Room temperature nickel-catalyzed cross-coupling of aryl-boronic acids with thiophenols: Synthesis of diarylsulfides

Article abstract of DOI:10.1039/d0ob00244e

A NiCl₂/2,2′-bipyridine-catalyzed cross-coupling of thiophenols with arylboronic acids has been developed for the synthesis of symmetric and unsymmetric diarylsulfides at room temperature and in air. This methodology is reliable and offers a mild and easy to operate process for the synthesis of arylthioethers, which are essential compounds with applications in the pharmaceutical and agricultural industries. This method avoids the use of expensive transition metals, such as Pd, Ir or Rh, sophisticated ligands and elevated temperatures. It also has a wide substrate scope (55 examples) and provides products in good to excellent yields (72-93%).

Full text of DOI:10.1039/d0ob00244e

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Room Temperature Nickel‐Catalyzed Cross‐Coupling of Aryl‐
boronic Acids with Thiophenols: Synthesis of Diarylsulfides
Amit Bhowmik, Mahesh Yadav, and Rodney A. Fernandes*
Received 00th January 20xx,
Accepted 00th January 20xx
A NiCl2/2,2′‐bipyridine‐catalyzed cross‐coupling of thiophenols with arylboronic acids for the synthesis of symmetric and
unsymmetric diarylsulfides has been developed at room temperature and in air conditions. This methodology is reliable and
offers a mild and easy operation for the synthesis of arylthioethers, which are essential compounds for pharmaceutical and
agricultural applications. The method avoids the use of expensive transition metals like Pd, Ir or Rh, sophisticated ligands
and elevated temperatures. It also displays wide substrate scope (55 examples) and provides good to excellent yields (72‐
93%) of the products.
DOI: 10.1039/x0xx00000x
catalyst and ligand loading due to strong binding of metals to
thiols.10,18 Many of the TMs are expensive, toxic in nature and the
Introduction
CS bond construction is one of the noteworthy organic conversion
as it is ubiquitous in various biologically active molecules.1 Sulfides
and thioethers are significant moieties in many natural products,2 in
material chemistry,3 pharmaceuticals,4 synthetic chemicals,5 and
food and agricultural industries6 (Figure 1). Diarylsulfides are widely
used in medical treatments like cancer, Alzheimer’s, Parkinson’s, IDS,
neoplastic, HCV, diabetic and parasitic diseases.7 Notably,
diarylsufide moiety is found in many marketed drugs like
chloropromazine (used to treat psychotic disorders),7d Axitinib and
Thymitaq (anticancer),7f Vortioxetane or Trintellix (for major
depressive disorder),7g and Esomeprazole (for gastroesophageal
reflux disease)7h (Figure 1). Moreover, sulfide derivatives like
sulfoxides and sulfones are also equally important in many aspects.4g
Based on various utilities of thioethers, many methods have been
developed over the years for their synthesis. A traditional process for
CS bond formation is StadlerZiegler reaction wherein an
aryldiazonium salt is reacted with thiolates to form diarylsulfides
(Scheme 1A).8 However, this method still faces challenges for the
preparation and isolation of diazonium salt and coupling partner
sodium thiolate. A recent photochemical StadlerZiegler method is
efficient for diarylsulfide synthesis, but the use of expensive
photocatalyst and the formation of side products like disulfide and
explosive diazosulfides make this method undesirable for industrial
use.9 On the other hand, frequent methods for CS bond formation
removal of the metal residues are problematic. Several approaches
for diarylsulfide formation utilize highly reactive catalysts and
ligands, with the drawbacks being air and moisture sensitivity.10 Ni‐
catalyzed cross‐coupling reactions are preferred nowadays than Pd,
Rh and Ir due to its availability, simple operation, facile oxidative
addition and economical aspects.19 Recently, Pd‐ and Ni‐catalyzed
decarbonylative CS bond formation are also reported using
expensive ligands and higher temperatures (Scheme 1C).10h,20
Figure 1 Biologically active drugs and valuable compounds
containing diarylsulfide motifs.
rely on the transition metal (TM)‐catalyzed cross‐coupling of an The Chan

Lam reaction is also
conventional C S cross‐coupling because of the eco‐friendly
reaction conditions and numerous examples of Cu‐catalyzed S‐
a good substitute for
arylhalide and thiol using Pd,10 Ni,11 Zn,12 Cu,13 Fe,14 Rh,15 Ag16 and

Ir,17 (Scheme 1B). Most of the TM‐catalyzed CS bond formations
require high temperatures, highly basic reaction conditions, high arylation that have been reported.13 However, there exists only
one report on Ni‐catalyzed coupling of arylboronic acids with
arylsulphonamides.21 Therefore, the development of a mild,
efficient, easily operative and eco‐friendly method is highly
exigent. Herein, we have developed a simple and easily
operational, cheap and environmentally benign method for the
Department of Chemistry, Indian Institute of Technology Bombay Powai, Mumbai
400076, Maharashtra, India. E‐mail: rfernand@chem.iitb.ac.in; Fax: +91 22
25767152; Tel: +91 22 25767174
Electronic Supplementary Information (ESI) available: [details of any supplementary
information available should be included here]. See DOI: 10.1039/x0xx00000x
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Table 1 Optimization of Reaction Conditions.a
synthesis of diarylsulfides by Ni‐catalyzed cross‐coupling of
different arylboronic acids with thiophenols at room
temperature and in air conditions.
Entry Catalyst
(10 mol%)
Ligand
(20
Base
(1.5 eq.)
Solvent
Yield Yield
(%) (%)
mol%)
3ab
4
1
2
3
4
5
6
NiCl2.6H2O
NiCl2.glyme
Ni(OAc)2
NiBr2.xH2O
Ni(SO4)2.6H2O
Ni(CO)3.
2Ni(OH)2.nH2O
NiO
NiCl2.6H2O
NiCl2.6H2O
t-BuOK CH3CN
t-BuOK CH3CN
t-BuOK CH3CN
t-BuOK CH3CN
t-BuOK CH3CN
t-BuOK CH3CN
82
54
NR
65
NR 16
NR 19
–
–
–
–
2,2-bipy
2,2-bipy
2,2-bipy
2,2-bipy
2,2-bipy
2,2-bipy
7
8
9
t-BuOK CH3CN
t-BuOK CH3CN
pyridine t-BuOK CH3CN
t-BuOK CH3CN
t-BuOK CH3CN
xantphos t-BuOK CH3CN
NR 10
2,2-bipy
PPh3
NR
NR
61
58
64
55
69
NR 37
NR 34
NR 31
NR 29
NR 36
43
30
77
65
93
–
–
–
–
–
–
–
10 NiCl2.6H2O
11 NiCl2.6H2O
12 NiCl2.6H2O
13 NiCl2.6H2O
14 NiCl2.6H2O
15 NiCl2.6H2O
16 NiCl2.6H2O
17 NiCl2.6H2O
18 NiCl2.6H2O
19 NiCl2.6H2O
20 NiCl2.6H2O
21 NiCl2.6H2O
22 NiCl2.6H2O
23 NiCl2.6H2O
24 NiCl2.6H2O
dppp
dppe
X-phos
t-BuOK CH3CN
t-BuONa CH3CN
K2CO3 CH3CN
Cs2CO3 CH3CN
2,2-bipy
2,2-bipy
2,2-bipy
2,2-bipy
2,2-bipy
2,2-bipy
2,2-bipy
2,2-bipy
2,2-bipy
2,2-bipy
2,2-bipy
DBU
K3PO4 CH3CN
Et3N CH3CN
CH3CN
t-BuOK dioxane
t-BuOK THF
t-BuOK DMF
t-BuOK DMSO
t-BuOK CH3CN/
DMF (5:1)
–
–
–
–
–
Scheme 1 Overview of diarylsulfide synthesis development.
25 NiCl2.6H2O
t-BuOK CH3CN/
63
59
9
–
–
2,2-bipy
2,2-bipy
2,2-bipy
2,2-bipy
2,2-bipy
–
Results and Discussion
DMSO (5:1)
t-BuOK CH3CN/
dioxane (5:1)
26 NiCl2.6H2O
We screened various nickel salts and suitable ligands for CS
cross‐coupling of phenylboronic acid 1a with 4‐
methylthiophenol 2b as model substrates with variation of
solvents and bases (Table 1). The use of 10 mol% of NiCl2.6H2O
and 20 mol% of 2,2′‐bipyridine in presence of t‐BuOK at room
temperature gave phenyl(p‐tolyl)sulfane 3ab with 82% yield
within 12 h. Further, various other nickel catalysts were
screened, however the yields of 3ab were not superior to
27b
t-BuOK
–
NiCl2.6H2O
CH3CN/
DMF (5:1)
t-BuOK CH3CN/
DMF (5:1)
t-BuOK CH3CN/
DMF (5:1)
t-BuOK CH3CN/
DMF (5:1)
28c NiCl2.6H2O
47
NR
–
–
29
–
–
30 NiCl2.6H2O
31 NiCl2.6H2O
32 NiCl2.6H2O
33 NiCl2.6H2O
34d NiCl2
42
36
–
–
CH3CN/
DMF (5:1)
–
2,2‐bipy
2,2‐bipy
2,2‐bipy
2,2-bipy
NiCl2.6H2O (entries 2‐7). A few Ni‐salts promoted the disulfide
4
formation in 10‐19% yields (entries 5‐7). Then different ligands
were tried, wherein PPh3 and pyridine failed to deliver the
product 3ab (entries 8‐9), while other ligands provided good to
moderate yields of 3ab (entries 10‐13) but not better when
compared to entry 1, indicating 2,2′‐bipyridine to be a superior
ligand. We next considered various bases for the cross‐coupling
reaction (entries 14‐19), however most of them yielded the
t‐BuOK CH3CN/
(1 equiv) DMF (5:1)
t‐BuOK CH3CN/
(2 equiv) DMF (5:1)
t-BuOK CH3CN/
DMF (5:1)
75
92
12
–
–
aReaction conditions: 1a (0.6 mmol), 2b (0.5 mmol), ligand (20
mol%), base (1.5 equiv). bUnder O2 (balloon). cUnder N2 (balloon).
d24 h reaction. NR = No reaction.
disulfide
4 instead of 3ab, except t‐BuONa (entry 14), which
gave 3ab in 69% yield. A further change in solvent did not alter
the yields of 3ab (entries 20‐23), although a solvent mixture like
CH3CN/DMF (5:1) was gratifyingly found to be the best for the
conversion and gave 3ab in 93% yield (entry 24 vs 25 and 26).
The boronic acid was less soluble in some solvents, lowering the
yields (e.g. DMSO). A reaction under oxygen atmosphere
retarded the reaction giving 3ab in only 9% yield (entry 27),
which could be due to ligand deactivation. Similarly, under N2
atmosphere the yield of 3ab decreased to 47% (entry 28). A
reaction without Ni‐catalyst gave no reaction, while that
without ligand or base provided the diaryldisulfide 4 in 42% and
36% yields (entries 29, 30 and 31, respectively). Change of base
2 | J. Name., 2012, 00, 1‐3
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concentration to 1.0 equiv gave 3ab in decreased yield (75%, thiophenol were well tolerated giving the products 3aa‐3aj in
entry 32), while that with increased amount of base was not 72‐93% yields. 4‐Formylphenylboronic acid also reacted with
beneficial (entry 33). A reaction with neat NiCl2 gave a sluggish benzenethiol and gave exclusively 4‐formyl‐diarylsulfide 3ak in
reaction providing 3ab in 12% yield (entry 34) with the recovery 77% yield. Naphthyl‐2‐thiol also reacted well with various
of starting materials. This study revealed that NiCl2.6H2O (10 arylboronic acids giving the products 3al‐3ao in 79‐86% yields.
mol%) and 2,2′‐bipyridine (20 mol%) in presence of t‐BuOK at A reaction of 4‐hydroxythiophenol and phenylboronic acid also
room temperature were optimum requirements for the worked well giving 4‐(phenylthio)phenol 3ap exclusively in 74%
synthesis of diarylsulfides
The scope and limitations of this method were further Reaction of phenylboronic acid and 2‐mercaptobenzothiozole
explored on a series of mono substituted arylboronic acids gave the product 3aq in 78% yield. The reaction of
and thiophenols using NiCl2.6H2O and 2,2′‐bipyridine to give phenylboronic acid with 2‐mercaptopyridine did not yield the
mono arylsubstituted diarylsulfides 3aa 3aq in good to product 3ar. It can be noted that ortho‐substituted arylboronic
excellent yields (Scheme 2). Various functional groups like Me, acid or the thiol did not pose any steric issues in the synthesis
3
.
yield. No biarylether formation was observed in the latter case.
1
2
‐
OMe, Br, Cl or F group on either the arylboronic acid or
of the diarylsulfides, e.g. 3ae, 3ai, 3aj and 3an. A gram‐scale
reaction of 1b with the thiophenol 2a (6.74 mmol) gave the
diarylsulfide 3ab in 85% yield indicating possible scale‐up of the
reaction (Scheme 2).
We continued the scope of substrates for synthesis of disubstituted
diarylsulfides 3 using both substituted boronic acids and thiophenols
as shown in Scheme 3. Various arylboronic acids with substituents like
OMe, Me, Ph, Br, Cl, I, F, and CHO worked well with substituted
Scheme
3 Substrate scope to synthesize disubstituted
Scheme 2 Substrate scope to synthesize mono substituted dia‐
diarylsulfides
3
.
rylsulfides 3.
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arylthiols having similar groups to provide the disubstituted
diarylsulfides 3ba‐3bw in good yields (72‐91%, Scheme 3). Notably, the
presence of ortho‐substituents or disubstituted arylboronic acids
worked well to provide diarylsulfides like 3bc, 3bd, 3bk, 3bl, and 3bu
in good yields. Also formyl substituent on arylboronic acid or the
thiophenol provided the products 3bt and 3bv efficiently. A reaction
of 4‐hydroxythiophenol and 3‐hydroxy‐phenylboronic acid also
worked well giving 3bw with 77% yield.
We considered exploring the synthetic utility of this method toward
useful scaffolds as shown in Scheme 4. The diarylsulfides 3ab, 3ac, 3af
and 3ag were oxidized to the sulfoxides 5a‐d, respectively in good
yields (76‐88%).22 Similarly, the oxidation of 3ac, 3af and 3ag to the
sulfones 6a‐c in 77‐82% yields was also achieved. Bisphenol S 6d is an
epoxy resin monomer used as a constituent of plastic substitute for
production of babybottles.23 Toward its synthesis, the coupling of
boronic acid 1p with the 4‐hydroxythiophenol 2p gave the diarylsulfide
3bx (81%) that on further oxidation provided bisphenol S 6d in 81%
yield. The coupling of 2‐aminoboronic acid 1q with 2‐bromothiophenol
2y occurred chemoselectively through the present protocol giving the
diarylsulfide 3by in 84% yield. This is a precursor to the drug molecule
promazine that is used as antipsychotic drug belonging to the
phenothiazine family.24 We also synthesized the dapsone precursor
3bz in 79% yield by coupling of 4‐amino‐ phenylboronic acid 1r with 4‐
nitrothiophenol 2z. Dapsone is used as a drug for skin diseases.25
Scheme 5 Plausible mechanism.
The reaction may take a similar course as the Chan
coupling.13,21 The co‐ordination of bipy ligand with NiCl2 will give
Lam‐type
8
8
(Scheme 5). The deprotonated thiol displaces a chloride from
giving the species . Transmetallation with arylboronic acid
9
1
give the species 10 that undergoes reductive elimination giving
the product in
11e,21 The Ni(0) complex 11 is oxidized to Ni(II)
3
.
8
air to continue the catalytic cycle. Since the NiCl2.6H2O (10
mol%) used is a hexahydrate, the actual content of Ni catalyzing
the reaction is well around 5.5 mol% if water molecules are
excluded.
Conclusion
In summary, in this paper, we have developed an efficient and
mild method for CS coupling using NiCl2.6H2O as the catalyst
and 2,2′‐bipy as ligand at room temperature. Various
arylboronic acids are cross‐coupled with thiols giving
diarylsulfides in 72‐93% yield (55 examples). Our protocol
showed good functional group tolerance, chemoselective
reaction of arylboronic acid with thiophenol and requires
ambient temperature. The method was applied to synthesize
various sulfoxides and sulfones and also drug intermediates.
Experimental Section
General information
. Thin‐layer chromatography was
performed on EM 250 Kieselgel 60 F254 silica gel plates. The
spots were visualized by staining with KMnO4 or by using a UV
lamp. 1H‐NMR and 13C‐NMR were recorded with a spectrometer
operating at 400 or 500 and 100 or 125 MHz for proton and
carbon nuclei, respectively. The chemical shifts are based on the
CDCl3 peak at
 = 7.26 ppm for proton NMR and the CDCl3 peak
at = 77.00 ppm (t) for carbon NMR. IR spectra were obtained

on an FT‐IR spectrometer by evaporating compounds dissolved
in CHCl3 on CsCl pellete. HRMS (ESI‐TOF) spectra were recorded
using positive electrospray ionization by the TOF method.
Scheme 4 Product modification and application towards the
synthesis of sulfoxides, sulfones, promazine and dapsone
precursors.
General procedure for synthesis of diarylsulfides (3). To a stirred
solution of thiol 2 (0.5 mmol) in acetonitrile/DMF (5:1, 6 mL) was
added NiCl2.6H2O (11.9 mg, 0.05 mmol, 10 mol%) and 2,2‐bipyridine
4 | J. Name., 2012, 00, 1‐3
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(d, J = 8.5 Hz, 2H) ppm. 13C{1H} NMR (100 MHz, CDCl3):  = 135.4,
134.8, 132.2, 132.0, 131.5, 129.3, 127.5, 120.8 ppm. IR (CHCl3): νmax
= 3071, 3059, 3016, 2928, 2850, 2803, 1581, 1473, 1439, 1385, 1300,
1175, 1158, 1093, 1082, 1068, 1024, 1008, 812, 742, 704, 690 cm−1.
(15.6 mg, 0.1 mmol, 20 mol%) at room temperature. After 5 min,
boronic acid (0.6 mmol) was added followed by t‐BuOK (84.2 mg,
0.75 mmol, 1.5 equiv) addition portionwise. The reaction mixture
was stirred at room temperature in air for 12 h. It was then quenched
with saturated aq. NH4Cl solution and the mixture was extracted with
EtOAc (2  10 mL). The combined organic layers were dried (Na2SO4)
and concentrated. The residue was purified by silica gel column
chromatography using petroleum ether/EtOAc (99:1) as eluent to
afford diarylsulfides 3.
(4‐Chlorophenyl)(phenyl)sulfane (3ag).13g Colorless oil (92.7 mg,
1
84% and 100.4 mg, 91%). H NMR (400 MHz, CDCl3):  = 7.39‒7.34
(m, 4H), 7.32‒7.28 (m, 5H) ppm. 13C{1H} NMR (100 MHz, CDCl3):  =
135.1, 134.6, 132.9, 132.0, 131.3 129.3, 129.26, 127.4 ppm. IR
(CHCl3): νmax = 3074, 3058, 3016, 1583, 1475, 1440, 1390, 1095, 1087,
1022, 1012, 912, 818, 740, 704, 690, 549 cm−1.
Diphenylsulfane (3aa).11g Colorless oil (76.4 mg, 82%). 1H NMR (500
MHz, CDCl3):  = 7.37‒7.35 (m, 4H), 7.33‒7.27 (m, 4H), 7.25‒7.24 (m,
2H) ppm. 13C{1H} NMR (125 MHz, CDCl3):  = 135.8, 131.0, 129.2,
127.0 ppm. IR (CHCl3): νmax = 3071, 3054, 3020, 2922, 1578, 1474,
1440, 1302, 1219, 1178, 1158, 1081, 1022, 997, 912, 770, 737, 688,
632 cm−1.
(4‐Fluorophenyl)(phenyl)sulfane (3ah).11g Colorless oil (89.9 mg,
88% and 87.8 mg, 86%). 1H NMR (500 MHz, CDCl3):  = 7.40 (dd, J =
8.8, 2.5 Hz, 2H), 7.34‒7.28 (m, 4H), 7.25‒7.22 (m, 1H), 7.05 (t, J = 8.5
Hz, 2H) ppm. 13C{1H} NMR (125 MHz, CDCl3):  = 163.4 and 161.4 (JC‐
F = 247.7 Hz), 136.6, 134.1 and 134.03 (JC‐F = 8.1 Hz), 130.2 and 130.15
(JC‐F = 2.9 Hz), 129.9, 129.15, 126.7, 116.5 and 116.3 (JC‐F = 21.8 Hz)
Phenyl(p‐tolyl)sulfane (3ab).11g Colorless oil (93.1 mg, 93% and 88.1
ppm. 19F NMR (471 MHz, CDCl3):  = ‒114.0 ppm. IR (CHCl3): νmax
=
1
mg, 88%). H NMR (400 MHz, CDCl3):  = 7.32 (d, J = 8.2 Hz, 2H),
3074, 3060, 1589, 1489, 1478, 1439, 1397, 1291, 1228, 1156, 1082,
1070, 1024, 1013, 831, 740, 706, 690, 667, 628 cm−1.
7.297.25 (m, 3H), 7.23‒7.18 (m, 2H), 7.16 (d, J = 7.9 Hz, 2H), 2.36 (s,
3H) ppm. 13C{1H} NMR (100 MHz, CDCl3):  = 137.5, 137.1, 132.2,
131.2, 130.0, 129.7, 129.0, 126.4, 21.1 ppm. IR (CHCl3): νmax = 3071,
3054, 3021, 2921, 2864, 1582, 1491, 1477, 1439, 1396, 1302, 1180,
1083, 1024, 1015, 905, 809, 739, 690 cm−1.
(2‐Bromophenyl)(phenyl)sulfane (3ai).13g Colorless oil (111.4 mg,
84% and 107.4 mg, 81%). 1H NMR (400 MHz, CDCl3):  = 7.57 (dd, J =
7.8, 1.2 Hz, 1H), 7.47–7.44 (m, 2H), 7.42–7.36 (m, 3H), 7.15 (dt, J =
7.6, 1.3 Hz, 1H), 7.03 (dt, J = 7.7, 1.5 Hz, 1H), 6.93 (dd, J = 8.0, 1.5 Hz,
1H) ppm. 13C{1H} NMR (100 MHz, CDCl3):  = 138.7, 133.5, 133.0,
132.8, 129.7, 129.6, 128.4, 127.8, 127.2, 123.0 ppm. IR (CHCl3): νmax
= 3059, 2915, 1658, 1578, 1475, 1446, 1427, 1310, 1251, 1158, 1120,
1105, 1020, 914, 705, 690, 649 cm−1.
(4‐Methoxyphenyl)(phenyl)sulfane (3ac).11g Yellow oil (83.3 mg,
77% and 81.1 mg, 75%). 1H NMR (400 MHz, CDCl3):  = 7.42 (d, J = 8.9
Hz, 2H), 7.24‒7.18 (m, 2H), 7.16‒7.12 (m, 3H), 6.90 (d, J = 8.9 Hz, 2H),
3.82 (s, 3H) ppm. 13C{1H} NMR (100 MHz, CDCl3):  = 159.8, 138.6,
135.4, 128.9, 128.1, 125.7, 124.2, 115.0, 55.3 ppm. IR (CHCl3): νmax
=
(2‐Chlorophenyl)(phenyl)sulfane (3aj).13g Colorless oil (90.5 mg, 82%
and 89.4 mg, 81%). 1H NMR (400 MHz, CDCl3):  = 7.45 (d, J = 7.9 Hz,
2H), 7.41‒7.37 (m, 4H), 7.13‒7.11 (m, 2H), 7.00‒6.97 (m, 1H) ppm.
13C{1H} NMR (100 MHz, CDCl3):  = 136.5, 133.2, 133.1, 132.6, 130.0,
129.7, 129.5, 128.3, 127.2, 127.16 ppm. IR (CHCl3): νmax = 3060, 3027,
2922, 1575, 1562, 1476, 1450, 1439, 1430, 1274, 1252, 1159, 1118,
1090, 1066, 1032, 1022, 1000, 912, 746, 705, 690, 660 cm−1.
3057, 3006, 2962, 2939, 2837, 1592, 1493, 1478, 1459, 1440, 1288,
1247, 1172, 1100, 1083, 1032, 909, 828, 797, 740, 690 cm−1.
(3‐Methoxyphenyl)(phenyl)sulfane (3ad).11g Yellow oil (85.4 mg,
79% and 80 mg, 74%). 1H NMR (400 MHz, CDCl3):  = 7.39 (d, J = 6.8
Hz, 2H), 7.34‒7.30 (m, 2H), 7.28‒7.27 (m, 1H), 7.22‒7.20 (m, 1H),
6.92 (dd, J = 8.1, 0.8 Hz, 1H), 6.88 (t, J = 2.2 Hz, 1H), 6.79 (dd, J = 8.4,
2.2 Hz, 1H), 3.76 (s, 3H) ppm. 13C{1H} NMR (100 MHz, CDCl3):  =
160.0, 137.2, 135.2, 131.4, 129.9, 129.2, 127.2, 122.9, 115.8, 112.7,
55.2 ppm. IR (CHCl3): νmax = 3064, 3003, 2952, 2935, 2837, 1590,
1477, 1439, 1425, 1307, 1283, 1247, 1230, 1180, 1071, 1044, 1024,
993, 910, 860, 846, 773, 738, 689, 649, 612 cm−1.
1
4‐(Phenylthio)benzaldehyde (3ak). Colorless oil (82.5 mg, 77%). H
NMR (400 MHz, CDCl3):  = 9.90 (s, 1H), 7.70 (d, J = 8.5 Hz, 2H), 7.53‒
7.50 (m, 2H), 7.43–7.40 (m, 3H), 7.23 (d, J = 8.3 Hz, 2H) ppm. 13C{1H}
NMR (100 MHz, CDCl3):  = 191.1, 147.1, 134.3, 133.6, 131.2, 130.0,
129.7, 129.1, 127.1 ppm. IR (CHCl3): νmax = 3064, 3007, 2961, 2937,
2834, 2735, 1698, 1670, 1589, 1562, 1480, 1442, 1424, 1414, 1387,
1355, 1303, 1283, 1248, 1232, 1168, 1087, 1074, 1040, 1012, 992,
861, 836, 816, 777, 690 cm−1. HRMS (ESI‐TOF) m/z: [M + K]+ calcd for
C13H10OSK 253.0084; Found 253.0086.
(2,5‐Dimethoxyphenyl)(phenyl)sulfane (3ae). Colorless oil (88.7 mg,
72%). 1H NMR (500 MHz, CDCl3):  = 7.397.34 (m, 2H), 7.32 (dt, J =
8.9, 1.7 Hz, 2H), 7.29‒7.27 (m, 1H), 6.83 (d, J = 8.9 Hz, 1H), 6.73 (dd,
J = 8.8, 2.5 Hz, 1H), 6.59 (d, J = 2.5 Hz, 1H), 3.83 (s, 3H), 3.66 (s, 3H)
ppm. 13C{1H} NMR (125 MHz, CDCl3):  = 154.0, 151.4, 133.8, 132.2,
129.3, 127.5, 125.8, 116.8, 112.4, 111.8, 56.6, 55.7 ppm. IR (CHCl3):
(4‐Chlorophenyl)(naphthalen‐2‐yl)sulfane (3al). White semi‐solid
(111.0 mg, 82%). 1H NMR (500 MHz, CDCl3):  = 7.85 (s, 1H), 7.82‒
7.80 (m, 1H), 7.78 (d, J = 8.6 Hz, 1H), 7.76‒7.74 (m, 1H), 7.49‒7.48
(m, 2H), 7.39 (dd, J = 8.7, 1.7 Hz, 1H), 7.27 (m, 4H) ppm. 13C{1H} NMR
(125 MHz, CDCl3):  = 134.7, 133.7, 133.0, 132.4, 132.3, 131.9, 130.3,
129.3, 129.1, 128.7, 127.7, 127.4, 126.7, 126.4 ppm. IR (CHCl3): νmax
= 2925, 2861, 1659, 1645, 1474, 1393, 1352, 1114, 1092, 964, 907,
ν
max = 3003, 2959, 2939, 2835, 1595, 1576, 1490, 1463, 1436, 1411,
1304, 1282, 1253, 1162, 1087, 1075, 1032, 937, 918, 836, 804, 636
cm−1. HRMS (ESI‐TOF) m/z: [M + K]+ calcd for C14H14O2SK 285.0346;
Found 285.0339.
(4‐Bromophenyl)(phenyl)sulfane (3af).13g Yellow oil (119.3 mg, 90%
and 112.7 mg, 85%). 1H NMR (400 MHz, CDCl3):  = 7.41 (d, J = 8.6 Hz,
2H), 7.38‒7.36 (m, 2H), 7.35‒7.31 (m, 2H), 7.30‒7.27 (m, 1H), 7.18
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868, 820, 816, 771, 748 cm−1. HRMS (ESI‐TOF) m/z: [M + K]+ calcd for (4‐Methoxyphenyl)(p‐tolyl)sulfane (3ba).10c Colorless oil (93.3 mg,
81% and 91 mg, 79%). 1H NMR (400 MHz, CDCl3):  = 7.39 (d, J = 6.8
Hz, 2H), 7.16 (d, J = 8.9 Hz, 2H), 7.09 (d, J = 7.7 Hz, 2H), 6.89 (d, J = 7.8
Hz, 2H), 3.82 (s, 3H), 2.32 (s, 3H) ppm. 13C{1H} NMR (100 MHz, CDCl3):
 = 159.4, 136.0, 134.3, 129.7, 129.3, 125.5, 114.8, 55.3, 20.9 ppm.
IR (CHCl3): νmax = 2965, 2942, 2908, 2841, 1593, 1571, 1497, 1464,
1403, 1289, 1250, 1185, 1120, 1107, 1098, 1032, 1005, 838, 815, 798,
648, 634 cm−1.
C16H11ClSK 308.9902; Found 308.9900.
(4‐Bromophenyl)(naphthalen‐2‐yl)sulfane (3am). White solid (132.4
mg, 84%), M.p. = 84‒86 oC. 1H NMR (400 MHz, CDCl3):  = 7.87 (d, J =
1.8 Hz, 1H), 7.83‒7.80 (m, 1H), 7.78 (d, J = 8.8 Hz, 1H), 7.76‒7.74 (m,
1H), 7.52‒7.47 (m, 2H), 7.43‒7.38 (m, 3H), 7.22–7.18 (m, 2H) ppm.
13C{1H} NMR (100 MHz, CDCl3):  = 135.5, 133.7, 132.5, 132.2, 132.0,
130.6, 129.1, 128.9, 127.8, 127.5, 126.7, 126.5, 120.9 ppm. IR (CHCl3):
ν
max = 2923, 2864, 1664, 1471, 1386, 1356, 1114, 1085, 905, 866, 822,
m‐Tolyl(p‐tolyl)sulfane (3bb).10c Colorless oil (87.9 mg, 82%). 1H
NMR (500 MHz, CDCl3):  = 7.29 (d, J = 8.3 Hz, 2H), 7.18‒7.07 (m, 5H),
7.02 (d, J = 7.5 Hz, 1H), 2.35 (s, 3H), 2.30 (s, 3H) ppm. 13C{1H} NMR
(125 MHz, CDCl3):  = 138.9, 137.4, 136.6, 132.0, 131.6, 130.6, 130.0,
128.9, 127.4, 127.1, 21.3, 21.1 ppm. IR (CHCl3): νmax = 3074, 3054,
3016, 2922, 2864, 1593, 1573, 1492, 1474, 1403, 1302, 1181, 1163,
1117, 1105, 1081, 1046, 1017, 873, 854, 809, 688 cm−1.
812, 648 cm−1. HRMS (ESI‐TOF) m/z: [M + K]+ calcd for C16H11BrSK
352.9396; Found 354.9395.
(2‐Bromophenyl)(naphthalen‐2‐yl)sulfane (3an). Colorless oil (135.5
mg, 86%). 1H NMR (400 MHz, CDCl3):  = 8.00 (s, 1H), 7.85 (d, J = 8.5
Hz, 2H), 7.82‒7.79 (m, 1H), 7.59 (dd, J = 8.0, 1.5 Hz, 1H), 7.54‒7.52
(m, 2H), 7.48 (dd, J = 8.6, 1.6 Hz, 1H), 7.12 (dt, J = 7.6, 1.4 Hz, 1H),
7.04 (dt, J = 7.8, 1.7 Hz, 1H), 6.95 (dd, J = 7.8, 1.7 Hz, 1H) ppm. 13C{1H}
NMR (100 MHz, CDCl3):  = 138.8, 133.9, 133.0, 133.97, 132.9, 130.3,
130.0, 129.8, 129.3, 127.8, 127.77, 127.7, 127.2, 126.8, 126.7, 122.9
ppm. IR (CHCl3): νmax = 3057, 2922, 2850, 1666, 1571, 1445, 1425,
1264, 1230, 1198, 1037, 1020, 961, 944, 909, 890, 858, 814, 770, 744,
626, 604 cm−1. HRMS (ESI‐TOF) m/z: [M + K]+ calcd for C16H11BrSK
352.9396; Found 354.9395.
(2,4‐Dimethoxyphenyl)(p‐tolyl)sulfane (3bc). Colorless oil (96.3 mg,
74%). 1H NMR (400 MHz, CDCl3):  = 7.24 (d, J = 8.4 Hz, 1H), 7.11 (d,
J = 8.3 Hz, 2H), 7.05 (d, J = 8.2 Hz, 2H), 6.51 (d, J = 2.5 Hz, 1H), 6.47
(dd, J = 8.4, 2.5 Hz, 1H), 3.82 (s, 3H), 3.81 (s, 3H), 2.30 (s, 3H) ppm.
13C{1H} NMR (100 MHz, CDCl3):  = 161.3, 159.7, 135.7, 135.4, 133.3,
129.6, 128.9, 113.6, 105.2, 99.1, 55.9, 55.4, 20.9 ppm. IR (CHCl3): νmax
= 3071, 3002, 2959, 2939, 2836, 1596, 1575, 1490, 1463, 1436, 1412,
1303, 1282, 1254, 1162, 1087, 1075, 1031, 936, 919, 834, 804, 636
cm−1. HRMS (ESI‐TOF) m/z: [M + Na]+ calcd for C15H16O2SNa
283.0763; Found 283.0758.
(4‐Fluorophenyl)(naphthalen‐2‐yl)sulfane (3ao). White semi‐solid
(100.4 mg, 79%). 1H NMR (400 MHz, CDCl3):  = 8.20 (d, J = 8.5 Hz,
1H), 7.91 (d, J = 8.9 Hz, 1H), 7.82 (d, J = 8.1 Hz, 1H), 7.53–7.49 (m, 1H),
7.40–7.36 (m, 1H), 7.34 (d, J = 9.1 Hz, 1H), 7.18 (s, 1H), 7.03‒7.00 (m,
2H), 6.88 (t, J = 8.7 Hz, 2H) ppm. 13C{1H} NMR (100 MHz, CDCl3):  =
162.6 and 160.2 (JC‐F = 245.6 Hz), 156.9, 135.2, 132.9, 130.3, 129.5,
128.6 and 128.4 (JC‐F = 25.5 Hz), 128.3 and 128.0 (JC‐F = 27.9 Hz),
(2,5‐Dimethoxyphenyl)(p‐tolyl)sulfane (3bd). White solid (97.6 mg,
75%), M.p. = 110‒112 oC. 1H NMR (500 MHz, CDCl3):  = 7.35 (d, J =
7.6 Hz, 2H), 7.17 (d, J = 7.6 Hz, 2H), 6.80 (d, J = 8.8 Hz, 1H), 6.67 (dd,
J = 9.3, 2.8 Hz, 1H), 6.47 (s, 1H), 3.84 (s, 3H), 3.64 (s, 3H), 2.36 (s, 3H)
ppm. 13C{1H} NMR (125 MHz, CDCl3):  = 153.9, 150.6, 138.1, 133.4,
130.2, 129.0, 127.4, 115.5, 111.4, 111.1, 56.4, 55.6, 21.1 ppm. IR
(CHCl3): νmax = 3003, 2938, 2833, 1598, 1584, 1508, 1485, 1459, 1440,
1432, 1407, 1324, 1298, 1274, 1232, 1216, 1188, 1176, 1149, 1141,
1105, 1059, 1045, 1019, 807, 790, 737, 709 cm−1. HRMS (ESI‐TOF)
m/z: [M + Na]+ calcd for C15H16O2SNa 283.0763; Found 283.0761.
124.5, 123.9, 116.9, 116.4 and 116.2 (JC‐F = 22.2 Hz), 108.5 ppm. 19
F
NMR (471 MHz, CDCl3):  = ‒116.30 ppm. IR (CHCl3): νmax = 2925,
2847, 1635, 1589, 1488, 1397, 1291, 1230, 1155, 1093, 1076, 1013,
826, 771, 622 cm−1. HRMS (ESI‐TOF) m/z: [M + K]+ calcd for C16H11FSK
293.0197; Found 293.0198.
4‐(Phenylthio)phenol (3ap).13g Yellow oil (74.8 mg, 74%). H NMR
1
(400 MHz, CDCl3):  = 7.34 (d, J = 8.5 Hz, 2H), 7.22 (d, J = 7.6 Hz, 2H),
7.18–7.11 (m, 3H), 6.83 (d, J = 8.5 Hz, 2H), 5.25 (s, 1H) ppm. 13C{1H}
NMR (100 MHz, CDCl3):  = 155.9, 138.5, 135.5, 128.9, 128.2, 125.8,
124.5, 116.5 ppm. IR (CHCl3): νmax = 3384, 3071, 3054, 2924, 2854,
1639, 1599, 1583, 1494, 1478, 1439, 1361, 1264, 1217, 1169, 1098,
1081, 1022, 830, 740, 690, 530 cm−1.
(3‐Bromophenyl)(p‐tolyl)sulfane (3be). Colorless oil (108.9 mg, 78%
and 110.3 mg, 79%). H NMR (400 MHz, CDCl3):  = 7.35–7.33 (m,
1
3H), 7.29–7.27 (m, 1H), 7.18 (d, J = 8.1 Hz, 2H), 7.14‒7.08 (m, 2H),
2.37 (s, 3H) ppm. 13C{1H} NMR (100 MHz, CDCl3):  = 140.3, 138.5,
133.3, 131.1, 130.3, 130.2, 129.5, 129.0, 127.2, 122.9, 21.2 ppm. IR
(CHCl3): νmax = 3054, 3023, 2918, 2861, 1574, 1556, 1492, 1458, 1402,
1300, 1286, 1254, 1247, 1180, 1147, 1117, 1081, 1068, 1017, 993,
866, 810, 773, 715, 705, 677, 653 cm−1. HRMS (ESI‐TOF) m/z: [M + K]+
calcd for C13H11BrSK 316.9396; Found 316.9404.
2‐(Phenylthio)benzo[d]thiazole (3aq). Colorless oil (95 mg, 78%). 1H
NMR (400 MHz, CDCl3):  = 7.88 (d, J = 8.2 Hz, 1H), 7.75–7.72 (m, 2H),
7.64 (d, J = 8.1 Hz, 1H), 7.54‒7.45 (m, 3H), 7.40 (dt, J = 7.8, 1.2 Hz,
1H), 7.26 (dt, J = 7.5, 1.2 Hz, 1H) ppm. 13C{1H} NMR (100 MHz, CDCl3):
 = 169.7, 153.8, 135.4, 135.3, 130.4, 129.9, 129.8, 126.1, 124.3,
121.9, 120.7 ppm. IR (CHCl3): νmax = 3006, 2962, 2942, 2837, 1632,
1600, 1556, 1498, 1478, 1451, 1434, 1388, 1344, 1285, 1256, 1195,
1178, 1161, 1100, 1059, 1042, 1031, 929, 902, 890, 861, 810, 744,
653 cm−1. HRMS (ESI‐TOF) m/z: [M + Na]+ calcd for C13H9NS2Na
266.0069; Found 266.0077.
Biphenyl‐4‐yl(p‐tolyl)sulfane (3bf). White solid (103.6 mg, 75%),
M.p. 104‒106 oC. 1H NMR (500 MHz, CDCl3):  = 7.56 (d, J = 7.8 Hz,
2H), 7.50 (d, J = 8.4 Hz, 2H), 7.43 (t, J = 7.4 Hz, 2H), 7.36‒7.32 (m, 5H),
7.17 (d, J = 8.1 Hz, 2H), 2.17 (s, 3H) ppm. 13C{1H} NMR (125 MHz,
CDCl3):  = 140.4, 139.3, 137.7, 136.3, 132.4, 131.1, 130.1, 130.0,
128.8, 127.7, 127.3, 126.9, 21.1 ppm. IR (CHCl3): νmax = 3063, 2919,
6 | J. Name., 2012, 00, 1‐3
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1592, 1578, 1507, 1489, 1476, 1446, 1394, 1374, 1178, 1161, 1125, 116.3 ppm. IR (CHCl3): νmax = 3061, 3044, 3033, 1592, 1574, 1559,
1105, 1085, 1046, 1019, 903, 825, 811, 688 cm−1. HRMS (ESI‐TOF) 1477, 1445, 1429, 1395, 1357, 1339, 1273, 1252, 1178, 1159, 1106,
m/z: [M + K]+ calcd for C19H16SK 315.0604; Found 315.0603.
1093, 1018, 910, 839, 746, 690 cm−1. HRMS (ESI‐TOF) m/z: [M + Na]+
calcd for C18H13ClSNa 319.0319; Found 319.0315.
(4‐Bromophenyl)(p‐tolyl)sulfane (3bg).13g White solid (114.5 mg,
82% and 117.2 mg, 84%), M.p. = 81‒84 C. 1H NMR (500 MHz, CDCl3):
 = 7.38 (dd, J = 6.7, 2.1 Hz, 2H), 7.32 (d, J = 8.0 Hz, 2H), 7.17 (d, J =
8.0 Hz, 2H), 7.11 (dd, J = 6.7, 2.0 Hz, 2H), 2.37 (s, 3H) ppm. 13C{1H}
NMR (125 MHz, CDCl3):  = 138.1, 136.7, 132.6, 132.0, 130.8, 130.3,
130.2, 120.0, 21.1 ppm. IR (CHCl3): νmax = 3077, 3054, 2959, 2861,
1491, 1472, 1388, 1363, 1307, 1110, 1095, 1082, 1006, 829, 811, 729,
705 cm−1.
Biphenyl‐4‐yl(4‐fluorophenyl)sulfane (3bm). White semi‐solid
(113.5 mg, 81%). 1H NMR (400 MHz, CDCl3):  = 7.57 (d, J = 7.3 Hz,
2H), 7.52 (d, J = 8.3 Hz, 2H), 7.46‒7.41 (m, 4H), 7.37‒7.32 (m, 3H),
7.05 (t, J = 8.6 Hz, 2H) ppm. 13C{1H} NMR (100 MHz, CDCl3):  = 140.2
and 139.7 (JC‐F = 50.4 Hz), 135.7, 134.18 and 134.1 (JC‐F = 7.9 Hz),
130.2, 128.8, 127.8, 127.5, 126.9, 116.6 and 116.3 (JC‐F = 22.1 Hz)
ppm. 19F NMR (471 MHz, CDCl3):  = ‒113.8 ppm. IR (CHCl3): νmax
=
3061, 3030, 2952, 2922, 2894, 2854, 1588, 1508, 1491, 1478, 1397,
1224, 1154, 1090, 1049, 909, 826, 690, 670, 624 cm−1. HRMS (ESI‐
TOF) m/z: [M + H]+ calcd for C18H14SF 281.0795; Found 281.0788.
(4‐Iodophenyl)(p‐tolyl)sulfane (3bh). Yellow solid (146.8 mg, 90%),
M.p. = 98‒100 C. 1H NMR (400 MHz, CDCl3):  = 7.55 (d, J = 8.3 Hz,
2H), 7.31 (d, J = 8.1 Hz, 2H), 7.16 (d, J = 8.0 Hz, 2H), 6.95 (dd, J = 8.3
Hz, 2H), 2.36 (s, 3H) ppm. 13C{1H} NMR (100 MHz, CDCl3):  = 138.2,
137.9, 137.8, 132.9, 130.8, 130.2, 130.0, 91.0, 21.2 ppm. IR (CHCl3):
(4‐Chlorophenyl)(4‐methoxyphenyl)sulfane (3bn).29 White semi‐
solid (102.8 mg, 82% and 101.5 mg, 81%). 1H NMR (400 MHz, CDCl3):
 = 7.40 (d, J = 8.8 Hz, 2H), 7.19 (d, J = 8.6 Hz, 2H), 7.07 (d, J = 8.7 Hz,
2H), 6.90 (d, J = 8.9 Hz, 2H) ppm. 13C{1H} NMR (100 MHz, CDCl3):  =
160.0, 137.3, 135.5, 131.6, 129.3, 129.0, 123.7, 115.1, 55.4 ppm. IR
(CHCl3): νmax = 3084, 2967, 2938, 2839, 1589, 1568, 1495, 1475, 1408,
1390, 1287, 1250, 1180, 1173, 1114, 1103, 1090, 1026, 1009, 837,
819, 741 cm−1.
ν
max = 2913, 1652, 1493, 1470, 1383, 1303, 1220, 1112, 1083, 1039,
873, 807, 770, 517 cm−1. HRMS (ESI‐TOF) m/z: [M + K]+ calcd for
C13H11ISK 364.9258; Found 364.9253.
Bis(4‐methoxyphenyl)sulfane (3bi).10c Colorless oil (97.3 mg, 79%).
1H NMR (400 MHz, CDCl3):  = 7.30 (d, J = 8.8 Hz, 4H), 6.85 (d, J = 8.7
Hz, 4H), 3.79 (s, 6H) ppm. 13C{1H} NMR (100 MHz, CDCl3):  = 158.9,
132.6, 127.3, 114.7, 55.2 ppm. IR (CHCl3): νmax = 3084, 3013, 2965,
2945, 2911, 2842, 1592, 1571, 1495, 1468, 1440, 1403, 1342, 1286,
1249, 1237, 1185, 1176, 1154, 1119, 1107, 1098, 1032, 1007, 837,
814, 798 cm−1.
(4‐Chlorophenyl)(4‐fluorophenyl)sulfane (3bo). Colorless oil (96.7
mg, 81%). 1H NMR (500 MHz, CDCl3):  = 7.38 (dd, J = 8.9, 2.6 Hz, 2H),
7.24 (d, J = 8.6 Hz, 2H), 7.17 (d, J = 8.8 Hz, 2H), 7.04 (t, J = 8.7 Hz, 2H)
ppm.13C{1H} NMR (125 MHz, CDCl3):  = 163.5 and 161.6 (JC‐F = 248.7
Hz), 135.4, 134.4 and 134.3 (JC‐F = 8.2 Hz), 132.7, 131.0, 129.6, 129.3,
116.7 and 116.5 (JC‐F = 21.9 Hz) ppm. 19F NMR (471 MHz, CDCl3):  =
‒113.29 ppm. IR (CHCl3): νmax = 3074, 3027, 2939, 1589, 1505, 1489,
1475, 1391, 1290, 1230, 1156, 1089, 1012, 832, 817, 746, 639, 625
cm−1. HRMS (ESI‐TOF) m/z: [M + K]+ calcd for C12H8ClFSK 276.9651;
Found 276.9652.
Biphenyl‐4‐yl(4‐methoxyphenyl)sulfane (3bj). White solid (105.3
mg, 72%), M.p. = 90‒93 C. 1H NMR (400 MHz, CDCl3):  = 7.55 (d, J =
8.0 Hz, 2H), 7.54‒7.40 (m, 6H), 7.35‒7.31 (m, 1H), 7.23 (d, J = 8.4 Hz,
2H), 6.92 (d, J = 8.8 Hz, 2H), 3.84 (s, 3H) ppm. 13C{1H} NMR (100 MHz,
CDCl3):  = 159.9, 140.4, 138.7, 137.7, 135.4, 128.8, 128.5, 127.6,
127.2, 126.8, 124.2, 115.0, 55.4 ppm. IR (CHCl3): νmax = 2962, 2938,
2840, 1590, 1493, 1479, 1479, 1397, 1289, 1247, 1219, 1183, 1173,
1129, 1100, 1032, 910, 838, 828, 766, 688 cm−1. HRMS (ESI‐TOF) m/z:
[M + K]+ calcd for C19H16OSK 331.0553; Found 331.0554.
Bis(4‐chlorophenyl)sulfane (3bp).26 White solid (116 mg, 91%), M.p.
1
= 95‒97 C. H NMR (500 MHz, CDCl3):  = 7.29 (d, J = 8.8 Hz, 4H),
7.25 (d, J = 8.8 Hz, 4H) ppm. 13C{1H} NMR (125 MHz, CDCl3):  = 134.0,
133.5, 132.3, 129.5 ppm. IR (CHCl3): νmax = 3081, 2925, 2844, 1523,
1474, 1425, 1394, 1295, 1249, 1094, 1078, 1011, 824, 814, 742 cm−1.
Biphenyl‐4‐yl(2‐bromophenyl)sulfane (3bk). Colorless oil (124.6 mg,
73%). 1H NMR (400 MHz, CDCl3):  = 7.65‒7.60 (m, 5H), 7.55–7.53 (m,
2H), 7.50 (t, J = 7.4 Hz, 2H), 7.42‒7.38 (m, 1H), 7.21‒7.17 (m, 1H), (4‐Bromophenyl)(4‐chlorophenyl)sulfane (3bq).13d White solid
7.09‒7.04 (m, 2H) ppm. 13C{1H} NMR (100 MHz, CDCl3):  = 141.2, (113.8 mg, 76%), M.p. = 96‒99 C. 1H NMR (400 MHz, CDCl3):  = 7.42
140.0, 138.7, 133.7, 133.0, 131.7, 129.8, 128.8, 128.2, 127.8, 127.7, (d, J = 8.5 Hz, 2H), 7.28 (d, J = 8.0 Hz, 4H), 7.17 (d, J = 8.5 Hz, 2H) ppm.
13C{1H} NMR (100 MHz, CDCl3):  = 134.7, 133.6, 133.5, 132.5, 132.3,
132.28, 129.5, 121.3 ppm. IR (CHCl3): νmax = 3088, 3069, 3054, 2942,
2850, 1493, 1473, 1391, 1093, 1085, 1069, 1008, 954, 820, 811, 743,
726 cm−1.
127.3, 127.0, 123.0 ppm. IR (CHCl3): νmax = 3064, 3054, 3027, 1592,
1576, 1554, 1477, 1445, 1428, 1396, 1360, 1334, 1274, 1251, 1176,
1106, 1095, 1038, 1016, 1006, 911, 839, 746, 718, 690, 662 cm−1.
HRMS (ESI‐TOF) m/z: [M + K]+ calcd for C18H13BrSK 378.9553; Found
378.9555.
Bis(4‐bromophenyl)sulfane (3br).26 White solid (134.2 mg, 78%),
M.p. = 114116 C. 1H NMR (400 MHz, CDCl3):  = 7.43 (d, J = 8.7 Hz,
4H), 7.18 (d, J = 8.5 Hz, 4H) ppm. 13C{1H} NMR (100 MHz, CDCl3):  =
134.4, 132.5, 132.4, 121.4 ppm. IR (CHCl3): νmax = 3062, 3040, 1503,
1486, 1472, 1391, 1090, 1081, 1066, 1007, 956, 815, 810, 724 cm−1.
Biphenyl‐4‐yl(2‐chlorophenyl)sulfane (3bl). Colorless oil (111.3 mg,
75%). 1H NMR (400 MHz, CDCl3):  = 7.60 (d, J = 7.6 Hz, 2H), 7.55 (d,
J = 8.2 Hz, 2H), 7.49‒7.44 (m, 4H), 7.40‒7.36 (m, 3H), 7.08 (t, J = 8.5
Hz, 2H) ppm. 13C{1H} NMR (100 MHz, CDCl3):  = 163.6, 161.1, 140.2,
139.7, 135.7, 134.1, 134.06, 130.2, 128.8, 127.8, 127.4, 126.9, 116.5,
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(4‐Bromophenyl)(4‐fluorophenyl)sulfane (3bs). Yellow oil (103.3 0.025 mmol, 5 mol%). Then H2O2 (2 mmol, 4 equiv) was added at
o
1
room temperature and the mixture stirred for 10 h at 80 C. After
mg, 73%). H NMR (400 MHz, CDCl3):  = 7.40‒7.37 (m, 4H), 7.11‒
6.99 (m, 4H) ppm. 13C{1H} NMR (100 MHz, CDCl3):  = 163.8 and 161.3
(JC‐F = 249 Hz), 136.2, 134.54 and 134.46 (JC‐F = 7.8 Hz), 132.2, 131.0,
129.27 and 129.24 (JC‐F = 3.2 Hz), 120.5, 116.7 and 116.5 (JC‐F = 21.4
Hz) ppm. 19F NMR (471 MHz, CDCl3):  = ‒113.0 ppm. IR (CHCl3): νmax
= 3067, 2922, 1473, 1391, 1092, 1082, 1068, 1007, 953, 819, 809, 727
cm−1. HRMS (ESI‐TOF) m/z: [M + K]+ calcd for C12H8BrFSK 320.9146;
Found 320.9145.
completion of the reaction, MeOH was evaporated and the mixture
extracted with EtOAc (2  15 mL). The combined organic layers were
dried (Na2SO4) and concentrated. The residue was purified by silica
gel column chromatography using petroleum ether/EtOAc (19:1) as
eluent to give 5a‐d.
1‐Methyl‐4‐(phenylsulfinyl)benzene (5a).26 White solid (89.8 mg,
83%), M. p. = 64‒65 oC. 1H NMR (500 MHz, CDCl3):  = 7.62 (dd, J =
7.9, 1.8 Hz, 2H), 7.52 (d, J = 8.2 Hz, 2H), 7.46–7.42 (m, 3H), 7.25 (d, J
= 8.0 Hz, 2H), 2.36 (s, 3H) ppm. 13C{1H} NMR (100 MHz, CDCl3):  =
145.7, 142.4, 141.7, 130.9, 130.0, 129.2, 125.0 124.7, 21.4 ppm. IR
(CHCl3): νmax = 2924, 2853, 1654, 1591, 1493, 1443, 1400, 1384, 1307,
1087, 1046, 1015, 955, 914, 814, 750, 705, 687, 621 cm−1.
4‐(4‐Bromophenylthio)benzaldehyde (3bt). White Solid (118.7 mg,
1
81%), M.p. = 62‒64 C. H NMR (400 MHz, CDCl3):  = 9.91 (s, 1H),
7.72 (d, J = 8.6 Hz, 2H), 7.52 (d, J = 8.5 Hz, 2H), 7.35 (d, J = 8.6 Hz, 2H),
7.24 (d, J = 8.5 Hz, 2H) ppm. 13C{1H} NMR (100 MHz, CDCl3):  = 191.0,
146.0, 135.4, 133.9, 132.9, 130.7, 130.2, 127.6, 123.4 ppm. IR (CHCl3):
νmax = 2925, 2845, 2740, 1699, 1673, 1590, 1563, 1472, 1409, 1387,
1302, 1283, 1168, 1089, 1078, 1008, 836, 820, 809, 771, 728, 693,
666 cm−1. HRMS (ESI‐TOF) m/z: [M + K]+ calcd for C13H9BrOSK
330.9189; Found 330.9189.
1‐Methoxy‐4‐(phenylsulfinyl)benzene (5b).26 White solid (102.2 mg,
88%), M.p. = 64‒65 oC. 1H NMR (400 MHz, CDCl3):  = 7.59 (dd, J =
8.0, 1.6 Hz, 2H), 7.55 (d, J = 8.8 Hz, 2H), 7.45–7.39 (m, 3H), 6.93 (d, J
= 8.8 Hz, 2H), 3.78 (s, 3H) ppm. 13C{1H} NMR (100 MHz, CDCl3):  =
161.9, 145.6, 136.6, 130.6, 129.1, 127.1, 124.5, 114.7, 55.4 ppm. IR
(CHCl3): νmax = 3071, 3002, 2959, 2939, 2836, 1596, 1575, 1490, 1463,
1436, 1412, 1303, 1282, 1254, 1210, 1162, 1087, 1075, 1031, 936,
919, 834, 804, 636 cm−1.
(4‐Bromophenyl)(2,5‐dimethoxyphenyl)sulfane (3bu). Colorless oil
(117.0 mg, 72%). 1H NMR (500 MHz, CDCl3):  = 7.41 (d, J = 8.5 Hz,
2H), 7.19 (d, J = 8.5 Hz, 2H), 6.84 (d, J = 8.8 Hz, 1H), 6.78 (dd, J = 9.1,
3.0 Hz, 1H), 6.69 (d, J = 2.9 Hz, 1H), 3.80 (s, 3H), 3.69 (s, 3H) ppm.
13C{1H} NMR (125 MHz, CDCl3):  = 153.9, 151.8, 133.8, 132.6, 132.2,
124.1, 121.0, 117.7, 113.3, 112.0, 56.5, 55.7 ppm. IR (CHCl3): νmax
=
1‐Chloro‐4‐(phenylsulfinyl)benzene (5c).27 Colorless oil (95.9 mg,
81%). 1H NMR (500 MHz, CDCl3):  = 7.63–7.62 (m, 2H), 7.58 (d, J =
8.1 Hz, 2H), 7.47–7.42 (m, 5H) ppm. 13C{1H} NMR (125 MHz, CDCl3): 
= 145.4, 144.3, 137.3, 131.4, 129.7, 129.5, 126.1, 124.8 ppm. IR
(CHCl3): νmax = 3081, 3057, 2928, 2854, 1655, 1644, 1571, 1474, 1444,
1390, 1171, 1086, 1048, 1011, 914, 823, 751, 740, 703, 688 cm−1.
2999, 2959, 2937, 2834, 1596, 1584, 1566, 1486, 1472, 1456, 1442,
1408, 1385, 1325, 1277, 1221, 1189, 1141, 1059, 1045, 1019, 1010,
862, 816, 801, 792, 739, 731, 688 cm−1. HRMS (ESI‐TOF) m/z: [M + K]+
calcd for C14H13BrSO2K 362.9451; Found 362.9448.
4‐(3‐Methoxyphenylthio)benzaldehyde (3bv). Colorless oil (90.4
mg, 74%). 1H NMR (400 MHz, CDCl3):  = 9.88 (s, 1H), 7.70 (d, J = 7.7
Hz, 2H), 7.31 (t, J = 8.1 Hz, 1H), 7.25 (d, J = 8.4 Hz, 2H), 7.08 (d, J = 8.0
Hz, 1H), 7.04 (t, J = 2.2 Hz, 1H), 6.93 (dd, J = 8.2, 2.2 Hz, 1H), 3.78 (s,
3H) ppm.13C{1H} NMR (100 MHz, CDCl3):  = 191.1, 160.3, 146.8,
133.6, 132.3, 130.5, 130.0, 127.3, 126.2, 119.1, 115.0, 55.3 ppm. IR
(CHCl3): νmax = 3061, 3006, 2961, 2936, 2834, 2734, 1697, 1672, 1590,
1563, 1480, 1442, 1425, 1415, 1387, 1303, 1283, 1247, 1232, 1168,
1087, 1073, 1041, 1013, 993, 861, 836, 816, 778, 690, 629 cm−1.
HRMS (ESI‐TOF) m/z: [M + K]+ calcd for C14H12O2SK 283.0190; Found
283.0185.
1‐Bromo‐4‐(phenylsulfinyl)benzene (5d).27 Colorless oil (106.8 mg,
76%). 1H NMR (400 MHz, CDCl3):  = 7.63–7.61 (m, 2H), 7.58 (d, J =
8.5 Hz, 2H), 7.50 (d, J = 8.6 Hz, 2H), 7.47–7.45 (m, 3H) ppm. 13C{1H}
NMR (100 MHz, CDCl3):  = 145.2, 144.8, 132.6, 131.4, 129.5, 126.3,
125.6, 124.8 ppm. IR (CHCl3): νmax = 2928, 1653, 1573, 1444, 1387,
1324, 1308, 1274, 1157, 1105, 1069, 1009, 812, 744, 687, 604 cm−1.
General procedure for synthesis of diarylsulfones (6a‐c). To a stirred
solution of 3ac, 3af or 3ag (0.5 mmol) in MeOH (2 mL) were added
ZnCl2 (6.8 mg, 0.05 mmol,10 mol%) and DBU (19 mg, 0.125 mmol, 25
mol%). Then H2O2 (2 mmol, 4 equiv) was added at room temperature
3‐(4‐Hydroxyphenylthio)phenol (3bw). Colorless oil (84.0 mg, 77%).
1H NMR (500 MHz, CDCl3):  = 8.66 (d, J = 5.9 Hz, 1H), 8.29 (d, J = 8.0
Hz, 1H), 7.82 (dt, J = 7.8, 1.5 Hz, 1H), 7.35–7.32 (m, 1H), 7.26 (d, J =
8.6 Hz, 2H), 6.72 (d, J = 8.6 Hz, 2H) ppm. 13C{1H} NMR (125 MHz,
CDCl3):  = 157.1, 155.3, 148.8, 137.7, 133.0, 127.5, 124.2, 121.9,
116.2 ppm. IR (CHCl3): νmax = 3383, 3077, 3054, 2929, 2861, 1658,
1595, 1581, 1561, 1492, 1458, 1424, 1362, 1267, 1241, 1167, 1093,
1041, 1003, 907, 828, 815, 809, 624, 600 cm−1. HRMS (ESI‐TOF) m/z:
[M + H]+ calcd for C12H11O2S 219.0475; Found 219.0469.
o
and the mixture stirred for 16 h at 80 C. After completion of the
reaction, MeOH was evaporated and the mixture extracted with
EtOAc (2  15 mL). The combined organic layers were dried (Na2SO4)
and concentrated. The residue was purified by silica gel column
chromatography using petroleum ether/EtOAc (19:1) as eluent to
give 6a‐c.
1‐Methoxy‐4‐(phenylsulfonyl)benzene (6a).28 White solid (101.8
mg, 82%). M.p. = 9193 oC. 1H NMR (500 MHz, CDCl3):  = 7.90 (d, J =
7.6 Hz, 2H), 7.86 (d, J = 8.8 Hz, 2H), 7.53–7.50 (m, 1H), 7.46 (t, J = 7.8
Hz, 2H), 6.95 (d, J = 8.9 Hz, 2H), 3.82 (s, 3H) ppm. 13C{1H} NMR (125
MHz, CDCl3):  = 163.3, 142.2, 133.0, 132.8, 129.8, 129.1, 127.2,
General procedure for synthesis of diarylsulfoxides (5a‐d). To a
stirred solution of 3ab, 3ac, 3af or 3ag (0.5 mmol) in MeOH (2 mL)
were added ZnCl2 (3.4 mg, 0.025 mmol, 5 mol%) and DBU (3.8 mg,
8 | J. Name., 2012, 00, 1‐3
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DOI: 10.1039/D0OB00244E
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ARTICLE
114.4, 55.6 ppm. IR (CHCl3): νmax = 2942, 1594, 1574, 1496, 1466, = 3474, 3380, 2938, 1621, 1576, 1492, 1331, 1295, 1183, 1079, 1049,
1446, 1315, 1297, 1261, 1183, 1147, 1107, 1072, 1017, 909, 836, 804, 910, 851, 841, 826, 743 cm−1. HRMS (ESI‐TOF) m/z: [M + H]+ calcd for
729, 693, 653, 626, 577, 556 cm−1.
C12H11N2O2S 247.0536; Found 247.0532.
1‐Bromo‐4‐(phenylsulfonyl)benzene (6b).28 Yellow solid (114.4 mg,
77%). M.p. = 101‒104 oC. H NMR (500 MHz, CDCl3):  = 7.93–7.91
Conflicts of interest
1
There are no conflicts to declare.
(m, 2H), 7.80 (d, J = 8.7 Hz, 2H), 7.63 (d, J = 8.6 Hz, 2H), 7.59–7.56 (m,
1H), 7.52–7.49 (m, 2H) ppm. 13C{1H} NMR (125 MHz, CDCl3):  =
141.1, 140.6, 133.4, 132.6, 129.4, 129.2, 128.4, 127.6 ppm. IR (CHCl3):
Acknowledgements
We thank SERB New Delhi, Grant No. EMR/2017/000499 for
financial support. A.B. thank IIT‐Bombay for research
fellowship.
ν
max = 3092, 3067, 2918, 1578, 1474, 1447, 1391, 1319, 1310, 1281,
1175, 1155, 1108, 1088, 1068, 834, 824, 768, 721, 687, 612, 568 cm−1.
1‐Chloro‐4‐(phenylsulfonyl)benzene (6c).28 White solid (99.8 mg,
79%), M.p. = 94‒95 oC. 1H NMR (400 MHz, CDCl3):  = 7.92 (d, J = 8.4
Hz, 2H), 7.87 (d, J = 8.7 Hz, 2H), 7.59–7.45 (m, 5H) ppm. 13C{1H} NMR
(100 MHz, CDCl3):  = 141.1, 140.1, 139.8, 133.4, 129.6, 129.4, 129.1,
127.6 ppm. IR (CHCl3): νmax = 3094, 2928, 1654, 1582, 1475, 1445,
1393, 1322, 1309, 1281, 1173, 1158, 1107, 1088, 1071, 1009, 828,
752, 720, 688, 616, 567 cm−1.
REFERENCES
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4,4'‐Thiodiphenol (3bx).29 The titled compound was prepared from
1p (82.8 mg, 0.6 mmol) and 2p (63.1 mg, 0.5 mmol) by following
similar procedure as described for 3ab to give 3bx (88.4 mg, 81%) as
o
1
white solid, M.p. = 155–157 C. H NMR (400 MHz, DMSO‐d6):  =
9.62 (s, 2H), 7.13 (d, J = 8.6 Hz, 4H), 6.73 (d, J = 8.7 Hz, 4H) ppm.
13C{1H} NMR (100 MHz, DMSO‐d6):  = 157.0, 132.8, 124.6, 116.3
ppm. IR (CHCl3): νmax = 3317, 2925, 1629, 1600, 1584, 1492, 1440,
1376, 1235, 1168, 1047, 936, 822, 770, 575 cm−1.
4,4'‐Sulfonyldiphenol (6d).26 The titled compound was prepared
from 3bx (109.1 mg, 0.5 mmol) by following a similar procedure as
described for 6a to give 6d (103.9 mg, 83%) as white solid, M.p. =
238–241 oC. 1H NMR (400 MHz, CD3OD):  = 7.90 (d, J = 8.9 Hz, 4H),
7.05 (d, J = 8.9 Hz, 4H), 5.05 (s, 2H), ppm. 13C{1H} NMR (100 MHz,
CD3OD):  = 164.6, 135.1, 132.0, 118.2 ppm. IR (CHCl3): νmax = 3416,
2922, 1643, 1378, 1300, 1219, 1149, 1107, 1049, 820, 771, 719, 558
cm−1.
2‐(2‐Bromophenylthio)aniline (3by).30 The titled compound was
prepared from 1q (82.1 mg, 0.6 mmol) and 2y (94.5 mg, 0.5 mmol)
by following similar procedure as described for 3ab to give 3by (117.7
mg, 84%) as yellow solid, M.p. = 58–60 oC. 1H NMR (400 MHz, CDCl3):
 = 7.52 (dd, J = 7.9, 1.1 Hz, 1H), 7.47 (dd, J = 7.7, 1.2 Hz, 1H), 7.29 (t,
J = 7.5 Hz, 1H), 7.10 (t, J = 7.5 Hz, 1H), 6.97 (dt, J = 7.5, 1.4 Hz, 1H),
6.84‒6.78 (m, 2H), 6.63 (dd, J = 8.0 Hz, 1.3 Hz, 1H), 4.06 (br s, 2H)
ppm. 13C{1H} NMR (100 MHz, CDCl3):  = 148.9, 137.9, 137.8, 132.7,
131.7, 127.7, 126.23, 126.2, 120.7, 119.1, 115.5, 113.2 ppm. IR
(CHCl3): νmax = 3467, 3368, 3062, 1607, 1478, 1445, 1427, 1309, 1271,
1250, 1159, 1134, 1102, 1036, 1018, 940, 848, 836, 750, 650 cm−1.
4‐(4‐Nitrophenylthio)aniline (3bz).31 The titled compound was
prepared from 1r (82.1 mg, 0.6 mmol) and 2z (77.6 mg, 0.5 mmol) by
following similar procedure as described for 3ab to give 3bz (97.3 mg,
79%) as yellow solid, M.p. = 142145 oC. 1H NMR (500 MHz, CDCl3):
 = 8.02 (d, J = 8.9 Hz, 2H), 7.33 (d, J = 8.5 Hz, 2H), 7.08 (d, J = 8.9 Hz,
2H), 6.74 (d, J = 8.6 Hz, 2H) ppm. 13C{1H} NMR (125 MHz, CDCl3):  =
151.0, 148.3, 144.8, 125.2, 123.9, 116.4, 116.1 ppm. IR (CHCl3): νmax
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DOI: 10.1039/D0OB00244E
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Journal Name
S. M. Guinness, B. M. Lillie, R. W. McLaughlin, C. W. Palmer, R.
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DOI: 10.1039/D0OB00244E
Abstract
Br
OH
S
B(OH)2
+
SH
S
O
NiCl2.6H2O/bIpy
A
S
B
B
A
O
t-BuOK, CH3CN
rt, in air, 12 h
NH2
bisphenol S
R1
R1
R2
R2
promazine precursor
55 examples
S
mild and easy operation
benign reaction conditions
good to excellent yields
OH
H2N
NO2
easy availabilty of starting materials
dapsone precursor
A mild and easily operated NiCl2/2,2′-bipyridine-catalyzed cross-coupling of thiophenols
with arylboronic acids for the synthesis of symmetric and unsymmetric diarylsulfides has
been developed at room temperature and in air conditions.