Photochemistry of Aryl Vinyl Sulfides and Aryl Vinyl Ethers:  Evidence for the Formation of Thiocarbonyl and Carbonyl Ylides

Abstract

Aryl vinyl thioethers 5a and 9a and aryl vinyl ethers 5b and 9b form ylide intermediates following laser irradiation at 308 nm. In benzene, the ylides possess long-lived absorption bands in the 600-800 nm region with a second weaker band at approximately 460 nm. In methanol, a known quencher of zwitterionic species, the lifetimes are reduced significantly. The decay kinetics measured within the long wavelength absorption envelope vary with wavelength, indicating the presence of more than one ylide species. Formation of the ylides occurs via a naphthalene-like triplet state in the case of aryl vinyl ethers, while for the thioethers the multiplicity of the ylide precursor could be either singlet or triplet. Product formation in benzene for 5a and 5b involves ring closure of the ylide to produce dihydrothiophene and dihydrofuran products, respectively. For short periods of irradiation (either lamps or laser) a mixture of cis- and trans-fused products is observed, while for prolonged irradiation only the cis-fused compound is detected, suggesting a photoenolization mechanism for conversion of trans to cis. In addition to products derived from ring closure, 9a provides intramolecular addition product 12. Conversely, the ylide derived from 9b gives rise to the [3 + 2] cycloaddition product 13.

Aromatic Thiols and Their Derivatives

“…It is assumed and confirmed by the data of ab initio calculations that the sulfonic cation acts as an active intermediate in the oxidative polymerization of diphenyl disulfide [81]. The photochemical study of aryl vinyl sulfides and aryl vinyl ethers proves the formation of thiocarbonyl and carbonyl ylides [82]. The investigation into non-oxidative Pummerer reaction, on the example of (R)-ethyl-p-tolylsulfoxide as an equivalent of chiral a-hydroxyethyl anion, evidences the stereoselectivity of S N 2 type.…”

1-(2-Chlorophenyl)-3-[(phenyl)(4-tolylimino)methyl]thiourea

“…Thiourea derivatives are very important intermediates in organic syntheses, which have been widely utilized in medicinal chemistry (Smith et al, 1996) and photochemistry (Dittami et al, 1996;Jayanthi et al, 1997). In order to study their photochemical behaviors, we have synthesized a series of new thiourea derivatives, and present here the crystal structure of one representative, viz.…”

1-[(Phenyl)(p-tolylimino)methyl]-3-(o-tolyl)thiourea

“…Thiourea derivatives are very important intermediates in organic syntheses, and have been widely utilized in medicinal chemistry (Smith et al, 1996) and photochemistry (Dittami et al, 1996;Jayanthi et al, 1997). In order to study their photochemical behavior, we synthesized a series of new thiourea derivatives (Xing & Zhao, 2006a,b).…”