TBAI-mediated sulfenylation of arenes with arylsulfonyl hydrazides in DPDME

Article abstract of DOI:10.1016/j.tet.2020.131646

An efficient TBAI (tetrabutylammonium iodide)-mediated C–H sulfenylation of arenes with arylsulfonyl hydrazides in dipropylene glycol dimethyl ether (DPDME) was described. Various electron-rich arenes were applicable in the reaction, such as naphthylamine, naphthol, aniline, indole, pyrrole, and imidaz o [1,2-a] pyridine. A wide range of the aryl sulfides were obtained with good functional group tolerance. This method features green reaction conditions (odorless and easily available sulfur reagent, recyclable TBAI, and DPDME as solvent), and broad substrate scope. The synthetic potential is demonstrated by gram-scale synthesis and downstream transformations. The mechanism studies show that the reaction is achieved through electrophilic substitution process, and diaryl disulfide may be the main intermediate.

Full text of DOI:10.1016/j.tet.2020.131646

Tetrahedron xxx (xxxx) xxx
Contents lists available at ScienceDirect
Tetrahedron
journal homepage: www.elsevier.com/locate/tet
TBAI-mediated sulfenylation of arenes with arylsulfonyl hydrazides in
DPDME
Wei Yueting, Liu Yali, He Jing, Li Xuezhen, Liu Ping*, Zhang Jie**
School of Chemistry and Chemical Engineering/Key Laboratory for Green Processing of Chemical Engineering of Xinjiang Bingtuan, Shihezi University,
Shihezi, 832004, China
a r t i c l e i n f o
a b s t r a c t
Article history:
An efficient TBAI (tetrabutylammonium iodide)-mediated CeH sulfenylation of arenes with arylsulfonyl
hydrazides in dipropylene glycol dimethyl ether (DPDME) was described. Various electron-rich arenes
were applicable in the reaction, such as naphthylamine, naphthol, aniline, indole, pyrrole, and imidaz o
[1,2-a] pyridine. A wide range of the aryl sulfides were obtained with good functional group tolerance.
This method features green reaction conditions (odorless and easily available sulfur reagent, recyclable
TBAI, and DPDME as solvent), and broad substrate scope. The synthetic potential is demonstrated by
gram-scale synthesis and downstream transformations. The mechanism studies show that the reaction is
achieved through electrophilic substitution process, and diaryl disulfide may be the main intermediate.
© 2020 Elsevier Ltd. All rights reserved.
Received 3 August 2020
Received in revised form
1 September 2020
Accepted 15 September 2020
Available online xxx
Keywords:
Arene
Arylsulfonyl hydrazides
DPDME
Metal-free
Sulfenylation
1. Introduction
the of arenes for the synthesis of aryl sulfides has been extensively
developed [9]. Various sulfur reagents and precursors including
Aryl sulfides as sulfur-containing organic compounds are
indispensable in natural products and bioactive molecules [1], and
also have wide applications in a range of fields such as drug
development [2], materials science [3], and organic syntheses [4].
In view of the important applications of sulfide compounds and the
broad potential application, chemists have developed a series of
methods to construct sulfides [5]. Traditionally, transition-metal-
catalyzed cross-couplings between C-X/CeH and various sulfur
sources have been developed [6]. In spite of some great advantages,
some of these processes could suffer from certain drawbacks,
including pre-functionalization of reactants, harsh reaction condi-
tions, and toxic metal catalysts [7]. Recently, non-metal-catalyzed
or mediated direct sulfenylation of arenes has received consider-
able attention. Compared with traditional synthetic methods, the
metal-free catalysis/participation in CeH functionalization often
has the following characteristics: 1) No prior functionalization to
prepare organic halides or organometallic reagents; 2) higher
atomic economy; 3) shorter synthesis steps; 4) less generated
waste [8]. In particular, iodine promotes direct CeH sulfenylation
thiols, disulfides, sulfonyl chlorides, sulfonyl hydrazines, N-(thio)
succinicmides, sodium sulfonates, and others have been employed
[10e16]. However, these current synthetic methodes suffer from
limitations, such as the use of bad odor, air-sensitive thiol sub-
strates, toxic organic solvents, and relatively narrow substrate
scopes. Therefore, the development of new sustainable protocols
for the synthesis of diverse aryl sulfides in green solvents, such as
water or DPDME (dipropylene glycol dimethyl ether), under simple
reaction conditions is still highly desirable.
In 2016, Lu et al. reported an I2/PPh3-mediated regioselective
arylthiolations of aromatic amines, arenols and ketones in an
aqueous system, whereby arylsulfenyl radicals in situ generated
from odorless sodium arylsulfinates could react with free anilines
containing electron-withdrawing groups and complex substrates
(estrone and progesterone) (Scheme 1a) [17]. Sinha et al. developed
a BSA-iodine cooperative catalyzed CeH sulfenylation of indoles/
hydroxyaryls with thiophenols in water. This green cooperative
protocol is extendable for sulfenylation of hydroxyaryls with
diverse thiols without using any toxic metal catalysts, bases or
oxidants (Scheme 1b) [18]. In 2018, Yuan et al. provided a Cobalt-
catalyzed aerobic cross-dehydrogenative coupling of arene and
thiols. This methodology achieved the CeS bond formation in water
with molecular oxygen as the sole oxidant while avoid the use of
* Corresponding author.
** Corresponding author.
E-mail addresses: liuping@shzu.edu.cn (L. Ping), zhangjie@shzu.edu.cn (Z. Jie).
https://doi.org/10.1016/j.tet.2020.131646
0040-4020/© 2020 Elsevier Ltd. All rights reserved.
Please cite this article as: W. Yueting, L. Yali, H. Jing et al., TBAI-mediated sulfenylation of arenes with arylsulfonyl hydrazides in DPDME,
Tetrahedron, https://doi.org/10.1016/j.tet.2020.131646

W. Yueting, L. Yali, H. Jing et al.
Tetrahedron xxx (xxxx) xxx
Table 1
Optimized reaction conditionsa.
Entry
n (mmol, 1a/2a)
PTC(equiv.)
T (ꢀC)
Solvent (mL)
Yield (%)b
1
2
3
4
5
6
7
8
0.3/0.6
0.3/0.9
0.3/0.9
0.3/0.9
0.3/0.9
0.3/0.9
0.3/0.9
0.3/0.9
0.3/0.9
0.3/0.9
0.3/0.9
0.3/0.6
0.3/0.9
/
/
100
100
100
100
100
100
80
100
100
100
100
100
100
H2O (3)
H2O (3)
H2O (3)
H2O (3)
H2O (3)
H2O (3)
H2O (3)
DPDME (3)
DPDME (3)
DPDME (0.5)
DPDME (0.5)
DPDME (0.5)
DPDME (0.5)
45
52
83
71
68
Nr
69
95
90
99
97
92
89
TBAI (3)
TBAB (3)
TBAC (3)
TBAF (3)
TBAI (3)
TBAI (3)
TBAI (2)
TBAI (2)
TBAI (2)
TBAI (2)
TBAI (1)
9
10
11c
12
13
Scheme 1. TBAI-Mediated sulfenylation of arenes.
[a]
Reaction conditions: 1a (0.3 mmol), 2a (0.6 or 0.9 mmol), TBAI (0.6 or 0.9 mmol),
solvent (3 mL or 0.5 mL), 100 ꢀC, 24 h.
[b]
Isolated yield.
12 h.
toxic solvents (Scheme 1c) [19]. Recently, we have demonstrated a
TBAI-mediated direct sulfenylation of arenes with ethyl arylsulfi-
nates in water, a series of aryl sulfides were obtained in excellent
yields. The advantages of this green protocol were simple reaction
conditions (metal-free, water as the solvent, in the air), odorless
and easily available sulfur reagent, broad substrate scope (Scheme
1d) [20]. As our continuing efforts exploring organosulfur chemis-
try [21], we report herein an environmentally benign method for
the synthesis of aryl sulfides via sulfenylation of arenes with aryl-
sulfonyl hydrazides in DPDME (Scheme 1e). This new method offers
some advantages, including a green reaction solvent, a stable and
odorless sulfur reagent, simple reaction condition, and recyclable
TBAI as promoter. Most importantly, this system has a wider range
of substrate than the reported methods.
[c]
optimal reaction conditions are: 1a (0.3 mmol), 2a (0.9 mmol), TBAI
(0.6 mmol), DPDME (0.5 mL), under air, at 100 ꢀC, for 12 h.
2.2. Scope and limitations of substrates
Under optimal conditions, we investigated the scope of aryl-
sulfonyl hydrazides for this sulfenylation, and the results were
summarized in Table 2. The arylsulfonyl hydrazides with a variety
of substituents, such as methyl, tert-butyl, methoxy, fluoro, chloro,
bromo, nitro, trifluoromethyl, and trifluoromethoxy groups were
tolerated to this sulfenylation of naphthalen-2-amine to provide
the desired products 3be3m in excellent yields. The reaction with
the sterically congested substrate proceeded very well, affording
the desired product 3n in 92% yield. The substrate with a certain
steric hindrance, 2,5-dimethylbenzenesulfonohydrazide, could also
2. Results and discussion
2.1. Optimization of the reaction conditions
First, we selected b-naphthylamine and p-toluenesulfonyl hy-
Table 2
drazide as model substrates to optimize the reaction conditions,
and the results are shown in Table 1. When the ratio of 1a and 2a is
1: 2, the reaction is performed in water at 100 ꢀC for 24 h, and the
product 1-(phenylthio)naphthalen-2-amine 3a is obtained in 45%
yield (entry 1). When the ratio of 1a and 2a is increased to 1: 3, the
yield was increased to 52% (entry 2). To our delight, when 3
equivalents of TBAI were added to the above system, 83% yield
could be obtained (entry 3). Also, other phase transfer catalyst
(PTC) such as TBAB or TBAC had a good promotion effect on the
model reaction, affording the product 3a in 71% and 68% yields,
respectively (entries 4 and 5). However, TBAF as a PTC inhibited the
reaction (entry 6). Lowering the reaction temperature was detri-
mental to the sulfenylation reaction (entry 7). When DPDME a
green solvent is used, the reaction could proceed smoothly and
provide an excellent yield of 95% (entry 8). Reducing the amount of
TBAI could also obtain 90% yield (entry 9). To our delight, when the
amount of DPDME was reduced to 0.5 mL, almost quantitative yield
of target product 3a was obtained (entry 10). By shortening the
reaction time to 12 h, an excellent yield could still be maintained
(entry 11). Based on the above reaction conditions, when the ratio
of 1a and 2a is 1: 2 or the amount of TBAI was one equivalent, the
reaction yield was slightly reduced (entries 12 and 13). Finally, the
Sulfenylation of b
-naphthylamine with ArSO2NHNH2 in DPDMEa.
2

W. Yueting, L. Yali, H. Jing et al.
Tetrahedron xxx (xxxx) xxx
react with b-naphthylamine smoothly to give the desired product
3n with excellent yields. 2-(Ethylsulfonyl)naphthalene performed
also quite well in the transformation, and the product 3o was ob-
tained in 96% yield. The optimal conditions were amenable to the
reaction of 6-bromonaphthalen-2-amine, affording the desired
product 3p in 95% yield. It is conceivable that a bromo substituent
group should be helpful for further transformation of the product
3p.
Fig. 1. The crystal structure of compound 4d.
Subsequently, we investigated the sulfenylation reaction of a-
naphthylamine with arylsulfonyl hydrazides. The results showed
that benzenesulfonyl hydrazide, 4-methylphenylsulfonyl hydra-
zide, and 4-chlorophenylsulfonyl hydrazide reacted with a-naph-
hydrazides to obtain para-substituted products 4a-4c in 91e95%
yields with the high regioselectivity. In contrast, the reactions of
[1,10-biphenyl]-2-amine with arylsulfonyl hydrazides also pro-
ceeded very well, and affording the products 4d-4f in 83e89%
yields. The structure of 4d was further confirmed by single crystal
X-ray diffraction (Fig. 1, CCDC: 2,017,288). In addition, we also tried
the reaction of diamino substituted substrate such as naphthalene-
2,3-diamine, the product 1,4-bis(phenylthio)naphthalene-2,3-
diamine 4g was obtained in 59% yield. Notably, the reaction was
compatible with some substituted aniline such as 2-
methoxyaniline and 2,5-dimethylaniline, affording the corre-
sponding products 4h and 4i in 81% and 99% yields, respectively.
To further examine the scope and limitations of the sulfenyla-
tion, the reactions of various arylsulfonyl hydrazides and 1H-indole
were tested (Table 5). The results indicated that the substituents
from arylsulfonyl hydrazides did not remarkably affect the reaction,
and providing the corresponding products 5a-5d with excellent
yields. Next, pyrrole and its derivatives were applicable in this re-
action, and the 2,5- or 3,4-disulfide substituted products 5e-5g
were isolated in 82e90% yields. In addition, the reactivity of imidaz
o [1,2-a] pyridine was also examined, the reactions with benzene-
sulfonohydrazide and 4-methylbenzenesulfonohydrazide worked
well, leading to 5h and 5i in excellent yields. The reaction with 4-
fluorobenzenesulfonohydrazide provided the target product in
58% yield.
thylamine to provide dithioether products 3q-3s with excellent
yields. However, 4-nitrophenylsulfonyl hydrazide with a strong
electron-withdrawing group as a reactant gave a monothioether
product 3t in 90% yield. It should be noted that when 1 equivalent
of benzenesulfonyl hydrazide was used, the monothioether product
4-(phenylthio)naphthalen-1-amine 3u was also obtained in 58%
yield. Table 3.
This excellent reaction system prompted us to investigate the
sulfenylation of other aromatic amines as substrates. As shown in
Table 4, aniline reacted smoothly with various arylsulfonyl
Table 3
Sulfenylation of a
-naphthylamine with ArSO2NHNH2 in DPDME a..
To further expand the substrate scope, we next examined the
sulfenylation of naphthalen-2-ol (Table 6). However, we found that
the reactions of naphthalen-2-ol with various arylsulfonyl hydra-
zides could proceed smoothly at 140 ꢀC, and the corresponding
products 6a-6i in 43e84% yields. The substrate naphthalene-2-
sulfonohydrazide provided the product 6j in 69% yield. The above
results showed that naphthalen-2-ol displayed lower reactivity
than b-naphthylamine. In addition, the reactions of naphthalen-1-
ol with arylsulfonyl hydrazides was also investigated, and the 2,4-
disubstituted aryl sulfides products 6k-6m were obtained in
77e82% yields.
Table 4
Sulfenylation of other aromatic amines with ArSO2NHNH2 in DPDME a..
Table 5
Sulfenylation of other aromatic amines with ArSO2NHNH2 in DPDME a..
3

W. Yueting, L. Yali, H. Jing et al.
Tetrahedron xxx (xxxx) xxx
Table 6
Sulfenylation of naphthol with ArSO2NHNH2 in DPDME a..
Scheme 3. Chemical transformations of 3a and 4d.
To demonstrate the practicality of this protocol, gram-scale re-
action was conducted under standard conditions (Scheme 2).
10 mmol of naphthalen-2-amine reacted with benzenesulfonohy-
drazide (30 mmol) in 10 mL of DPDMF to give 3a (2.32 g) in 92%
yield (Scheme 2a). The reaction of [1,10-biphenyl]-2-amine
(10 mmol) with benzenesulfonohydrazide (30 mmol) was also
performed to provide the product 4d (2.26 g) in 82% yield (Scheme
2b). It is worth mentioning that after the above two reactions are
completed, TBAI could be easily recovered through simple filtration
in 93% and 91% yields, respectively.
The multifunctional sulfenylated products allowed many
possible further derivations (Scheme 3). For example, oxidation of
compound 3a by m-CPBA afforded the product 1-(phenylsulfonyl)
naphthalen-2-amine 3aa in 58% yield (Scheme 3a). Compound 4d
reacted with bromobenzene through CeN coupling in the presence
of Pd2 (dba)3/XPhos as catalyst, furnishing the product N-phenyl-5-
(phenylthio)-[1,10-biphenyl]-2-amine 4da in 87% yield (Scheme
3b).
Scheme 4. The control experiments.
To gain reasonable insight into the reaction mechanism, a series
of control experiments were conducted. As Scheme 4 shown, in the
presence of TEMPO or BHT, the reaction of naphthalen-2-amine
with benzenesulfonohydrazide was not suppressed, and the
product 3a was obtained in 91% and 89% yields, respectively
(Scheme 4a). The results showed that the sulfenylation reaction
should not be a free radical process. The benzenesulfonohydrazide
was treated under standard conditions, affording the products
sulfinothioyldibenzene and S-phenyl benzenesulfonothioate in 80%
and 16% yields, respectively (Scheme 4b). This observation implies
that sulfinothioyldibenzene and S-phenyl benzenesulfonothioate
may be important intermediates generated during the reaction.
Treatment of naphthalen-2-amine with sulfinothioyldibenzene or
S-phenyl benzenesulfonothioate respectively could successfully
obtain the desired product 3a in excellent yields, which further
confirms our above speculation (Scheme 4c and 4d). Further, we
found that the reaction of 2-naphthylamine and sulfinothioyldi-
benzene was difficult to proceed in the absence of TBAI (Scheme
4c). This result indicated that TBAI was involved in this sulfenyla-
tion reaction. In contrast, the reaction of 2-naphthylamine with
diphenyldisulfide in the absence of TBAI can also occur (Scheme
4d). This fact is consistent with the experimental results of the
model reaction in the absence of TBAI (Scheme 4e). Using benze-
nethiol as sulfur to react with 1a, the desired product 3a was not
obtained (Scheme 4f). This phenomenon indicates that benzene-
thiol should not be an intermediate in the reaction. When benze-
nesulfinic acid was treated under the standard conditions, 3a can
be generated in 43% yield (Scheme 4g). This showed that benze-
nesulfinic acid may be involved in the catalytic cycle of the reaction.
Scheme 2. Gram-scale synthesis of 3a and 4d.
4

W. Yueting, L. Yali, H. Jing et al.
Tetrahedron xxx (xxxx) xxx
3.3. 1-(Phenylthio)naphthalen-2-amine [3a] [13a]
The crude mixture was purified via column chromatography
using ethyl acetate/petroleum ether (1 : 30) as eluent to give the
product 3a as a red solid (73.1 mg, 97%); mp 96.5e99.1 ꢀC; 1H NMR
(400 MHz, DMSO‑d6)
d
8.06 (d, J ¼ 8.4 Hz, 1H), 7.79 (d, J ¼ 8.8 Hz,
1H), 7.73 (d, J ¼ 7.6 Hz,1H), 7.37 (t, J ¼ 7.8 Hz,1H), 7.25e7.14 (m, 2H),
7.06 (t, J ¼ 7.2 Hz, 1H), 6.99 (d, J ¼ 8.0 Hz, 1H), 6.04 (s, 1H); 13C NMR
(101 MHz, DMSO‑d6)
d 150.4, 136.9, 136.3, 131.5, 129.0, 128.4, 127.5,
127.2, 125.6, 124.9, 122.9, 121.5, 118.2, 100.6.
3.4. 1-(p-Tolylthio)naphthalen-2-amine [3b] [13a]
The crude mixture was purified via column chromatography
using ethyl acetate/petroleum ether (1 : 30) as eluent to give the
product 3b as a red solid (72.4 mg, 95%); mp 112.4e117.0 ꢀC; 1H
NMR (400 MHz, DMSO‑d6)
d
8.06 (d, J ¼ 8.5 Hz, 1H), 7.77 (d,
J ¼ 8.8 Hz, 1H), 7.71 (d, J ¼ 7.7 Hz, 1H), 7.37 (td, J ¼ 7.5, 1.3 Hz, 1H),
Scheme 5. Proposed reaction mechanism.
7.22e7.14 (m, 2H), 7.00 (d, J ¼ 8.1 Hz, 2H), 6.90 (d, J ¼ 8.2 Hz, 2H),
5.99 (s, 2H), 2.18 (s, 3H); 13C NMR (101 MHz, DMSO‑d6)
d 150.2,
136.3, 134.3, 133.3, 131.4, 129.6, 128.4, 127.4, 127.2, 125.9, 123.0,
121.4, 118.2, 101.4, 39.5, 20.4.
Based on above investigation and analysis, a plausible mecha-
nism is outlined in Scheme 5. The reaction is initiated by
PhSO2NHNH2, which can be transformed by TBAI to form the in-
termediate sulfinothioyldibenzene 2aa and the intermediate S-
phenyl benzenesulfonothioate 2 ab. Next, the sulfenylation of
arenes is mainly achieved through the following two routes: (1)
Path 1 (major): Iodothiobenzene formed by the reaction of 2aa
3.5. 1-((4-(tert-Butyl)phenyl)thio)naphthalen-2-amine [3c]
The crude mixture was purified via column chromatography
using ethyl acetate/petroleum ether (1 : 30) as eluent to give the
product 3c as a red solid (85.5 mg, 93%); mp 120.2e122.4 ꢀC; 1H
with I2 undergoes electrophilic substitution with b-naphthylamine
NMR (400 MHz, DMSO‑d6)
d
8.08 (d, J ¼ 8.4 Hz, 1H), 7.78 (d,
to give intermediate I. The intermediate I loses HI to provide final
product 3a; (2) Path 2 (minor): the intermediate 2 ab as an elec-
trophile reacted with 1a to form the desired product 3a. The ben-
zenesulfinic acid generated can be converted into 2 ab in the
presence of TBAI. Finally, a sulfenylation cycle was established.
J ¼ 8.9 Hz, 1H), 7.72 (d, J ¼ 7.7 Hz, 1H), 7.37 (td, J ¼ 7.7, 1.2 Hz, 1H),
7.24e7.14 (m, 4H), 6.91 (d, J ¼ 8.5 Hz, 2H), 6.00 (s, 2H), 1.18 (s, 3H);
13C NMR (101 MHz, DMSO‑d6)
d 150.3, 147.6, 136.4, 133.4, 131.4,
128.4, 127.4, 127.2, 125.9, 125.5, 123.0, 121.4, 118.1, 101.2, 39.5, 34.0,
31.0; HRMS (ESI): m/z calcd for C20H21NS (M þ Na)þ: 330.1287,
found: 330.1281.
3. Experimental section
3.6. 1-((4-Methoxyphenyl)thio)naphthalen-2-amine [3d] [13a]
3.1. Materials and instruments
The crude mixture was purified via column chromatography
using ethyl acetate/petroleum ether (1 : 30) as eluent to give the
product 3d as a red solid (81.0 mg, 96%); mp 101.8e105.5 ꢀC; 1H
Unless otherwise noted, all synthetic steps were performed
under air atmosphere using Schlenk tubes. The materials obtained
from commercial sources were used without further purification.
Melting points were determined with a fusiometer and are not
corrected. 1H NMR and 13C NMR spectra were recorded on a Bruker
Advance III HD 400 MHz spectrometer in CDCl3 or DMSO‑d6 solu-
NMR (400 MHz, DMSO‑d6)
d
8.11 (d, J ¼ 8.5 Hz, 1H), 7.75 (d,
J ¼ 8.9 Hz, 1H), 7.71 (d, J ¼ 7.7 Hz, 1H), 7.41e7.36 (m, 1H), 7.16 (d,
J ¼ 8.9 Hz, 1H), 6.99 (d, J ¼ 8.9 Hz, 1H), 6.80 (d, J ¼ 8.9 Hz, 1H), 6.01
(s, 1H), 3.65 (s, 1H); 13C NMR (101 MHz, DMSO‑d6)
d 157.5, 150.0,
136.2, 131.2, 128.4, 128.0, 127.4, 127.3, 127.2, 123.0, 121.4, 118.1, 114.8,
102.6, 55.1, 39.5.
tion. All chemical shifts were reported in ppm (d) relative to the
internal standard TMS (0 ppm). High resolution mass spectra
(HRMS) were acquired in electrospray ionization (ESI) or
atmospheric-pressure chemical ionization (APCI) modes using a
TOF mass analyzer.
3.7. 1-((4-Fluorophenyl)thio)naphthalen-2-amine [3e] [22]
The crude mixture was purified via column chromatography
using ethyl acetate/petroleum ether (1 : 30) as eluent to give the
product 3e as a red solid (80.0 mg, 99%); mp 90.6e92.8 ꢀC; 1H NMR
3.2. General procedure for TBAI-mediated direct sulfenylation of
arenes with arylsulfonyl hydrazides
(400 MHz, DMSO‑d6)
d
8.05 (d, J ¼ 8.5 Hz, 1H), 7.78 (d, J ¼ 8.9 Hz,
1H), 7.72 (d, J ¼ 7.7 Hz, 1H), 7.39 (td, J ¼ 8.0 Hz, 1.3 Hz, 1H), 7.21e7.14
(m, 2H), 7.09e6.99 (m, 4H), 6.06 (s, 2H); 13C NMR (101 MHz,
A
mixture of arene (0.3 mmol), arylsulfonyl hydrazide
DMSO‑d6) d 161.6, 159.0,150.3,136.2,132.4,131.6,128.5,127.8,127.2,
(0.6 mmol), TBAI (0.6 mmol), and DPDME (0.5 mL) were added into
a Schlenk tube. The solution was stirred and heated to 100 ꢀC for
12 h in air. After completion of the reaction, the mixture was
quenched with the saturated solution of NaCl (5 mL) and extracted
with CH2Cl2 (10 mL ꢁ 3). The combined CH2Cl2 extracts were dried
over anhydrous Na2SO4, filtered and concentrated under reduced
pressure. The crude residue was purified by flash column chro-
matography on silica gel using PE/EtOAc as the eluent.
122.8, 121.5, 118.2, 116.1, 115.9, 101.1, 39.5.
3.8. 1-((4-Chlorophenyl)thio)naphthalen-2-amine [3f] [13a]
The crude mixture was purified via column chromatography
using ethyl acetate/petroleum ether (1 : 30) as eluent to give the
product 3f as a red solid (84.8 mg, 99%); mp 123.1e125.8 ꢀC; 1H
NMR (400 MHz, DMSO‑d6)
d
8.01 (d, J ¼ 8.4 Hz, 1H), 7.79 (d,
5

W. Yueting, L. Yali, H. Jing et al.
Tetrahedron xxx (xxxx) xxx
J ¼ 8.9 Hz, 1H), 7.72 (d, J ¼ 7.9 Hz, 1H), 7.38 (t, J ¼ 7.6 Hz, 1H),
7.28e7.11 (m, 4H), 6.97 (d, J ¼ 8.6 Hz, 2H), 6.07 (s, 2H); 13C NMR
138.2, 136.7, 136.3, 131.5, 128.9, 128.4, 127.4, 127.2, 126.1, 125.8,
122.9, 122.6, 121.4, 118.2, 100.8, 39.5, 21.0.
(101 MHz, DMSO‑d6)
d 150.5, 136.2, 136.1, 129.5, 128.9, 128.5, 127.6,
127.2, 122.7, 121.5, 118.2, 100.0, 39.5.
3.14. 1-((3-Bromophenyl)thio)naphthalen-2-amine [3l]
3.9. 1-((4-Bromophenyl)thio)naphthalen-2-amine [3g] [13a]
The crude mixture was purified via column chromatography
using ethyl acetate/petroleum ether (1 : 30) as eluent to give the
product 3l as a red liquid (98.0 mg, 99%); 1H NMR (400 MHz,
The crude mixture was purified via column chromatography
using ethyl acetate/petroleum ether (1 : 30) as eluent to give the
product 3g as a red solid (97.9 mg, 99%); mp 107.5e109.5 ꢀC; 1H
DMSO‑d6)
d
8.00 (d, J ¼ 8.6 Hz, 1H), 7.81 (d, J ¼ 8.8 Hz, 1H), 7.73 (d,
J ¼ 7.7 Hz, 1H), 7.39 (td, J ¼ 7.9, 1.3 Hz, 1H), 7.26 (dq, J ¼ 7.9, 0.9 Hz,
NMR (400 MHz, DMSO‑d6)
d
8.00 (d, J ¼ 8.3 Hz, 1H), 7.80 (d,
1H), 7.23e7.12 (m, 3H), 7.07 (t, J ¼ 1.8 Hz, 1H), 6.98 (dq, J ¼ 7.9,
J ¼ 8.9 Hz, 1H), 7.73 (d, J ¼ 7.5 Hz, 1H), 7.40 (td, J ¼ 3.5, 1.5 Hz, 2H),
7.37 (d, J ¼ 2.0 Hz, 1H), 7.23e7.17 (m, 2H), 6.92 (d, J ¼ 2.0 Hz,1H),
6.90 (d, J ¼ 2.0 Hz, 1H), 6.07 (s, 2H); 13C NMR (101 MHz, DMSO‑d6)
1.0 Hz, 1H), 6.10 (s, 2H); 13C NMR (101 MHz, DMSO‑d6)
d 150.6,
140.0,136.1,132.0,130.9,128.5,127.7, 127.7, 127.4, 127.2, 122.6,122.2,
121.6, 118.2, 99.3, 39.5; HRMS (ESI): m/z calcd for C16H12BrNS
(M þ Na)þ: 351.9766, found: 351.9772.
d
150.5,131.8, 128.5,127.6,127.5, 127.2,122.6,121.5, 118.2,117.7, 99.8,
39.5.
3.15. 1-((3-(Trifluoromethyl)phenyl)thio)naphthalen-2-amine [3m]
3.10. 1-((4-Nitrophenyl)thio)naphthalen-2-amine [3h]
The crude mixture was purified via column chromatography
using ethyl acetate/petroleum ether (1 : 30) as eluent to give the
product 3m as a red liquid (93.9 mg, 98%); 1H NMR (400 MHz,
The crude mixture was purified via column chromatography
using ethyl acetate/petroleum ether (1 : 30) as eluent to give the
product 3h as
a
bright yellow solid (88.0 mg, 99%);
DMSO‑d6)
J ¼ 7.8 Hz, 1H), 7.39 (dd, J ¼ 10.0, 7.1 Hz, 2H), 7.33 (s, 1H), 7.27e7.14
(m, 1H), 6.14 (s, 1H); 13C NMR (101 MHz, DMSO‑d6)
150.7, 139.1,
136.2, 132.1, 130.0, 129.7, 129.1, 128.5, 127.7, 127.2, 125.2, 122.5, 121.7,
121.6, 121.5, 118.3, 99.0, 39.5; HRMS (ESI): m/z calcd for C17H21F3NS
(M þ H)þ: 320.0715, found: 320.0718.
d
8.02 (d, J ¼ 8.5 Hz, 1H), 7.82 (d, J ¼ 8.9 Hz, 1H), 7.74 (d,
mp160e160.5 ꢀC; 1H NMR (400 MHz, DMSO‑d6)
d
8.06 (d, J ¼ 9.0 Hz,
2H), 7.91 (d, J ¼ 8.5 Hz,1H), 7.84 (d, J ¼ 8.9 Hz,1H), 7.75 (d, J ¼ 7.8 Hz,
1H), 7.44e7.33 (td, J ¼ 7.7, 1.2 Hz, 1H), 7.27e7.17 (m, 2H), 7.13 (d,
d
J ¼ 9.0 Hz, 2H), 6.15 (s, 2H). 13C NMR (101 MHz, DMSO‑d6)
d 150.9,
147.5, 144.6, 136.0, 132.4, 128.6, 127.9, 127.2, 125.5, 124.1, 122.2,
121.8, 118.4, 97.7, 39.5; HRMS (ESI): m/z calcd for C20H21NS
(M þ Na)þ: 297.0692, found: 297.0691.
3.16. 1-((2,5-Dimethylphenyl)thio)naphthalen-2-amine [3n] [13a]
3.11. 1-((4-(Trifluoromethyl)phenyl)thio)naphthalen-2-amine [3i]
[13a]
The crude mixture was purified via column chromatography
using ethyl acetate/petroleum ether (1 : 30) as eluent to give the
product 3n as a red solid (71.0 mg, 92%); mp 62.7e65.1 ꢀC; 1H NMR
The crude mixture was purified via column chromatography
using ethyl acetate/petroleum ether (1 : 30) as eluent to give the
product 3i as a red solid (92.7 mg, 97%); mp 120.6e121.9 ꢀC; 1H
(400 MHz, DMSO‑d6)
d
7.99 (d, J ¼ 8.5 Hz, 1H), 7.80 (d, J ¼ 8.9 Hz,
1H), 7.73 (d, J ¼ 7.7 Hz, 1H), 7.37 (td, J ¼ 7.7, 1.3 Hz, 1H), 7.22 (d,
J ¼ 8.9 Hz, 1H), 7.18 (td, J ¼ 7.4, 1.1 Hz, 1H), 7.08 (d, J ¼ 7.6 Hz, 1H),
6.78 (d, J ¼ 8.3 Hz, 1H), 6.18 (s, 1H), 5.96 (s, 2H), 2.45 (s, 3H), 1.91 (s,
NMR (400 MHz, DMSO‑d6)
d
8.00 (d, J ¼ 8.4 Hz, 1H), 7.82 (d,
J ¼ 8.9 Hz, 1H), 7.74 (d, J ¼ 7.7 Hz, 1H), 7.46e7.36 (m, 3H), 7.31 (s,
3H); 13C NMR (101 MHz, DMSO‑d6)
d 150.5,136.4,135.4,135.2,131.5,
1H), 7.25e7.11 (m, 3H), 6.12 (s, 2H); 13C NMR (101 MHz, DMSO‑d6)
130.0, 128.4, 127.4, 127.3, 125.3, 124.0, 123.0, 121.5, 118.2, 100.0, 39.5,
20.7, 19.2.
d
150.7, 139.1, 136.2, 132.1, 130.0, 129.2, 128.6, 127.8, 127.2, 125.2,
122.5, 121.7, 121.6, 121.5, 118.3, 98.9, 39.5.
3.17. 1-(Naphthalen-2-ylthio)naphthalen-2-amine [3o]
3.12. 1-((4-(Trifluoromethoxy)phenyl)thio)naphthalen-2-amine
[3j]
The crude mixture was purified via column chromatography
using ethyl acetate/petroleum ether (1 : 30) as eluent to give the
product 3o as a red solid (86.6 mg, 96%); mp 120.7e122.3 ꢀC; 1H
The crude mixture was purified via column chromatography
using ethyl acetate/petroleum ether (1 : 30) as eluent to give the
product 3j as a red liquid (94.4 mg, 94%); 1H NMR (400 MHz,
NMR (400 MHz, DMSO‑d6)
d
8.10 (d, J ¼ 8.4 Hz, 1H), 7.83 (d,
J ¼ 8.9 Hz, 1H), 7.76 (t, J ¼ 8.2 Hz, 3H), 7.66e7.57 (d, J ¼ 7.9 Hz, 1H),
7.46 (s, 1H), 7.43e7.33 (m, 3H), 7.26 (d, J ¼ 8.9 Hz, 1H), 7.17 (td,
J ¼ 8.8, 4.2 Hz, 2H), 6.09 (s, 2H); 13C NMR (101 MHz, DMSO‑d6)
DMSO‑d6)
d
8.04 (d, J ¼ 8.5 Hz, 1H), 7.80 (d, J ¼ 8.9 Hz, 1H), 7.73 (d,
J ¼ 7.9 Hz, 1H), 7.39 (t, J ¼ 7.6 Hz, 1H), 7.25e7.20 (m, 2H), 7.20e7.15
(m, 2H), 7.06 (d, J ¼ 8.8 Hz, 2H), 6.10 (s, 2H); 13C NMR (101 MHz,
d
150.5, 136.3, 134.7, 133.3, 131.7, 130.9, 128.5, 128.5, 127.6, 127.5,
DMSO‑d6)
d
150.6,145.8, 136.6, 136.3, 131.9, 128.5, 127.7, 127.3, 127.0,
127.3, 126.6, 125.2, 124.5, 123.0, 122.9, 121.5, 118.3, 100.5, 39.5;
HRMS (ESI): m/z calcd for C20H15NS (M þ H)þ: 302.0998, found:
302.0995.
122.6, 121.9, 121.6, 118.3, 39.5; 19F NMR (376 MHz, DMSO‑d6)
d
ꢂ57.1; HRMS (ESI): m/z calcd for C17H12F3NOS (M þ H)þ:
336.0664, found: 336.0667.
3.18. 6-Bromo-1-(phenylthio)naphthalen-2-amine [3p]
3.13. 1-(m-Tolylthio)naphthalen-2-amine [3k] [19]
The crude mixture was purified via column chromatography
using ethyl acetate/petroleum ether (1 : 30) as eluent to give the
product 3p as a reddish solid (93.9 mg, 95%); mp 122.4e123.0 ꢀC;
The crude mixture was purified via column chromatography
using ethyl acetate/petroleum ether (1 : 30) as eluent to give the
product 3k as a red solid (74.8 mg, 94%); mp 88.8e89.9 ꢀC; 1H NMR
1H NMR (400 MHz, DMSO‑d6)
d
7.96 (dd, J ¼ 12.0, 5.5 Hz, 1H), 7.77
(400 MHz, DMSO‑d6)
1H), 7.72 (d, J ¼ 7.7 Hz,1H), 7.37 (td, J ¼ 7.7,1.3 Hz,1H), 7.22e7.13 (m,
2H), 7.05 (t, J ¼ 7.9 Hz, 1H), 6.92e6.84 (m, 2H), 6.69 (d, J ¼ 7.9 Hz,
d
8.04 (d, J ¼ 8.5 Hz, 1H), 7.78 (d, J ¼ 8.9 Hz,
(d, J ¼ 8.9 Hz, 1H), 7.48 (dd, J ¼ 9.0, 2.1 Hz, 1H), 7.28e7.15 (m, dd,
J ¼ 17,5, 8.4 Hz, 3H), 7.08 (tt, J ¼ 7.7, 1,1 Hz, 1H), 7.02e6.86 (m, 2H),
6.15 (s, 2H); 13C NMR (101 MHz, DMSO‑d6)
d 150.9, 136.5, 135.1,
1H), 5.99 (s, 2H), 2.16 (s, 3H); 13C NMR (101 MHz, DMSO‑d6)
d
150.4,
130.7, 130.2,130.1,129.1,128.4,125.6,125.3, 125.1, 119.4,114.0, 100.6,
6

W. Yueting, L. Yali, H. Jing et al.
Tetrahedron xxx (xxxx) xxx
39.5; HRMS (ESI): m/z calcd for C16H12BrNS (M þ H)þ: 329.9947,
3.24. 4-(Phenylthio)aniline [4a] [24]
found: 329.9951.
The crude mixture was purified via column chromatography
using ethyl acetate/petroleum ether (1 : 10) as eluent to give the
product 4a as an orange solid (57.3 mg, 94%); mp 83.4e84.5 ꢀC; 1H
3.19. 2,4-Bis(phenylthio)naphthalen-1-amine [3q]
NMR (400 MHz, CDCl3)
d
7.36e7.28 (dt, J ¼ 8.6, 2.8 Hz, 2H),
The crude mixture was purified via column chromatography
using ethyl acetate/petroleum ether (1 : 30) as eluent to give the
product 3q as a white solid (107.8 mg, 94%); mp 100e101 ꢀC; 1H
7.24e7.19 (t, J ¼ 7.5 Hz, 2H), 7.17e7.07 (m, 3H), 6.72e6.64 (dt,
J ¼ 4.3, 2.4 Hz, 2H), 3.79 (s, 2H); 13C NMR (101 MHz, CDCl3)
d 147.1,
139.8, 136.2, 128.9, 127.4, 125.4, 120.6, 116.0, 77.2.
NMR (400 MHz, CDCl3)
d
8.38 (d, J ¼ 9.3 Hz, 1H), 7.97 (s, 1H), 7.79 (d,
J ¼ 7.8 Hz, 1H), 7.54e7.42 (m, 2H), 7.2e7.15 (t, J ¼ 7.5 Hz, 2H),
3.25. 4-(p-Tolylthio)aniline [4b] [25]
7.1e7.06 (m, 5H), 7.03 (t, J ¼ 7.5 Hz, 3H), 5.20 (s, 2H); 13C NMR
(101 MHz, CDCl3)
d 147.8, 143.5, 139.2, 136.6, 136.1, 129.2, 128.9,
The crude mixture was purified via column chromatography
using ethyl acetate/petroleum ether (1 : 10) as eluent to give the
product 4b as a yellow liquid (61.4 mg, 95%); 1H NMR (400 MHz,
128.3,127.2,126.6,126.5,126.0,125.7,125.1,123.9,122.0,117.3,108.1,
77.2; HRMS (ESI): m/z calcd for C22H17NS2 (M þ H)þ: 360.0877,
found: 360.0870.
CDCl3)
d
7.26 (dt, J ¼ 6.5, 2.3 Hz, 2H), 7.07 (d, J ¼ 8.3 Hz, 2H), 7.02 (d,
J ¼ 8.2 Hz, 2H), 6.68e6.53 (dt, J ¼ 8.6, 2.3 Hz, 2H), 2.27 (s, 3H); 13
C
3.20. 2,4-Bis(p-tolylthio)naphthalen-1-amine [3r]
NMR (101 MHz, CDCl3)
21.0.
d 146.8, 135.4, 129.7, 128.2, 121.6, 115.9, 77.2,
The crude mixture was purified via column chromatography
using ethyl acetate/petroleum ether (1 : 30) as eluent to give the
product 3r as a white solid (110.4 mg, 95%); mp 101e102 ꢀC; 1H
3.26. 4-((4-Fluorophenyl)thio)aniline [4c] [25]
NMR (400 MHz, CDCl3)
d
8.38 (d, J ¼ 9.0 Hz, 1H), 7.93 (s, 1H), 7.76 (d,
The crude mixture was purified via column chromatography
using ethyl acetate/petroleum ether (1 : 10) as eluent to give the
product 4c as an orange liquid (59.8 mg, 91%); 1H NMR (400 MHz,
J ¼ 8.0 Hz, 1H), 7.51e7.46 (t, J ¼ 6.8 Hz, 1H), 7.43 (t, J ¼ 7.5 Hz, 1H),
7.05e6.97 (m, 4H), 6.95 (t, J ¼ 6.5 Hz, 4H), 5.14 (s, 2H), 2.24 (s, 3H),
2.21 (s, 3H); 13C NMR (101 MHz, CDCl3)
d 147.3, 142.8, 135.8, 135.7,
CDCl3)
2H), 6.98e6.89 (dt, J ¼ 8.6, 2.4 Hz, 2H), 6.71e6.64 (m, 2H), 3.82 (s,
2H); 13C NMR (101 MHz, CDCl3)
162.6, 160.2, 146.8, 135.5, 134.3,
130.1, 130.0, 121.6, 116.1, 115.9, 77.2; 19F NMR (376 MHz, CDCl3)
ꢂ117.1.
d
7.30e7.25 (dt, J ¼ 8.5, 2.4 Hz, 2H), 7.14 (tt, J ¼ 8.7, 2.4 Hz,
135.4, 135.0, 132.9, 130.0, 129.7, 128.1, 127.2, 127.0, 125.9, 123.9,
122.0, 118.0, 109.0, 77.2, 21.0, 21.0; HRMS (ESI): m/z calcd for
d
C
24H21NS2 (M þ Na)þ: 410.1007, found: 410.1004.
d
3.21. 2,4-Bis((4-chlorophenyl)thio)naphthalen-1-amine [3s]
3.27. 5-(Phenylthio)-[1,10-biphenyl]-2-amine [4d]
The crude mixture was purified via column chromatography
using ethyl acetate/petroleum ether (1 : 30) as eluent to give the
product 3r as a white solid (124.6 mg, 97%); mp 98e99 ꢀC; 1H NMR
The crude mixture was purified via column chromatography
using ethyl acetate/petroleum ether (1 : 30) as eluent to give the
product 4d as a white solid (74.1 mg, 89%), mp 83.4e84.5 ꢀC; 1H
(400 MHz, CDCl3)
d
8.32 (d, J ¼ 8.7 Hz, 1H), 7.92 (s, 1H), 7.81 (d,
NMR (400 MHz, DMSO‑d6)
d
7.27e7.21 (t, J ¼ 7.7 Hz, 2H), 7.18 (d,
J ¼ 8.9 Hz, 1H), 7.58e7.47 (m, 2H), 7.15 (d, J ¼ 8.6 Hz, 2H), 7.09 (d,
J ¼ 2.0 Hz, 1H), 7.17 (d, J ¼ 2.1 Hz, 1H), 7.12e7.06 (tt, J ¼ 7.7, 1.3 Hz,
1H), 7.01 (dd, J ¼ 8.0, 1.6 Hz, 2H), 6.64e6.59 (dt, J ¼ 8.6, 2.4 Hz, 2H),
J ¼ 8.6 Hz, 2H), 7.00 (d, J ¼ 8.7 Hz, 2H), 6.93 (d, J ¼ 8.6 Hz, 2H), 5.24
(s, 2H); 13C NMR (101 MHz, CDCl3)
d 148.0, 143.2, 137.7, 135.9, 135.1,
5.52 (s, 2H); 13C NMR (101 MHz, DMSO‑d6)
d 146.3, 139.5, 138.5,
131.7, 131.0, 129.3, 129.0,128.6,127.9, 127.8, 127.0, 126.2,123.9,122.1,
117.0, 107.6, 77.2; HRMS (ESI): m/z calcd for C22H15Cl2NS2 (M þ H)þ:
428.0098, found: 428.0093.
136.7, 135.1, 129.0,128.9,128.5, 127.1, 126.7, 126.5,125.2,116.4, 116.3,
39.5; HRMS (APCI): m/z calcd for C18H15NS (M þ H)þ: 278.0998,
found: 278.0995.
3.22. 4-((4-Nitrophenyl)thio)naphthalen-1-amine [3t]
3.28. 5-(p-Tolylthio)-[1,10-biphenyl]-2-amine [4e]
The crude mixture was purified via column chromatography
using ethyl acetate/petroleum ether (1 : 10) as eluent to give the
product 3t as a yellow liquid (79.9 mg, 90%); 1H NMR (400 MHz,
The crude mixture was purified via column chromatography
using ethyl acetate/petroleum ether (1 : 30) as eluent to give the
product 4e as a yellow liquid (74.1 mg, 85%), 1H NMR (400 MHz,
CDCl3)
2H), 7.45 (d, J ¼ 8.5 Hz,1H), 7.31 (d, J ¼ 8.5 Hz,1H), 7.11 (d, J ¼ 8.9 Hz,
2H), 5.01 (s, 2H); 13C NMR (101 MHz, CDCl3)
147.4, 146.4, 145.4,
d
8.03 (d, J ¼ 8.9 Hz, 2H), 7.90e7.78 (m, 2H), 7.63e7.49 (m,
CDCl3)
d
7.45 (d, J ¼ 4.4 Hz, 4H), 7.36 (q, J ¼ 4.5 Hz, 1H), 7.31e7.25
(m, 2H), 7.15 (d, J ¼ 8.1 Hz, 2H), 7.06 (d, J ¼ 8.3 Hz, 2H), 6.76 (d,
d
J ¼ 8.1 Hz, 1H), 2.30 (s, 3H); 13C NMR (101 MHz, CDCl3)
d 143.6,
135.6, 133.2, 128.9, 127.8, 125.9, 125.6, 124.2, 123.2, 121.7, 119.2,
105.0, 77.2; HRMS (ESI): m/z calcd for C16H12N2O2S (M þ H)þ:
297.0694, found: 297.0690.
138.6, 136.1, 135.7, 135.4, 134.3, 129.8, 129.1, 129.0, 128.6, 127.6,
122.3, 116.6, 77.2, 21.1. HRMS (APCI): m/z calcd for C19H17NS
(M þ H)þ: 292.1155, found: 292.1149.
3.23. 4-(Phenylthio)naphthalen-1-amine [3u] [23]
3.29. 5-((4-Fluorophenyl)thio)-[1,10-biphenyl]-2-amine [4f]
The crude mixture was purified via column chromatography
using ethyl acetate/petroleum ether (1 : 8) as eluent to give the
product 3u as a red liquid (43.7 mg, 58%); 1H NMR (400 MHz,
The crude mixture was purified via column chromatography
using ethyl acetate/petroleum ether (1 : 10) as eluent to give the
product 4f as a brown liquid (73.4 mg, 83%); 1H NMR (400 MHz,
CDCl3)
d
7.83 (t, J ¼ 9.7 Hz, 2H), 7.52 (m, 3H), 7.28 (d, J ¼ 8.5 Hz, 1H),
CDCl3)
7.22e7.16 (m, 2H), 6.98e6.88 (m, 2H), 6.73 (d, J ¼ 8.1 Hz, 1H), 3.87
(s, 2H); 13C NMR (101 MHz, CDCl3)
162.6, 160.2, 144.1, 138.5, 136.2,
134.4, 134.2 (d, J ¼ 3.2 Hz), 130.2, 129.1, 129.0, 128.6, 127.7, 121.7,
d 7.45e7.40 (m, 4H), 7.38e7.32 (m, 1H), 7.28e7.23 (m, 2H),
7.21 (t, J ¼ 7.5 Hz, 2H), 7.13e7.06 (m, 3H), 5.06 (s, 2H); 13C NMR
(101 MHz, CDCl3)
126.5, 125.5, 123.3, 121.7, 118.7, 77.2.
d
145.9, 137.2, 135.2, 133.8, 129.1, 128.8, 127.1,
d
7

W. Yueting, L. Yali, H. Jing et al.
Tetrahedron xxx (xxxx) xxx
116.5, 116.2, 115.9; 19F NMR (376 MHz, CDCl3)
d
ꢂ116.9. HRMS (ESI):
121.2, 119.6, 111.8, 102.6.
m/z calcd for C18H14FNS (M þ H)þ: 296.0904, found: 296.0901.
3.30. 1,4-Bis(phenylthio)naphthalene-2,3-diamine [4g]
3.36. 3-((4-Nitrophenyl)thio)-1H-indole [5d] [21d]
The crude mixture was purified via column chromatography
using ethyl acetate/petroleum ether (1 : 10) as eluent to give the
product 5d as a yellow solid (80.1 mg, 99%), mp 121.2e121.7 ꢀC; 1H
The crude mixture was purified via column chromatography
using ethyl acetate/petroleum ether (1 : 30) as eluent to give the
product 4g as a white solid (66.2 mg, 59%), mp 110e112 ꢀC; 1H NMR
NMR (400 MHz, CDCl3)
(m, 3H), 7.36e7.26 (m, 1H), 7.23e7.15 (m, 1H), 7.15e7.08 (m, 2H);
13C NMR (101 MHz, CDCl3)
150.0, 145.0, 136.7, 131.4, 128.5, 125.2,
d 8.71 (s, 1H), 8.02e7.96 (m, 2H), 7.58e7.45
(400 MHz, CDCl3)
3.3 Hz, 1H), 7.20 (t, J ¼ 7.5 Hz, 1H), 7.10 (dd, J ¼ 16.3, 7.8 Hz, 2H), 4.68
(s, 1H); 13C NMR (101 MHz, CDCl3)
140.7, 136.3, 131.1, 129.2, 126.3,
d
8.35 (dd, J ¼ 6.3, 3.3 Hz, 1H), 7.34 (dd, J ¼ 6.4,
d
d
124.0, 123.6, 121.5, 119.3, 112.1, 100.2.
125.5,125.2,124.9,110.8, 77.2; HRMS (ESI): m/z calcd for C22H18N2S2
(M þ H)þ: 375.0986, found: 375.0980.
3.37. 2,5-Bis(phenylthio)-1H-pyrrole [5e] [21d]
3.31. 2-Methoxy-4-(phenylthio)aniline [4h] [25]
The crude mixture was purified via column chromatography
using ethyl acetate/petroleum ether (1 : 100) as eluent to give the
product 5e as a light gray liquid (77.1 mg, 92%); 1H NMR (400 MHz,
The crude mixture was purified via column chromatography
using ethyl acetate/petroleum ether (1 : 10) as eluent to give the
product 4h as a gray liquid (56.2 mg, 81%); 1H NMR (400 MHz,
DMSO‑d6) d 12.21 (s,1H), 7.31 (s,1H), 7.30 (s, 2H), 7.28 (s,1H), 7.15 (t,
J ¼ 7.4 Hz, 2H), 7.05 (d, J ¼ 1.2 Hz, 2H), 7.03 (d, J ¼ 1.0 Hz, 2H), 6.58
(d, J ¼ 2.4 Hz, 2H); 13C NMR (101 MHz, DMSO‑d6)
d
138.5, 129.1,
CDCl3)
d
7.25e7.18 (m, 2H), 7.15e7.07 (m, 3H), 7.01 (dd, J ¼ 8.0,
1.9 Hz, 1H), 6.96 (d, J ¼ 1.8 Hz, 1H), 6.71 (d, J ¼ 8.0 Hz, 1H), 3.82 (s,
125.7, 125.6, 119.5, 119.2, 39.5.
3H); 13C NMR (101 MHz, CDCl3)
125.2, 116.8, 115.2, 77.2, 55.7.
d 147.6, 139.9, 137.1, 128.9, 128.4,
3.38. 1-Methyl-2,5-bis(phenylthio)-1H-pyrrole [5f]
3.32. 2,5-Dimethyl-4-(phenylthio)aniline [4i] [26]
The crude mixture was purified via column chromatography
using ethyl acetate/petroleum ether (1 : 100) as eluent to give the
product 5f as a colourless liquid (77.7 mg, 88%); 1H NMR (400 MHz,
The crude mixture was purified via column chromatography
using ethyl acetate/petroleum ether (1 : 10) as eluent to give the
product 4i as a gray liquid (68.4 mg, 99%); 1H NMR (400 MHz,
CDCl3)
d
7.24 (dd, J ¼ 12.5, 4.8 Hz, 1H), 7.12 (t, J ¼ 7.4 Hz, 1H), 6.99 (t,
J ¼ 7.5 Hz, 1H), 6.69 (s, 1H), 3.50 (s, 1H); 13C NMR (101 MHz, CDCl3)
CDCl3)
1H), 7.01e6.97 (m, 2H), 6.62 (s, 1H), 3.72 (s, 2H), 2.26 (s, 3H), 2.11 (s,
3H); 13C NMR (101 MHz, CDCl3)
145.9, 141.7, 139.8, 138.9, 128.9,
d
7.24 (s, 1H), 7.20e7.14 (m, 2H), 7.08e7.02 (tt, J ¼ 7.4, 1.4 Hz,
d
138.1, 129.2, 125.9, 125.7, 122.2, 119.5, 77.2, 31.5; HRMS (ESI): m/z
calcd for C17H15NS2 (M þ H)þ: 298.0719, found: 298.0724.
d
126.0, 124.7, 120.9, 118.7, 117.1, 77.2, 20.5, 16.8.
3.39. 2,5-Dimethyl-3,4-bis(phenylthio)-1H-pyrrole [5g] [21d]
3.33. 3-(Phenylthio)-1H-indole [5a] [21d]
The crude mixture was purified via column chromatography
using ethyl acetate/petroleum ether (1 : 100) as eluent to give the
product 5g as a white solid (76.6 mg, 82%), mp 89.7e91.5 ꢀC; 1H
The crude mixture was purified via column chromatography
using ethyl acetate/petroleum ether (1 : 10) as eluent to give the
product 5a as a white solid (67.6 mg, 98%), mp 121.3e122.6 ꢀC; 1H
NMR (400 MHz, DMSO‑d6)
7.04e6.97 (tt, J ¼ 7.4, 1.3 Hz, 2H), 6.89 (dd, J ¼ 8.4, 1.1 Hz, 4H), 2.22
(s, 6H); 13C NMR (101 MHz, DMSO‑d6)
139.7, 133.4, 128.6, 124.8,
d
11.59 (s, 1H), 7.14 (t, J ¼ 7.7 Hz, 4H),
NMR (400 MHz, CDCl3)
d
8.33 (s, 1H), 7.61 (d, J ¼ 8.0 Hz, 1H),
d
7.46e7.38 (m, 2H), 7.29e7.22 (m, 1H), 7.15 (td, J ¼ 7.8, 3.2 Hz, 3H),
7.10 (d, J ¼ 6.8 Hz, 2H), 7.04 (t, J ¼ 7.2 Hz, 1H); 13C NMR (101 MHz,
124.2, 107.5, 39.5, 11.6; HRMS (ESI): m/z calcd for C18H17NS2
(M þ Na)þ: 334.0695, found: 334.0700.
CDCl3)
d 139.3, 136.6, 130.8, 129.2, 128.8, 126.0, 124.9, 123.2, 121.0,
119.8, 111.7, 102.9.
3.40. 3-(Phenylthio)imidaz o [1,2-a] pyridine [5h] [27]
3.34. 3-(p-Tolylthio)-1H-indole [5b] [21d]
The crude mixture was purified via column chromatography
using ethyl acetate/petroleum ether (1 : 5) as eluent to give the
product 5h as a white solid (61.1 mg, 90%); mp 97e99 ꢀC; 1H NMR
The crude mixture was purified via column chromatography
using ethyl acetate/petroleum ether (1 : 10) as eluent to give the
product 5b as a white solid (68.7 mg, 96%), mp 137.6e138.8 ꢀC; 1H
(400 MHz, CDCl3)
d
8.21 (dt, J ¼ 6.8, 1.1 Hz, 1H), 7.99 (s, 1H), 7.71 (dt,
J ¼ 9.1, 1.0 Hz,1H), 7.31 (m,1H), 7.23e7.17 (m, 2H), 7.15e7.10 (m,1H),
NMR (400 MHz, CDCl3)
d
8.35 (s, 1H), 7.61 (d, J ¼ 8.0 Hz, 1H), 7.47 (d,
6.99 (dd, J ¼ 7.1, 1.4 Hz, 2H), 6.87 (td, J ¼ 6.8, 1.0 Hz, 1H), 13C NMR
J ¼ 2.0 Hz, 1H), 7.42 (d, J ¼ 8.0 Hz, 1H), 7.28e7.23 (m, 2H), 7.18e7.13
(m, 1H), 7.03 (d, J ¼ 8.4 Hz, 2H), 6.97 (d, J ¼ 8.0 Hz, 2H), 2.24 (s, 3H);
(101 MHz, CDCl3)
d 148.2, 142.5, 135.3, 129.4, 126.3, 126.2, 126.1,
13C NMR (101 MHz, CDCl3)
d 136.6, 135.6, 134.8, 130.5, 129.6, 129.2,
124.4, 118.2, 113.3, 110.7, 77.2.
126.4, 123.1, 121.0, 119.8, 111.6, 103.7, 21.0.
3.41. 3-(p-Tolylthio)imidaz o [1,2-a]pyridine e[5i] [27]
3.35. 3-((4-Chlorophenyl)sulfinyl)-1H-indole [5c] [21d]
The crude mixture was purified via column chromatography
using ethyl acetate/petroleum ether (1 : 5) as eluent to give the
product 5i as a white solid (71.7 mg, 99%); mp 100e102 ꢀC; 1H NMR
The crude mixture was purified via column chromatography
using ethyl acetate/petroleum ether (1 : 10) as eluent to give the
product 5c as a white solid (74.1 mg, 95%), mp 137.6e138.8 ꢀC; 1H
(400 MHz, CDCl3)
d
8.20 (dt, J ¼ 6.8, 1.1 Hz, 1H), 7.98 (s, 1H), 7.69 (dt,
NMR (400 MHz, CDCl3)
d
8.39 (s, 1H), 7.57 (d, J ¼ 8.0 Hz, 1H), 7.48 (d,
J ¼ 9.0, 1.0 Hz, 1H), 7.27 (td, J ¼ 6.9, 1.3 Hz, 1H), 7.00 (d, J ¼ 8.1 Hz,
J ¼ 2.8 Hz, 1H), 7.44 (d, J ¼ 8.4 Hz, 1H), 7.30e7.25 (m, 1H), 7.20e7.14
2H), 6.96e6.89 (m, 2H), 6.84 (td, J ¼ 6.8, 1.0 Hz, 1H), 2.25 (s, 3H); 13
C
(m, 1H), 7.11 (d, J ¼ 8.4 Hz, 2H), 7.01 (d, J ¼ 8.8 Hz, 2H); 13C NMR
NMR (101 MHz, CDCl3) d 147.9,142.1,136.3,131.4,130.0,126.6,125.9,
(101 MHz, CDCl3)
d
137.9, 136.6, 130.8, 130.7, 128.9, 127.2, 123.3,
124.3, 118.1, 113.1, 111.3, 77.2, 20.9.
8

W. Yueting, L. Yali, H. Jing et al.
Tetrahedron xxx (xxxx) xxx
3.42. 3-((4-Fluorophenyl)thio)imidazo [1,2-a]pyridine [5j] [28]
132.3, 129.6, 128.8, 128.3, 128.0, 124.6, 124.1, 119.8, 117.1, 107.6, 77.2.
The crude mixture was purified via column chromatography
using ethyl acetate/petroleum ether (1 : 5) as eluent to give the
product 5j as a yellow liquid (42.0 mg, 58%); 1H NMR (400 MHz,
3.48. 1-((4-Nitrophenyl)thio)naphthalen-2-ol [6f] [13a]
The crude mixture was purified via column chromatography
using ethyl acetate as eluent to give the product 6f as a yellow solid
CDCl3)
J ¼ 8.6, 4.9 Hz, 1H), 7.39e7.22 (m, 1H), 7.02 (q, J ¼ 7.0, 5.3 Hz, 2H),
6.91 (m, 3H), 13C NMR (101 MHz, CDCl3)
162.9, 160.5, 148.1, 142.4,
130.1 (d, J ¼ 3.2 Hz), 128.6, 128.5, 126.2, 124.2, 118.3, 116.7, 116.4,
113.4; 19F NMR (376 MHz, CDCl3)
ꢂ115.7.
d
8.20 (t, J ¼ 5.6 Hz, 1H), 7.98 (d, J ¼ 5.5 Hz, 1H), 7.70 (dd,
(74.9 mg, 84%); mp 119e121 ꢀC; 1H NMR (400 MHz, CDCl3)
d 8.08 (d,
d
J ¼ 8.6 Hz, 1H), 8.00 (m, 3H), 7.86 (d, J ¼ 8.0 Hz, 1H), 7.56e7.49 (m,
1H), 7.42 (t, J ¼ 7.0 Hz,1H), 7.37 (d, J ¼ 9.0 Hz,1H), 7.08 (d, J ¼ 9.0 Hz,
d
2H), 6.90 (s, 1H); 13C NMR (101 MHz, CDCl3)
d 157.4, 145.9, 145.2,
135.0, 134.0,129.7,129.0,128.6,126.1,124.5,124.4,124.1,117.3,105.7.
3.43. 1-(Phenylthio)naphthalen-2-ol [6a] [13a]
3.49. 1-((4-Nitrophenyl)thio)naphthalen-2-ol [6g] [30]
The crude mixture was purified via column chromatography
using ethyl acetate as eluent to give the product 6a as a yellow solid
The crude mixture was purified via column chromatography
using ethyl acetate as eluent to give the product 6g as a yellow solid
(61.3 mg, 81%); mp 65e67 ꢀC; 1H NMR (400 MHz, CDCl3)
d 8.23 (d,
J ¼ 8.3 Hz, 1H), 7.92 (d, J ¼ 8.8 Hz, 1H), 7.83 (d, J ¼ 7.7 Hz, 1H), 7.51 (t,
(57.1 mg, 57%); mp 51e53 ꢀC; 1H NMR (400 MHz, CDCl3)
d 8.18 (d,
J ¼ 7.5 Hz, 1H), 7.37 (m, 2H), 7.17 (d, J ¼ 8.5 Hz, 3H), 7.15e7.08 (m,
J ¼ 8.4 Hz, 1H), 7.93 (d, J ¼ 8.9 Hz, 1H), 7.83 (d, J ¼ 8.1 Hz,1H), 7.52 (t,
1H), 7.04 (d, J ¼ 6.6 Hz, 2H), 13C NMR (101 MHz, CDCl3)
d 157.1,135.6,
J ¼ 8.2 Hz, 1H), 7.40 (t, J ¼ 8.0 Hz, 1H), 7.35 (d, J ¼ 8.9 Hz, 1H), 7.10 (s,
135.5, 133.0, 132.8, 129.6, 129.2, 128.7, 128.0, 126.5, 126.0, 124.8,
124.0, 117.0, 108.2, 77.2.
1H), 7.03 (s, 4H); 13C NMR (101 MHz, CDCl3)
d 157.1, 147.4, 135.2,
134.1, 133.2, 129.6, 128.7, 128.2, 127.5, 124.4, 124.1, 121.9, 117.0, 107.5;
19F NMR (376 MHz, CDCl3)
d
ꢂ58.1.
3.44. 1-(p-Tolylthio)naphthalen-2-ol [6b] [13a]
3.50. 1-(m-Tolylthio)naphthalen-2-ol [6h] [19]
The crude mixture was purified via column chromatography
using ethyl acetate as eluent to give the product 6b as a yellow solid
The crude mixture was purified via column chromatography
using ethyl acetate as eluent to give the product 6h as a yellow solid
(59.8 mg, 75%); mp 77e79 ꢀC, 1H NMR (400 MHz, CDCl3)
d 8.24 (d,
J ¼ 8.5 Hz, 1H), 7.90 (d, J ¼ 8.9 Hz,1H), 7.82 (d, J ¼ 8.1 Hz, 1H), 7.50 (t,
(62.2 mg, 78%); mp 87e89 ꢀC; 1H NMR (400 MHz, CDCl3)
d 8.26 (d,
J ¼ 7.1 Hz, 1H), 7.40e7.32 (m, 2H), 7.23 (s, 1H), 6.98 (q, J ¼ 8.4 Hz,
J ¼ 8.5 Hz, 1H), 7.92 (d, J ¼ 8.9 Hz, 1H), 7.84 (d, J ¼ 8.1 Hz, 1H), 7.52
4H), 2.25 (s, 3H); 13C NMR (101 MHz, CDCl3)
d 157.0, 136.0, 135.6,
(td, J ¼ 7.6, 7.0, 1.2 Hz, 1H), 7.43e7.34 (m, 2H), 7.22 (s, 1H), 7.07 (t,
132.8, 131.9, 130.1, 129.6, 128.7, 128.0, 126.8, 124.9, 123.9, 117.0,
108.8, 77.2, 21.0.
J ¼ 7.9 Hz, 1H), 6.95 (s, 2H), 6.82 (d, J ¼ 7.9 Hz, 1H), 2.24 (s, 3H); 13
C
NMR (101 MHz, CDCl3)
d 157.1, 139.2, 135.6, 135.2, 132.9, 129.6,
129.2, 128.7, 128.0, 127.1, 127.0, 124.9, 123.6, 117.0, 108.3, 77.2, 21.5.
3.45. 1-((4-Fluorophenyl)thio)naphthalen-2-ol [6c] [29]
3.51. 1-((3-Bromophenyl)thio)naphthalen-2-ol [6i]
The crude mixture was purified via column chromatography
using ethyl acetate as eluent to give the product 6c as a yellow solid
The crude mixture was purified via column chromatography
using ethyl acetate as eluent to give the product 6i as a white solid
(60.0 mg, 74%); mp 63e65 ꢀC. 1H NMR (400 MHz, CDCl3)
d 8.22 (d,
J ¼ 8.5 Hz, 1H), 7.92 (d, J ¼ 8.9 Hz, 1H), 7.83 (d, J ¼ 8.1 Hz, 1H),
7.55e7.47 (td, J ¼ 7.7, 1.1 Hz, 1H), 7.43e7.32 (m, 2H), 7.20 (s, 1H),
7.06e6.99 (m, 2H), 6.94e6.85 (m, 2H), 13C NMR (101 MHz, CDCl3)
(42.6 mg, 43%); mp 55e56 ꢀC; 1H NMR (400 MHz, CDCl3)
d 8.17 (d,
J ¼ 8.5 Hz, 1H), 7.94 (d, J ¼ 8.9 Hz, 1H), 7.83 (d, J ¼ 8.1 Hz, 1H), 7.52
(td, J ¼ 7.7, 1.2 Hz, 1H), 7.40 (td, J ¼ 7.5, 1.0 Hz, 1H), 7.35 (d, J ¼ 8.9 Hz,
1H), 7.27e7.19 (m, 2H), 7.07 (s, 1H), 7.02 (t, J ¼ 7.9 Hz, 1H), 6.89 (dq,
d
161.5, 157.1, 135.4, 133.1, 130.5, 129.7, 128.9, 128.5, 128.4, 128.2,
124.6, 124.1, 117.0, 116.6, 116.3, 108.6; 19F NMR (376 MHz, CDCl3)
ꢂ116.2.
J ¼ 7.9, 1.7 Hz, 1H); 13C NMR (101 MHz, CDCl3)
d 157.3, 137.9, 135.3,
d
133.4, 130.6, 129.7, 129.2, 129.0, 128.8, 128.3, 124.9, 124.6, 124.2,
123.3, 117.1, 107.1, 77.2; HRMS (ESI): m/z calcd for C16H11BrOS
(M þ H)þ: 330.9789, found: 330.9782.
3.46. 1-((4-Chlorophenyl)thio)naphthalen-2-ol [6d] [13a]
The crude mixture was purified via column chromatography
using ethyl acetate as eluent to give the product 6d as a yellow solid
3.52. 1-(Naphthalen-2-ylthio)naphthalen-2-ol [6j]
(60.1 mg, 70%); mp 85e87 ꢀC. 1H NMR (400 MHz, CDCl3)
d
8.17 (d,
The crude mixture was purified via column chromatography
using ethyl acetate as eluent to give the product 6j as a white solid
J ¼ 8.4 Hz, 1H), 7.92 (d, J ¼ 8.9 Hz, 1H), 7.83 (d, J ¼ 8.1 Hz, 1H),
7.55e7.47 (td, J ¼ 7.7, 1.1 Hz, 1H), 7.43e7.32 (m, 2H), 7.17e7.09 (m,
(62.2 mg, 69%); mp 91e93 ꢀC; 1H NMR (400 MHz, CDCl3)
d 8.24 (d,
3H), 6.99e6.90 (m, 2H), 13C NMR (101 MHz, CDCl3)
d
157.2, 135.3,
J ¼ 8.5 Hz, 1H), 7.92 (d, J ¼ 8.9 Hz, 1H), 7.82 (d, J ¼ 8.0 Hz, 1H), 7.70
(d, J ¼ 9.3 Hz, 1H), 7.64 (d, J ¼ 8.7 Hz, 1H), 7.54 (d, J ¼ 9.4 Hz, 1H),
7.46 (td, J ¼ 7.6, 7.0, 1.2 Hz, 1H), 7.41 (d, J ¼ 1.5 Hz, 1H), 7.40e7.32 (m,
4H), 7.22 (d, J ¼ 5.2 Hz, 1H), 7.17 (dd, J ¼ 8.7, 1.9 Hz, 1H); 13C NMR
134.1, 133.3, 132.0, 129.7, 129.4, 128.8, 128.3, 127.8, 127.8, 124.6,
124.1, 117.1, 107.7, 77.2.
3.47. 1-((4-Bromophenyl)thio)naphthalen-2-ol [6e] [13a]
(101 MHz, CDCl3) d 157.2, 135.6, 133.8, 133.1, 132.9, 131.9, 129.7,
129.0, 128.7, 128.1, 127.8, 127.2, 126.8, 125.8, 124.8, 124.7, 124.0, 117.1,
108.2.
The crude mixture was purified via column chromatography
using ethyl acetate as eluent to give the product 6e as a yellowe
solid (63.5 mg, 64%); mp 103e105 ꢀC; 1H NMR (400 MHz, CDCl3)
3.53. 2,4-Bis(phenylthio)naphthalen-1-ol [6k] [30]
d
8.17 (d, J ¼ 8.4 Hz, 1H), 7.93 (d, J ¼ 8.9 Hz, 1H), 7.83 (d, J ¼ 8.1 Hz,
1H), 7.57e7.47 (m, 1H), 7.42e7.37 (m, 1H), 7.35 (d, J ¼ 8.9 Hz, 1H),
7.33e7.24 (dt, J ¼ 8.6, 2.3 Hz, 2H), 7.10 (s, 1H), 6.93e6.85 (dt, J ¼ 8.6,
The crude mixture was purified via column chromatography
using ethyl acetate/petroleum ether (1 : 10) as eluent to give the
product 6k as a bright yellow solid (89.7 mg, 82%), mp 98e100 ꢀC;
2.3 Hz, 2H); 13C NMR (101 MHz, CDCl3)
d 157.2, 135.3, 134.8, 133.3,
9

W. Yueting, L. Yali, H. Jing et al.
Tetrahedron xxx (xxxx) xxx
1H NMR (400 MHz, CDCl3)
d
8.37 (dt, J ¼ 7.6, 3.2 Hz, 2H), 7.97 (s, 1H),
(400 MHz, DMSO‑d6)
d
8.31 (dd, J ¼ 8.7, 1.0 Hz, 1H), 8.00e7.87 (m,
7.63e7.53 (m, 2H), 7.38 (s, 1H), 7.27e7.21 (m, 2H), 7.20e7.16 (m,
2H), 7.82 (d, J ¼ 9.0 Hz, 1H), 7.67 (dd, J ¼ 7.9, 1.2 Hz, 1H), 7.64e7.59
2H), 7.16e7.13 (m, 2H), 7.13e7.04 (m, 4H); 13C NMR (101 MHz,
(tt, J ¼ 7.3,1.8 Hz,1H), 7.59e7.53 (m, 2H), 7.38 (m, 3H), 7.23e7.15 (m,
CDCl3)
d
156.3, 141.2, 138.4, 136.5, 135.6, 129.4, 129.1, 129.0, 127.2,
1H), 7.10 (d, J ¼ 9.1 Hz, 1H); 13C NMR (101 MHz, DMSO‑d6)
d 145.0,
127.0, 126.5, 126.3, 125.5, 124.8, 123.9, 121.3, 109.7.
143.4, 135.8, 133.2, 130.5, 129.4, 129.0, 128.3, 126.6, 125.5, 122.3,
121.9, 120.5, 105.3; HRMS (APCI): m/z calcd for C16H13NO2S
(M þ H)þ: 284.0742, found: 284.0736.
3.54. 2,4-Bis(p-tolylthio)naphthalen-1-ol [6l]
The crude mixture was purified via column chromatography
using ethyl acetate/petroleum ether (1 : 10) as eluent to give the
product 6l as a bright yellow solid (92.1 mg, 79%), mp 95e97 ꢀC; 1H
3.59. Typical procedure for the synthesis of [4da]
To a 25 mL tube were added 4d (0.3 mmol), bromobenzene
(0.3 mmol), Pd2 (dba)3 (2 mol%), XPhos (4%), and K2CO3 (0.6 mmol)
in 2 mL of DCE. The reaction vessel was allowed to stir at 100 ꢀC for
18 h under argon atmosphere. After completion of the reaction, the
mixture was quenched with the saturated solution of NaCl (5 mL)
and extracted with dichloromethane (3 ꢁ 10 mL). The organic
phase was dried over Na2SO4 and concentrated in vacuum. The
crude mixture was purified via column chromatography using ethyl
acetate/petroleum ether (1 : 10) as eluent to give the final product
N-phenyl-5-(phenylthio)-[1,10-biphenyl]-2-amine 4da in 87% yield.
NMR (400 MHz, CDCl3)
J ¼ 6.7 Hz, 2H), 7.37 (s,1H), 7.06 (s, 4H), 7.01 (s, 4H), 2.30 (s, 3H), 2.27
(s, 3H); 13C NMR (101 MHz, CDCl3)
155.7, 140.4, 136.6, 136.2, 135.6,
d 8.41e8.31 (m, 2H), 7.91 (s, 1H), 7.58 (p,
d
134.5, 132.0, 130.2, 129.8, 128.9, 127.8, 127.7, 124.8, 123.8, 122.1,
110.4, 21.1; HRMS (APCI): m/z calcd for C24H20OS2 (M ꢂ H)þ:
287.0881, found: 287.0884.
3.55. 2,4-Bis((4-chlorophenyl)thio)naphthalen-1-ol [6m]
The crude mixture was purified via column chromatography
using ethyl acetate/petroleum ether (1 : 10) as eluent to give the
product 6m as a bright yellow solid (98.4 mg, 77%), mp 89e91 ꢀC;
3.60. N-phenyl-5-(phenylthio)-[1,10-biphenyl]-2-amine [4da]
1H NMR (400 MHz, CDCl3)
d
8.36 (dd, J ¼ 6.9, 2.4 Hz, 1H), 8.28 (dd,
The crude mixture was purified via column chromatography
using ethyl acetate/petroleum ether (1 : 10) as eluent to give the
product 4da as a red liquid (61.5 mg, 87%); 1H NMR (400 MHz,
J ¼ 7.1, 2.2 Hz, 1H), 7.90 (s, 1H), 7.60 (dt, J ¼ 8.7, 2.2 Hz, 2H), 7.31 (dt,
J ¼ 8.7, 2.4 Hz, 1H), 7.25e7.17 (dt, J ¼ 8.7, 2.4 Hz, 2H), 7.17e7.09 (dt,
J ¼ 8.7, 2.4 Hz, 2H), 7.07e7.01 (m, 2H), 7.01e6.91 (m, 2H); 13C NMR
CDCl3)
d
7.47 (d, J ¼ 3.9 Hz, 4H), 7.40 (d, J ¼ 9.4 Hz, 2H), 7.36 (s, 2H),
(101 MHz, CDCl3)
d 156.5, 140.89, 136.9, 136.3, 134.1, 132.7, 131.5,
7.33e7.27 (m, 6H), 7.22e7.14 (m, 1H), 7.10 (d, J ¼ 7.8 Hz, 2H), 7.01 (t,
J ¼ 7.4 Hz, 1H); 13C NMR (101 MHz, CDCl3)
d 142.4, 140.9, 138.6,
129.6, 129.5, 129.2, 128.6, 128.3, 126.8, 126.2, 125.0, 124.1, 121.2,
109.4.
138.2, 136.3, 134.0, 131.7, 129.5, 129.4, 129.2, 129.1, 128.5, 128.0,
125.9, 123.9, 122.2, 119.5, 116.9; HRMS (APCI): m/z calcd for
C
24H19NS (M þ H)þ: 354.1313, found: 354.1306.
3.56. General procedure for gram-scale synthetic experiment of
[3a] and [4d]
4. Conclusions
A mixture of naphthalen-2-amine or [1,10-biphenyl]-2-amine
(10 mmol), benzenesulfonohydrazide (30 mmol), TBAI (2 equiv.),
and DPDMF (10 mL) were added into a Schlenk tube. The solution
was stirred and heated to 100 ꢀC for 48 h in air. After completion of
the reaction, the mixture was cooled to room temperature, and the
insoluble TBAI was filtered and washed with ethyl acetate
(10 mL ꢁ 3). Subsequently, the TBAI were recoverd in 93% and 91%
yields, respectively. The filtrate was concentrated in vacuum, and
the crude mixture was purified via column chromatography using
ethyl acetate/petroleum ether (1 : 10) as eluent to afford the final
product 3a and 4d in 92% (2.32 g) and 82% (2.26 g) yields,
respectively.
In summary, we have developed an efficient TBAI-mediated
sulfenylation of arenes with arylsulfonyl hydrazides. DPDME was
identified as excellent green solvent that are crucial for the elec-
trophilic substitution process. A series of aryl sulfides was obtained
in moderate to excellent yields. The reaction exhibited green re-
action condition (recyclable TBAI and DPDME as solvent), broad
substrate scope, and good functional group compatibility. The po-
tential application is exemplified by gram-scale synthesis and
further transformations. The mechanism studies show that diaryl
disulfide may be the main intermediate.
Declaration of competing interest
3.57. Typical procedure for the synthesis of [3aa]
The authors declare that they have no known competing
financial interests or personal relationships that could have
appeared to influence the work reported in this paper.
To a 25 mL tube were added 3a (0.3 mmol), and m-CPBA
(0.9 mmol) in 2 mL of CHCl3. The reaction vessel was allowed to stir
at 65 ꢀC for 15 h. After completion of the reaction, the mixture was
quenched with the saturated solution of NaCl (5 mL) and extracted
with dichloromethane (3 ꢁ 10 mL). The organic phase was dried
over Na2SO4 and concentrated in vacuum, and the crude mixture
was purified via column chromatography using ethyl acetate/pe-
troleum ether (1 : 5) as eluent to afford the final product 1-(phe-
nylsulfonyl)naphthalen-2-amine 3aa in 58% yield.
Acknowledgments
We gratefully acknowledge financial support of this work by the
National Natural Science Foundation of China (No. 21563025). We
also thank Jixing Zhao of Analysis and Testing Center of Shihezi
University for the help with X-ray single-crystal analysis.
3.58. 1-(Phenylsulfonyl)naphthalen-2-amine [3aa]
Appendix A. Supplementary data
The crude mixture was purified via column chromatography
using ethyl acetate/petroleum ether (1 : 5) as eluent to give the
product 3aa as a red solid (48.2 mg, 58%), mp 88e89 ꢀC; 1H NMR
Supplementary data to this article can be found online at
https://doi.org/10.1016/j.tet.2020.131646.
10

W. Yueting, L. Yali, H. Jing et al.
Tetrahedron xxx (xxxx) xxx
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