Electrochemical synthesis of 1-: N -phenyl-4-(sulfonyl)benzene-1,2-diamine derivatives: A mild and regioselective protocol

Article abstract of DOI:10.1039/c5nj03514g

Regioselective synthesis of 1-N-phenyl-4-(sulfonyl)benzene-1,2-diamine derivatives was carried out by the anodic oxidation of 2-aminodiphenylamine in a water/ethanol mixture in the presence of sulfinic acids as nucleophiles using both controlled-potential

Full text of DOI:10.1039/c5nj03514g

View Article Online
View Journal
NJC
Accepted Manuscript
This article can be cited before page numbers have been issued, to do this please use: D. Nematollahi,
M. Sharafi-Kolkeshvandi, F. Nikpour and E. Salahifar, New J. Chem., 2016, DOI: 10.1039/C5NJ03514G.
This is an Accepted Manuscript, which has been through the
Royal Society of Chemistry peer review process and has been
accepted for publication.
Accepted Manuscripts are published online shortly after
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
Information for Authors.
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 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.
www.rsc.org/njc

Please do not adjust margins
New Journal of Chemistry
Page 1 of 6
View Article Online
DOI: 10.1039/C5NJ03514G
NJC
LETTER
Electrochemical Synthesis of 1-N-phenyl-4-(sulfonyl)benzene-1,2-
diamine Derivatives. A Mild and Regioselective Protocol†
Mahnaz Sharafi-Kolkeshvandi,a Davood Nematollahi,*b Farzad Nikpoura and Eslam Salahifarb
Received 00th January 20xx,
Accepted 00th January 20xx
DOI: 10.1039/x0xx00000x
www.rsc.org/
Regioselective synthesis of 1-N-phenyl-4-(sulfonyl)benzene-1,2- numerous synthesis strategies have been reported.15
diamine derivatives was carried out by anodic oxidation of 2- The most common strategies towards diarylsulfone synthesis
aminodiphenylamine in water/ethanol mixture in the presence of typically involve the oxidation of corresponding sulfides and
some sulfinic acids as nucleophiles using both controlled-potential sulfoxides,16 the sulfonylation of arenes in the presence of strong
and constant current techniques. Our voltammetric data indicate acids17 and classic Friedel−Craꢀs type sulfonaꢁon reacꢁons.18 The
that the anodic oxidation of 2-aminodiphenylamine produces 1-N- majority of these processes19 generally suffer from significant
phenyl-o-benzoquinone diamine. This compound acts as a Michael limitations, such as harsh conditions, high temperature, lack of
acceptor
providing
1-N-phenyl-4-(arylsulfonyl)benzene-1,2- regiospecificity or incompatibility with numerous functional
diamines in high yields. In this new methodology, a mixture of groups.20 Therefore, more effective and environmentally friendly
water/ethanol was used as the solvent, a carbon rod as the anode methods are needed. In contrast to one-pot chemical synthesis
and avoids the use of toxic and/or hazardous reagents.
where the control on the oxidation of a single component is
difficult, controlled-potential electrolysis serves as powerful
a
Introduction
method for the synthesis of a desirable product via selective
oxidation of a target reagent.21
Aryl sulfone-containing compounds are important synthetic
targets and widely used as synthons for synthetic organic chemists
due to their chemical properties1 and biological activities.2 These
These findings (including the importance of diarylsulfone
compounds, significant limitations in their synthesis, efficiency of
electrochemical methods in organic synthesis and the synthesis of
compounds that may have medicinal properties) motivated us to
synthesize some new organic compounds under greener conditions,
based on the anodic oxidation of 2ADPA (Fig. 1). Electrochemical
oxidation of 2ADPA in the absence of nucleophiles has been studied
previously by Cotarelo et al.22 and Losito et al.23 In both studies, the
authors reported the dimerization of 2ADPA.
compounds are useful building blocks in medicinal chemistry and
3
found on several drugs, including antimigraine Vioxx
®
®
,
.
5
antibacterial dapsone (Fig. 1)4 and antiandrogen Casodex
Furthermore, these compounds have shown promising antitumor,6
antifungal,7 antibacterial activities8 and are used as inhibitors for
several enzymes such as cyclooxygenase-2 (COX-2),9 HIV-1 reverse
transcriptase,10 integrin VLA-411 and ATPase.12 It should be noted
that, despite the importance of dapsone, it has some
haematological side effects due to its hydroxylamine metabolites.13
The formation of hydroxylamine is catalyzed either by hepatic
enzymes such as cytochrome P450.14
On the other hand, 2-aminodiphenylamine (2ADPA) and its
derivatives are interesting compounds due to their wide application
as precursors for the synthesis of biologically active compounds, as
fluorescent material, as lubricant antioxidants, in dye formulations
and in polymer synthesis.15 Due to their important applications,
Fig. 1 The structures of dapsone and synthesized compounds (3a-3d).
Following our experience in electrochemical synthesis of new
compounds with medicinal activity based on the in-situ generation
of Michael acceptor,24 in the present study, we aimed to synthesize
some new compounds with both structures of diarylsulfone and
2ADPA (Fig. 1) by electrochemical oxidation of 2ADPA in the
presence of sulfinic acids (1a-1d) as nucleophiles under greener
a.Department of Chemistry, Faculty of Sciences, University of Kurdistan, P.O. Box
66315-416, Sanandaj, Iran.
b.Faculty of Chemistry, Bu-Ali-Sina University, Hamedan 65174, Iran.
nemat@basu.ac.ir.
† Electronic Supplementary Information (ESI) available: Electrolysis cell, 1H NMR,
2D NMR, 13C NMR, FT-IR, MS, elemental analysis of all compounds and details of X-
ray crystallography. See DOI: 10.1039/x0xx00000x
This journal is © The Royal Society of Chemistry 20xx
New J. Chem., 2015, 00, 1-4 | 1
Please do not adjust margins

Please do not adjust margins
New Journal of Chemistry
Page 2 of 6
View Article Online
DOI: 10.1039/C5NJ03514G
LETTER
NJC
conditions (Scheme 1). The method allows a one-pot regioselective
These observations indicate that electrochemically generated
synthesis of 1-N-phenyl-4-(sulfonyl)benzene-1,2-diamines. In this NPBQD is consumed by a chemical reaction with 1a. Controlled
paper, we also discussed the reaction mechanism of the synthesis potential coulometry (CPC) was used to investigate the number of
of 1-N-phenyl-4-(sulfonyl)benzene-1,2-diamine derivatives.
electrons being transferred during oxidation of 2ADPA in the
presence of 1a. It was carried out at potential beyond the oxidation
peak for 2ADPA (0.53 V versus Ag/AgCl 3M Cl-). CPC establishes the
occurrence of an overall two-electron process. From the diagnostic
criteria of the cyclic voltammetry and controlled potential
coulometry, the electrochemical behavior of 2ADPA in the presence
of 1a is characteristic of an EC mechanism (Scheme 2).
H
NH2
-2e-, -2H+
N
R
SO2H
+
O
N
H
1a-1d
S
NH2
R
O
2ADPA
3a-3d
R
Isolated yield
mp (oC)
160-162
136-138
145-147
137-139
H2N
N
-2e-, -2H+
80
85
78
90
a
b
c
N
H
NH
Me
NPBQD
2ADPA
SO2H
R
1a-1d
Cl
Path A
Path B
d
Me
Scheme 1 The overall reaction of electrooxidation of 2ADPA in the presence of 1a-1d.
O
O
H
H
R
H
N
R
Results and discussion
H2N
N
S
S
O
O
Cyclic voltammogram of 2ADPA in water (phosphate buffer,
c=0.2 M, pH = 2.0)/ethanol (70/30, v/v) mixture is shown in Fig. 2
curve a. As can be observed, one anodic A1 and its corresponding
cathodic peak (C1) was obtained, which correspond to the
transformation of 2ADPA to 1-N-phenyl-o-benzoquinone diimine
(NPBQD) and vice versa within a quasi-reversible two-electron
process. Fig. 2 curve b, shows the recorded cyclic voltammogram
for a solution containing both 2ADPA and benzenesulfinic acid (1a).
Comparing the voltammograms in Fig. 2, it can be observed that the
cathodic peak current (IpC1) disappears. Under these conditions, the
peak current ratio (IpC1/IpA1) depends on the potential scan rate and
1a concentration. It increases with increasing potential scan rate
and decreasing 1a concentration.
2a-2d
4a-4d
HN
Aromatization
Aromatization
O
R
S
H
N
H
N
O
S
O
H2N
H2N
5a-5d
R
O
3a-3d
Scheme 2 Proposed mechanism for the electrochemical oxidation of 2ADPA in the
presence of sulfinic acids.
According to the Scheme 2, the generation of NPBQD (Er step)
is followed by addition of 1a-1d to quinonediimine ring (Ci step),
giving rise to a 3a-3d as the final products. The oxidation of 3a-3d is
more difficult than the oxidation of the starting molecule (2ADPA)
because of the presence of the electron-withdrawing sulfonyl group
as well as by the insolubility of the final products 3a-3d in H2O/EtOH
(70/30, v/v) mixture. Consequently, the oxidation of 3a-3d did not
occur during the electrochemical oxidation at the potential of 0.53
V
versus Ag/AgCl 3M Cl-. The experimental details and
characterization data for 3a-3d are given in Electronic
Supplementary Informaꢁon (ESI†). In the proposed mechanism, the
generated NPBQD can be attacked by 1a-1d through the paths A or
B to form the final products 3a-3d or 5a-5d respectively. However,
single-crystal X-ray diffraction analysis of product confirms selective
formation of 3a-3d (Fig. 3).
This phenomenon can be explained by the fact that the
regioisomers 2a-2c are more stable than the regioisomers 4a-4c
due to the conjugation of a phenyl (aryl) ring with the 2,5-
cyclohexadien-1-imine 2a-2c. Hyperconjugation with the methyl
group in 2d appears to be sufficiently stabilizing to ensure a high
regioselectivity of the addition of RSO2H to NPBQD as well. These
Fig. 2 Cyclic voltammograms of 2ADPA (0.25 mM) (a) in the absence of benzenesulfinic
acid (b) and in the presence of benzenesulfinic acid (0.25mM). (c) Benzenesulfinic acid
(0.25 mM) in the absence of 2ADPA. These voltammograms were performed at a glassy
carbon electrode in water (phosphate buffer, c= 0.2 M, pH = 2.0)/ethanol (70/30, v/v)
mixture. Scan rate 3 V s−1. Temperature = 25 oC.
2 | New J. Chem., 2015, 00, 1-4
This journal is © The Royal Society of Chemistry 20xx
Please do not adjust margins

Please do not adjust margins
New Journal of Chemistry
Page 3 of 6
View Article Online
DOI: 10.1039/C5NJ03514G
NJC
LETTER
results show that, for the addition of a soft nucleophile such as
According to the second principle of green chemistry (atom
economy), which was developed by Trost,26 “synthetic methods
should be designed to maximize incorporation of all materials used
in the process into the final product”.27 The atom economy was
calculated according to the equation: % atom economy = (FW of
atoms utilized/FW of all reactants) × 100. According to Scheme 1,
the % atom economy in the synthesis 3a-3d are 99.38, 99.41, 99.44,
and 99.24%, respectively. The high atom economy confirms that all
atoms (except two hydrogen atoms) from the starting materials are
incorporated into the product.
RSO2H to NPBQD, the transition state is late.
Constant-current synthesis was also performed to improve the
synthetic procedure of 3a-3d. To achieve high yield of product (3a-
3d), the effect of current density was investigated in the range of
0.05 to 1.5 mA cm−2, while the other parameters (temperature =
298 K, charge = 50 C, electrode surface = 31 cm2, 2ADPA = 0.25
mmol, and 1a-1d = 0.25 mmol) are kept constant. The results
showed that, the highest products yields (75-85%) were obtained at
low current densities (0.35-0.50 mA cm−2) (Table 1). The lower
current densities result in longer reaction time and the higher
current densities result in occurrence of some side reactions such as
oxidation of water, nucleophile and product, and consequently, a
decrease in the product yield and energy efficiency. In addition, the
current efficiency at optimum current density is shown in Table 1.
Our results also indicate that, with increasing the current density,
the current efficiency decreases. The lower current efficiency in
higher current densities is attributed to the large contribution of
side reactions (oxidation of water, nucleophile and product).
Fig. 3 ORTEP view of X-ray crystal structure of 3c
On the other hand the pKa values for 2ADPAH+ and 2ADPAH2
2+
are 3.90 and -3.59, respectively.25 It shows that 2ADPA is highly
resistant to the formation of 2ADPAH22+. This also means that at
our experimental conditions (pH = 2.0), only the terminal imino
group is in the protonated form and for this reason nucleophilic
attack to NPBQD is highly regioselective, occurring at the meta
+
.
position of the C=NH2
In order to investigate the electrochemical properties of 3a,
cyclic voltammogram of it was recorded (Fig. 4, curve b).The cyclic
voltammogram shows one anodic (A2) and
a corresponding
cathodic peak (C2), which correspond to the transformation of 3a
into o-quinone-diimine 3aox and vice versa within a two-electron
process (Scheme 3). In comparison with 2ADPA (curve b), the half
wave potential (E1/2) of 3a is more positive than E1/2 of 2ADPA. The
result was predictable: the attachment of an electron-withdrawing
group to the phenyl ring increases the oxidation potential.
entry
current density
(mA cm-2)
0.40
current efficiency
product yield
(%)
91
90
85
95
(%)
80
80
75
85
3a
3b
3c
3d
0.40
0.50
0.35
Table 1 The effect of current density on the current efficiency and product yield
of 3a-3d.
Conclusions
In this work, the synthesis of compounds 3a-3d was carried out
successfully by the electrochemical oxidation of 2ADPA in the
presence of sulfinic acid derivatives, using both constant current
and controlled-potential techniques. The presented constant
current method has two series of advantages over conventional
methods. Firstly, it is practically convenient to carry out. It uses mild
and one-pot conditions with high atom economy (> 99%) and high
current efficiency (> 90%). It proceeds at room temperature and in
H2O/EtOH mixture solution, without any catalysis, strong acids or
bases. Secondly, in this method, the products were obtained
regioselectively in high yields (> 75%).
Fig. 4 Cyclic voltammogram of (a) 2ADPA (1.0mM), (b) 3a (1.0 mM). Other conditions
are as same as Fig. 2
Experimental section
Apparatus and reagents
Cyclic voltammetry, controlled-potential coulometry and
preparative electrolysis were performed using an Autolab
model PGSTAT 20 potentiostat/galvanostat. The working
Scheme 3 Electrochemical oxidation of 3a.
This journal is © The Royal Society of Chemistry 20xx
New J. Chem., 2015, 00, 1-4 | 3
Please do not adjust margins

Please do not adjust margins
New Journal of Chemistry
Page 4 of 6
View Article Online
DOI: 10.1039/C5NJ03514G
LETTER
NJC
electrode used in the voltammetry experiments was a glassy from diethyl ether. It should be noted that, the supporting
carbon disc (1.8 mm2 area) and platinum wire was used as electrolyte can be recycled and reused.33 For this purpose after
counter electrode. The working electrode used in controlled- separation of precipitate, duo to removing the trace organic
potential coulometry and preparative electrolysis was an materials including substrates and by-products, the extraction
assembly of four carbon rods (31 cm2 from KIGCO, Mashhad, method was used with ethylacetate. The aqueous phase can be
Iran) and large platinum gauze (35 cm2 area) constitute the reused in subsequent reactions. The products were characterized
counter electrode placed as single rods in the edges of a square by their physical, crystallographic and spectroscopic data.
with a distance of 3 cm
.
The electrochemical oxidations were
1-N-phenyl-4-(phenylsulfonyl)benzene-1,2-diamine
performed under controlled-potential and constant current (C18H16N2O2S) (3a). Isolated yield: 80%. mp 160-162 °C; FT-IR (KBr)
conditions in one compartments cell equipped with a magnetic (cm-1): 3440, 3390 and 3351 (medium, stretching NH2 and NH),
stirrer (see Supporting Information). The working electrode 1590, 1508 (medium, stretching C=C), 1294 (strong, stretching
potentials were measured versus Ag/AgCl 3M Cl- (all electrodes aromatic C–N and S=O), 1151 (strong, stretching S=O); 1H NMR, δ
from AZAR electrode). All experiment was carried out at a ppm (500 MHz, CDCl3): 3.73 (s, 2H, NH2, disappeared by addition of
temperature of 25 ± 1 °C. 2-Aminodiphenylamine (2ADPA), D2O), 5.61 (s, 1H, NH, disappeared by addition of D2O), 6.94 (d, 2H, J
sulfinic acids (1a-1d), phosphate salts and ethanol were = 7.5 Hz, Ar-H), 6.99 (t, 1H, J = 8.5 Hz, Ar-H), 7.17 (d, 1H, J = 8.0 Hz,
obtained from commercial sources. These chemicals were Ar-H), 7.27-7.33 (m, 4H, Ar-H), 7.46-7.54 (m, 3H, Ar-H), 7.91 (s, 2H,
used without further purification. The glassy carbon electrode Ar-H); 13C NMR, δ ppm (125 MHz, CDCl3): 115.9, 118.1, 119.3, 120.3,
was polished using alumina slurry (from Iran Alumina Co.). 122.5, 127.7, 129.6, 129.9, 133.2, 134.2, 136.9, 138.3, 142.3, 142.9;
Melting points were measured with an Electrothermal 9100 Anal. Calcd for C18H16N2O2S (324.09): C, 66.64; H, 4.97; N, 8.64; O,
apparatus (Rochford, UK). IR spectra (KBr) were recorded on 9.86; S, 9.88. Found: C, 66.69; H, 4.99; N, 8.69; O, 9.90; S, 9.93. MS
Perkin–Elmer GX FT-IR spectrometer. NMR spectra were recorded (EI) m/z (%): 324 (100).
with a Bruker DRX-500, 400 AVANCE (Rheinstetten, Germany)
instruments (500, 400 MHz for 1H and 125, 100 MHz for 13C). Isolated yield: 85%. mp 136-138 °C; FT-IR (KBr) (cm-1): 3444,
Chemical shifts are given in ppm ( ) relative to internal TMS, and 3392 and 3353 (medium, stretching NH2 and NH), 1589 and
1-N-Phenyl-4-tosylbenzene-1,2-diamine (C19H18N2O2S) (3b).
δ
coupling constants, J, are reported in Hz. Mass spectra were 1508 (medium, stretching C=C), 1297 (strong, stretching
recorded with an Agilent-5975C inert XL MSD mass spectrometer aromatic C–N and S=O), 1149 (strong, stretching S=O); 1H
(USA) operating at an ionization potential of 70 eV. X-ray data for 3c NMR, δ ppm (500 MHz, CDCl3): 2.37 (s, 3H, CH3), 3.77 (s, 2H,
(CCDC 1407863) was collected on a STOE IPDS-II diffractometer NH2, disappeared by addition of D2O), 5.61 (s, 1H, NH,
with graphite monochromated Mo-Kα radiation. For 3c, a blue disappeared by addition of D2O), 6.94 (d, 2H, J = 7.5 Hz, Ar-H),
crystal was chosen using a polarizing microscope and mounted on a 6.98 (t, 1H, J = 7.5 Hz, Ar-H), 7.16 (d, 1H, J = 8.5 Hz, Ar-H), 7.27-
glass fibre which is used for data collection. Data was collected at a 7.31 (m, 6H, Ar-H), 7.78 (d, 2H, J = 8.0 Hz, Ar-H); 13C NMR, δ
temperature of 298(2) K in a series of ω scans in 1° oscillations and ppm (125 MHz, CDCl3): 21.9 (CH3), 115.7, 118.3, 119.1, 120.1,
integrated using the Stöe X-AREA28 software package. The 122.4, 127.8, 129.9, 130.2, 134.8, 136.6, 138.5, 139.9, 142.4,
numerical absorption correction was applied using the X-RED29 and 144.1; Anal. Calcd for C19H18N2O2S (338.11): C, 67.43; H, 5.36;
X-SHAPE30 software packages. The data was corrected for Lorentz N, 8.28; O, 9.46; S, 9.47. Found: C, 67.49; H, 5.41; N, 8.30; O,
and Polarizing effects. The structures were solved by direct 9.49; S, 9.51; MS (EI) m/z (%): 338 (100).
methods using SIR2004.31 The non-hydrogen atoms were refined
4-((4-Chlorophenyl)sulfonyl)-1-N-phenylbenzene-1,2-
anisotropically by the full-matrix least-squares method on F2 using diamine (C18H15ClN2O2S) (3c). Isolated yield: 78%. mp 135-136
SHELXL.32 The hydrogen atoms of the –NH and NH2 groups were °C; FT-IR (KBr) (cm-1): 3428 and 3353 (medium, N–H), 1590 and
found in difference Fourier maps and refined isotropically. Other 1496 (medium, C=C), 1315 (strong, stretching aromatic C–N),
hydrogen atoms were added at ideal positions and constrained to 1301 and 1149 (strong, stretching S=O), 758 (strong, stretching
1
ride on their parent atoms. The Flack parameter 0.35(4) means that C-Cl); H NMR, δ ppm (400 MHz, DMSO-d6): 5.38 (s, 2H, NH2,
the absolute structure could not be confirmed. For more disappeared by addition of D2O), 6.92 (t, 1H, J = 7.6 Hz, Ar-H),
information about structure of 3c please see Supporting 7.05 (d, 2H, J = 7.6 Hz, Ar-H), 7.08 (dd, 1H, J = 8.5 Hz, Jmeta = 2.0
Information.
Hz, Ar-H), 7.14 (d, 1H, J = 8.5 Hz, Ar-H), 7.22 (d, 1H, Jmeta = 2.0
Hz, Ar-H), 7.27 (t, 2H, J = 7.6 Hz, Ar-H), 7.59 (s, 1H, NH,
disappeared by the addition of D2O), 7.69 (d, 2H, J = 8.8 Hz, Ar-
H), 7.86 (d, 2H, J = 8.8 Hz, Ar-H); 13C NMR, δ ppm (100 MHz,
DMSO-d6): 113.1, 115.8, 117.1, 119.1, 121.5, 129.1, 129.7,
130.1, 131.4, 135.3, 138.4, 139.6, 142.0, 142.8; Anal. Calcd for
C18H15ClN2O2S (358.05): C, 60.25; H, 4.21; N, 7.81; O, 8.92; S,
8.94. Found: C, 60.31; H, 4.27; N, 7.86; O, 8.96; S, 8.98; MS (EI)
m/z (%): 358 (100, M+), 360 [33, (M+ + 2)].
General electrochemical procedure
In a typical procedure, a water (phosphate buffer, c = 0.2
M, pH = 2.0)/ethanol (70/30, v/v) mixture (ca. 100 ml),
containing 2ADPA (0.25 mmol) and 1 (0.25 mmol), was
electrolyzed in an undivided cell at 0.53 V vs Ag/AgCl 3M Cl-
,
equipped with a carbon anode and a large platinum gauze
cathode at 25 °C (see Supporting Information). The electrolysis
was terminated when the decay of the current became more
than 95%. At the end of electrolysis, the cell was placed in a
refrigerator overnight. The precipitated solid was collected by
filtration, washed copiously with distilled water, recrystallized
1-N-phenyl-4-(methylsulfonyl)benzene-1,2-diamine
(C13H14N2O2S) (3d). Isolated yield: 80%. mp 137-139 °C; FT-IR (KBr)
(cm-1): 3337, and 3357 (medium, stretching NH2 and NH), 2925
(medium, stretching C-H aliphatic) 1591, 1511 (medium, stretching
4 | New J. Chem., 2015, 00, 1-4
This journal is © The Royal Society of Chemistry 20xx
Please do not adjust margins

Please do not adjust margins
New Journal of Chemistry
Page 5 of 6
View Article Online
DOI: 10.1039/C5NJ03514G
NJC
LETTER
16 (a) A. M. Faucher, P. W. White, C. Brochu, C. Grand-Maitre, J.
Rancourt and G. Fazal, J. Med. Chem., 2004, 47, 18-21; (b) K.
Schank, In The Chemistry of Sulfones and Sulfoxides, S. Patai,
Z. Rappoport and C. J. M. Stirling, Eds., Wiley, New York,
1988, Chapter 7.
17 (a) T. G. Back, Tetrahedron, 2001, 57, 5263-5301; (b) W. E.
Truce, T. C. Klinger and W. W. Brand, Organic Chemistry of
Sulfur, S. Oae, Ed., Plenum Press, New York, 1977.
18 (a) M. Ueda, K. Uchiyama and T. Kano, Synthesis, 1984, 323-
235; (b) D. U. Singh, P. R. Singh and S. D. Samant,
Tetrahedron Lett., 2004, 45, 9079-9082; (c) B. M. Graybill, J.
Org. Chem., 1967, 32, 2931-2933.
C=C), 1295 (stretching aromatic C–N and S=O) 1137 (strong,
stretching S=O); 1H NMR, δ ppm (500 MHz, CDCl3): 3.05 (s, 3H, CH3),
3.53 (s, 2H, NH2, disappeared by addition of D2O), 5.66 (s, 1H, NH,
disappeared by addition of D2O), 7.01-7.05 (m, 3H, Ar-H), 7.24-7.35
(m, 5H, Ar-H); 13C NMR, δ ppm (125 MHz, CDCl3): 44.8 (CH3), 115.2,
115.8, 117.9, 118.8, 119.4, 122.2, 129.6, 136.7, 137.9, 141.9; Anal.
Calcd for C13H14N2O2S (262.08): C, 59.52; H, 5.38; N, 10.68; O, 12.20;
S, 12.22. Found: C, 59.58; H, 5.42; N, 10.63; O, 12.17; S, 12.25. MS
(EI) m/z (%): 262 (100).
19 (a) S. Cacchi, G. Fabrizi, A. Goggiamani and L. M. Parisi, Org.
Acknowledgements
Lett., 2002,
and J. Phopase, Org. Lett., 2004,
20 J. M. Baskin and Z. Wang, Org. Lett., 2002,
4
, 4719-4721; (b) B. P. Bandgar, S. V. Bettigeri
, 2105-2108.
, 4423-4425.
We acknowledge the Bu-Ali Sina University Research Council
and the Center of Excellence in Development of
Environmentally Friendly Methods for Chemical Synthesis
(CEDEFMCS) for their support of this work.
6
4
21 (a) J. Yoshida, K. Kataoka, R. Horcajada and A. Nagaki, Chem.
Rev., 2008, 108, 2265-2299; (b) D. Nematollahi and M.
Rafiee, Green Chem., 2005, 7, 638-644; (c) F. Varmaghani, D.
Nematollahi, S. Mallakpour and R. Esmaili, Green Chem.,
2012, 14, 963-967; (d) H. Shayani-Jam and D. Nematollahi,
Chem. Commun., 2010, 46, 409-411.
References
22 M. A. Cotarelo, F. Huerta, R. Mallavia, E. Morallón and J. L.
Vázquez, Synthetic Met., 2006, 156, 51-57.
23 I. Losito, N. Cioffi, M. P. Vitale and F. Palmisano, Rapid
commun. Mass Sp., 2003, 17, 1169-1179.
24 (a) D. Nematollahi, A. Afkhami, E. Tammari, T.
Shariatmanesh, M. Hesari, and M. Shojaeifard, Chem.
Commun., 2007, 162-164; (b) D. Nematollahi and M. Rafiee,
1
E. J. Emmett, B. R. Hayter and M. C. Willis, Angew. Chem. Int.
Ed., 2013, 52, 12679-12683.
2
(a) W. K. Hagmann, J. Med. Chem., 2008, 51, 4359-4369; (b)
M. Murar, G. Addova and A. Bohac, Beilstein J. Org. Chem.,
2013, 9, 173-179.
3
4
5
6
N. Vicker, P. A. Charlton and W. A. Denny, J. Med. Chem.,
2002, 45, 740-743.
R. L. Lopez de Compadre, R. A. Pearlstein, A. J. Hopfinger and
J. K. Seyde, J. Med. Chem., 1987, 30, 900-906.
T. G. Back, K. N. Clary and D. Gao, Chem. Rev., 2010, 110
4498-4553.
M. L. Kantam, B. Neelima, B. Sreedhar and R. Chakravarti,
Synlett, 2008, 1455-1458.
Green Chem., 2005,
7, 638-644; (c) H. Salehzadeh, D.
Nematollahi and H. Hesari, Green Chem., 2013, 15, 2441-
2446; (d) S. Khazalpour and D. Nematollahi, Green Chem.,
2015, 17, 3508-3514; (e) A. Maleki and D. Nematollahi, Org.
Lett., 2011, 13, 1928-1931.
,
25 B. Kasterka, Mikrochim. Acta, 1989, I, 337-347.
26 B. M. Trost, The Atom Economy-A Search for Synthetic
Efficiency, Science, 1991, vol. 254, pp 1471-1477.
27 M. C. Cann and M. E. Connelly, Real-World Cases in Green
Chemistry, American Chemical Society, Washington, D. C.
2000.
28 Stoe & Cie, X-AREA, version 1.30: program for the acquisition
and analysis of data, Stoe & Cie GmbH, Darmstadt, Germany,
2005.
7
8
W. Zhu and D. Ma, J. Org. Chem., 2005, 70, 2696-2700.
T. Otzen, E. G. Wempe, B. Kunz, R. Bartels, G. Lehwark-
Yvetot, W. Hansel, K. J. Schaper and J. K. Seydel, J. Med.
Chem., 2004, 47, 240-253.
9
P. Prasit, Z. Wang, C. Brideau, C. C. Chan, S. Charleson, W.
Cromlish, D. Ethier, J. F. Evans, A. W. Ford-Hutchison, J. Y.
Gauthier, R. Gordon, J. Guay, M. Gresser, S. Kargman, B.
Kennedy, Y. Leblanc, S. Leger, J. Mancini, G. P. O’Neill, M.
Ouellet, M. D. Percival, H. Perrier, D. Riendeau, I. Rodger, P.
Tagari, M. Therien, P. Vickers, E. Wong, L. J. Xu, R. N. Young
29 Stoe
& Cie, X-RED, version 1.28b: program for data
reduction and absorption correction, Stoe & Cie GmbH,
Darmstadt, Germany, 2005.
30 Stoe & Cie, X-SHAPE, version 2.05: program for crystal
optimization for numerical absorption correction, Stoe & Cie
GmbH, Darmstadt, Germany, 2004.
31 M. C. Burla, R. Caliandro, M. Camalli, B. Carrozzini, G. L.
Cascarano, L. De Caro, C. Giacovazzo, G. Polidori and R.
Spagna, J. Appl. Crystallogr., 2005, 38, 381.
32 G. M. Sheldrick, Acta Crystallogr., Sect. A: Found.
Crystallogr., 2008, 64, 112.
33 (a) C. Gütz, M. Bänziger, C. Bucher and T. R. Galvão, Org.
Process Res. Dev., 2015, 19, 1428-1433; (b) E. Steckhan,
Angew. Chrm. Int. Ed. Engl., 1986, 28, 683-701; (c) B. R.
Buckley, Y. Chan, N. Dreyfus, C. Elliott, F. Marken and P. C.
Bulman Page, Green Chem., 2012, 14, 2221-2225; (d) G. de
Robillard, C. H. Devillers, D. Kunz, H. Cattey, E. Digard and J.
Andrieu, Org. Lett., 2013, 15, 4410-4413.
and R. Zamboni, Bioorg. Med. Chem. Lett., 1999, 9, 1773-
1778.
10 (a) M. Pal, V. R. Veeramaneni, M. Nagabelli, S. R. Kalleda, P.
Misra, S. R. Casturi and K. R. Yeleswarapu, Bioorg. Med.
Chem. Lett., 2003, 13, 1639-1643; (b) W. Hu, Z. Guo, F. Chu,
A. Bai, X. Yi, G. Cheng and J. Li, Bioorg. Med. Chem. Lett.,
2003, 13, 1153-1160.
11 M. Artico, R. Silvestri, E. Pagnozzi, B. Bruno, E. Novellino, G.
Greco, S. Massa, A. Ettorre, A. G. Loi, F. Scintu and P. La
Colla, J. Med. Chem., 2000, 43, 1886-1891.
12 G. A. Doherty, T. Kamenecka, E. McCauley, G. V. Riper, R. A.
Mumford, S. Tong and W. K. Hagmann, Bioorg. Med. Chem.
Lett., 2002, 12, 729-731.
13 R. Wolf, H. Matz, E. Orion, B. Tuzun and Y. Tuzun,
Dermatology, 2002, 8, 2-3.
14 S. Ganesan, R. Sahu, L. A Walker and B. L. Tekwani, J. Appl.
Toxicol., 2010, 30, 271-275.
15 (a) M. Jereb, Green Chem., 2012, 14, 3047-3052; (b) S. K.
Nayaki and M. Swaminathan, Spectrochim. Acta A, 2001, 57
,
1361-1367; (c) R. Kumar, L. J. Garces, Y. C. Son, S. L. Suib and
R. E. Malz, J. Cat., 2005, 236, 387-391; (d) W. C. Chen, T. C.
Wen and A. Gopalan, J. Electrochem. Soc., 2001, 148, E427-
E434.
This journal is © The Royal Society of Chemistry 20xx
New J. Chem., 2015, 00, 1-4 | 5
Please do not adjust margins

New Journal of Chemistry
Page 6 of 6
View Article Online
DOI: 10.1039/C5NJ03514G
Electrochemical Synthesis of N-phenyl-4-(arylsulfonyl)benzene-
1,2-diamine Derivatives. A Mild and Regioselective Protocol
Mahnaz Sharafi-Kolkeshvandi, Davood Nematollahi,* and Farzad Nikpour
Graphical Abstract
Regioselective synthesis of 1-N-phenyl-4-(arylsulfonyl)benzene-1,2-diamine derivatives was carried out by electrochemical
oxidation of 2-aminodiphenylamine in aqueous solution in the presence of some sulfinic acids as nucleophiles.