Hammett correlations in the photosensitized oxidation of 4-substituted thioanisoles

被引:49
作者
Bonesi, SM [1 ]
Fagnoni, M [1 ]
Albini, A [1 ]
机构
[1] Univ Pavia, Dept Organ Chem, I-27100 Pavia, Italy
关键词
D O I
10.1021/jo035679e
中图分类号
O62 [有机化学];
学科分类号
070303 ; 081704 ;
摘要
Singlet oxygen is quenched by a series of 4-substituted thioanisoles (methoxy to nitro), with rate constant k(t) = 7 x 10(4) to 7 x 10(6) M-1 s(-1), close to the value observed for the myoglobin-catalyzed sulfoxidation of the same sulfides. Correlations with sigma (rho = -1.97) and with E-ox (slope -3.9 V-1) are evidence for an electrophilic mechanism. In methanol sulfoxides are formed (85%) via an intermediate quenched by diphenyl sulfoxide; competing minor paths lead to arylthiols, arylsulfenic acid, and aryl sulfoxides. In aprotic solvents, the sulfoxidation is quite sluggish, but carboxylic acids (mostly less than or equal to 0.1 M) enhance the rate by a factor of > 100. The protonated persulfoxide is formed in this case and acts as an electrophile with sulfides, again with a rate constant correlating with sigma (rho = -1.78).
引用
收藏
页码:928 / 935
页数:8
相关论文
共 69 条
[1]   OXIDATION OF THIOANISOLES AND METHYL PHENYL SULFOXIDES BY OXO(PHOSPHINE)RUTHENIUM(IV) COMPLEXES [J].
ACQUAYE, JH ;
MULLER, JG ;
TAKEUCHI, KJ .
INORGANIC CHEMISTRY, 1993, 32 (02) :160-165
[2]  
AIDO T, 1976, B CHEM SOC JPN, V49, P1441
[3]   REACTION OF SINGLET OXYGEN WITH THIIRANE - PEROXYSULFENIC ACID INTERMEDIATE AS A NEW OXIDIZING SPECIES [J].
AKASAKA, T ;
KAKO, M ;
SONOBE, H ;
ANDO, W .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1988, 110 (02) :494-496
[4]  
ALOISI GG, 1974, J CHEM SOC FARADAY T, V70, P208
[5]   NATURE OF PEROXY INTERMEDIATES PRODUCED BY THE PHOTOSENSITIZED OXYGENATION OF DIETHYL SULFIDE AND PHENYLBENZOYL DIAZOMETHANE - KINETIC-STUDIES BY CO-OXIDATION WITH 4-MONO SUBSTITUTED DIPHENYL SULFIDES [J].
ANDO, W ;
KABE, Y ;
MIYAZAKI, H .
PHOTOCHEMISTRY AND PHOTOBIOLOGY, 1980, 31 (03) :191-194
[6]  
[Anonymous], SINGLET O2
[7]  
ARMITAGE DA, 1984, SYNTHESIS-STUTTGART, P1042
[8]   Mechanism of the oxidation of aromatic sulfides catalysed by a water soluble iron porphyrin [J].
Baciocchi, E ;
Gerini, MF ;
Lanzalunga, O ;
Lapi, A ;
Lo Piparo, MG .
ORGANIC & BIOMOLECULAR CHEMISTRY, 2003, 1 (02) :422-426
[9]   Oxidation of aromatic sulfides photosensitized by TiO2 in CH3CN in the presence of Ag2SO4. The role of TiO2 in the chemistry of sulfide radical cations [J].
Baciocchi, E ;
Del Giacco, T ;
Ferrero, MI ;
Rol, C ;
Sebastiani, GV .
JOURNAL OF ORGANIC CHEMISTRY, 1997, 62 (12) :4015-4017
[10]  
BACIOCCHI E, 1997, TETRAHEDRON LETT, V53, P9771