A THEORETICAL AND EXPERIMENTAL INVESTIGATION OF THE ELECTROPHILIC OXIDATION OF THIOETHERS AND SULFOXIDES BY PEROXIDES

被引：30

作者：

BONCHIO, M ^{[1
]}

CAMPESTRINI, S ^{[1
]}

CONTE, V ^{[1
]}

DIFURIA, F ^{[1
]}

MORO, S ^{[1
]}

机构：

[1] UNIV PADUA,DIPARTIMENTO CHIM ORGAN,CNR,CTR STUDIO MECCANISMI REAZ ORGAN,I-35131 PADUA,ITALY

来源：

TETRAHEDRON | 1995年 / 51卷 / 45期

关键词：

D O I：

10.1016/0040-4020(95)00780-C

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

In the electrophilic oxidation by peroxides the reactivity of sulfoxides is considerably less affected by structural effects than that of thioethers. This feature has not been, so far, rationalized. We have calculated by semiempirical methods the charge on the sulfur atom, Q(S), and the energy of the HOMO for a series of thioethers and sulfoxides. Then we have correlated the rate constants for the oxidation of thioethers by H3O2+ and of sulfoxides by perbenzoic acid with Q(S) and with F (F = (E(LUMO)(Ox) - E(HOMO)(Sub))(-1) respectively. We find that the reactivity of thioethers is mainly dependent on Q(S), while that of sulfoxides is dominated by F.

引用

页码：12363 / 12372

页数：10

共 26 条

[1] THIANTHRENE 5-OXIDE AS A MECHANISTIC PROBE FOR ASSESSING THE ELECTRONIC CHARACTER OF OXYGEN-TRANSFER AGENTS [J].

ADAM, W ;

HAAS, W ;

LOHRAY, BB .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1991, 113 (16) :6202-6208

[2] APPLICATION OF THE THIANTHRENE 5-OXIDE MECHANISTIC PROBE TO PEROXOMETAL COMPLEXES [J].

BALLISTRERI, FP ;

TOMASELLI, GA ;

TOSCANO, RM ;

CONTE, V ;

DIFURIA, F .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1991, 113 (16) :6209-6212

[3] ENANTIOSELECTIVE OXIDATION OF THIOETHERS1 - AN EASY ROUTE TO ENANTIOPURE C-2 SYMMETRICAL BIS-METHYLSULFINYLBENZENES [J].

BENDAZZOLI, P ;

DIFURIA, F ;

LICINI, G ;

MODENA, G .

TETRAHEDRON LETTERS, 1993, 34 (18) :2975-2978

[4] THE RELATIVE REACTIVITY OF THIOETHERS AND SULFOXIDES TOWARD OXYGEN-TRANSFER REAGENTS - THE OXIDATION OF THIANTHRENE 5-OXIDE AND RELATED-COMPOUNDS BY MOO(5)HMPT [J].

BONCHIO, M ;

CONTE, V ;

DECONCILIIS, MA ;

DIFURIA, F ;

BALLISTRERI, FP ;

TOMASELLI, GA ;

TOSCANO, RM .

JOURNAL OF ORGANIC CHEMISTRY, 1995, 60 (14) :4475-4480

[5] METAL CATALYSIS IN OXIDATION BY PEROXIDES .11. KINETICS AND MECHANISM OF MOLYBDENUM-CATALYZED OXIDATION OF SULFIDES AND ALKENES WITH HYDROGEN-PEROXIDE [J].

BORTOLINI, O ;

DIFURIA, F ;

MODENA, G ;

SCARDELLATO, C ;

SCRIMIN, P .

JOURNAL OF MOLECULAR CATALYSIS, 1981, 11 (01) :107-118

[6] METAL CATALYSIS IN OXIDATION BY PEROXIDES .28. ANIONIC MOLYBDENUM-PICOLINATE N-OXIDO-PEROXO COMPLEX - AN EFFECTIVE OXIDANT OF PRIMARY AND SECONDARY ALCOHOLS IN NONPOLAR-SOLVENTS [J].

BORTOLINI, O ;

CAMPESTRINI, S ;

DIFURIA, F ;

MODENA, G ;

VALLE, G .

JOURNAL OF ORGANIC CHEMISTRY, 1987, 52 (24) :5467-5469

[7] METAL CATALYSIS IN OXIDATION BY PEROXIDES .13. THE ELECTROPHILIC CHARACTER OF THE OXYGEN-TRANSFER FROM PEROXOMOLYBDENUM(VI) TO SULFIDES [J].

BORTOLINI, O ;

DIFURIA, F ;

MODENA, G .

JOURNAL OF MOLECULAR CATALYSIS, 1982, 14 (01) :53-62

[8]

Burkert U., 1982, ACS MONOGRAPH

[9] MECHANISM OF ALCOHOL OXIDATIONS BY ANIONIC PEROXOMOLYBDENUM COMPLEXES [J].

CAMPESTRINI, S ;

DIFURIA, F .

TETRAHEDRON, 1994, 50 (17) :5119-5130

[10] METAL CATALYSIS IN OXIDATION BY PEROXIDES .30. ELECTROPHILIC OXYGEN-TRANSFER FROM ANIONIC, COORDINATIVELY SATURATED MOLYBDENUM PEROXO COMPLEXES [J].

CAMPESTRINI, S ;

CONTE, V ;

DIFURIA, F ;

MODENA, G ;

BORTOLINI, O .

JOURNAL OF ORGANIC CHEMISTRY, 1988, 53 (24) :5721-5724

← 1 2 3 →