation of α, β - unsaturated thiones by singlet oxygen

Photo-oxidation of α,β-unsaturated thiones yields the corresponding ketones as the only product. Studies carried out on three systems, namely thioketones, α,β-unsaturated thiones and thioketenes, have revealed that there exists a similarity in their mechanism of oxidation. It has been suggested that the thiocarbonyl chromophore is the site of attack by singlet oxygen in α,β-unsaturated thiones and that the adjacent C-C double bond is inert under these conditions. Absence of sulphine during the oxidation of α,β-unsaturated thiones is attributed to the electronic factors operating on the zwitterionic/diradical intermediate. While α,β-unsaturated ketones are poorly reactive, α,β-unsaturated thiones are highly reactive toward singlet oxygen

Synthesis and Stability of α,β - unsaturated Sulfines

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Mechanism of oxidation of α,β-unsaturated thiones by singlet oxygen

Photo-oxidation of α,β-unsaturated thiones yields the corresponding ketones as the only product. Studies carried out on three systems, namely thioketones, α,β-unsaturated thiones and thioketenes, have revealed that there exists a similarity in their mechanism of oxidation. It has been suggested that the thiocarbonyl chromophore is the site of attack by singlet oxygen in α,β-unsaturated thiones and that the adjacent C-C double bond is inert under these conditions. Absence of sulphine during the oxidation of α,β-unsaturated thiones is attributed to the electronic factors operating on the zwitterionic/diradical intermediate. While α,β-unsaturated ketones are poorly reactive, α,β-unsaturated thiones are highly reactive toward singlet oxygen

Triplet-state photophysics and transient photochemistry of cyclic enethiones. A laser flash photolysis study

The triplets of four cyclic enethiones, including thiocoumarin, have been investigated by nanosecond laser flash photolysis. Data are presented for transient spectra and kinetics associated with triplets, quantum yields of intersystem crossing and singlet oxygen photosensitization. The quenching of the thiocoumarin triplet (λ<SUP>T</SUP><SUB>max</SUB>= 485 nm, Iμ<SUP>T</SUP><SUB>max</SUB>= 8.8 × 10<SUP>3</SUP> dm<SUP>3</SUP> mol<SUP>−1</SUP> cm<SUP>−1</SUP> in benzene) by several olefins, amines and hydrogen donors occurs with rate constants of 10<SUP>7</SUP>-5 × 10<SUP>9</SUP> dm<SUP>3</SUP> mol<SUP>−1</SUP> s<SUP>−1</SUP>; the lower limits of quantum yields (⊕ PC) for the related photoreactions, estimated from ground-state depletion, are generally small (0.0-0.11 in benzene, except for good hydrogen donors, namely, p-methoxythiophenol and tri-n-butylstannane). The radical anion of thiocoumarin (λmax= 405-435 nm) is formed in two stages upon triplet quenching by triethylamine in acetonitrile; the fast component is the result of direct electron transfer to the triplet and the slower component is assigned to secondary photoreduction of the thione ground state by the α-aminoalkyl radical derived from the triethylamine radical-cation