Elemental sulfur mediated 2-substituted benzothiazole formation from 2-aminobenzenethiols and arylacetylenes or styrenes under metal-free conditions

Article abstract of DOI:10.1039/c7ob02430d

An oxidative cyclization of 2-aminothiophenols and arylacetylenes or styrenes for the synthesis of 2-alkylbenzothiazoles and 2-acylbenzothiazoles has been developed. Elemental sulfur was used as the effective oxidant to give the corresponding product in g

Full text of DOI:10.1039/c7ob02430d

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Takeharu Haino et al.
Solvent-induced emission of organogels based on tris(phenylisoxazolyl)
benzene
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Elemental sulfur mediated 2-substituted benzothiazole formation
from 2-aminobenzenethiols and arylacetylenes or styrenes under
metal-free condition
Received 00th January 20xx,
Accepted 00th January 20xx
DOI: 10.1039/x0xx00000x
Guozheng Li,a Jingjing Jiang,a Feng Zhang,a,b* Fuhong Xiao,a GuoꢀJun Denga,*
www.rsc.org/chemcomm
An oxidative cyclization of 2-aminothiophenols and under metalꢀfree and mild conditions with good functional group
arylacetylenes or styrenes for the synthesis of 2-alkyl compatibility is still highly desirable. Elemental sulfur widely exists
benzothiazoles and 2-acylbenzothiazoles has been developed. in nature, and due to its nontoxicity and stability under normal
Elemental sulfur was used as the effective oxidant to give conditions, it was employed for the vulcanization of rubber and the
the corresponding product in good yield under metal-free synthesis of sulfuric acids and as sulfur source for preparing other
conditions.
sulfurꢀcontaining compounds.10ꢀ11 Moreover, elemental sulfur could
serve as an effective oxidant in organic synthesis to enable oxidative
coupling reactions.12 Recently, the Nguyen group,7,13 we14 and
others15 have developed various methods for sulfurꢀcontaining
heterocycle synthesis using elemental sulfur as the sulfur source
under transitionꢀmetalꢀfree conditions. As our continuing interest in
heterocycle preparation from readily available starting materials
under transitionꢀmetal free conditions,16 herein, we report a metalꢀ
free oxidative cyclization reaction of 2ꢀaminothiaphenols and
arylacetylenes or styrenes for the facile synthesis of 2ꢀalkyl
benzothiazoles and 2ꢀacylbenzothiazoles, in which elemental sulfur
was found to be the key for the success of this aerobic cyclization
process (Scheme 1, b).
Benzothiazole derivatives are privileged motif frequently found in
pharmaceuticals and many other biologically active products.1
Moreover, benzothiazole moieties are also found in many functional
molecules such as ligands for catalytic reactions.2 Therefore, the
development of efficient methods for construction of benzothiazole
derivatives attracted considerable interest. Over the past few
decades, tremendous progress has been made to synthesize 2ꢀ
substituted benzothiazoles, an important class of benzothiazole
derivatives.3 The condensation reaction of 2ꢀaminothiphenols with
carboxylic acids or aldehydes under oxidative conditions is the most
common used method to construct various 2ꢀsubstituted
benzothiazoles (Scheme 1, a).4 However, most of these
transformations involve the use of harsh reaction conditions, such
strong acidic or oxidative conditions. Recently, the Bao and Yu
developed a Brϕnsted acids catalyzed 2ꢀsubstituted benzothiazoles
formation from 2ꢀaminothiophenols and βꢀketones under relative
mild conditions.5 The transitionꢀmetalꢀcatalyzed intramolecular
cyclization of 2ꢀhaloanilides/analogues provided an efficient
alternative approach.6 The reaction of oꢀhalonitrobenzenes,
elemental sulfur and another reducing partners such as
benzylamines, benzaldehydes, methylhetarenes, acetophenones and
Previous work:
R1 COOH
NH2
SH
N
S
[O]
R1
R
(a)
+
R
or
R1 CHO
This work:
N
S
R
R
S
Ar
Ar
DMF, air
NH2
SH
or
+
(b)
R
S
phenylacetic acids provided
a convenient approach by using
O
N
S
Ar
nitroarenes as the substrates.7 In recent years, great attention has
been paid on the transitionꢀmetalꢀcatalyzed direct functionalization
of the benzothiazole core for 2ꢀsubstituted benzothiazole
preparation.8
[O]
Ar
Scheme 1 Different methods for 2ꢀsubstituted benzothiazole
formation from 2ꢀaminobenzenethiols.
In most cases, however, the aforementioned synthetic methods
involve 2ꢀaminothiophenol starting materials required strong oxidant
or high temperature, which is a challenging for functional group
tolerance. In addition, arylacetic acids or aryl acetaldehydes were
required for 2ꢀbenzylic benzothiazole formation.9 The substrate
scope is limited for this kind of chemicals. Therefore, the
development of efficient method for 2ꢀsubstituted benzothiazoles
We started our investigation using phenylacetylene (1a) and 2ꢀ
aminothiophenol (2a) as the model system. No desired product 3aa
was observed when the reaction was carried out in NMP (
Nꢀmethyl pyrrolidone) in the absence of oxidant (Table 1, entry 1).
TBHP and H2O2 both were not effective oxidant for this kind of
transformation (entries 2 and 3). The desired product could be
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 1
a Key Laboratory for Green Organic Synthesis and Application of Hunan Province,Key Laboratory of
Environmentally Friendly Chemistry and Application of Ministry of Education, College of Chemistry,
Xiangtan University, Xiangtan 411105, China. E-mail: zhangf@iccas.ac.cn; gjdeng@xtu.edu.cn
b College of Science, Hunan Agricultural
University, Changsha, 410128, China. Please do not adjust margins

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observed when K2S2O8 and DDQ were used as the oxidants (entries phenylacetylene also suitable substrate in this system to give the
4 and 5). To our delight, 3aa was obtained in 32% yield when 1 corresponding product 3ka in good yield.
equiv. of sulfur powder was used as the oxidant (entry 6).
Encouraged by this discovery, we screened several organic solvents Table 2 Substrate scope with respect to various arylacetylenes a
N
for this reaction using sulfur powder as the oxidant. Better yield was
obtained when the reaction was carried out in DMF (entry 7).
However, much lower yield was observed when the reaction was
carried out in toluene and chlorobenzene (entries 8 and 9). The use
of DMSO as the solvent completely inhibited the reaction (entry 10).
The reaction yield could be improved to 87% when increasing the
sulfur powder to 2 equiv. (entry 11). Further increasing the sulfur
powder to 3 equiv. could not increase the reaction yield (entry 12).
Similar yield was obtained when the reaction was carried out in
oxygen or nitrogen (entries 12 and 14). This indicates that sulfur
powder should acted as the oxidant solely for this kind of reaction.
NH2
S
+
R
S
DMF, air
SH
R
1
2a
3
N
N
N
S
S
S
b
Et
3ca
, 72%
3aa
3ba
, 85% (81%)
, 82%
N
S
N
S
N
S
Table 1 Optimization of the reaction conditionsa
N
NH2
S
OEt
n-Pr
Ph
+
n-pentyl
S
Ph
DMF, air
SH
3da
3ea
, 67%
, 62%
, 76%
, 77%
3fa
N
, 70%
3aa
2a
1a
N
S
N
S
yieldb (%)
entry
oxidant
solvent
S
ND
1
2
3
4
NMP
NMP
NMP
NMP
TBHP
H2O2
trace
Br
F
Cl
3ga
3ha
3ia
, 81%
, 82%
trace
K2S2O8
5
N
S
N
S
5
6
DDQ
S
NMP
NMP
DMF
6
Cl
32
7
S
S
S
S
51
12
3ka
3ja
, 83%
8
toluence
PhCl
a
1
2a
(0.4 mmol), solvent (0.6 mL), S (0.4
Reaction conditions: (0.2 mmol),
mmol), 110 oC, under air, 15 h. b 6 mmol scale reaction.
9
10
Table 3 Substrate scope with various 2ꢀaminobenzenethiolsa
10
11
DMSO
DMF
trace
87
NH2
N
S
R1
S (0.4 mmol)
S (0.6 mmol)
S (0.4 mmol)
S (0.4 mmol)
R1
Ph
+
DMF, air
S
Ph
SH
DMF
DMF
DMF
12
86
86
86
3
2
1a
Cl
13c
14d
N
Cl
N
N
S
S
Ph
S
Ph
a Reaction conditions: 1a (0.2 mmol), 2a (0.4 mmol), oxidant (0.2 mmol),
Ph
solvent (0.6 mL), S (0.2 mmol), 110 oC, under air, 15 h. b GC yield.
c
3ab
3ac
3af
, 72%
N
, 73%
3ad
, 67%
Under N2. d Under O2.
N
S
N
S
With the optimized reaction conditions in hand, we then
investigated the substrate scope of the reaction with respect to
various arylacetylenes (Table 2). Slightly lower yields were obtained
when alkyl substituents were presented at the C4 position of
phenylacetylene especially for those bulky groups (3baꢀ3ea).
Halogens such as fluoro, chloro and bromo were compatible to give
the corresponding products in high yield (3gaꢀ3ia). Interestingly, the
desired product 3ja was obtained in 83% yield when 2ꢀ
chlorophenylacetylene was used. In addition, 3ꢀsubstituted
Ph
Ph
S
F
Ph
Ph
O
Cl
3ae
3ag
, 85%
, 68%
, 76%
N
S
N
S
Ph
Br
3ah
, 58%
3ai
, 90%
a
1a
2
(0.2 mmol), (0.4 mmol), solvent (0.6 mL), S (0.2
Reaction conditions:
mmol), 110 oC, under air, 15 h.
2 | J. Name., 2013, 00, 1-3
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The substrate scope with respect to various substituted 2ꢀ acylbenzothiazole formation from phenylacetylene (1a) and 2ꢀ
amonothiophenols were further evaluated (Table 3). The position of aminothiophenol (2a) via "oneꢀpot, twoꢀstep" process (Table 5).
the substituent slightly affected the reaction yield (3ab, 3ad and 3ag) After systematic optimization of the reaction conditions, we got the
and the desired product 3ag could be obtained in 85% yield when 5ꢀ optimized conditions for 2ꢀacylbenzothiazole: phenylacetylene
chloroꢀ2ꢀamonothiophenol was used. Active bromo substituent was reacted with 2ꢀaminothiophenol at 110 oC for 15 h using sulfur as the
tolerated under the give conditions to give the corresponding product oxidant then CuI and AcOH/DMSO were added to the reaction and
3ah in moderate yield. Interestingly, high yield could be achieved the resulted mixture was further stirred for 24 h. For the model
when 4,5ꢀdimethylꢀ2ꢀamonothiophenol was used as the substrate.
reaction, 4a was isolated in 83% yield. Various 4ꢀsubstituented
To identify the best reaction conditions, styrene (1m) phenylacetylenes could smoothly reacted with 2a to give the
and 2ꢀaminobenzenethiol (2a) were initially used as the corresponding products in good yields (4bꢀ4e). Halogens such as
standard substrates under different conditions. To get a better fluoro, chloro and bromo were compatible at the given conditions.
substrate scope for this kind of transformation, we investigated the The position of substituent slightly affected the reaction yield (4eꢀ4g,
styrene substrate under the aforementioned optimized conditions 4i, 4k) and the desired product 4g was obtained in 80% yield when
(Table 4). However, much lower yield was obtained as comparing 3ꢀchloroꢀ2ꢀamonothiophenol was used as the substrate.
with the arylacetylene substrate. We then reꢀoptimized the reaction Unfortunately, aliphatic alkynes and alkenes were not suitable
conditions for styrene substrate and found that the addition of substrates for this kind of reaction.
KHCO3 could significantly improve the reaction yield (Table S1 in
ESI†). With KHCO3 as the additive and sulfur powder as the Table 5 Substrate scope with respect to various arylacetylenes and
oxidant, the desired product 3aa could be obtained in 77% yield. 2ꢀaminobenzenethiolsa
O
N
a) S, DMF
Interestingly,
substituted
styrenes
such
as
(E)ꢀ(2ꢀ
NH2
SH
R1
110 oC, 15 h
bromovinyl)benzene and (E)ꢀ(2ꢀnitrovinyl)benzene also suitable
coupling partners to give the same product in 83% and 59% yield,
respectively. Substituent at the phenyl ring of styrene significantly
affected the reaction yield. Good yield was obtained when a methyl
group presented at the para position (3ba). Functional groups such
as fluoro, chloro and bromo were well tolerated. Interestingly, 3ia
could be obtained in 82% yield although a reactive bromo group is
existed. In addition, position of substituent has profoundly affect the
reaction yield and better yields were obtained when the chloro group
was located at the meta and ortho position (3sa and 3ja).
+
R1
S
R
b) CuI, AcOH
DMSO, O2, 24 h
R
4
2
1
O
O
O
O
O
O
N
S
N
S
N
S
F
4c, 78%
4b, 81%
4a, 83%
N
S
N
S
N
S
Cl
Table 4 Substrate scope with respect various styrenes a
N
R3
NH2
Br
Cl
KHCO3, S
R2
4e, 74%
S
4f
, 75%
+
4d, 71%
DMF, air
SH
R2
Cl
O
Cl
N
O
N
S
1
2a
3
O
N
S
S
N
S
N
S
4i, 68%
4h, 62%
4g, 80%
O
O
N
S
N
S
R2
R2 = Me 3ba, 72%
R3 = H
3aa, 77%
3aa, 83%
Br
Cl
R3 = Br
R2 = F
R2 = Cl
R2 = Br
3ga, 50%
3ha, 68%
R3 = NO2 3aa, 59%
4j, 70%
4k, 78%
3ia
, 82%
N
N
S
a Reaction conditions: 1 (0.2 mmol), 2 (0.4 mmol), S (0.4 mmol), 110 oC, CuI (20
S
Cl
mol%), AcOH (0.4 mmol), DMF (0.5 mL), DMSO (0.5 mL).
Cl
3sa, 85%
R3 = H
3ja, 82%
R3 = NO2 3ja, 65%
a
1
2a
(0.4 mmol), KHCO3 (0.4 mmol),
Reaction conditions: (0.2 mmol),
solvent (0.6 mL), S (0.6 mmol), 110 oC, under air, 15 h.
After we have realized 2ꢀalkylbenzothiazole synthesis using
elemental sulfur as the oxidant, we turned our attention to 2ꢀ
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H
N
Sn
1a
Ph
H
N
L. Stone, T. D. Bradshaw, M. F. G. Stevens, A. D. Westwell, J. Med.
Chem., 2006, 49, 179; (d) B. TekinerꢀGulbas, O. TemizꢀArpaci, I. Yildiz,
N. Altanlar, Eur. J. Med. Chem., 2007, 42, 1293; (e) R. S. Keri, M. R.
Patil, S. A. Patil, S. Bugagumpi, Eur. J. Med. Chem., 2015, 89, 207.
2. (a) J. P. Zhang, Y. B. Zhang, J. B. Lin, X. M. Chen, Chem. Rev., 2012,
112, 1001; (b) S. Rajasekhar, B. Maiti, K. Chanda, Synlett, 2017, 28,
521; (c) V. O. Rodionov, S. I. Presolski, S. Gardinier, Y. H. Lim, M. G.
Finn, J. Am. Chem. Soc., 2007, 129, 12696.
NH2
R
SH
S n-1
S
R
R
S n-1
Ph
R = 2-SHC6H4
1
2a
2
RNH2
H
H
N
SH
S
N
S
H
R
S n-2
Ph
R
S n-1
Ph
SH
N
NH
SH
NH
SH
S
5
Ph
H2S
4
3
H
N
SH
H
N
3. For selected recent 2ꢀsubstituted benzothiazole synthesis, see: (a) D. W.
Ma, S. W. Xie, P. Xue, X. J. Zhang, J. H. Dong, Y. W. Jiang, Angew.
Chem. Int. Ed., 2009, 48, 4222; (b) L. Liu, F. Zhang, H. L. Wang, N.
Zhu, B. Liu, H. L. Hong, L. M. Han, Phosphorus, Sulfur and Silicon,
2017, 192, 464.
N
R
S n-1
[O]
S
Ph
S
Ph
3aa
6
Scheme 2 Possible reaction pathway.
4. For selected examples, see: (a) A. R. Wade, H. R. Pawar, M. V. Biware, R.
C. Chikate, Green Chem., 2015, 17, 3879; (b) Y. D. Sun, H. F. Jiang, W.
Q. Wu, W. Zeng, X. Wu, Org. Lett., 2013, 15, 1598; (c) T. H. Zhu, S. Y.
Wang, G. N. Wang, S. J. Ji, Chem. Eur. J., 2013, 98, 5850; (d) J. T. Yu,
J. Xu, M. Lu, Appl. Organometal. Chem., 2013, 27, 606; (e) Y. F. Liao,
H. R. Qi, S. P. Chen, P. C. Jiang, W. Zhou, G. J. Deng, Org. Lett., 2012,
14, 6004; (f) M. J. Thompson, H. Adams, B. Chen, J. Org. Chem., 2009,
74, 3856; (g) B. Shi, A. Blake, I. B. Campbell, B. D. Judkins, C. J.
Moody, Chem. Commun., 2009, 3291; (h) Y. X. Da, Z. Yang, Z. J. Quan,
Z. Zhang, X. C. Wang, J. Heterocycl. Chem., 2009, 46, 737.
Although the exact reaction mechanism is unknown at this stage,
based on the experimental results and relative literatures,17 we
proposed a possible reaction pathway to illustrate this transformation.
Reaction of 2ꢀaminothiophenol (2a) with elemental sulfur generates
11b, 12c
an intermediate 1.11a,
Addition reaction of 1 with
phenylacetylene (1a) affords an alkene intermediate 2, which can
further react with another equiv. of 2a to give compound 3. A
thioamide intermediate 4 is generated from 3 via SꢀS bond cleavage
process and cyclization of 4 provides an intermediate 5, which can
give the final product 3aa via extrusion H2S. Meanwhile, there is
another possible reaction pathway for conversion of 3 into the
desired product 3aa. 2ꢀBenzylꢀ2,3ꢀdihydrobenzo[d]thiazole (6) can
be produced from 3 via SꢀS bond cleavage and cyclization process.
This compound can convert into the final product 3aa under
oxidative conditions.
5. M. S. Mayo, X. Q. Yu, X. Y. Zhou, X. J. Feng, Y. Yamamoto, M. Bao,
Org. Lett., 2014, 16, 764.
6. For selected examples, see: (a) G. T. Zhang, C. Liu, H. Yi, Q. Y. Meng, C.
L. Bian, H. Chen, J. X. Jian, L. Z. Wu, A. W. Lei, J. Am. Chem. Soc.,
2015, 137, 9273; (b) H. B. Wang, L. Wang, J. S. Shang, X. Li, H. Y.
Wang, J. Cui, A. W. Lei, Chem. Commun., 2012, 76; (c) Y. N. Cheng, J.
Yang, Y. Qu, P. X. Li, Org. Lett., 2012, 14, 98; (d) S. Ranjit, X. G. Liu,
Chem. Eur. J., 2011, 17, 1105; (e) S. Tamba, Y. Okubo, S. Tanaka, D.
Monguchi, A. Mori, J. Org. Chem., 2010, 75, 6998; (f) K. Inamoto, C.
Hasegawa, J. Kawasaki, K. Hiroya, T. Doi, Adv. Synth. Catal., 2010, 32,
2643; (g) P. Sha, T. Ramana, N. Purkait, M. Ali, R. Paul, T.
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Hasegawa, K. Hiroya, T. Doi, Org. Lett., 2008, 10, 5147.
In summary, we have developed a novel approach for the
synthesis of
2ꢀsubstituted benzothiazoles from
2ꢀ
aminobenzenethiols and arylacetylenes or styrenes under metalꢀ
free conditions. In this transformation, elemental sulfur was
used as the efficient oxidant to promote the reaction under mild
conditions. This method affords a simple approach for
benzothiazoles under metalꢀfree conditions. The mechanism
and the further synthetic applications of this reaction are in
progress in our laboratory.
7. (a) T. B. Nguyen, P. Retailleau, Org. Lett., 2017, 19, 4558; (b) T. B.
Nguyen, L. Frmolenko, W. A. Dean, A. AlꢀMourabit, Org. Lett., 2012,
14, 5948; (c) T. B. Nguyen, L. Ermolenko, A. AlꢀMourabit, Org. Lett.,
2013, 15, 4218; (d) L. A. Nguyen, Q. A. Ngo, P. Retailleau, T. B.
Nguyen, Green Chem., 2017, 19, 4289.
ACKNOWLEDGMENT
8. For selected reviews, see: (a) T. W. Lyons, M. S. Sanford, Chem. Rev.,
2010, 110, 1147; (b) O. Daugulis, H. Q. Du, D. Shabashov, Acc. Chem.
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Wang, J. Q. Yu, Angew. Chem. Int. Ed., 2009, 48, 5094; (e) J. C. Lewis,
R. G. Bergman, J. A. Ellman, Acc. Chem. Res.,2008, 41, 1013; (f) D.
Alberico, M. E. Scott, M. Lautens, Chem. Rev., 2007, 107, 174.
This work was supported by the National Natural Science
Foundation of China (21572194, 21502160, 21372187), the
Collaborative Innovation Center of New Chemical Technologies for
Environmental Benignity and Efficient Resource Utilization, the
Hunan Provincial Innovative Foundation for Postgraduate
(CX2017B301) and the Natural Science Foundation of Hunan
Provincial Natural Science Foundation (14JJ3091).
9. (a) J. A. Seijas, M. P. VazquezꢀTato, M. R. CarballidoꢀReboredo, J.
CrecenteꢀCampo, L. RomarꢀLopez, Synlett, 2007, 313; (b) A. K.
Chakraborti, K. Selvam, G. Kaur, S. Bhagat, Synlett, 2004, 851; (c) H.
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4 | J. Name., 2013, 00, 1-3
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Tetrahedron Lett., 2017, 58, 874; (h) X. S. Fan, Y. He, Y. Y. Wang, Z.
K. Xue, X. Y. Zhang, J. J. Wang, Tetrahedron Lett., 2011, 52, 899.
10. For recent reviews on application of elemental sulfur, see: (a) D. A.
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