6974-50-1Relevant academic research and scientific papers
Photosensitized electron transfer oxidation of sulfides: A steady-state study
Bonesi, Sergio M.,Fagnoni, Maurizio,Albini, Angelo
scheme or table, p. 2612 - 2620 (2009/04/05)
The photosensitized electron-transfer oxidation of a series of ethyl sulfides RSEt (1, R = C12H25; 2, PhCH2CH 2; 3, PhCH2; 4, PhCMe2; 5, Ph2CH) has been examined in acetonitrile and the product distribution discussed on the basis of the mechanisms proposed. In nitrogen-flushed solutions, cleaved alcohols and alkenes are formed, whereas under oxygen, in reactions that are 10-70 times faster, sulfoxides and cleaved aldehydes and ketones are formed in addition to the afore-mentioned products. Two sensitizers are compared, 9,10-dicyanoanthracene (DCA) and 2,4,6-triphenylpyrylium tetrafluoroborate (TPP+BF4-), the former giving a higher proportion of the sulfoxide, the latter of cleaved carbonyls. The sulfoxidation is due to the contribution of the singlet oxygen path with DCA. Oxidative cleavage, on the other hand, occurs both with DCA and with TPP+ which is known to produce neither singlet oxygen nor the superoxide anion. This process involves deprotonation from the α position of the sulfide radical cation, but the TPP+ results suggest that O2.- is not necessarily involved and non-activated oxygen forms a weak adduct with the radical cation promoting α-hydrogen transfer, particularly with benzylic derivatives. Wiley-VCH Verlag GmbH & Co. KGaA, 2008.
The photooxygenation of benzyl, heteroarylmethyl, and allyl sulfides
Bonesi, Sergio M.,Torriani, Rosangela,Mella, Mariella,Albini, Angelo
, p. 1723 - 1728 (2007/10/03)
The photosensitised oxidation of benzyl ethyl sulfides in aprotic solvents (benzene or acetonitrile) gives the corresponding aldehydes under mild conditions. This is a general reaction which applies to benzyl derivatives containing either electron-donating or electron-withdrawing substituents and furthermore to hereto analogues such as 2-pyridinylmethyl sulfide (not to the 3-indolylmethyl sulfide, since reaction at the heterocycle moiety competes) as well as to allyl sulfides. In a protic solvent (methanol) these sulfides give the sulfoxides instead (except for the nitrobenzyl derivatives, where the aldehyde remains the major product). Among the α-substituted sulfides tested, the α-phenylbenzyl and the 3- cyclohexenyl sulfide give the corresponding ketone (the latter in a low yield), but the α-methylbenzyl sulfide gives the sulfoxide as the main product. The rate for singlet oxygen quenching and for chemical reaction have been measured for representative benzyl sulfides. The reaction is discussed in the frame of the currently accepted mechanism for sulfide photooxygenation. The key step for oxidative C-S bond cleavage appears to be hydrogen transfer from the activated α position in the first formed intermediate, the persulfoxide. This reaction is inhibited in methanol where the persulfoxide is hydrogen-bonded.
Photosensitized oxygenation of some benzyl sulfides. The role of persulfoxide
Bonesi, Sergio M.,Freccero, Mauro,Albini, Angelo
, p. 703 - 707 (2007/10/03)
Benzyl ethyl sulfide (6a) is photo-oxidized to benzaldehyde in benzene, whereas diethyl sulfide is known to give inefficiently the sulfoxide under these conditions. Oxidative C-S cleavage is the main process also with benzhydryl ethyl sulfide (6c), but not with α-methylbenzyl ethyl sulfide (6b), which mainly gives the sulfoxide. The carbonyl derivatives reasonably arise from S-hydroperoxy ylides (3). Consistently with this finding, calculations at the PM3 level suggest that the first intermediate, the persulfoxide (1), undergoes intramolecular hydrogen transfer when an activated α-hydrogen is available and gives 3. This is the case for the above benzyl sulfides (ΔH* for the process decreases with decreasing C-H BDE). However, only some of the persulfoxide conformations are correctly oriented for this rearrangement, and this may slow this process and make other reactions compete, as happens with 6b. Copyright
