catalysts

Article
The Selective Oxidation of Sulfides to Sulfoxides or
Sulfones with Hydrogen Peroxide Catalyzed by
a Dendritic Phosphomolybdate Hybrid
Qiao-Lin Tong † , Zhan-Fang Fan † , Jian-Wen Yang, Qi Li, Yi-Xuan Chen, Mao-Sheng Cheng and
Yang Liu *
Key Laboratory of Structure-Based Drug Design & Discovery of Ministry of Education, School of
Pharmaceutical Engineering, Shenyang Pharmaceutical University, Shenyang 110016, China;
qltongchina@163.com (Q.-L.T.); FZF11201604@163.com (Z.-F.F.); fyysy123@163.com (J.-W.Y.);
liqicherry@163.com (Q.L.); cyx2047259245@163.com (Y.-X.C.); mscheng@syphu.edu.cn (M.-S.C.)
* Correspondence: y.liu@syphu.edu.cn
† Qiao-Lin Tong and Zhan-Fang Fan contributed equally to this work.




Received: 6 September 2019; Accepted: 20 September 2019; Published: 22 September 2019


Abstract: The oxidation of sulfides to their corresponding sulfoxides or sulfones has been achieved
using a low-cost poly(amidoamine) with a first-generation coupled phosphomolybdate hybrid as the
catalyst and aqueous hydrogen peroxide as the oxidant. The reusability of the catalyst was revealed
in extensive experiments. The practice of this method in the preparation of a smart drug Modafinil
has proved its good applicability.

Keywords: dendritic phosphomolybdate hybrid; sulfides; selective oxidation; hydrogen

peroxide; reusability

1. Introduction
Many biologically and chemically active molecules are constructed from sulfoxides and
sulfones [1–5]. The oxidation of sulfides is a fundamental reaction as one of the most straightforward
methods to afford sulfoxides and sulfones [6]. Many reagents, including peracids and halogen
derivatives, are used in the common approaches of sulfoxidation reactions [7,8]. However, these
common reactions often suffer from the formation of many environmentally unfriendly byproducts
and low oxygen atom efficiency [6,9]. The development of environmentally benign catalysts and
oxidants has become a research hotspot in recent green chemistry pursuits.
Among various oxidants, aqueous hydrogen peroxide, which is inexpensive, is readily available,
has a high effective oxygen content, is safe in operation and storage, and yields stoichiometric amounts of
environmentally friendly water as a byproduct, is generally considered one of the most environmentally
benign “green oxidants”. These characteristics of aqueous hydrogen peroxide have led to the development
of many valuable methods for the oxidation of sulfides to sulfoxides and sulfones with various
transition metal catalysts, including Ti(SO4 )2 /GOF [10], PDDA-SiV2 W10 [11], the cobalt(III)–salen
ion [12], TiO2 /AA/MoO2 [13], a copper–Schiff base complex [14], (C19 H42 N)2 [MoO(O2 )2 (C2 O4 )]·H2 O [6],
vanadium Schiff base complexes [15], and so on [16–19].
Polyoxometalates (POMs), which are composed of anionic transition metal–oxygen clusters [20–23],
have been widely studied in the field of catalysis due to their excellent catalytic characteristics,
including efficient catalytic activity and selectivity, controllable redox potential and acidity through
the choice of the countercations and constituent elements [24,25]. Among these POMs, Keggin-type
phosphomolybdic acid (H3 Mo12 O40 , HPMo) has shown excellent catalytic performance in oxidation
reactions with aqueous hydrogen peroxide [26–29].

Catalysts 2019, 9, 791; doi:10.3390/catal9100791 www.mdpi.com/journal/catalysts

Catalysts 2019, 9, x FOR PEER REVIEW 2 of 10
Catalysts 2019, 9, 791 2 of 10

Dendritic poly(amidoamine) (PAMAM), which contains many amino groups, is an excellent

organic modifier
Dendritic for POMs [30–32].(PAMAM),
poly(amidoamine) PAMAMs can be functionalized
which contains manytoamino
couplegroups,
to various POMs,
is an and
excellent
the dendritic
organic modifierstructure,
for POMs which is different
[30–32]. PAMAMs fromcanthe
becommon organic
functionalized tomodifier,
couple to can provide
various POMs,a local
and
microenvironment for the POMs, which may result in a helpful “dendritic effect”
the dendritic structure, which is different from the common organic modifier, can provide a local on the reaction
[33,34]. PAMAM-G1
microenvironment for (poly(amidoamine)
the POMs, which may with theinfirst
result generation)
a helpful dendrimers
“dendritic effect” onhave been used
the reaction in
[33,34].
industrial
PAMAM-G1 production and are relatively
(poly(amidoamine) with the inexpensive. Moreover,
first generation) the amino
dendrimers havegroups of the
been used in PAMAM-
industrial
G1 dendrimer can be protonated by HPMo, and the PMo anions and PAMAM-G1
production and are relatively inexpensive. Moreover, the amino groups of the PAMAM-G1 dendrimer can strongly bond
together through electrostatic
can be protonated by HPMo, and interactions
the PMo anions[35]. and PAMAM-G1 can strongly bond together through
Herein, we report a
electrostatic interactions [35]. heterogeneous, simple, recyclable, efficient, and green protocol for the
oxidation of sulfides to sulfoxides and
Herein, we report a heterogeneous, simple, sulfones withrecyclable,
30 wt% H2efficient,
O2 under and
mildgreen
conditions in excellent
protocol for the
yield, catalyzed
oxidation by a composite
of sulfides to sulfoxides based
andon PAMAM-G1
sulfones with 30andwt%HPMo
H2 O2(denoted as PAMAM-G1-PMo).
under mild conditions in excellent To
the best of our knowledge, this is the first report of PAMAM-G1-PMo
yield, catalyzed by a composite based on PAMAM-G1 and HPMo (denoted as PAMAM-G1-PMo). as the catalyst used in the
oxidation
To the bestofofsulfides to sulfoxides
our knowledge, thisand sulfones.
is the first report of PAMAM-G1-PMo as the catalyst used in the
oxidation of sulfides to sulfoxides and sulfones.
2. Results and Discussion
2. Results and Discussion
In this oxidation system, PAMAM-G1-PMo is utilized as the catalyst, and 30 wt% H2O2 is used
as theInoxidant. We selected
this oxidation system,thioanisole
PAMAM-G1-PMo(1a) as a ismodel substrate
utilized and found
as the catalyst, andthat
30 less
wt%than
H2 O5%2 is of
used1a
could be directly oxidized by 30 wt% H O alone, even when the reaction time lasted
as the oxidant. We selected thioanisole (1a) as a model substrate and found that less than 5% of 1a
2 2 to 6 hours (Table
1, entry
could be1). However,
directly when
oxidized by5030mgwt%of HPAMAM-G1PMo was added
2 O2 alone, even when to the time
the reaction above mixture,
lasted to 6 hsulfoxide
(Table 1,
(1b)
entrywas
1). generated
However, whensoon as50the
mgoxidation product. In was
of PAMAM-G1PMo addition,
addedcontrol
to the experiments
above mixture,were performed
sulfoxide (1b)
to assess
was the individually
generated soon as thecatalytic
oxidationactivity
product.of HPMo and PAMAM-G1
In addition, dendrimer.were
control experiments Regrettably,
performed only
to
8% of starting
assess material could
the individually be activity
catalytic oxidizedofby 30 wt%
HPMo andHPAMAM-G1
2O2 catalyzing by HPMo alone
dendrimer. (Table only
Regrettably, 1, entry
8%
2), and much
of starting less yield
material couldwas obtained by
be oxidized when catalyzing
30 wt% by PAMAM-G1
H2 O2 catalyzing by HPModendrimer alone1,(Table
alone (Table entry 2),1,
entry 3). When
and much the reaction
less yield was carried
was obtained out in thebypresence
when catalyzing PAMAM-G1 of PAMAM-G1-PMo, up to 1,
dendrimer alone (Table 85% of 1a
entry 3).
could be
When theoxidized
reactionwithin 4 hours
was carried (Table
out in the 1, presence
entry 4), indicating that PAMAM-G1-PMo
of PAMAM-G1-PMo, up to 85% of played a very
1a could be
significant role in4 prompting
oxidized within the process
h (Table 1, entry of this oxidation
4), indicating effectively. played a very significant role
that PAMAM-G1-PMo
in prompting the process of this oxidation effectively.
Table 1. Control experiments with different components as catalyst a.
Table 1. Control experiments with different components as catalyst a .

Entry Catalyst Time (h) Temperature (◦ C) Yield b (%)

Entry Catalyst Time (h) Temperature (°C) Yield b (%)
1 — 6.0 25 4
1 — 6.0 25 4
2 HPMo 8.0 25 8
32 HPMo
PAMAM-G1 8.0
8.0 25 25 8 0.5
43 PAMAM-G1
PAMAM-G1-PMo 8.0
4.0 25 25 0.5 85
4 PAMAM-G1-PMo 4.0 25 85
a Reaction conditions: 1a (62 mg, 0.5 mmol), solvent (8 mL), catalyst (50 mg), 30 wt% H2 O2 (63 mg, 0.55 mmol);
b Reaction conditions:
HPMo:1aKeggin-type
(62 mg, 0.5 phosphomolybdic
mmol), solvent (8acid.
mL),PAMAM-G1:
catalyst (50 mg), 30 wt% H2O2 with
(63 mg,
the 0.55
a
Isolated yield. poly(amidoamine) first
mmol); b Isolated
generation. yield. HPMo:
PAMAM-G1-PMo: Keggin-type
composite phosphomolybdic
based on acid. PAMAM-G1: poly(amidoamine)
PAMAM-G1 and HPMo.
with the first generation. PAMAM-G1-PMo: composite based on PAMAM-G1 and HPMo.
To optimize
To optimize the
the conditions for the
conditions for the oxidation of sulfides
oxidation of sulfides toto sulfoxides,
sulfoxides, wewe first
first investigated the
investigated the
effects of the solvent in the PAMAM-G1-PMo-catalyzed reaction system. The
effects of the solvent in the PAMAM-G1-PMo-catalyzed reaction system. The results are listed in results are listed in
Table
Table 1. Afterscreening
1. After screeningdifferent
differentsolvents,
solvents,weweobserved
observedthat
thatwhen
when MeOH
MeOH oror95%95% EtOH
EtOH waswas used
used as
the solvent in the presence of PAMAM-G1-PMo, we obtained the desired sulfoxide products (1b)(1b)
as the solvent in the presence of PAMAM-G1-PMo, we obtained the desired sulfoxide products in
in relatively
relatively high
high yields
yields of 85–90%
of 85–90% andand a minor
a minor amount
amount of starting
of starting material
material (1a) (1a) remained,
remained, without
without any
any sulfones
sulfones (Table
(Table 2, entries
2, entries 1–2).1–2). However,
However, the conversion
the conversion was relatively
was relatively poorpoorwhenwhen the reaction
the reaction was
was carried out in other solvents, including EtOH,
carried out in other solvents, including EtOH, CH3COCH CH 3 COCH , CH
3, 3CH3COOC
3 COOC 2H
H and i-PrOH
and i-PrOH (Table
25, 5, (Table 2,
2,
entries 3–6). After comprehensive considerations of various factors, we selected
entries 3–6). After comprehensive considerations of various factors, we selected environmentally environmentally
friendly and
friendly and low-cost
low-cost 95%95% EtOH
EtOH as as the
the solvent.
solvent. Next,
Next, the
thetemperature
temperature of ofthe
thereaction
reaction waswasoptimized.
optimized.
Catalysts 2019,
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As shown in Table 2, when the temperature increased from 25 °C to 30 °C, the yield of the desired
As shown in Tableto 2,more
whenthan
the 90%
temperature increased from 25to◦ C to 30 ◦ C, the yield of the desired
product increased and reaction time reduced 2 hours, but when the temperature
product
increased to 35 °C, the yield of the sulfoxide appeared to decreasetodue
increased to more than 90% and reaction time reduced 2 h,tobut
thewhen the in
increase temperature
byproduct
increased ◦
to 35 C,(Table2,
the yield of the2,sulfoxide appeared to decrease duetemperature
to the increase
sulfone formation entries 7–9). Hence, 30 °C was the optimal for in
thebyproduct
oxidation
sulfone formation (Table in
2, entries 2, 7–9). Hence, ◦ C was the optimal temperature for the oxidation
302O
of sulfides to sulfoxides the system of 30 wt% H 2/PAMAM-G1-PMo.

of sulfides to sulfoxides in the system of 30 wt% H2 O2 /PAMAM-G1-PMo.

Table 2. Oxidation of sulfide to sulfoxide in different conditions a.
Table 2. Oxidation of sulfide to sulfoxide in different conditions a .

Entry Solvent Time (h) Temperature (◦ C) Yield b (%)

Entry Solvent Time (h) Temperature (°C) Yield b (%)
1 MeOH 4.0 25 90
1 MeOH 4.0 25 90
2 95%EtOH 4.0 25 85
2 3 95%EtOH EtOH 4.0 4.0 25
25 60 85
3 4 EtOH CH3 COCH3 4.0 4.0 25
25 45 60
4 5
CH3COCH33 CH COOC H
2 5 4.0 4.0 25
25 40 45
5 6 3COOC2H
CH i-PrOH
5 4.0 4.0 25
25 52 40
7 95%EtOH 2.0 25 72
6 i-PrOH 4.0 25 52
8 95%EtOH 2.0 30 91
7 9 95%EtOH95%EtOH 2.0 2.0 25
35 88 72
8 95%EtOH 2.0 30 91
a Reaction conditions: 1a (62 mg, 0.5 mmol), solvent (8 mL), catalyst (50 mg), 30 wt% H O (63 mg, 0.55 mmol);
b
9 95%EtOH 2.0 35 2 2 88
Isolated yield.
aReaction conditions: 1a (62 mg, 0.5 mmol), solvent (8 mL), catalyst (50 mg), 30 wt% H2O2 (63 mg, 0.55
mmol); b Isolated yield.
Furthermore, 1a was still chosen to be the model substrate to optimize the conditions for the
Furthermore,
oxidation of sulfides1ato was still chosen
sulfones. to be the model
In our experience, substrate
the formation to optimize
of sulfones needsthe conditions
higher for the
concentration
oxidation
of of sulfides
the oxidant. to sulfones.
The contrast In our
experiments experience,that
demonstrated the30formation
wt% H2 O2ofitself,
sulfones
even if needs higher
the amount
concentration
was increasedof tothe
300oxidant.
mol%, couldThe contrast experiments
not complete demonstrated
the oxidation. that 30once
However, wt%more,
H2O2 itself, even if
this process
the amount
was was increased
greatly promoted by theto 300 mol%,
catalyst could not complete
PAMAM-G1-PMo. Thethe oxidation. However,
temperature oncewas
of the reaction more, this
firstly
process wasAs
optimized. greatly
shown promoted
in Table 3, bywhen
the catalyst PAMAM-G1-PMo.
the temperature increased Thefromtemperature
30 C to 40 of
◦ ◦ C the reaction
in the system wasof
30 wt% H2 O2 /PAMAM-G1-PMo, the yield of the desired sulfone product (1c) increased, but when
firstly optimized. As shown in Table 3, when the temperature increased from 30 °C to 40 °C in the
system
the of 30 wt%
temperature H2O2/PAMAM-G1-PMo,
increased to 50 ◦ C, the yieldthe yield ofdid
of sulfone thenot
desired
notablysulfone
change product
(Table (1c) increased,
3, entries 1–3).
but when
Hence, 40 the
◦ temperature
C was the optimal increased to 50for
temperature °C,the
theoxidation
yield of sulfone
of sulfidesdidtonot notably
sulfones inchange
the system(Tableof 303,
wt% H2 O2 /PAMAM-G1-PMo. In addition, the effects of 30 wt% H2 O2 in the reaction were investigated.
entries 1–3). Hence, 40 °C was the optimal temperature for the oxidation of sulfides to sulfones in the
systemthe
When ofamount
30 wt%ofH30 2Owt%
2/PAMAM-G1-PMo.
H2 O2 increased from In addition,
300 mol%the effects
to 400 mol%,of 30 wt%
there Hno
was 2O2major
in thedifference
reaction
were
in theinvestigated. When the
yield of the desired amount
product of 303,wt%
(Table H2O2,4).
entries 2 increased
However, fromif 300
the mol%
amount to of40030mol%,
wt% H there
2 O2
was no major difference in the yield of the desired product (Table 3, entries 2,4).
decreased to 200 mol%, the yield of the desired product decreased accordingly (Table 3, entry 5). Hence, However, if the
amount
300 mol%ofwas 30 an
wt% H2O2quantity
optimal decreasedof 30towt%
200 Hmol%, the yield of the desired product decreased
2 O2 for this catalytic oxidation reaction.
accordingly
Next, we studied the scope of application of this an
(Table3, entry 5). Hence, 300 mol% was optimal
system quantity
by testing of 30 wt%
a diverse rangeH 2of
O2sulfides,
for this
catalytic oxidation reaction.
and the results are presented in Table 4. Notably, we observed that most of the substrates tested
in the oxidation system were converted to their corresponding products in excellent yields under
the optimized reactionTable 3. Oxidation
conditions. of sulfide
However, wetofound
sulfone in different
that conditions a.
(2-chloro-4-nitrophenyl)(phenyl)sulfane
(5a), with a strong electron-deficient phenyl group, did not successfully convert to 2-chloro-4-nitro-1-
(phenylsulfinyl)benzene (5b) (Table 4, entry 5) and 2-chloro-4-nitro-1-(phenylsulfonyl)benzene (5c)
(Table 4, entry 12). Additionally, (2-chlorophenyl)(methyl)sulfane (6a) did not successfully convert
to 1-chloro-2-(methylsulfonyl)benzene (6c) (Table 4, entry 13), partially because the ortho-substituted
chlorine on the benzene ring is also an electron-withdrawing group and has a certain steric hindrance.

Entry 30 wt% H2O2 (mol%) Time (h) Temperature (°C) Yield b (%)
1 300 3.0 30 60
2 300 3.0 40 93
were investigated. When the amount of 30 wt% H2O2 increased from 300 mol% to 400 mol%, there
was no major difference in the yield of the desired product (Table 3, entries 2,4). However, if the
amount of 30 wt% H2O2 decreased to 200 mol%, the yield of the desired product decreased
accordingly (Table3, entry 5). Hence, 300 mol% was an optimal quantity of 30 wt% H 2O2 for this
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300
300 3.0
3.0 50
50 92 444 of
92 of 10
of 10
10
333 300
Table300
300 3. Oxidation of sulfide
3.0
3.0
3.0
to sulfone in different
50
50
50
conditions a.
92
92
92
343 43343
300
400
400
300
300 3.0
3.0
3.0 50
40
40
50
50 92
93
93
92
92
344
4
3 400
300
300
400
300
400
300
Table
4003. Oxidation of sulfide to
3.0
3.0
3.0
3.0
3.0
40
50
50
40
50
40
50
sulfone in different conditions
40
a. 93
92
92
93
92
93
92
93
44555454 200
200
400
400
200
400
400
200 3.0
3.0
3.0
3.0 40
40
40
40 81
81
93
93
81
93
93
81
4545 aa
55
400
400
200
200
200
200
3.0
3.0EtOH (10 mL), catalyst
3.0
3.0
3.0
40
40 (150 mg); bb Isolated yield.
40
40
40
93
93
81
81
81
81
5 5 5 Reaction
aaaa Reaction
Reaction conditions:
conditions:
conditions:2001a
1a
200
1a
200 (62
(62
(62 mg,
mg,
mg, 0.5
0.5
0.5 mmol),
mmol),
mmol), 95%
95%
95%3.0
3.0
3.0 EtOH
EtOH (10
(10 mL),
mL), catalyst
40
catalyst
40
40 (150
(150 mg);
mg); b bb Isolated
Isolated yield.
81
yield.
81
81
Reaction
55 aaaaaaaa Reaction
Reaction conditions:
conditions:
Reaction conditions:
conditions:2001a
200
1a (62
(62
1a (62 mg,
mg,
(62 mg, 0.5
0.5
mg, 0.5 mmol),
mmol),
0.5 mmol),
mmol), 95% 95%
95%
3.0
95% EtOH
3.0EtOH
EtOH
EtOH (10 (10
(10 mL),
mL),
(10 mL), catalyst
catalyst
mL), catalyst 40
catalyst (150
40 (150
(150
(150 mg); mg);
mg);
b b Isolated yield.
Isolated
mg); bbbbbbbbbIsolated 81
yield.
81
Isolated yield.
yield.
Reaction conditions:
conditions: 1a
1a (62
(62 mg,
mg, 0.5
0.5 mmol),
mmol), 95%
95% EtOH (10
(10 mL),
mL), catalyst
catalyst (150 mg);
mg); Isolated
Isolated yield.
yield.
aaaaaaReaction
Reaction conditions: 1a
1a (62 mg, 0.5 mmol), 95% EtOH
EtOH (10 mL), catalyst (150
(150 mg); Isolated yield.
aa Reaction conditions:
the1a (62
(62 mg, 0.5
0.5 mmol),
mmol), 95% of EtOH (10
(10 mL), catalyst (150 mg);
mg); bbbbIsolatedrange yield.
b
Next,
Next,
Next, Reaction
we
Reaction
we
Reaction conditions:
we studied
studied
studied the
conditions:
the
conditions: 1a
scope
scope
1a (62
scope
1a (62 mg,
of application
of
mg,
of
mg, application
0.5
0.5 mmol),
application
mmol), 95%
95%
95%of
of EtOH
this system
this
EtOH
this
EtOH system
(10
system
(10 mL),
mL),
mL), by
by
by catalyst
testing
testing
catalyst
testing
catalyst (150
aaaa diverse
(150
(150 diverse
mg);
diverse
mg);
b Isolated
range
Isolated
range
Isolated yield.
of sulfides,
of sulfides,
yield.
of sulfides,
yield.
Next,
Next, we
we studied
studied the
the scope
scope of
of application
application of
of this
this system
system by
by testing
testing diverse
aa diverse range
range of
of sulfides,
sulfides,
and the
and
and the
the Next,
Next,Next,
Next, we
results
results
we
results
we studied
are
we studied
studied
are
studied the
are presented
presented
the
presented
the scope
the scope
scope
scope in
in of
in Table
of application
Table 4. Notably,
4.
of application
Table
of Notably,
application
4. Notably,
application of
of this
of this
of this
we
this system
we observed
we observed
system
system by
observed
system by
by testing
that
bythat mostaaaaof
most
testing
testing
that most
testing diverse
of
diverse
of the substrates
the
diverse
diverse the range
substrates
range
range of
substrates
range of
of sulfides,
tested
of tested
sulfides,
sulfides,
tested
sulfides,in
in
in
and
and
and the
the
the Next,
Next,
Next, we
results
we
we
results
results studied
are
studied
studied
are the
presented
the
the
are presented
presented
presented scope
scope
scope in
in of
Table
of
of
in Table
Tableapplication
4. Notably,
application
application
Table 4.their
4. Notably,
Notably, of
of
of this
we
this
this
we system
observed
system
system
we observed
observed
observed by
by
by testing
that most
testing
testing
that
that most
most of diverse
aaexcellent
diverse
diverse
of
of the
the substrates
the range
substrates
range
range
substrates
substrates of
of
of sulfides,
tested
sulfides,
sulfides,
tested
tested in
in
in
and
the
the
and
the the
oxidation
oxidation
the
andoxidation
the results results
results
results are
system
system
are presented
were
were
are presented
system presented
were in
in Table
converted
converted
in Table
converted Tableto 4.
to
to4. Notably,
their
Notably,
4.their
Notably, we
we observed
corresponding
corresponding
we observed
observed
corresponding that
products
products
that most
most
that most
products mostin
in
in of
excellent
of
of the
excellentthe
the substrates
the substrates yields
yields
substrates
yields tested
under
under
tested in
the
the
testedthe
under in
in
and
and
the
and
and the
the
oxidation
the
the results
results
results are
are
system
are
are presented
were
presented
presented in
in
converted
in Table
Table to4.
4.
4. Notably,
Notably,
their
Notably, we
we observed
corresponding
we observed that
that
products
that most
in
most of
of
excellent
of the
the substrates
yields
substrates tested
tested
under
tested in
in
the
in
the
the
the
the
the
oxidation
oxidation
oxidation
optimized
optimized
oxidation
oxidation
optimized
the oxidation
system
system
system
reaction
reaction
system
Entry
system
reaction
system
were
were
were
conditions.
conditions.
were
30
werewt%
conditions.
were Hin OTable
converted
converted
converted
2However,
However,
converted
converted
However,
converted to
to
2 (mol%)
4.
to
to
to
to
Notably,
their
their
their
we
we
theirfound
their
we
their Time we(h)observed
corresponding
corresponding
corresponding
found that
that
corresponding
corresponding
found that
corresponding
that
products
products
products mostin
in
in(◦ C)of
excellent
excellent
excellentthe
(2-chloro-4-nitrophenyl)(phenyl)sulfane
(2-chloro-4-nitrophenyl)(phenyl)sulfane
products
Temperature
products in
in excellent
excellent
(2-chloro-4-nitrophenyl)(phenyl)sulfane
products in excellent Yield substrates
yields
yields
yields
yields
yields
tested
under
b (%) under
yields under
under
under
under (5a),in
the
the
the
(5a),
the
the
(5a),
the
the
the oxidation
optimized
oxidation
optimized
theEntry
oxidation system
reaction
system
reaction
30
system were
conditions.
were
conditions.
wt% converted
H2Oconverted
were However,
2converted
However,
(mol%) to their
to
to their
weTime
their
we corresponding
found
found (h)that
corresponding products in
Temperature
products in excellent
in excellent
that (2-chloro-4-nitrophenyl)(phenyl)sulfane
corresponding (2-chloro-4-nitrophenyl)(phenyl)sulfane
products excellent
(° C) to yields
yields under
under
Yieldunder
yields the
(5a),
the
b (%)(5a),
the
optimized
with
with
optimized
optimized
optimized
with aaaa strong reaction
strong
reaction
reaction
strong conditions.
electron-deficient
1electron-deficient
reaction conditions.
conditions.300
conditions.
electron-deficient However,
phenyl
phenyl
However,
However,
However,
phenyl we
we
we found
group,
group,
we found
found
found
group, did
did
did that
that
3.0 not
not
that
that (2-chloro-4-nitrophenyl)(phenyl)sulfane
successfully
successfully convert
30 convert
(2-chloro-4-nitrophenyl)(phenyl)sulfane
not(2-chloro-4-nitrophenyl)(phenyl)sulfane
(2-chloro-4-nitrophenyl)(phenyl)sulfane
successfully convert to 2-chloro-4-nitro-1-
to 2-chloro-4-nitro-1-
2-chloro-4-nitro-1-
60 (5a),
(5a),
(5a),
(5a),
optimized
with
optimized
optimized
with
with 1 aa strong reaction
strong
reaction
reaction
strong conditions.
electron-deficient
conditions.
conditions.
electron-deficient
electron-deficient
300 However,
phenyl
However,
However,
phenyl
phenyl we
we
we found
group,
found
found
group,
group, did
did
did that
thatnot
that (2-chloro-4-nitrophenyl)(phenyl)sulfane
successfully convert
(2-chloro-4-nitrophenyl)(phenyl)sulfane
(2-chloro-4-nitrophenyl)(phenyl)sulfane
not
not successfully
successfully convert to
convert to 2-chloro-4-nitro-1-
to 2-chloro-4-nitro-1-
to 2-chloro-4-nitro-1-
2-chloro-4-nitro-1- (5a),
(5a),
(5a),
with
with aaaaaa strong
(phenylsulfinyl)benzene
(phenylsulfinyl)benzene
with
(phenylsulfinyl)benzene
with
with
(phenylsulfinyl)benzene
strong
strong
strong
electron-deficient
(5b) (Table
(5b)
strong 2electron-deficient
electron-deficient
(5b)
electron-deficient
electron-deficient
(5b)
300 phenyl
(Table
(Table
(Table 4,
phenyl
phenyl
4,
phenyl
phenyl
4,
group,
4, entry
entry
group,
entry
group,
group,
entry 5)3.0
5)
group,
5)
5)
did
and
and
did
3.0
did
and
did
did
and
not
not
successfully
successfully
successfully
successfully 4030convert
convert
2-chloro-4-nitro-1-(phenylsulfonyl)benzene
2-chloro-4-nitro-1-(phenylsulfonyl)benzene
not
not successfully convert to
2-chloro-4-nitro-1-(phenylsulfonyl)benzene
not convert
convert
2-chloro-4-nitro-1-(phenylsulfonyl)benzene
to 93 60
2-chloro-4-nitro-1-
to 2-chloro-4-nitro-1-
to 2-chloro-4-nitro-1-
2-chloro-4-nitro-1- (5c)
(5c)
(5c)
(5c)
with
(phenylsulfinyl)benzene
with 2 a
(phenylsulfinyl)benzene strong
strong 3electron-deficient
300(5b)
electron-deficient
(5b) phenyl
(Table
(Table
300 4,
phenyl
4, group,
entry
group,
entry 5)
5) 3.0did
and
did
and3.0 not
not successfully
successfully 40 convert
2-chloro-4-nitro-1-(phenylsulfonyl)benzene
convert
2-chloro-4-nitro-1-(phenylsulfonyl)benzene
50 to
to 2-chloro-4-nitro-1-
2-chloro-4-nitro-1-
92 93 (5c)
(5c)
(Table
(Table
(phenylsulfinyl)benzene
(phenylsulfinyl)benzene
(Table
(phenylsulfinyl)benzene
(phenylsulfinyl)benzene
(Table 4,
4,
4, entry
entry
entry
4, entry 12).
12).
12).
entry412). Additionally,
Additionally,
(5b)
(5b) (Table
Additionally,
(5b)
(5b)
12). Additionally,
Additionally, (Table
(Table
(Table(2-chlorophenyl)(methyl)sulfane
(2-chlorophenyl)(methyl)sulfane
4,
4, entry
entry 5) 5) and
(2-chlorophenyl)(methyl)sulfane
4,
4, entry
entry 5)
5) and
and (6a)
(6a)
(6a) did
did
and 2-chloro-4-nitro-1-(phenylsulfonyl)benzene
did not
not
2-chloro-4-nitro-1-(phenylsulfonyl)benzene
not
2-chloro-4-nitro-1-(phenylsulfonyl)benzene
2-chloro-4-nitro-1-(phenylsulfonyl)benzene
(2-chlorophenyl)(methyl)sulfane (6a) did
did not successfully
successfully
successfully
not successfully
successfully convert
convert
(5c)
(5c)
convert
(5c)
(5c)
convert
(phenylsulfinyl)benzene
(Table
(phenylsulfinyl)benzene
(Table 4,
4, entry 12). (5b)
(5b)
Additionally, (Table 4, entry
entry 5)
5) and
400 (2-chlorophenyl)(methyl)sulfane
(Table 4, and 2-chloro-4-nitro-1-(phenylsulfonyl)benzene
(6a)
3.0 2-chloro-4-nitro-1-(phenylsulfonyl)benzene
(2-chlorophenyl)(methyl)sulfane 40
(6a) did not 93
successfully (5c)
convert
(5c)
convert
to
to 1-chloro-2-(methylsulfonyl)benzene
1-chloro-2-(methylsulfonyl)benzene
(Table
(Table
to 4,
4, entry
entry 12).
12).
1-chloro-2-(methylsulfonyl)benzene
(Table 4,
4, entry
entry512). Additionally,
Additionally,
12). Additionally, (6c)
(6c) (Table
(Table 4,
4, entry
entry
(2-chlorophenyl)(methyl)sulfane
(2-chlorophenyl)(methyl)sulfane
(6c) (Table 4, entry 13),
13),
13), partially
partially
(6a)
(6a)
partially because
because
did
did
because not
not the
the ortho-substituted
ortho-substituted
successfully
thesuccessfully convert
convert
ortho-substituted
(Table
to 1-chloro-2-(methylsulfonyl)benzene
(Table
(Table 4,
4, entry
entry 12).
12). Additionally,
Additionally,
Additionally, 200 (2-chlorophenyl)(methyl)sulfane
(2-chlorophenyl)(methyl)sulfane
(6c) (Table 4, entry
(2-chlorophenyl)(methyl)sulfane
(Table3.0 13), (6a)
partially
(6a)
40 did
did not
(6a) because
because
did not successfully
not thesuccessfully
the convert
convert
ortho-substituted
successfully
81 convert
to
to
to
to
to
to
1-chloro-2-(methylsulfonyl)benzene
1-chloro-2-(methylsulfonyl)benzene
1-chloro-2-(methylsulfonyl)benzene
chlorine
chlorine
to on
on the benzene
the benzene
1-chloro-2-(methylsulfonyl)benzene
1-chloro-2-(methylsulfonyl)benzene
chlorine on the benzene
1-chloro-2-(methylsulfonyl)benzene
1-chloro-2-(methylsulfonyl)benzene
chlorine on the benzene ring is
ring
ring
ring is
is also(2-chlorophenyl)(methyl)sulfane
is also
also
also an
an
(6c) (Table
(6c)
(6c)
(6c)
(6c)
(Table
(Table
an electron-withdrawing
an electron-withdrawing
(6c) (Table
electron-withdrawing
(6c) (Table
(Table
electron-withdrawing
4, entry
4,
4,
4,
4,
4,
4,
entry 13),
entry
entry
entry
entry
entry
13),
13),
13),
13),
13),
13),
(6a)
partially
partially
partially
group
group and
and
partially
partially
group and
partially
partially
group and
did
because
because
has
has
because
because
has
because
because
has aaaanot successfully
the
the
certain
certain
the
the
certain
the
the
certain
convert
ortho-substituted
ortho-substituted
ortho-substituted
steric hindrance.
steric hindrance.
ortho-substituted
ortho-substituted
steric hindrance.
ortho-substituted
ortho-substituted
steric hindrance.
to 1-chloro-2-(methylsulfonyl)benzene
to 1-chloro-2-(methylsulfonyl)benzene
chlorine
chlorine on
on the benzene ring
a the benzene ring is
is also
also an
an (6c) (Table
(6c) (Table 4,
electron-withdrawing
electron-withdrawing4, entry
entry 13),
13), partially
group and
partially
group and because
has
because
has aabcertain the ortho-substituted
the
certain ortho-substituted
steric
steric hindrance.
hindrance.
chlorine
chlorine on
chlorine
chlorine on
on the
the benzene
onReaction
the
the benzene
benzene ring
conditions:
benzene ring1a
ring
ring is
is
is also
is(62 mg,
also
also
also an
an
an electron-withdrawing
an0.5 mmol), 95% EtOH (10 mL),
electron-withdrawing
electron-withdrawing
electron-withdrawing group
catalyst
group
group
group and
(150has
and
and
and mg);a
has
has
has aaaa certain
Isolated steric
certain
certain
certain steric hindrance.
yield.
steric
steric hindrance.
hindrance.
hindrance.
chlorine
chlorine Table 4.
on
on the
the
4. The
benzene
benzene
The oxidation
ring
ring
oxidation of
is
is also
also
of sulfides
sulfides to
an
an electron-withdrawing
electron-withdrawing
to sulfoxides
sulfoxides and and sulfones
sulfones with
group
group
with 30
and
and
30 wt%
wt% H
has
has
H22O a
O22catalyzed
certain
certain
catalyzed by
steric
steric
by PAMAM–
hindrance.
hindrance.
PAMAM–
Table
Table 4. The oxidation of sulfides to sulfoxides and sulfones with 30 wt% H 222O 222 catalyzed by PAMAM–
Table
Table
Table 4.
4. The
The
4. The
The oxidation
oxidation of
of
oxidation of sulfides
sulfides
of sulfides to
to
sulfides to sulfoxides
sulfoxides
to sulfoxides and
and
sulfoxides and sulfones
sulfones
and sulfones with
with
sulfones with 30
30
with 30 wt%
wt%
30 wt% H
wt% HH O
H222222222O
O catalyzed
O222222222catalyzed
catalyzed
catalyzed by by
by PAMAM–
PAMAM–
by PAMAM–
PAMAM–
Table
Table
G1–PMo
G1–PMo
Table 4.
4.
4. The
a,b.. oxidation
The
a,b
a,b oxidation
oxidation of
of sulfides
sulfides to
to sulfoxides
sulfoxides and
and sulfones
sulfones with
with 30
30 wt%
wt% H
H O
O catalyzed
catalyzed by
by PAMAM–
PAMAM–
G1–PMo
Table
G1–PMo
Table
Table
Table 4.
4.
4.
4.
a,b
The
a,b
a,b
The
The
The
a,b .
. oxidation
oxidation
oxidation
oxidation of
of
of
of sulfides
sulfides
sulfides
sulfides to
to
to
to sulfoxides
sulfoxides
sulfoxides
sulfoxides and
and
and
and sulfones
sulfones
sulfones
sulfones with
with
with
with 30
30
30
30 wt%
wt%
wt%
wt% HHH
H 222O O
O
O catalyzed
222catalyzed
catalyzed
catalyzed by
by
by PAMAM–
PAMAM–
PAMAM–
Table
G1–PMo
G1–PMo
G1–PMo
Table
G1–PMo4.
4. The
a,b... oxidation of sulfides to sulfoxides and sulfones with 30 wt% H
a,b
a,b
The oxidation of sulfides to sulfoxides and sulfones with 30 wt% H 22 222OO22 catalyzed
222catalyzed by
by PAMAM–
PAMAM–
a,b...
a,b
a,b
a,b 2 2
G1–PMo
G1–PMo
G1–PMo
G1–PMo
a,b
a,b
a,b
a,b
a,b . .
G1–PMo
G1–PMo a,b a,b
a,b Entry
a,b.Entry
.Entry Substrates
Substrates Products
Products Time (h)
Time (h) Yield Yield ccccc (%)
c c (%)
G1–PMo Entry Substrates
Substrates Products Time
Products(h) Yield
Time (h) (%) Yield (%)
Entry
Entry
Entry
Entry Substrates
Substrates
Substrates
Substrates Products
Products
Products
Products Time (h)
Time
Time
Time (h)
(h)
(h) Yield ccccccccc(%)
Yield
Yield
Yield (%)
(%)
(%)
Entry
Entry
Entry
Entry
Entry Substrates
Substrates
Substrates
Substrates
Substrates Products
Products
Products
Products
Products Time
Time
Time
Time
Time (h)
(h)
(h)
(h) Yield
Yield
Yield
Yield
Yield ccccc(%)
c
(%)
(%)
(%)
(%)
Entry
1111 Substrates Products Time
2.0(h)
2.0 Yield
91 (%)
91
c

1 1a
1a 2.0
2.0
2.0 91
91
91
11111 1a
1a 1b
1b
1b 2.0
2.0 91
91
1 1a
1a
1a
1a 1b
1b
1b 2.0
2.0
2.0
2.0 91
91
91
91
11 1a
1a
1a 1b
1b 2.0
2.0 91
91
1a
1a
1a 1b
1b
1b
1b
2222 1b
1b 1.5
1.5 90
90
2 2a
2a 1.5
1.5
1.5 90
90
90
22222 2a
2a
2a 2b
2b
2b 1.5
1.5 90
90
22 2 2a 2b
2b 1.5
1.5
1.5
1.5
1.5 90
90
90
90
90
2a
2a
2a
2a 2b
2b 1.5 90
2a
2a
2a 2b
2b
2b
2b
2b
333 2b 3.0
3.0 85
85
3.0 85
3333
3 3a
3a
3a
3a 3b
3b
3.0
3.0
3.0
3.0
3.0
85
85
85
85
85
33 3 3b
3b 3.0
3.0 85
85
85
333 3a
3a
3a
3a
3a
3a
3a
3a
3b
3b
3b
3b
3.0
3.0
3.0 85
85
85
3a
3a 3b
3b
3b
3b
3b
444 3b 3.5
3.5
3.5 85
85
85
4444
4
4a
4a
4a
4a 4b
4b
4b
3.5
3.5
3.5
3.5
3.5
85
85
85
85
85
4 44 4 4a
4a
4a 4b 3.5
3.5
3.5 85
85
85
85
44 4a
4a
4a
4a
4a
4a
4b
4b
4b
4b
4b
4b
3.5
3.5 85
85
4a 4b
4b
4b
4b
5555 5.0
5.0
5.0
5.0 trace
trace
trace
trace
55
5
555 5a
5a
5a 5.0
5.0
5.0
trace
trace
trace
55
5555 5a
5a 5b
5b
5b
5b 5.0
5.0
5.0
5.0 trace
trace
trace
trace
5a
5a
5a
5a 5b
5b 5.0
5.0 trace
trace
5a
5a
5a
5a 5b
5b
5b
5b
5a 5b
5b
5b
5b
6666 6.0
6.0
6.0
6.0 93
93
93
93
66
66 6a
6a
6a
6a 6b
6b 6.0
6.0
6.0 93
93
93
66 6a 6b
6b 6.0
6.0
6.0 93
93
93
666 6.0 93
6a
6a
6a 6b 6.0 93
6a
6a
6a 6b
6b
6b 6.0 93
6a
6a 6b
6b
6b
6b
777 6b 4.5
4.5
4.5 93
93
93
7
77 7a
7a
7a 4.5
4.5
4.5 93
93
93
77777 7a
7a
7a 7b
7b
7b
7b 4.5
4.5
4.5 93
93
93
77 7a
7a
7a
7a 7b
7b
7b 4.5
4.5
4.5
4.5 93
93
93
93
7a
7a
7a 7b
7b
7b
7b
88 7b
7b 3.5
3.5 93
93
88
88 1a
1a 3.5
3.5
3.5
3.5 93
93
93
93
88888 1a
1a
1a
1a 1c
1c
1c 3.5
3.5 93
93
1a 1c
1c
1c 3.5
3.5
3.5 93
93
93
88 1a
1a
1a
1a
1a 1c
1c
1c
1c
3.5
3.5 93
93
1a 1c
1c
1c
99 9 2.0
2.0 94
94
999 2a
2a 2.0
2.0
2.0 94
94
94
9999999 2a
2a
2a
2a
2a
2a
2c
2c
2c
2c
2c
2.0
2.0
2.0
2.0
2.0
2.0
2.0
94
94
94
94
94
94
94
99 2a
2a
2a 2c
2c
2c 2.0
2.0 94
94
2a
2a
2a
2a 2c
2c
2c
2c
2c
2c
10
1010
10
10 4.0
4.0
4.0
4.0
4.0 92
92
92
92
92
10
10 3a
3a
3a
3a 3c
3c 4.0
4.0 92
92
10
10
10
10 3a
3a 3c
3c
3c 4.0
4.0
4.0
4.0 92
92
92
92
10
10 3a
3a 3c
3c 4.0
4.0 92
92
3a
3a
3a
3a 3c
3c
3c
3a 3c
3c
3c
1111
11
11 4.0
4.0
4.0
4.0 93
93
93
93
11
11 4a
4a
4a
4a 4c
4.0
4.0 93
93
11
11
11 4a
4a
4a 4c
4c
4c
4c 4.0
4.0
4.0 93
93
93
11
11
11 4a
4a 4c 4.0
4.0
4.0 93
93
93
11 4a
4a
4a
4a 4c
4c
4c
4c 4.0 93
4a 4c
4c
4c
12
12
12
12 5.0
5.0
5.0
5.0 NA ddddddd
NA
NA
NA dd
12
12
12
12 5a
5a
5a
5a 5c
5c 5.0
5.0
5.0
5.0 NA
NA
NA
NA
d
dddd
12
12
12
12 5a
5a 5c
5c 5.0
5.0
5.0
5.0 NA
NA
NA
NA d d
d dd
12 5a
5a
5a
5a
5c
5c
5c 5.0 NA d
d d
5a
5a 5c
5c
5c
5c
5c
 1a 1c

9 2.0 94
2a 2c
Catalysts 2019, 9, 791 5 of 10
10 4.0 92
3a 3c
Table 4. Cont.
11 4.0 93
Entry Substrates4a Products 4c Time (h) Yield c (%)

Catalysts 2019, 9, x FOR PEER REVIEW 5 of 10

Catalysts
Catalysts 2019,
2019, 9,
9, x
x FOR
1212PEER
FOR PEER REVIEW
REVIEW 5.0
5.0 NAddd
NA 55 of
of 10
10
5a
5a 5c
13 5.0 trace
1313 6a 6c 5.0
5.0 trace
trace
6a
6a 6c
6c
14 4.0 91
1414
14 7a 7c 4.0
4.0
4.0 91
9191
7a
7a 7c
7c
a Reaction conditions of sulfides to sulfoxides: sulfide (0.5 mmol), 95% EtOH (8 mL), catalyst (50 mg),
aaaReaction conditions of sulfides to sulfoxides: sulfide (0.5 mmol), 95% EtOH (8 mL), catalyst (50 mg), 30 wt% H O
a Reaction conditions of sulfides to sulfoxides: sulfide (0.5 mmol), 95% EtOH (8 mL), catalyst (50 mg), 2 2
30
(63 wt% H 2O
mg, 0.55 2 (63 mg,
mmol), 0.55
30 ◦ C; mmol),conditions
b Reaction 30 °C; b Reaction
of sulfidesconditions
to sulfones: of sulfides
sulfide to sulfones:
(0.5 mmol), 95% EtOHsulfide (0.5
(10 mL),
30 wt% H222O222 (63 mg, 0.55 mmol), 30 °C; bbb Reaction◦conditions of sulfides to sulfones: sulfide (0.5 mmol),
mmol), 95%mg),
catalyst (150 EtOH 30 (10
wt%mL),
H2 O2catalyst
(170 mg,(150 mg), 3040wt%
1.5 mmol), C; c H 2O2 (170
Isolated mg,d 1.5
yield; Notmmol), 40 °C; c Isolated yield;
available.
d 95% EtOH (10 mL), catalyst (150 mg), 30 wt% H222O222 (170 mg, 1.5 mmol), 40 °C; ccc Isolated yield; ddd Not
Not available.
available.
To study
To study thethe recyclability
recyclability of
of the
the PAMAM-G1-PMo
PAMAM-G1-PMo catalyst, catalyst, we
we again
again chose
chose the
the oxidation
oxidation of
of
To study
To
thioanisole study
(1a) the
the
to recyclability of
recyclability of the
the PAMAM-G1-PMo
(methylsulfinyl)benzene PAMAM-G1-PMo
(1b) or catalyst, we
catalyst, we again
(methylsulfonyl)benzene again(1c)
chose
chose
as the oxidation
the
model oxidation of
of
reactions.
thioanisole (1a) to (methylsulfinyl)benzene (1b) or (methylsulfonyl)benzene (1c) as model reactions.
thioanisole
The (1a) to (methylsulfinyl)benzene
catalystPAMAM-G1-PMo
PAMAM-G1-PMo waseasily
easily (1b) or (methylsulfonyl)benzene
recovered (1c) as model reactions.
The catalyst was recovered byby filtration
filtration after
after the the reaction,
reaction, washedwashed
with with
95%
The
95% catalyst
EtOH, PAMAM-G1-PMo
and dried in a was
vacuum easily
at room recovered by
temperature. filtration
After theafter the
above reaction,
treatment, washed
the with was
catalyst 95%
EtOH, and dried in a vacuum at room temperature. After the above treatment, the catalyst was reused
EtOH, for
reused andsubsequent
dried in a vacuum at room temperature.
experiments Afternothemajor
abovedifferences
treatment, the catalyst was reused
for subsequent experiments (up to(upfiveto runs),
five runs),
and and
no major differences in in the
the yieldor
yield or required
required
for subsequent
reaction times wereexperiments
observed, (up
as to five runs),
summarized in and no1.major differences in the yield or required
Figure
reaction times were observed, as summarized in Figure 1.
reaction times were observed, as summarized in Figure 1.

Figure 1. Study of the PAMAM-G1-PMo recyclability for the oxidation of thioanisole to sulfoxide (left)
and sulfone
Figure (right).
1. Study of the PAMAM-G1-PMo recyclability for the oxidation of thioanisole to sulfoxide
Figure 1. Study of the PAMAM-G1-PMo recyclability for the oxidation of thioanisole to sulfoxide (left)
(left) and sulfone (right).
After being(right).
and sulfone used for five times and separated from the reaction system, the catalysts were
characterized
After being by used
Fourier-transform
for five timesinfrared spectroscopy
and separated from (FT-IR, Figuresystem,
the reaction 2), X-ray the diffraction
catalysts (XRD,
were
Figure After
3), andbeing used
scanning for five
electron times and
microscopy separated
(SEM, Figure from
4). the
As reaction
shown in system,
Figure 2, the
the catalysts
IR were
frequencies
characterized by Fourier-transform infrared spectroscopy (FT-IR, Figure 2), X-ray diffraction (XRD,
characterized
of reused by Fourier-transform
PAMAM-G1-PMo (958, infrared
3373, 3100 −1
spectroscopy
cmFigure (FT-IR, Figure
) are4).consistent 2),those
X-rayofdiffraction (XRD,
Figure 3), and scanning electron microscopy (SEM, As shownwith in Figure 2, thefresh-prepared
IR frequencies
Figure 3),
PAMAM-G1-PMo, and scanning electron
indicating(958, microscopy
the PMo (SEM, Figure 4). As shown in Figure 2, the IR frequencies
of reused PAMAM-G1-PMo 3373, anions
3100 cm are
−1) still
are successfully
consistent with immobilized on protonated
those of fresh-prepared
of reused
of reused PAMAM-G1-PMo
PAMAM-G1. PAMAM-G1-PMo
As shown in Figure(958,
(958,3, 3373,
the XRD
3373, 3100
3100 cm−1
patterns
cm −1) are consistent with those of fresh-prepared
−1 ) for
areboth fresh-prepared
consistent with PAMAM-G1-PMo
those of fresh-preparedand
PAMAM-G1-PMo, indicating the PMo anions are still successfully immobilized on protonated
PAMAM-G1-PMo,
reused one show a indicating
broad band the
in PMo
the anions
range of 2θ =
are 14−40 ◦ , which confirms
still successfully
PAMAM-G1. As shown in Figure 3, the XRD patterns for both fresh-prepared PAMAM-G1-PMo and
immobilized
the high on protonated
dispersion of
PAMAM-G1.
the PMo anions As shown in Figure 3, the XRD patterns for both fresh-prepared PAMAM-G1-PMo and
reused one showon PAMAM-G1
a broad band in support.
the rangeAt last,= 14−40°,
of 2θ it can bewhich observed via the
confirms theSEM highspectra (Figure
dispersion of the 4)
reused
that one show a broad
fresh-prepared band in the range
PAMAM-G1-PMo and of 2θ = 14−40°,
reused one have which confirms
similar the high dispersion
micromorphology, such asofthe
the
PMo anions on PAMAM-G1 support. At last, it can be observed via the SEM spectra (Figure 4) that
PMoprojections
tiny anions on PAMAM-G1
on the amorphous support. At last,The
surface. it can be observed viaabove
the SEM spectraprove
(Figure 4) that
fresh-prepared PAMAM-G1-PMo and reused oneresults of all the
have similar detections
micromorphology, that
such as the the
tiny
fresh-prepared
PAMAM-G1-PMo, PAMAM-G1-PMo and
no matter fresh-prepared reused one
or reused, have similar micromorphology, such as the tiny
projections on the amorphous surface. The results of all has the aabove
higher surface-to-volume
detections prove thatratio and more
the PAMAM-
projections
reactive on theBesides,
cavities. amorphousthere surface.
are no The results
noticeable of all the above
differences between detections
the prove that the
fresh-prepared PAMAM-
catalysts and
G1-PMo, no matter fresh-prepared or reused, has a higher surface-to-volume ratio and more reactive
G1-PMo,
the reused no matter fresh-prepared
ones, demonstrating or reused,
that the catalysts has a higher
have good surface-to-volume
stability ratio and more reactive
cavities. Besides, there are no noticeable differences between the in the process of oxidation
fresh-prepared reaction.
catalysts and the
cavities. Besides,
cavities. Besides, there
there are
are nono noticeable
noticeable differences
differences betweenbetween the the fresh-prepared
fresh-prepared catalystscatalysts and
and thethe
reused ones, demonstrating that the catalysts have good stability in the process of oxidation reaction.
reused ones, demonstrating that the catalysts have good stability in the process of oxidation reaction.
reused one show a broad band in the range of 2θ = 14−40°, which confirms the high dispersion of the
PMo anions on PAMAM-G1 support. At last, it can be observed via the SEM spectra (Figure 4) that
fresh-prepared PAMAM-G1-PMo and reused one have similar micromorphology, such as the tiny
projections on the amorphous surface. The results of all the above detections prove that the PAMAM-
G1-PMo, no matter fresh-prepared or reused, has a higher surface-to-volume ratio and more reactive
Catalysts 2019, 9, 791 6 of 10
cavities. Besides, there are no noticeable differences between the fresh-prepared catalysts and the
reused ones, demonstrating that the catalysts have good stability in the process of oxidation reaction.

Catalysts 2019,
Catalysts 2019, 9,
9, xx FOR
FOR PEER
PEER REVIEW
REVIEW 66 of
of 10
10

Figure 2.
Figure 2. The
The IR
IR spectra
spectra of
of fresh-prepared
fresh-prepared PAMAM-G1-PMo
PAMAM-G1-PMo (left)
(left) and
and reused
reused PAMAM-G1-PMo
PAMAM-G1-PMo
(right).
(right).
Figure 2. The IR spectra of fresh-prepared PAMAM-G1-PMo (left) and reused PAMAM-G1-PMo (right).

Figure
Figure 3. TheXRD
3. The
3. XRD patterns
patterns of fresh-prepared
of fresh-prepared
fresh-prepared PAMAM-G1-PMo
PAMAM-G1-PMo (left)(left) and reused
and reused
reused PAMAM-G1-
PAMAM-G1-PMo
Figure The XRD patterns of PAMAM-G1-PMo (left) and PAMAM-G1-PMo
PMo (right).
(right).
(right).

Figure 4. The SEM spectra of fresh-prepared PAMAM-G1-PMo (top) and reused PAMAM-G1-
Figure 4.
Figure 4. The
The SEM
SEM spectra
spectra of
of fresh-prepared
fresh-prepared PAMAM-G1-PMo
PAMAM-G1-PMo (top)
(top) and
and reused
reused PAMAM-G1-PMo
PAMAM-G1-PMo
PMo (bottom).
(bottom).
(bottom).

The present
The present catalytic
catalytic system
system was
was also
also applied
applied to
to the
the preparation
preparation of of aa well-known
well-known smart
smart drug
drug
Modafinil (2-[(diphenylmethyl)sulfinyl]acetamide,
Modafinil (2-[(diphenylmethyl)sulfinyl]acetamide, 9),9), which
which is
is aa clinically
clinically wakefulness-promoting
wakefulness-promoting
agent to
agent to treat
treat disorders
disorders such
such as
as narcolepsy
narcolepsy and
and excessive
excessive daytime
daytime sleepiness.
sleepiness. Traditionally,
Traditionally, Modafinil
Modafinil
Catalysts 2019, 9, 791 7 of 10

The present catalytic system was also applied to the preparation of a well-known smart drug
Modafinil (2-[(diphenylmethyl)sulfinyl]acetamide, 9), which is a clinically wakefulness-promoting
agent to treat disorders such as narcolepsy and excessive daytime sleepiness. Traditionally, Modafinil
was produced by the oxidation of 2-[(diphenylmethyl)thio]acetamide (8) with 30 wt% H2 O2 in acetic
acid. However, a considerable amount of sulfone as the main by-product was often generated and
difficult to be removed by recrystallization due to its similar physical property with Modafinil [36].
Inspired by the selective oxidation property of the 30 wt% H2 O2 /PAMAM-G1-PMo system, we practiced
Catalysts 2019, 9, x FOR PEER REVIEW 2 of 10
its application for the oxidation process in preparation of Modafinilf. The final product was obtained
in a good yield of 89% and excellent purity of 99.79% after the crude product was collected and
obtained in a good yield of 89% and excellent purity of 99.79% after the crude product was collected
recrystallized with acetone (Scheme 1).
and recrystallized with acetone (Scheme 1).

Scheme 1. The oxidation process in preparation of Modafinil.

Scheme 1. The oxidation process in preparation of Modafinil.
3. Materials and Methods
3. Materials and Methods
All reactants and solvents were directly obtained from commercial sources and used without
further 1 H and 13 C NMR spectra were recorded with a Bruker Avance-III 600 spectrometer
Allpurification.
reactants and solvents were directly obtained from commercial sources and used without
(Bruker, Zürich, Switzerland).
further purification. 1 H and 13 The purity spectra
C NMR of the products was determined
were recorded by HPLC
with a Bruker with areas600
Avance-III of
spectrometer
peak (Bruker,
normalization Zürich,
method Switzerland).
(pump: waters 1525,The purity of the
detector: products
waters 2489. was determined bycolumn:
Chromatographic HPLC
WondaSil
with areas C-18,ofmonitoring wavelength used
peak normalization 210 nm).
method (pump: waters 1525, detector: waters 2489.
Chromatographic
Infrared spectra column:
were WondaSil C-18,Fourier-transform
obtained from monitoring wavelength used
infrared 210 nm). (FT-IR, Thermo
spectroscopy
Scientific IS5) spectra
Infrared at universal
wereattenuated total Fourier-transform
obtained from reflection (ATR) mode in thespectroscopy
infrared range 400–4000 cm−1Thermo
(FT-IR, , using
Scientificsamples
catalyst IS5) at universal
supportedattenuated total reflection
on KBr wafers. (ATR) mode
X-ray diffractometer in the
(XRD, range 400–4000
PERSEE cm ,Persee
XD-3, Beijing −1 using
catalyst samples
instrument supported
co. LTD, on KBr wafers.
Beijing, China.) X-ray diffractometer
with monochromated Cu–Kα(XRD, PERSEE
radiation sourceXD-3, Beijing
at 30 kV and Persee
30 mA
instrument
was used to co. LTD, Beijing,
investigate China.)
the crystal with monochromated
structure change between Cu–Kα radiation
fresh-prepared source
and reusedat catalysts,
30 kV andand 30
mA was
X-ray used to investigate
diffraction patterns were the crystal
obtained structure change
in a scan 2θ = 10–80
rangebetween ◦
fresh-prepared
with a scanand of 4 /min.
ratereused◦ catalysts,
SEM
and X-ray
spectra wasdiffraction patterns
obtained from were obtained
Scanning in a scan range
electron microscope (SEM,2θFEIQ45,
= 10–80° with a Tokyo,
Hitachi, scan rate of 4°/min.
Japan.).
SEM spectra was obtained from Scanning electron microscope (SEM, FEIQ45, Hitachi, Tokyo, Japan.).
3.1. Preparation and Characterization of PAMAM-G1-PMo
3.1. Preparation
In a typicaland Characterization
experiment, of PAMAM-G1-PMo
PAMAM-G1 (1.0 g, 2.0 mmol) was dissolved in deionized water (35 mL)
underInroom temperature,
a typical and
experiment, Keggin-type(1.0
PAMAM-G1 H3g,PMo2.012 O40 (7.3
mmol) g,dissolved
was 4.0 mmol)inwas added while
deionized water stirring.
(35 mL)
The resulting
under mixture was stirred
room temperature, for 48 h and
and Keggin-type H3filtered.
PMo12OThe solids
40 (7.3 g, 4.0were washed
mmol) was with
addeddeionized water
while stirring.
and ethanol, and dried under vacuum at 40 ◦ C for 12 h to afford an aqua powder of PAMAM-G1-PMo.
The resulting mixture was stirred for 48 h and filtered. The solids were washed with deionized water
and ethanol, and dried under vacuum at 40 °C for 12 h to afford an aqua powder of PAMAM-G1-
3.2. Catalytic Reactions
PMo.
3.2.1. General Experimental Procedure for the Oxidation of Sulfides to Sulfoxides
3.2. Catalytic Reactions
A 50 mL, three-necked flask was charged with sulfide (0.5 mmol), the catalyst (50 mg), and
95%
3.2.1.EtOH (8 mL).
General The resulting
Experimental solution
Procedure forwas
the stirred of◦Sulfides
at 30
Oxidation C, and 30towt% H2 O2 (63 mg, 0.55 mmol)
Sulfoxides
was added slowly into the above mixture. The reaction was monitored by TLC (petroleum ether:ethyl
A 50 mL, three-necked flask was charged with sulfide (0.5 mmol), the catalyst (50 mg), and 95%
acetate = 7:3). After the reaction was finished, the catalyst was separated from the mixture by filtration,
EtOH (8 mL). The resulting solution was stirred at 30 °C, and 30 wt% H2O2 (63 mg, 0.55 mmol) was
washed with 95% EtOH, and dried in a vacuum at room temperature overnight for recycle use. The
added slowly into the above mixture. The reaction was monitored by TLC (petroleum ether:ethyl
filtrate and the washing solution were combined, concentrated under reduced pressure, followed by a
acetate = 7:3). After the reaction was finished, the catalyst was separated from the mixture by filtration,
freeze-drying. The crude products were purified by column chromatography on a silica gel column
washed with 95% EtOH, and dried in a vacuum at room temperature overnight for recycle use. The
filtrate and the washing solution were combined, concentrated under reduced pressure, followed by
a freeze-drying. The crude products were purified by column chromatography on a silica gel column
with n-hexane/ethyl acetate (2:1) as eluent to afford the desired products. The 1H NMR and 13C NMR
data and spectra for corresponding products are available online at Supplementary Materials.

3.2.2. General Experimental Procedure for the Oxidation of Sulfides to Sulfones

Catalysts 2019, 9, 791 8 of 10

with n-hexane/ethyl acetate (2:1) as eluent to afford the desired products. The 1 H NMR and 13 C NMR
data and spectra for corresponding products are available online at Supplementary Materials.

3.2.2. General Experimental Procedure for the Oxidation of Sulfides to Sulfones

A 50 mL, three-necked flask was charged with sulfide (0.5 mmol), the catalyst (150 mg), and
95% EtOH (10 mL). The resulting solution was stirred at 40 ◦ C, and 30 wt% H2 O2 (170 mg, 1.5 mmol)
was added slowly into the above mixture. The reaction was monitored by TLC (petroleum ether:ethyl
acetate = 7:3). After the reaction was finished, the catalyst was separated from the mixture by filtration,
washed with 95% EtOH, and dried in a vacuum at room temperature overnight for recycle use. The
filtrate and the washing solution were combined, concentrated under reduced pressure, followed by a
freeze-drying. The crude products were purified by column chromatography on a silica gel column
with n-hexane/ethyl acetate (2:1) as eluent to afford the desired products. The 1 H NMR and 13 C NMR
data and spectra for corresponding products are available online at Supplementary Materials.

3.2.3. Synthesis of Modafinil

A 250 mL, three-necked flask was charged with 2-[(diphenylmethyl)thio]acetamide (13 g, 50 mmol),
the catalyst (5 g), and 95% EtOH (80 mL). The resulting solution was stirred at 30 ◦ C, and 30 wt% H2 O2
(6.3 g, 55 mmol) was added slowly into the reaction mixture. The mixture was allowed stirring for 2 h at
30 ◦ C. After the reaction was finished, the catalyst was separated from the mixture by filtration, washed
with 95% EtOH, and treated for recycle use. The filtrate and washings were combined and transferred
to a 1 L beaker containing 500 mL deionized water to form white solid, which was collected by filtration
and purified by a recrystallization with 30 mL of acetone to provide 12.3 g of desired product with a
HPLC purity of 99.79%. 1 H NMR (400 MHz, DMSO-d6 ) δ 7.66–7.49 (m, 5H), 7.44–7.28 (m, 7H), 5.34
(s, 1H), 3.36 (d, J = 13.7 Hz, 1H), 3.22 (d, J = 13.6 Hz, 1H). 13 C NMR (151 MHz, CDCl3 ) δ 165.22, 133.37,
133.06, 128.46, 128.37, 127.93, 127.85, 127.79, 127.66, 70.50, 50.56. The 1 H NMR, 13 C NMR and HPLC
spectra for Modafinil are available online at Supplementary Materials.

4. Conclusions
In summary, we developed a PAMAM-G1-PMo-catalyzed method for the oxidation of sulfides to
sulfoxides or sulfones via an efficient and mild procedure. This system is environmentally benign since
30 wt% H2 O2 and 95% EtOH are used as the oxidant and solvent, respectively, and the catalysts are
recyclable. Moreover, the catalysts are inexpensive, stable during the reaction, and easily recovered by
filtration after the reaction and for reuse in additional runs without a noticeable loss of catalytic activity.
This is the first report of PAMAM-G1-PMo as the heterogeneous catalyst used in the oxidation of
sulfides to sulfoxides or sulfones, which will help the enrichment and development of future research
on the dendrimers’ hybrid.

Supplementary Materials: The following are available online at http://www.mdpi.com/2073-4344/9/10/791/s1,

Figure S1: XRD patterns of HMo.
Author Contributions: Y.L. and M.-S.C. supervised the whole experiment and provided technical guidance.
Q.-L.T. and Z.-F.F. performed the preparation and identification of the catalysts, and the investigation of the
oxidation conditions. J.-W.Y., Q.L. and Y.-X.C. assisted in the synthesis work.
Funding: The financial supports from the Program for Liaoning Innovative Talents in University (LR2017043)
and the Career Development Support Plan for Young and Middle-aged Teachers in Shenyang Pharmaceutical
University (ZQN2016005) are gratefully appreciated.
Conflicts of Interest: The authors declare no conflict of interest.
Catalysts 2019, 9, 791 9 of 10

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