1227-49-2Relevant articles and documents
Orthogonal or simultaneous use of disulfide and hydrazone exchange in dynamic covalent chemistry in aqueous solution
Rodriguez-Docampo, Zaida,Otto, Sijbren
, p. 5301 - 5303 (2008)
Hydrazone and disulfide exchange have been combined in a single system, but can be addressed independently: by adjusting the pH of the solution from acidic to mildly basic it is possible to switch from exclusively hydrazone exchange to exclusively disulfide exchange, while at intermediate pH both reactions occur simultaneously. The Royal Society of Chemistry.
Photodeoxygenation of dibenzothiophene S-oxide derivatives in aqueous media
Korang, James,Grither, Whitney R.,McCulla, Ryan D.
scheme or table, p. 4466 - 4476 (2010/06/13)
The use of atomic oxygen (O(3P)) as potent oxidant In water has suffered from the lack of a facile, efficient source. The photodeoxygenatlon of aromatic sulfoxides to the corresponding sulfides in organic solvents has been suggested to produce O(3P) in low quantum yields. The photolysis of 4,6-dihydroxymethyldibenzothiophene S-oxide and 2,8- dihydroxymethyldibenzothiophene S-oxide in water results in deoxygenation at significantly higher quantum yields than In organic solvents. Depending upon conditions, a variable amount of oxidation of the hydroxymethyl substituent into an aldehyde was observed to accompany deoxygenation. Analysis of the photoproducts Indicated the deoxygenation occurred by at least two different pH-sensitive mechanisms. Under basic conditions, photoinduced electron transfer yielding a hydroxysulfuranyl radical that decomposed by heterolytlc S-O cleavage was thermodynamically feasible. The thermodynamics of photoinduced electron transfer were expected to become increasingly unfavorable as the pH of the solution decreased. Thus, at neutral and acidic pH, an S-O bond scission mechanism was suspected. The observed increase In the photodeoxygenation quantum yields was consistent with charge separation accompanying S-O bond scission. Oxidative cleavage of alkenes In aerobic conditions suggested O(3P) was produced during photolysis In these conditions; however, the formation of discrete O-/HO may occur, particularly at low pH.
Investigations on Benzothiirene
Meier, Herbert,Konnerth, Ursula,Graw, Sylvia,Echter, Toni
, p. 107 - 126 (2007/10/02)
Thermolysis and photolysis of 1,2,3-benzothiadiazole 10c furnish the products 11c - 15c. 13C-labelling experiments demonstrate that an intermediate benzothiirene 1c is not formed.Isotopomeric reaction products are due to H-shifts.Electron withdrawing ester groups in 6-position enable the ring closure to the substituted benzothiirenes 1d, e on the photochemical but not on the thermal route.A proof is given by an extensive study of the disulfides 14d, e, 14d', e', and 14d'', e'', generated in the thermolysis, photolysis and by an independent procedure.The results are based on 13C and 1H NMR measurements.Unequivocal signal correlations were made by deuterations and heteronuclear double resonances.
