Paired electrochemical conversion of nitroarenes to sulfonamides, diarylsulfones and bis(arylsulfonyl)aminophenols

Article abstract of DOI:10.1039/c7gc03576d

A paired electrochemical method using nitrobenzene (NB) derivatives and arylsulfinic acids (ASAs) as starting materials was developed for the synthesis of some new sulfonamides, diarylsulfones and bis(arylsulfonyl)aminophenols. The synthetic strategy was designed using the data provided by electrochemical studies involving cyclic voltammetry on NB oxidation in the absence and presence of ASAs. The reactions have been successfully performed in an undivided cell, at carbon rod electrodes, in aqueous solutions, by constant current electrolysis at room temperature. This strategy does not require catalysts, toxic solvents and challenging workups. It is also applicable for a wide range of nitroarenes.

Full text of DOI:10.1039/c7gc03576d

View Article Online
View Journal
Green
Chemistry
Accepted Manuscript
This article can be cited before page numbers have been issued, to do this please use: D. Nematollahi, B.
Mokhtari and H. Salehzadeh, Green Chem., 2018, DOI: 10.1039/C7GC03576D.
This is an Accepted Manuscript, which has been through the
Volume 18 Number
7 7 April 2016 Pages 1821–2242
Royal Society of Chemistry peer review process and has been
accepted for publication.
Green
Chemistry
Accepted Manuscripts are published online shortly after
Cutting-edge research for a greener sustainable future
www.rsc.org/greenchem
acceptance, before technical editing, formatting and proof reading.
Using this free service, authors can make their results available
to the community, in citable form, before we publish the edited
article. We will replace this Accepted Manuscript with the edited
and formatted Advance Article as soon as it is available.
You can find more information about Accepted Manuscripts in the
author guidelines.
Please note that technical editing may introduce minor changes
to the text and/or graphics, which may alter content. The journal’s
standard Terms & Conditions and the ethical guidelines, outlined
in our author and reviewer resource centre, still apply. In no
event shall the Royal Society of Chemistry be held responsible
for any errors or omissions in this Accepted Manuscript or any
consequences arising from the use of any information it contains.
ISSN 1463-9262
CRITICAL REVIEW
G. Chatel et al.
Heterogeneous catalytic oxidation for lignin valorization into valuable
chemicals: what results? What limitations? What trends?
rsc.li/green-chem

Please do not adjust margins
Green Chemistry
Page 1 of 7
View Article Online
DOI: 10.1039/C7GC03576D
Green Chemistry
PAPER
Paired electrochemical conversion of nitroarenes to sulfonamides,
diarylsulfones and bis(arylsulfonyl)aminophenols.†
Banafsheh Mokhtari,a Davood Nematollahi,*a and Hamid Salehzadehb
Received 00th January 20xx,
Accepted 00th January 20xx
DOI: 10.1039/x0xx00000x
www.rsc.org/
A paired electrochemical method using nitrobenzene derivatives activated esters,5,6 halides,7-10 arylboronicacids11-13 and
(NBs) and arylsulfinic acids (ASAs) as starting materials was alcohols.14-19 This is a straightforward strategy for the synthesis
developed for the synthesis of some new sulfonamides, of N-arylsulfonamides and doesn’t require the use of anilines,
diarylsulfones and bis(arylsulfonyl)aminophenols. The synthetic but various catalysts, harsh conditions, bases and/or ligands
strategy was designed using the data provided by electrochemical should be used and also starting materials must first be
studies involving cyclic voltammetry on NBs oxidation in the synthesized. In another strategy, we have used
absence and presence of ASAs. The reactions have been electrochemical methods for the synthesis of some
successfully performed in an undivided cell, at carbon rod sulfonamide derivatives.20-22 However, these methods need to
electrodes, in aqueous solutions, by constant current electrolysis use aromatic amines as a starting reagents
at room temperature. This strategy does not need to use catalysts,
In this context, we have developed a mild electrochemical
toxic solvents and challenging workups. It is also applicable to a procedure for the synthesis of new N-hydroxyaryl
wide range of nitroarenes.
sulfonamides,
diarylsulfones
and
bis(arylsulfonyl)
aminophenols without using organic solvents, catalysts and
ligands in room temperature using nitrobenzene (NB) and
arylsulfinic acid derivatives (ASAs) as starting materials.
Introduction
Sulfonamides are a class of antibacterial compounds which
have no interference with the mechanism of host defense.1
They are widely used for the treatment of various diseases
Results and discussion
such as gut infections, mucous membrane and urinary tract Cyclic voltammograms of NB were recorded in two potential
infections. In veterinary medicine, sulfonamides are classified ranges (Fig. 1 part I). When the potential was scanned from -
as highly soluble, standard, topical and potentiated 0.40 V to +0.34 V vs. Ag/AgCl, NB does not show any oxidation
compounds.2,3 These bioactivities have motivated researchers or reduction peak (curve a). But, upon scanning the electrode
to the development of efficient methods for the synthesis of potential from +0.34 V to a sufficiently negative voltage (−1.20
sulfonamide derivatives. The most general method to prepare V) (curve b), the cyclic voltammogram exhibits a large
of N-arylsulfonamides is direct N–S bond formation.4 This irreversible cathodic peak (C0) corresponding to the reduction
method is effective, but employs aromatic amines as nitrogen of NB to phenylhydroxylamine (PHA) and a reversible redox
sources which are genotoxic and lead to undesired impurities system
(A1/C1)
ascribed
to
the
redox
couple
in the synthesis of pharmaceutical ingredients.4 Also, phenylhydroxylamine/nitrosobenzene (PHA
/NSB) (Scheme 1,
functional groups such as hydroxyl, thiols and amines may Eq. 1).23
need to be protected to avoid undesired reactions.
To overcome these problems, the use of metal-catalysts for nitroaniline
the formation of C–N bond has been widely proposed.5-19 In nitrobenzene (CNA) were studied (Fig. 1, Parts II-IV). A similar
these methods, desired products were produced by the behavior was observed for CNA NA and NP (Scheme 1, Eq. 1).
In the same manner, electrochemical behavior of p-
(
NA), p-nitrophenol NP and 1-chloro-2-
(
)
,
reaction of sulfonamides as nitrogen-based source with aryl However, in the case of NP, a new redox couple (A2/C2)
appears at less positive potentials than the A1/C1 peaks
potential. The pathway leading to the oxidation/reduction
aFaculty of Chemistry, Bu-Ali-Sina University, Hamedan 65174, Iran.
nemat@basu.ac.ir.
peaks A1/C1 and A2/C2 is given in Scheme 1. An important
bFaculty of Chemistry, Kharazmi University, Tehran, Zip Code 15719-14911. Iran.
†Electronic Supplementary Informaꢀon (ESI) available: Cyclic voltammograms of all
starting materials and FT-IR and MS of all compounds.. See
DOI: 10.1039/x0xx00000x
feature of the peak current ratio, IpA2/IpA1 (and IpC2/IpC1) is that
the current ratio is depends on the potential scan rate, as, with
increasing potential scan rate, IpA2/IpA1 (and IpC2/IpC1) increases
This journal is © The Royal Society of Chemistry 20xx
Green Chem., 2015, 00, 1-4 | 1
Please do not adjust margins

Please do not adjust margins
Green Chemistry
Page 2 of 7
View Article Online
DOI: 10.1039/C7GC03576D
COMMUNICATION
Green Chem
(ESI, Fig. S10). From this data it can be concluded that with
increasing potential scan rate, the required time to convert 4-
(hydroxyamino)phenol to 4-aminophenol (six-electron
reduction process) is not sufficient, which results is a decrease
A1
NO2
NHOH
NO
+4e- +4H+
-H2O
R2
-2e- -2H+
R2
R2
(1)
C0
in the IpA1 and IpC1
.
+2e- +2H+
R1
PHA R1
R1
NSB
C1
R1 = R2 = H NB
R1 = H, R2 = Cl
CNB
R1 = NH2, R2 = H NA
A1
-2e- -2H+
NH
O
NH2
(2b)
+
H
+2e- +2H+
2
+
-
e
2
OH
C1
+
A2
-2e- -2H+
NO2
OH
NHOH
NO
+4e- +4H+
-H2O
(2a)
C0
+2e- +2H+
OH
NP
OH
C2
Scheme 1 Electrochemical behaviour of NB, CNB, NA and NP.
NH3
NH3
NH3
NH3
NH3
OH
Cl
Figure 2. The structure of protonated aniline derivatives.
The effect of pH on the cyclic voltammetric response of NB
has been examined (Fig. 3).The data show that the potential of
all three peaks (A1, C1 and C0) are pH-dependent. In addition,
the potential-pH diagram for phenylhydroxylamine/nitroso
Figure 1. Cyclic voltammograms of 1.0 mM of I) NB, II) CNA, III) NA and IV) NP at glassy
carbon electrode, in aqueous solution containing phosphate buffer (c = 0.2 M, pH =
3.5). Scan rate: 100 mV s-1; t = 25 ± 1 oC.
benzene
(PHA/NSB) redox system (redox couple A1/C1)
The difference observed between the cyclic voltammogram
confirms a two-electron/two-proton process
.
of NP and those of other nitroarenes (NB, CNA, NA) can be
related to the effect of solution pH on the substituent
appended to the aromatic ring. The protonation of the amine
group changes it from an electron-donating group to an
electron-withdrawing substituent. Under our experimental
conditions (pH, 3.5), if a six-electron reduction process takes
place, an amine substituted adduct could result which is
converted into the corresponding protonated form (Fig. 2).
Under these conditions, the oxidation of protonated aniline
synthesized from NB, CNA and NA, does not take place within
the potential window examined. In contrast, in the case of NP
,
the hydroxyl group is not in the protonated form, acting as an
electron-donating group and facilitate oxidation of protonated
aminophenol. This can be the reason for the presence of two
anodic peaks (A1 and A2) in the cyclic voltammogram of NP
(Fig. 1, Part IV).
Figure 3. Cyclic voltammograms of 1.0 mM nitrobenzene at glassy carbon electrode, in
water/ethanol (80/20) mixture with various pH values and same ionic strength. pHs
from (a) to (d) are: 1.0, 4.0, 5.0 and 7.0. Working electrode: glassy carbon. Scan rate:
2 | Green Chem., 2015, 00, 1-4
This journal is © The Royal Society of Chemistry 20xx
Please do not adjust margins

Please do not adjust margins
Green Chemistry
Page 3 of 7
View Article Online
DOI: 10.1039/C7GC03576D
Green Chem
COMMUNICATION
100 mV/s. Inset: The potential-pH diagram of phenylhydroxylamine/nitrosobenzene
(redox couple A1/C1). Temperature = 25 oC.
aqueous solution containing phosphate buffer (c = 0.2 M, pH = 3.5). Scan rate: 100 mV
-1; t = 25 ± 1 oC.
s
The influence of pH on the cyclic voltammograms of NA
,
NP
These studies were followed by controlled potential
and CNA was also studied (ESI Figs. S1-S3). Our data show that, coulometry of a solution containing NB (1.0 mM) and BSA (1.0
the influence of pH on the half wave potential of the redox mM) at -1.0 V vs. Ag/AgCl. In addition, cyclic voltammetry was
couple A1/C1 (and also A2/C2, in the case of NP) of these employed for electrolysis monitoring to obtain more
nitroarenes are similar to that of NB
.
information on the reaction process and the number of
The effect of benzenesulfinic acid (BSA) on the cyclic transferred electrons. The voltammograms of peak C0 show a
voltammetric response of NB was also examined (Fig. 4, part I). gradual decrease with the progress of electrolysis (Fig. 5). The
As can be seen, the important change in the cyclic current of peak C0 (IpC0) becomes about zero after the transfer
voltammogram of NB in the presence of BSA is the decrease of of about 4e- per molecule of NB (Fig. 5, inset).
ꢀͥ
̓
+
which is a sign of the reaction between electro-generated
NSB and BSA 24-27
.
The increasing of peak current ratio
ꢀͥ ꢁͥ
(
̓
/
̓
) with increasing potential sweep rate (ESI Fig. S6) is
+
+
another sign of the occurrence of a chemical reaction between
electrogenerated NSB and BSA 24-27
The influence of BSA on the cyclic voltammograms of NA
and NP was also shown in Fig 4, parts II and III. In these cases,
a new anodic peak (Ap) also appears in more positive
potentials which is related to the oxidation of product ( ). It
.
,
.
1-4
also should be noted that, in the case of NP in the presence of
BSA all cathodic peaks were removed (Fig. 4, part III).
Figure 5. Cyclic voltammograms of NB (1.0 mmol) in the presence of BSA (1.0 mmol), in
phosphate buffer solution (c = 0.2 M, pH 3.0), at glassy carbon electrode during
controlled-current coulometry at -1.0 V, after consumption of: (a) 0, (b) 100, (c) 200, (d)
300 and (e) 400 C. Inset: variation of IpC0 versus charge consumed. Scan rate 100 mV/s;
t = 25±1 ◦C.
The synthesis of desired products was carried out by
constant-current electrolysis of NB
presence of ASAs. The suggested mechanism for the synthesis
of N-hydroxy-N-phenylbenzenesulfonamide ( ) is shown in
, NP, NA and CNB in the
1
Scheme 2. As can be seen, the cathodically generated PHA is
oxidized at the anode (direct oxidation) to produce NSB. The
reaction of NSB with ASAs produces sulfonamide 1 28
.
In order
to get higher yields of
1, an indirect method, mediated by
ferrocyanide ions (indirect oxidation) was also developed. A
similar pathway was found for the electrochemical conversin
of CNB in the presence of ASAs
.
The Schemes for the electrochemical oxidation of NA and
NP in the presence of ASAs are shown below. The synthesis
mechanism of diarylsulfones 3 is shown in Scheme 3. As can be
seen, the cathodically generated phenylhydroxylamine is
oxidized at the anode to related nitroso benzene. The reaction
of this compound with ASAs as a nucleophile give the
corresponding sulfonamide (IntR). At the applied current
density, IntR oxidized and converted into Intox. The reaction of
ASAs with this electrochemically generated Michael acceptor
(
Intox) produces diarylsulfones
3
as a final product.20-22,28,29
Figure 4. Cyclic voltammograms of 1.0 mM I) NB, II) NA and III) NP: a) in the absence
(blue line) and b) in the presence of 1 mM BSA (red line) at glassy carbon electrode, in
This journal is © The Royal Society of Chemistry 20xx
Green Chem., 2015, 00, 1-4 | 3
Please do not adjust margins

Please do not adjust margins
Green Chemistry
Page 4 of 7
View Article Online
DOI: 10.1039/C7GC03576D
COMMUNICATION
Green Chem
pull system supported by intramolecular hydrogen bonding.
Comparison of 2,5-bis(methylsulfonyl)-1,4-diaminobenzene
structure with that of
4, reveals that the phenol group in
compounds 4, also can be act as push moiety in push-pull
system. So, here, we have reported a facile, green and one-pot
method for the synthesis of some sulfonylaniline derivatives.
The Scheme for the synthesis of 4, is different from the
previous ones in that the electrochemical reduction is a six-
electron transfer process which converts NP to p-
aminophenol. This compound after oxidation to p-
quinoneimine, was attacked by ASAs to form IntR. From a
molecular point of view, IntR is a substituted p-aminophenol
which oxidizes at the applied current density to the
corresponding p-quinoneimine (Intox). The reaction of another
nucleophile
(
ASA
)
with Intox
,
in the next step, gives
).30
Scheme 2. Electrochemical oxidation of NB in the presence of ASAs.
disubstituted p-aminophenol as a final product (
4
According to Scheme 4, the anodic peak Ap (Fig. 1, part III)
belongs to the oxidation of 4-amino-2-(phenylsulfonyl)phenol
According to this mechanism, the anodic peak Ap is related
to the oxidation of IntR (intermediate in reduced form) to Intox
(intermediate in oxidized form) (Fig. 1, part II).
(
IntR) to related phenylsulfonyl-quinoneimine (Intox). The
reaction of electro-generated p-quinoneimine with ASAs, in
addition to removing the cathodic peak C1, removed peaks A2
and C2 because of the predominance of six-electron reduction
of nitro group over the four-electron reduction (Scheme 1, Eq.
2b).
HO
HO
HO
NO2
+4H+
-H2O
NP
NHOH
NH2
+2H+
-H2O
SO2H
-2H+
R
R
H2N
OH
O
O
NH
S
O
O S O
O S O
IntR
H2N
-2H+
R
OH
HO2S
R
HN
O
O
S
O
Scheme 3. Electrochemical oxidation of NA in the presence of ASAs.
R = H, Cl, CH3
R
4
IntOX
l.
R
Scheme 4. Electrochemical synthesis 4-amino-2,5-
bis(phenylsulfonyl)phenols using NP as starting materia
A mechanism accounting for the synthesis of 4-amino-2,5-
4
bis(phenyl sulfonyl)phenols
shown in Scheme 4. Recently, Beppu and coworkers31 reported
that slufonylaniline-based dyes such as 2,5-
bis(methylsulfonyl)-1,4-diaminobenzene are green strong
fluorophores. They have stated that the fluorescence activity
4, using NP, as starting material is
Current density, charge passed and solution pH are
important parameters affecting the yield of products. The
experiments performed showed that the optimal charge
needed to synthesize products 1-4, is its theoretical value. For
:
of these compounds is established based on an effective push–
4 | Green Chem., 2015, 00, 1-4
This journal is © The Royal Society of Chemistry 20xx
Please do not adjust margins

Please do not adjust margins
Green Chemistry
Page 5 of 7
View Article Online
DOI: 10.1039/C7GC03576D
Green Chem
COMMUNICATION
example, in the case of NB, the maximum yield of 75% was platinum wire was used as the counter electrode. Before each
obtained for the synthesis of 1a after consumption of 4.1 experiment, the GC electrode was polished using alumina
F/mol (Fig. 6, inset). The over-reduction of PHA and/or 1a (or slurry (from Iran Alumina Co). The anode used in controlled-
over-oxidation of NSB and/or 1a) are the main factors in potential coulometry, constant current electrolysis and
decreasing product yield when more electricity is consumed. preparative electrolysis was an assembly of two carbon plates
The data also suggest that the optimum current density for the (each one, 10 cm diameter and 7 cm length). The similar
synthesis of products 1-4 is 0.7 mA/cm2 (Fig. 6). The configuration carbon constitutes the cathode electrode.
insufficient amount of over-voltage at lower current densities
and over-reduction of PHA and/or 1a (or over-oxidation of
R3
SO2H
R1
NSB and/or 1a) at higher current densities are responsible for
decreasing the yield. In addition, the optimum pH value for the
synthesis of products 1-5 is 3.0. The products and their yields
are summarized in Table 1.
NO2
Product 1-4
Q = Theoretical amount
Anode = Cathode = C
J = 0.7 mA/cm2
R2
mp o
C
Entry
1
Substrate
NO2
Product
Yield %
70
OH
O
N
S
133-134
O
1a
OH
NO2
O
N
S
2
3
4
5
6
75
78
73
75
72
139-141
128-129
153-155
139-140
143-145
O
H3C
1b
NO2
NO2
OH
O
N
S
O
1c
Cl
OH Cl
O
Cl
Cl
N
S
O
2a
NO2
NO2
OH
Cl
O
N
S
O
H3C
Cl
2b
OH
Cl
O
N
S
O
2c
Cl
NO2
H
O
S
N
O
170-1172
158-159
156-158
158-160
7
60
Figure 6. The effect of charge passed (inset) and current density on electrochemical
synthesis of 1a.
O
S
N
3a
O
H
NH2
NO2
H
CH3
O
N
S
O
Conclusions
8
72
O
S
S
N
H
b
3
O
O
H3C
Synthesis of the title compounds (1-4) via a paired
NH2
NO2
electrolysis, using a simple cell, and under constant current
conditions, in safe water/ethanol solvent mixture, without any
catalysis, easy work up (filtration and washing with distilled
water), at room-temperature, using the common electrodes
(carbons electrodes) with high atom economy and good yields
are the prominent features of this work. In addition, another
important feature of this method is its adaptability to a wide
range of nitroarenes. The results of this study also indicate
that the product selectivity was greatly affected by the nature
of the functional group.
H
Cl
O
N
S
O
9
77
70
O
3c
N
Cl
H
NH2
NO2
H2N
O
O
S
S
10
O
OH
O
4a
OH
NO2
H2N
O
O
S
CH3
S
H3C
70
72
158-159
157-159
11
12
O
O
4b
4c
OH
OH
NO2
H2N
O
O
S
Experimental section
Cl
S
Cl
O
O
Apparatus and reagents
OH
OH
Cyclic voltammetry, controlled-potential coulometry,
constant current electrolysis and preparative electrolysis were
performed using an Autolab model PGSTAT 20
potentiostat/galvanostat. The working electrode used in the
voltammetry experiments was a glassy carbon disc and a
The working electrode potentials were measured vs.
Ag/AgCl (saturated KCl) electrode (all electrodes from AZAR
This journal is © The Royal Society of Chemistry 20xx
Green Chem., 2015, 00, 1-4 | 5
Please do not adjust margins

Please do not adjust margins
Green Chemistry
Page 6 of 7
View Article Online
DOI: 10.1039/C7GC03576D
COMMUNICATION
Green Chem
12 C. Pan, J. Cheng, H. Wu, J. Ding and M. Liu, Synth. Commun.,
2009, 39, 2082-2092.
13 S. Y. Moon, J. Nam, K. Rathwell and W. S. Kim, Org. Lett.,
2014, 16, 338-341.
14 H. Qin, N. Yamagiwa, S. Matsunaga and M. Shibasaki, Angew.
Chem., 2007, 119, 413-417.
Electrodes). More details are described in our previous
paper.32
Nitrobenzene (NB), p-nitroaniline (NA), p-nitrophenol (NP),
arylsulfinic acids (ASAs), phosphate salts and ethanol were
obtained from commercial sources.
15 F. Shi, M. K. Tse, S. Zhou, M. M. Pohl, J. r. Radnik, S. Hübner,
K. Jähnisch, A. Brückner and M. Beller, J. Am. Chem. Soc.,
2009, 131, 1775-1779.
Table 1. Galvanostatic paired electrochemical synthesis of
compounds 1-4
.
16 F. Shi, M. K. Tse, X. Cui, D. Gördes, D. Michalik, K. Thurow, Y.
Deng and M. Beller, Angew. Chem., 2009, 121, 6026-6029.
17 A. J. Watson, A. C. Maxwell and J. M. Williams, J. Org. Chem.,
2011, 76, 2328-2331.
18 X. Yu, C. Liu, L. Jiang and Q. Xu, Org. Lett., 2011, 13, 6184-
6187.
General electrochemical procedure
Electroorganic synthesis of compounds 1-4 were
performed under constant current conditions In a typical
procedure, a solution (80 mL) of water (phosphate buffer, pH =
3.0, c = 0.2 M)/ethanol mixture (20/80, v/v) containing
19 P. Qu, C. Sun, J. Ma and F. Li, Adv. Synth. Catal., 2014, 356
447-459.
,
nitrobenzene derivatives (NB
, CNB, NA or NP) (1 mmol) and
arylsulfinic acids sodium salt (1 mmol for the synthesis of
20 D. Nematollahi and A. Maleki, Electrochem. Commun., 2009,
11, 488-491.
21 F. Varmaghani, D. Nematollahi, S. Mallakpour and R. Esmaili,
Green Chem., 2012, 14, 963-967.
compounds
compounds
1
and
2, and 2 mmol for the synthesis of
3
and ) was electrolyzed in an undivided cell at 25
4
oC under a constant-current density of 0.7 mA/cm2. The
electrolysis was terminated after consumption of the
theoretical amount of the charge consumed. Since, the
products are insoluble in water (phosphate buffer, pH = 3.0, c
= 0.2 M)/ethanol mixture (80/20, v/v), separation is carried out
only by filtration. The collected solids were washed several
times with distilled water.
22 H. Beiginejad and D. Nematollahi, J. Org. Chem., 2014, 79
6326-6329.
,
23 (a) C. Cougnon, F. Gohier, D. Bélanger and J. Mauzeroll,
Angew. Chem., 2009, 121, 4066-4068; (b) P. Zuman, Z.
Fijalek, D. Dumanovic and D. Sužnjević, Electroanalysis, 1992,
4, 783–794; (c) P. Zuman, E. Rupp, Electroanalysis, 1995,
132–137.
7,
24 E. Salahifar, D. Nematollahi, M. Bayat, A. Mahyari and H.
Amiri Rudbari, Org. Lett., 2015, 17, 4666–4669.
25 A. Maleki and D. Nematollahi, Org. Lett., 2011, 13, 1928–
1931.
Conflicts of Interest
26 D. Nematollahi, M. S. Workentin and E. Tammari, Chem.
Commun., 2006, 1631–1633.
27 R. J. Cremlyn, An Introduction to Organosulfur Chemistry,
There are no conflicts of interest to declare.
Acknowledgements
John Wiley & Sons Inc, 1996
28 (a) S. Khazalpour and D. Nematollahi, Green Chem., 2015, 17
.
,
We acknowledge the Bu-Ali Sina University Research Council
and Center of Excellence in Development of Environmentally
Friendly Methods for Chemical Synthesis (CEDEFMCS) for their
support of this work.
3508-3514; (b) D. Nematollahi, A. Namdarand Sh. Momeni, J.
Electroanal. Chem., 2018, 810, 161–170.
29 S. Khazalpour, D. Nematollahi, A. Ahmad and B. Dowlati,
Electrochim. Acta, 2015, 180, 909–913.
30 D. Nematollahi, S. Khazalpour, M. Ranjbar and Sh. Momeni,
Sci. Rep., 2017, 7, Article number: 41963.
31 (a) T. Beppu, K. Tomiguchi, A. Masuhara, Y. J. Pu and H.
Katagiri, Angew. Chem. Int. Ed., 2015, 54, 7332-7335; (b) T,
Beppu, S. Kawata, N. Aizawa, Y. J. Pu, Y. Abe, Y. Ohba and H.
Katagiri, ChemPlusChem., 2014, 79, 536-545.
32 D. Nematollahi, S. Dehdashtian and A. Niazi, J. Electroanal.
Chem., 2008, 616, 79-86.
Notes and references
1
2
3
4
5
6
7
8
9
D. A. Smith and R. M. Jones, Curr. Opin. Drug Discov. Devel.,
2008, 11, 72-79.
E. P. Tolika, V. F. Samanidou and I. N. Papadoyannis, Curr.
Pharm. Anal., 2010, 6, 198-212.
A. K. Gadad, C. S. Mahajanshetti, S. Nimbalkar and A.
Raichurkar, Eur. J. Med. Chem., 2000, 35, 853-857.
P. L. Skipper, M. Y. Kim, H. L. P. Sun, G. N. Wogan and S. R.
Tannenbaum, Carcinogenesis, 2010, 31, 50-58.
J. D. Hicks, A. M. Hyde, A. M. Cuezva and S. L. Buchwald, J.
Am. Chem. Soc., 2009, 131, 16720-16734.
S. Shekhar, T. B. Dunn, B. J. Kotecki, D. K. Montavon and S. C.
Cullen, J. Org. Chem., 2011, 76, 4552-4563.
J. Yin and S. L. Buchwald, J. Am. Chem. Soc., 2002, 124, 6043-
6048.
J. Baffoe, M. Y. Hoe and B. B. Touré, Org. Lett., 2010, 12
1532-1535.
B. R. Rosen, J. C. Ruble, T. J. Beauchamp and A. Navarro, Org.
Lett., 2011, 13, 2564-2567.
,
10 B. Y. H. Tan, Y. C. Teo and A. H. Seow, Eur. J. Org. Chem.,
2014, 2014, 1541-1546.
11 P. Y. S. Lam, G. Vincent, C. G. Clark, S. Deudon and P. K.
Jadhav, Tetrahedron Lett., 2001, 42, 3415-3418.
6 | Green Chem., 2015, 00, 1-4
This journal is © The Royal Society of Chemistry 20xx
Please do not adjust margins

Page 7 of 7
Green Chemistry
View Article Online
DOI: 10.1039/C7GC03576D
Paired electrochemical conversion of nitroarenes to
sulfonamides, diarylsulfones and bis(arylsulfonyl)aminophenols.
A green strategy
Banafsheh Mokhtari, Davood Nematollahi,* and Hamid Salehzadeh
Graphical Abstract
A paired electrochemical synthesis of sulfonamides, diarylsulfones and bis(arylsulfonyl)aminophenols using nitrobenzene
derivatives and arylsulfinic acids as starting materials under green conditions.