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Oxidation of Symmetric Disulfides with Hydrogen Peroxide

Catalyzed by Methyltrioxorhenium(VII)
Yi ng Wang and James H. Espenson*
Ames Laboratory and Department of Chemistry, I owa StateUniversity of Scienceand Technology,
Ames, I owa 50011
Received J uly 12, 1999
Organi c di sul fi des wi th both al kyl and aryl substi tuents are oxi di zed by hydrogen peroxi de when
CH
3
ReO
3
(MTO) i s used as a catal yst. The fi rst step of the reacti on i s compl ete usual l y i n about an
hour, at whi ch poi nt the thi osul fi nate, RS(O)SR, can be detected i n nearl y quanti tati ve yi el d. The
thi osul fi nate i s then converted, al so by MTO-catal yzed oxi dati on under these condi ti ons, to the
thi osul fonate and, over l ong peri ods, to sul foni c aci ds, RSO
3
H. I n the absence of excess peroxi de,
RS(O)SR (R ) p-tol yl ), underwent di sproporti onati on to RS(O)
2
SR and RSSR. Ki neti cs studi es of
the fi rst oxi dati on reacti on establ i shed that two peroxorheni um compounds are the acti ve forms of
the catal yst, CH
3
ReO
2
(
2
-O
2
) (A) and CH
3
ReO(
2
-O
2
)
2
(OH
2
) (B). Thei r reacti vi ti es are si mi l ar; typi cal
rate constants (L mol
-1
s
-1
, 25 C, aqueous acetoni tri l e) are k
A
) 22, k
B
) 150 (Bu
2
S
2
) and k
A
) 1.4,
k
B
) 11 (Tol
2
S
2
). An anal ysi s of the data for (p-XC
6
H
4
)
2
S
2
by a pl ot of l og k
B
agai nst the Hammett
constant gave F ) -1.89, supporti ng a mechani sm i n whi ch the el ectron-ri ch sul fur attacks a
peroxo oxygen of i ntermedi ates A and B.
Introduction
Oxi dati on of the di sul fi de functi onal group (1, Chart
1) has been studi ed qui te extensi vel y because of i ts
i mportant rol e i n metabol i sm, vi a a vari ety of mechani sti c
paths.
1
Wi th the use of di fferent oxi dants and wel l -
control l ed si tuati ons, vari ous i ntermedi ate compounds
have been obtai ned.
2-6
Among these are thi osul fi nates,
2, whi ch can provi de a sul fi nyl group that acts as a
removabl e source of di asterosel ecti vi ty i n asymmetri c
syntheses.
7
Si mi l arl y, such reacti ons can produce thi o-
sul fonates, 3, whi ch are powerful sul fenyl ati ng agents
useful for the temporary bl ocki ng of mercapto groups i n
protei n chemi stry.
8
Peraci ds are the reagents most commonl y used to
oxi di ze di sul fi des, al though hydrogen peroxi de i n aceti c
aci d al so fi nds appl i cati on. The hydrogen peroxi de reac-
ti ons, i n the absence of a catal yst, often requi re a l arge
excess and a hi gher temperature.
1,3
Oxometal compl exes
are catal ysts for the oxi dati on; mol ybdates and tungstates
are effective, especially under phase-transfer conditions.
9-11
Methyl tri oxorheni um, CH
3
ReO
3
or MTO, has been
wi del y used as a catal yst for reacti ons that use hydrogen
peroxi de as a stoi chi ometri c oxi dant.
12-15
One can anti ci -
pate that ei ther or both of the peroxorheni um speci es that
exi st i n an equi l i bri um or a steady-state rel ati on wi th
MTO, as shown i n Scheme 1, wi l l be the acti ve form of
the catal yst. Si nce a sequence of oxi dati on steps wi l l
occur, the experi ments were carri ed out. The pri nci pal
objecti ve of thi s research i s the study of the reacti on
ki neti cs, of the fi rst stage i n parti cul ar, as wri tten i n eq
1.
The fi rst reacti on proved to be faster than the subse-
quent oxi dati ons. Thi s al l owed, when hydrogen peroxi de
was taken i n onl y 1:1 rati o to the di sul fi de, the detecti on
of the thi osul fi nates, otherwi se di ffi cul t to real i ze owi ng
to thei r transi ent nature. We al so report, qual i tati vel y,
on the formati on of thi osul fonates and sul foni c aci ds.
Experimental Section
Reagents. Aqueous acetoni tri l e was used as the reacti on
sol vent, the water bei ng puri fi ed by a Mi l l i pore-Q water
puri fi cati on system. The di sul fi des were used as recei ved from
Al dri ch, save for p-chl orophenyl di sul fi de, whi ch was prepared
(1) Organic Sulfur Chemistry: Structureand Mechanism; Oae, S.,
Ed.; CRC Press: Boca Raton, 1991; Vol . 1, pp 213-216.
(2) Bhattacharya, A. K.; Hortman, A. G. J . Org. Chem. 1978, 43,
2728.
(3) Al l en, P., Jr; Brook, J. W. J . Org. Chem. 1962, 27, 1019.
(4) Gu, D.; Harpp, D. N. Tetrahedron Lett. 1993, 34, 67.
(5) Fol ki ns, P. L.; Harpp, D. N. J . Am. Chem. Soc. 1993, 115, 3066.
(6) Freeman, F. Chem. Rev. 1984, 84, 117-135.
(7) Cogan, D. A.; Li u, G.; Ki m, K.; Backes, B. J.; El l man, J. A. J .
Am. Chem. Soc. 1998, 120, 8011.
(8) Trost, B. M. Chem. Rev. 1978, 78, 8.
(9) Ani si mov, A. V.; Mokhammad, R.; Akhmad, S. A.; Bori senkova,
A. V.; Tarakanova, S. V.; Barkhanova, S. V.; Dergacheva, V. M.;
Negri movski i , V. M.; Kal i ya, O. L.; Lukyanets, E. A. Neftekhimiya
1994, 34, 358.
(10) Ani si mov, A. V.; Mokhammad, R. A.; Tarakanova, A. V.;
Bori senkova, S. A. Neftekhimiya 1994, 34, 421.
(11) Si ngh, P. K.; Fi el d, L. J. J . Org. Chem. 1988, 53, 2608.
(12) Espenson, J. H.; Abu-Omar, M. M. Adv. Chem. Ser. 1997, 253,
99-134.
(13) Gabl e, K. P. Adv. Organomet. Chem. 1997, 41, 127-161.
(14) Herrmann, W. A.; Kuhn, F. E. Acc. Chem. Res. 1997, 30, 169-
180.
(15) Espenson, J. H. J . Chem. Soc., Chem. Commun. 1999, 479-
488.
Chart 1. Disulfide and Oxidation Products; R )
Alkyl, Aryl
A/B + RSSR f MTO/A + RS(O)SR + H
2
O (1)
104 J . Org. Chem. 2000, 65, 104-107
10.1021/jo991109w CCC: $19.00 2000 Ameri can Chemi cal Soci ety
Publ i shed on Web 12/09/1999
by the l i terature method
16
and puri fi ed by recrystal l i zati on
from ethanol -water, and for tert-butyl di sul fi de, whi ch was
vacuum di sti l l ed.
Kinetics. Both UV/vi si bl e and
1
H NMR methods were used.
Quanti tati ve measurements were made at 25 C i n 4:1 v/v
acetoni tri l e-water at pH 1 (to stabi l i ze MTO i n peroxi de-
contai ni ng medi a)
17
mai ntai ned by tri fl uoromethanesul foni c
aci d. Owi ng to the l arge mol ar absorpti vi ti es of the di aryl
di sul fi des, i t was often necessary to use cuvettes of 0.01-0.05
cm opti cal path. One or more wavel engths were chosen for each
compound to al l ow quanti tati ve moni tori ng of the reacti on
progress. The condi ti ons and wavel engths sel ected were such
that the l oss of ArSSAr was fol l owed, al though at other
wavel engths not used for ki neti cs, a ri se i n absorbance
accompanyi ng the bui l dup of 2 coul d be seen. Under the
condi ti ons of the spectrophotometri c determi nati ons, pri nci -
pal l y that [ArSSAr] was qui te l ow and [H
2O2] effecti vel y
constant, the reacti ons fol l owed pseudo-fi rst-order ki neti cs.
The absorbance-ti me data from each experi ment were ana-
l yzed accordi ng to eq 2, from whi ch a val ue of k was obtai ned
by nonl i near l east-squares fi tti ng. I n the case of di al kyl
di sul fi des, where there are no useful UV absorpti ons, the
reacti on ki neti cs was eval uated from NMR i ntensi ti es. These
val ues were converted by computer program
18
to concentra-
ti ons based on the total i ntensi ty of the starti ng materi al .
Certai n data sets were anal yzed by fi rst-order ki neti cs accord-
i ng to eq 3. That was al l owabl e at hi gh concentrati ons of
hydrogen peroxi de, where (see l ater) the rate becomes peroxi de-
i ndependent. However, at l ower peroxi de concentrati ons the
data conform to the Mi chael i s-Menten form for catal yti c
reacti ons, and the data cannot be anal yzed by an i ntegrated
rate l aw. I n these ci rcumstances the method of i ni ti al rates
was used. To determi ne the val ue of the i ni ti al rate, v
i , the
concentrati on was expressed as a pol ynomi al functi on (eq 4)
by l east-squares fi tti ng, from whi ch i t can be seen that v
i )
a1. For one compound, wi th R ) p-tol yl , i t was confi rmed that
both UV and NMR methods gave the same ul ti mate parameter
val ue.
Products. The procedure used to i denti fy the reacti on
products was based on chromatography and spectroscopy. A
sol uti on contai ni ng MTO (2.5 mol ) and hydrogen peroxi de (1
mmol ) was sl owl y added to 1 mmol p-di tol yl di sul fi de (for
exampl e) i n 5.0 mL of acetoni tri l e. The reacti on was al l owed
to run for 2 h, duri ng whi ch ti me i ts progress was moni tored
peri odi cal l y by TLC. When thi s test showed that the reacti on
progress had nearl y stopped, the mi xture was separated by
preparati ve TLC, usi ng cycl ohexanes-ethyl acetate (95:5) as
the el uti ng agent. Thi s gave p-tol yl p-tol uenethi osul fi nate, 2,
as the major product, al ong wi th a barel y detectabl e amount
of p-tol yl p-tol uenethi osul fonate, 3. These products were
i denti fi ed ei ther by
1
H NMR and GC-MS techni ques, i n
compari son wi th the val ues of the authenti c compounds, or
l i terature val ues.
7,19-21
Addi ng excess hydrogen peroxi de i nto
the above sol uti on eventual l y afforded the fi nal product,
p-tol uenesul foni c aci d. The reacti on was al so moni tored by
1
H
NMR, duri ng whi ch both the thi osul fi nate 2and thi osul fonate
3were detected. No R,R-di sul fonate 4was detected for any of
the substrates used i n thi s study.
Results
PreliminaryExperiments. No si gni fi cant i nteracti on
was found between the di sul fi des and MTO on the basi s
of
1
H NMR resul ts. Thi s fi ndi ng i mpl i es that the reacti on
does not proceed by way of a pri or compl ex between these
two. The resul t further suggests that the reacti on, when
i t does occur as hydrogen peroxi de i s added, does not
feature attack of the sul fur at the rheni um center, for
there i s no reason to bel i eve that thi s i nteracti on woul d
occur then, when i t di d not do so on i ts own. Al l si x
substrates (see Tabl e 1) were i ni ti al l y exami ned i n the
absence of a catal yst. Wi thout MTO, there was no
evi dence for a reacti on, even wi th excess hydrogen
peroxi de, as i ndi cated ei ther by a UV spectrum that
remai ned nearl y unchanged for several hours or by the
absence of new peaks growi ng i n the NMR spectrum.
Once MTO had been added, however, the spectra
i mmedi atel y began to show the bui l dup of the product.
These determi nati ons were al so performed wi th equal
i ni ti al concentrati ons of the di sul fi de and hydrogen
peroxi de. A certai n smal l amount of the thi osul fonate was
detected al ong wi th the major thi osul fi nate for R ) Ph,
p-tol yl , and p-chl orophenyl . Wi th three of the compounds,
those wi th R ) Me,
t
Bu, and p-ni trophenyl , the thi osul -
fi nate was very nearl y the onl y product. I sosbesti c poi nts
were mai ntai ned duri ng these reacti ons, even wi th a
smal l excess of hydrogen peroxi de. Such a seri es of
repeti ti ve scans i s shown i n Fi gure 1.
For thi s second group of di sul fi des, the further steps
of oxi dati on beyond the thi osul fi nate are a great deal
sl ower, and for al l of the di sul fi des studi ed there i s a
(16) Overman, L. E.; Matzi nger, D.; OConnor, E. M.; Overman, J.
D. J . Am. Chem. Soc. 1974, 96, 6089.
(17) Abu-Omar, M.; Hansen, P. J.; Espenson, J. H. J . Am. Chem.
Soc. 1996, 118, 4966-4974.
(18) We are grateful to Dr. M. Engl ehardt of Bruker Corp. for
suppl yi ng thi s program.
(19) Kozzuka, S.; Takahashi , H.; Oae, S. Bull. Chem. Soc. J pn. 1970,
43, 129 and references therei n.
(20) Cheml a, F. Synlett 1998, 894.
(21) Sas, W. J . Chem. Res. 1993, 160.
Scheme 1
Abs
t
) Abs

+ (Abs
0
- Abs

) exp
-k

t
(2)
C
t
) C
0
e
-k

t
(3)
C
t
) C
0
- a
1
t - a
2
t
2
- a
3
t
3
- ... (4)
Table 1. Rate Constants at 298 K for the Oxidation of
Disulfides by PeroxorheniumComplexes A (k3) and B
(k4) in Aqueous Acetonitrile
a-c
Containing 0.100 M
CF3SO3H
Hydrogen Peroxi de Oxi dati on of Symmetri c Di sul fi des J . Org. Chem., Vol. 65, No. 1, 2000 105
consi derabl e rate advantage found i n the fi rst stage of
oxi dati on. Thi s i nformati on was used to pl an the quan-
ti tati ve studi es of the ki neti cs, so that onl y the fi rst
oxi dati on stage was i mportant duri ng the data acqui si -
ti on ti me.
KineticsStudies. The fi rst part of understandi ng the
reacti on scheme l i es i n the two ki neti c steps shown i n
Scheme 1. I n thi s sol vent system, these are the rel evant
parameters at 298 K: k
1
) 15.5 L mol
-1
s
-1
, k
-1
) 0.17
s
-1
, K
1
) 91 L mol
-1
, K
2
) 347 L mol
-1
.
22
I t i s useful to
di fferenti ate studi es at l ow and hi gh concentrati ons
of hydrogen peroxi de, by whi ch we mean experi ments at
<7 mM and >0.5 M, respecti vel y. We start by presumi ng
that A and B are separate parti ci pants i n the oxi dati on
and denote thei r respecti ve rate constants as k
3
and k
4
.
We further presumed, and l ater confi rmed for two
compounds, that k
3
and k
4
are of the same order of
magni tude. I f so, then the term i n the rate l aw for the
reacti on of B wi th di sul fi de makes e10%contri buti on i n
experi ments wi th l ow concentrati ons of hydrogen per-
oxi de. Under those condi ti ons, the reacti on proceeds
l argel y wi th the A form of the catal yst, and i ts vel oci ty
i s gi ven by
For purposes of data anal ysi s, the val ues of k
1
and k
-1
were set at thei r known val ues.
22
Wi th that, the onl y
unknown i n eq 5 i s k
3
. I ts val ue coul d be determi ned for
each experi ment, whether the data were i n the form of
v
i
or k

. Under those condi ti ons the vari ati on i n the i ni ti al


rate wi th hydrogen peroxi de concentrati on, at fi xed
concentrati ons of the di sul fi de and MTO, defi nes a
rectangul ar hyperbol a. Data from experi ments wi th
Me
2
S
2
are presented i n Fi gure 2. A second method for
data anal ysi s, based on the same chemi cal mechani sm,
was used for di -tert-butyl di sul fi de. The concentrati on-
ti me data for al l of the experi ments wi th
t
Bu
2
S
2
were fi t
gl obal l y wi th the use of the program Fi tSi m.
23
At hi gh hydrogen peroxi de, when [B] . [A], the
absorbance-ti me (UV-vi s) or concentrati on-ti me (NMR)
data fi t fi rst-order ki neti cs. Because [B] = [Re]
T
, the rate
l aw under thi s condi ti on becomes
For these determi nati ons, a seri es of experi ments was
carri ed out wi th constant [H
2
O
2
] and [R
2
S
2
] i n whi ch [Re]
T
was vari ed, typi cal l y 0.1-0.5 mM. The pl ot of k

agai nst
[Re]
T
was l i near, as depi cted for three compounds i n
Fi gure 3. The val ues of k
4
gi ven by the sl opes of these
l i nes are summari zed i n Tabl e 1.
I t shoul d be noted that the vari ous aspects of the data
anal ysi s presented are al l di fferent components of the
same reacti on scheme. The di fferences ari se from the
di fferent ranges of concentrati on chosen for di fferent sets
of experi ments and al so because the rel ati ve rate con-
stants are di fferent from one di sul fi de to the next.
Fate of the Thiosulfinates. Compounds of the for-
mul a RS(O)SR tend to be unstabl e and usual l y cannot
be i sol ated. Careful NMR measurements were made
duri ng the reacti on between 20 mM di (p-tol yl ) di sul fi de
and a l i mi ted (10 mM) concentrati on of hydrogen perox-
i de. Once the thi osul fi nate had been formed, i t sl owl y
decomposed wi th the formati on of the thi osul fonate, RS-
(O)
2
SR, and parti al regenerati on of the di sul fi de. Thi s i s
compati bl e wi th a di sproporti onati on process:
A compani on experi ment wi th di (tert-butyl ) di sul fi de gave
a thi osul fi nate that seemed stabl e for a much l onger
(22) Huang, R.; Espenson, J. H. J . Org. Chem. 1999, 64, 6374. (23) Zi mmerl e, C. T.; Fri eden, C. Biochem. J . 1989, 258, 381-387.
Figure 1. Spectral changes at 5.0 mi n i nterval s for the
oxi dati on of p-ni trophenyl di sul fi de (0.5 mM) wi th H2O2 (0.65
M) i n the presence of 0.1 mM MTO at pH 1 i n 4:1 CH3CN-
H2O.
v )
k
1
k
3
[Re]
T
[R
2
S
2
][H
2
O
2
]
k
-1
+ k
3
[R
2
S
2
] + k
1
[H
2
O
2
]
(5)
Figure 2. Vari ati on of i ni ti al rate of reacti on of di methyl
di sul fi de wi th the concentrati on of hydrogen peroxi de. The
curve i s a fi t to eq 5.Thi s i s appl i cabl e when [B] i s negl i gi bl e
compared to [A]. The val ues of k1 and k-1 (Scheme 1) were
fi xed at 15.5 L mol
-1
s
-1
and 0.17 s
-1
. Condi ti ons used: 0.5
mM MTO, 5 mM Me2S2 i n 4:1CH3CN-H2O at 25.0 C and pH
1.
v ) k
4
[Re]
T
[R
2
S
2
] ) k

[R
2
S
2
] (6)
2RS(O)SR f RS(O)
2
SR + RSSR (7)
106 J . Org. Chem., Vol. 65, No. 1, 2000 Wang and Espenson
peri od, suggesti ng that di sproporti onati on i s steri cal l y
i mpeded by the bul ky R group.
Discussion
To assess the extent to whi ch el ectroni c factors pl ay a
rol e i n the transi ti on state, the rate constants for the
di aryl di sul fi des were exami ned by the Hammett cor-
rel ati on. The pl ot of l og(k
4
) vs , the Hammett substi tuent
constant, was constructed (Fi gure 4. The four poi nts
defi ne a reasonabl e strai ght l i ne; i ts sl ope i s the reacti on
constant, F ) -1.89 (correl ati on coeffi ci ent 0.997). The
negati ve val ue of F i mpl i es that the reacti on center (the
sul fur atom) shows a bui l dup of posi ti ve charge rel ati ve
to that i n the free mol ecul e. Thi s effect, al though i n the
same di recti on, i s consi derabl y l arger than that found
for RSAr (F ) -0.98).
24
We argue that the enhanced F
val ue ari ses pri nci pal l y from the conjugati ve effect caused
by the para-conjugated phenyl mercapto group. I n thi s
case, the el ectroni c effect of thi s group seems comparabl e
to that of a phenyl group. The el ectroni c effect of the para
substi tuent on the sul fur atom that i s not bei ng oxi di zed
appears muted.
When these resul ts are combi ned wi th the i nformati on
al ready avai l abl e about organi c sul fi des
24
and thi oke-
tones,
22
compari sons can be made to gai n an understand-
i ng of these resul ts. The di sul fi des are some 10
3
-10
4
l ess
reacti ve than ei ther of those fami l i es of compounds. Thi s
compari son does not requi re a preci se one-to-one match
of substi tuents, because the rate effects are qui te l arge.
Thi s i s one seri es that i s reasonabl e for compari son: for
Et
2
S, thi ocamphor, and Me
2
S
2
, val ues of k
3
are 2 10
4
,
3 10
3
, and 6.4 L mol
-1
s
-1
. Thi s l arge di fference can be
ascri bed to the substi tuti on of an SR group for an R
group. Despi te the el ectron-rel easi ng conjugati ve effect,
the SMe group i s el ectron-wi thdrawi ng; i ts Hammett
val ue i s +0.07 and the Taft
1
val ue i s +0.23. Thi s effect
may l ower the nucl eophi l i ci ty of the sul fur atom to whi ch
i t i s bound i n the di sul fi de, thus l oweri ng, rel ati ve to the
sul fi des and thi oketones, the rate at whi ch i t attacks the
peroxorheni um compound.
The reacti vi ty of B as compared to A i s gi ven by the
rati o k
4
/k
3
. Wi th but the one excepti on of al l yl al cohol s,
25
cl earl y a speci al case, the reacti vi ty of these two are
comparabl e and often i n favor of A. I n the two cases
exami ned here (and by extrapol ati on, l i kel y al l si x) B i s
somewhat more reacti ve than A by a factor of ca. 7.
From the resul ts obtai ned here and the general pattern
set by other reagents wi th the MTO-H
2
O
2
system, we
propose a transi ti on state i n whi ch one sul fur atom of
the substrate nucl eophi cal l y attacks the peroxo group of
A or B. Probi ng more cl osel y, we note that certai n
reacti ons show vi rtual l y no steri c effect, such as observed
for R
2
S
2
: the val ues of k
3
are 6.4 (R ) Me) and 5.6 (R )
t
Bu) L mol
-1
s
-1
. Thi s i nsensi ti vi ty of rate to steri c bul k
i s i n accord wi th val ues for PAr
3
,
26
R
2
S,
24
and Br
-
.
27
I n
contrast, the epoxi dati on of ol efi ns show an i mportant
steri c effect.
28
Oxi dati on of MeSS
t
Bu by peraceti c aci d
forms MeS(O)S
t
Bu and MeSS(O)
t
Bu i n 1:2 yi el d,
29
show-
i ng that these reacti ons al so have smal l steri c effects.
Acknowledgment. Thi s research was supported by
the U. S. Department of Energy, Offi ce of Basi c Energy
Sci ences, Di vi si on of Chemi cal Sci ences under contract
W-7405-Eng-82.
JO991109W
(24) Vassel l , K. A.; Espenson, J. H. I norg. Chem. 1994, 33, 5491.
(25) Tetzl aff, H. A. R.; Espenson, J. H. I norg. Chem. 1999, 38, 881-
885.
(26) Abu-Omar, M. M.; Espenson, J. H. J . Am. Chem. Soc. 1995,
117, 272.
(27) Espenson, J. H.; Pestovsky, O.; Huston, P.; Staudt, S. J . Am.
Chem. Soc. 1994, 116, 2869.
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Figure3. The pseudo-fi rst-order rate constants (4:1 CH3CN-
H2O at 25.0 C and pH 1) for the oxi dati on of di aryl di sul fi des
(0.5 mM) by H2O2 (0.65 M) vary l i nearl y wi th the total catal yst
concentrati on, as shown i n order of i ncreasi ng sl ope for the
para substi tuents NO2, Cl , and H. The sl ope of thi s l i ne affords
the val ues of k4.
Figure 4. Hammett pl ot for the oxi dati on of substi tuted
phenyl di sul fi des by the peroxorheni um compound B. The
sl ope of the l i ne gi ves F ) -1.89.
Hydrogen Peroxi de Oxi dati on of Symmetri c Di sul fi des J . Org. Chem., Vol. 65, No. 1, 2000 107