Soft liquid-phase oxidation sulfides with the systems on the base of the element-containing alkoxides and tert-butylhydroperoxide

Full text of DOI:10.1080/10426500590913519

This article was downloaded by: [University of York]
On: 02 December 2014, At: 07:02
Publisher: Taylor & Francis
Informa Ltd Registered in England and Wales Registered Number: 1072954
Registered office: Mortimer House, 37-41 Mortimer Street, London W1T 3JH,
UK
Phosphorus, Sulfur, and Silicon
and the Related Elements
Publication details, including instructions for
authors and subscription information:
http://www.tandfonline.com/loi/gpss20
Soft Liquid-Phase Oxidation
Sulfides with the Systems
on the Base of the Element-
Containing Alkoxides and Tert-
Butylhydroperoxide
Elena A. Zaburdaeva a , Viktor A. Dodonov a , Larisa
P. Stepovik a & Irina A. Kapuskina a
a N. I. Lobachevsky Nizhny Novgorod State
University , Nizhny Novgorod, Russia
Published online: 16 Aug 2006.
To cite this article: Elena A. Zaburdaeva , Viktor A. Dodonov , Larisa P. Stepovik
& Irina A. Kapuskina (2005) Soft Liquid-Phase Oxidation Sulfides with the Systems
on the Base of the Element-Containing Alkoxides and Tert-Butylhydroperoxide,
Phosphorus, Sulfur, and Silicon and the Related Elements, 180:5-6, 1521-1522, DOI:
10.1080/10426500590913519
To link to this article: http://dx.doi.org/10.1080/10426500590913519
PLEASE SCROLL DOWN FOR ARTICLE
Taylor & Francis makes every effort to ensure the accuracy of all the
information (the “Content”) contained in the publications on our platform.
However, Taylor & Francis, our agents, and our licensors make no
representations or warranties whatsoever as to the accuracy, completeness,
or suitability for any purpose of the Content. Any opinions and views
expressed in this publication are the opinions and views of the authors, and
are not the views of or endorsed by Taylor & Francis. The accuracy of the
Content should not be relied upon and should be independently verified with

primary sources of information. Taylor and Francis shall not be liable for any
losses, actions, claims, proceedings, demands, costs, expenses, damages,
and other liabilities whatsoever or howsoever caused arising directly or
indirectly in connection with, in relation to or arising out of the use of the
Content.
This article may be used for research, teaching, and private study purposes.
Any substantial or systematic reproduction, redistribution, reselling, loan,
sub-licensing, systematic supply, or distribution in any form to anyone is
expressly forbidden. Terms & Conditions of access and use can be found at
http://www.tandfonline.com/page/terms-and-conditions

Phosphorus, Sulfur, and Silicon, 180:1521–1522, 2005
Copyright © Taylor & Francis Inc.
ISSN: 1042-6507 print / 1563-5325 online
DOI: 10.1080/10426500590913519
Soft Liquid-Phase Oxidation Sulfides with the Systems
on the Base of the Element-Containing Alkoxides and
Tert-Butylhydroperoxide
Elena A. Zaburdaeva
Viktor A. Dodonov
Larisa P. Stepovik
Irina A. Kapuskina
N. I. Lobachevsky Nizhny Novgorod State University,
Nizhny Novgorod, Russia
Keywords Electron-excited dioxigen; metal containing trioxides; oxidation; sulfides; sul-
fones; tert-butoxides of aluminum and titanium; tert-butylhydroperoxide
The tri-tert-butoxyaluminum (1)-tert-butylhydroperoxide (2) and tetra-
tert-butoxytitanium (3)-hydroperoxide (2) systems in molar ratio alkox-
ide:(2) = 1:2 in soft conditions (rt, 1 h) oxidize alkyl and alkylaryl
sulfides to corresponding sulfones with practically quantitative yields
(Table I).
Oxidation proceeds under the action of the electron-excited (singlet)
dioxygen generating by the (1)-(2) or (3)-(2) systems. Such active dioxy-
gen forms by the consecutive reactions with participation of the coordi-
native sphere of the atoms of the elements (Al or Ti).1,2
The intermediate formation of thiadioxirane is supposed.2
Received July 9, 2004; accepted October 5, 2004.
Address correspondence to Elena A. Zaburdaeva, N. I. Lobachevsky Nizhny Novgorod
State University, 23 prosp. Gagarina, 603950 Nizhny Novgorod, Russia. E-mail: zaea4@
rambler.ru
1521

1522
E. A. Zaburdaeva et al.
TABLE I Oxidation of Sulfides RSRꢀ with the
Tri–tert-butoxyaluminum–tert-butylhydroperoxide System (1:2)a,b
Products in volatile
fraction, mol per
1 mol RSRꢀ
Products after hydrolyzes
of insoluble residue,
mol per 1 mol RSRꢀ
Sulfide
Rꢀ
N
R
t-BuOOH t-BuOH
RSRꢀ
t-BuOOH t-BuOH
RSRꢀ
RSO2Rꢀ
1
2
3
4
5
6
7
Me Me
0.04
0.06
0.06
0.05
0.04
—
2.26
2.30
1.73
2.40
1.96
2.24
2.29
0.04
Traces
Traces
—
0.05
—
0.03
—
0.15
0.14
0.04
—
1.62
—
—
—
0.94
0.79
0.98
0.96
0.93
0.80
0.96
Et
Pr
Et
Pr
2.22
1.92
2.38
2.46
—
Traces
0.03
0.02
0.12
—
Bu Bu
Me Ph
Ph Ph
Bn Bn
0.05
—
0.22
a20◦C, solvent C6H6; C6H5Cl (N 2) and CCl4(N 6).
bMiddle dates, mol per 1 mol RSRꢀ.
It is known3,4 that photooxidation of sulfides forms the corresponding
sulfoxides. Hydroperoxide (2) and (t-BuO)n−1MOOBu-t present in our
systems do not oxidize sulfides to sulfones under the same conditions.
REFERENCES
[1] L. P. Stepovik, I. M. Martinova, V. A. Dodonov, and V. K. Cherkasov, Russ. Chem.
Bull. Int. Ed., 51, 638 (2002).
[2] V. A. Dodonov, E. A. Zaburdaeva, and L. P. Stepovik, Russ. Chem. Bull. Int. Ed., 53,
1729 (2004).
[3] J. H. Liang, C. L. Gu, M. L. Kacher, and C. S. Foote, J. Am. Chem. Soc., 105, 4717
(1983).
[4] Y. Watanabe, N. Kuriki, N. Ishiguro, and T. Sawaki, J. Am. Chem. Soc., 113, 2677
(1991).