OXIDATION OF THIOLS TO

DISULFIDES WITH
MOLECULAR BROMINE ON
HYDRATED SILICA GEL SUPPORT
Mohammed Hashmat Ali*, J. Mario
McDermott
Chemistry Department
Southeast Missouri State University
Cape Girardeau, Missouri 63701.

Reaction Scheme
Hydrated Silica gel,
Methylene chloride
Bromine

RSH
SH
SH

Hydrated Silica gel,

Methylene chloride
Bromine

RSSR
S
S

Introduction
We have developed a procedure for oxidation
of thiols to disulfides with moleculer bromine
on hydrated silica gel support. This procedure
is simple, highly efficient, and very selective.
Presence of a base to neutralize the hydrogen
bromide formed in the reaction is not
necessary. A variety of thiols can be oxidized
to the corresponding disulfides.
Cyclic
disulfides of various ring size can also be
easily prepared from dithiols utilizing this
procedure.

Oxidation of Thiols to Disulfides with Molecular Bromine

CH3(CH2)6CH2SH

CH3(CH2)6CH2S-SCH2(CH2)6CH3
100%

CH3CH2CH2CH2SH

CH3CH2CH2CH2S-SCH2CH2CH2CH3
100%

HOCH2CH2SH

CH3CH2CHCH3SH

HOCH2CH2S-SCH2CH2OH
98%

CH3CH2CHCH3S-SCH3CHCH2CH3
100%

(CH 3)3CSH

(CH 3)3CS-SC(CH 3)3

97%

CH3CH2SH

CH3CH2S-SCH 2CH 3
98%

(CH 3)2CHSH

(CH 3)2CHS-SCH(CH 3)2

98%

PhCH 2SH

PhCH 2S-SCH 2Ph

97%

PhCH 2CH2CH 2SH

Ph(CH 2)2CH2S-SCH 2(CH 2)2Ph

92%

SH

CH3

H3C

S S

CH3

100%

CH3O

SH

CH3O

S S

OCH3

100%

Cl

SH

Cl

S S
97%

SH
SH

S
S
100%

Cl

SH

SH

S
86%
HO

HO

SH
SH

HO

HO

94%

SH

S
S
95%

SH

S S

SH

SH

S
91%

SH

SH

S
89%

Experimental Procedure
The following procedure is general for the
reported reactions.
2.5 mL of water was added dropwise to a 5 gm
of silica gel with stirring. Stirring continued
until a free flowing solid was obtained. 25 mL of
methylene chloride was added to the flask
followed by the addition of 2-3 mmole of the
thiol under investigation. A solution of bromine
on methylene chloride was added drop by drop

until a faint orange color persisted or TLC

indicated the complete disappearance of the
starting thiol. The reaction mixture was
then filtered and the solid was washed with
about 75-80 mL of methylene chloride.
Removal of the solvent from the filtrate
produced the disulfide product which was
often pure by NMR and TLC. Impure
products were purified by radial
chromatography.

Advantages of Hydrated Silica Gel

Support

Organic solvents can be employed

in the reactions which previously
required aqueous media.

Activates reagents by dispersing

active sites.

Simplifies work-up of the reaction .

Eliminates or reduces exposure to toxic

reagents.

Produces easy-to-handle solid

waste.

Generates smaller amounts of

waste.

Conclusions:

The procedure described has the

following desirable qualities:

Employs non-aqueous media.

Simple procedure.

Presence of a base is not required

to neutralize the hydrogen bromide
formed in order to prevent side
reactions. Hydrogen bromides are
absorbed on the silica gel and are
removed from the reaction.

Excellent efficiency.

Highly selective.

Work-up is trivial.

Environmentally benign.

Acknowledgment
Grants and Research Funding Committee
Chemistry Department
Southeast Missouri State University
Cape Girardeau, Missouri 63701

Southeast Missouri State University

Southeast Missouri State University