Co-Catalyzed Intramolecular S-N Bond Formation in Water for 1,2-Benzisothiazol-3(2H)-ones and 1,2,4-Thiadiazoles Synthesis

Article abstract of DOI:10.1002/ejoc.201801642

An efficient and versatile Co-catalyzed intramolecular S-N bond formation in water to synthesize 1,2-benzisothiazol-3(2H)-one and 1,2,4-thiadiazoles derivatives in good to excellent yields was developed. The transformation showed great tolerance with a broad range of substituents. The mother liquor was able to be recycled 6 times with minor loss in product yield.

Full text of DOI:10.1002/ejoc.201801642

A Journal of
Accepted Article
Title: Co-Catalyzed Intramolecular S-N Bond Formation in Water for
1,2-Benzisothiazol-3(2H)-ones and 1,2,4-Thiadiazoles Synthesis
Authors: Guanyu Yang, Lijuan Song, Shanyu Tang, Longjia Li, Heng
Li, Bingxin Yuan, and Liting Yang
This manuscript has been accepted after peer review and appears as an
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of the final Version of Record (VoR). This work is currently citable by
using the Digital Object Identifier (DOI) given below. The VoR will be
published online in Early View as soon as possible and may be different
to this Accepted Article as a result of editing. Readers should obtain
the VoR from the journal website shown below when it is published
to ensure accuracy of information. The authors are responsible for the
content of this Accepted Article.
To be cited as: Eur. J. Org. Chem. 10.1002/ejoc.201801642
Link to VoR: http://dx.doi.org/10.1002/ejoc.201801642
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10.1002/ejoc.201801642
European Journal of Organic Chemistry
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Co-Catalyzed Intramolecular S-N Bond Formation in Water for 1,2-
Benzisothiazol-3(2H)-ones and 1,2,4-Thiadiazoles Synthesis
Liting Yang, Lijuan Song, Shanyu Tang, Longjia Li, Heng Li, Bingxin Yuan,* and Guanyu Yang*[a][+]
Abstract: An efficient and versatile Co-catalyzed intramolecular S-N
bond formation in water to synthesize 1,2-benzisothiazol-3(2H)-one
and 1,2,4-thiadiazoles derivatives in good to excellent yields was
developed. The transformation showed great tolerance with a broad
range of substituents. The mother liquor was able to be recycled 6
times with minor loss in product yield.
Introduction
1,2-Benzisothiazol-3(2H)-one (BIT) derivatives,
a significant
class of heterocyclic compounds, have attracted wide attention
and play important roles in drug discovery, agriculture, food
science and industrial settings.[1] Since the first synthesis by
Mckibben and McClelland in 1923,[2] 1,2-benzisothiazol-3(2H)-
ones were discovered to show broad spectrum bioactivity, such
as antibacterial,[3] fungistatic,[4] antipsychotic,[5] antiviral,[6]
antithrombotic[7] and analgesic[8]. Nowadays, it’s widely used as
a preservative in numerous daily products, such as paints,
cleaning detergents, leather processing, pesticides and gas
preservation.[9] A study in 2014 declared that BIT was found in
96% of the paints from five European countries.[10] Furthermore,
it has been reported that some certain derivatives could process
anti-HIV activity.[11]
Owing to BITs’ excellent performance in pharmathutical
science, a number of synthetic routes have been disclosed in
literatures, as summarized in Figure 1. Reaction pathways
involving intramolecular cyclization starts from N-substituted
Figure 1. Previous and present methods to synthesize 1,2-benzisothiazol-
3(2H)-one derivatives.
benzodithiol-3-one-1-oxide,[20] and 1,3-benzoxathiin-4-one 1-
oxide.[21] Despite these great advances, the shortcomings are
apparent, such as toxic waste, extra additives or bases,
screening a large variety of ligands, tedious work-up procedures,
and long reaction hours. More importantly, among all the
methods mentioned above, there are just a few catalytic
transformations and copper catalyst is the only catalyst specie
that has been investigated. Besides, strong organic and
inorganic oxidizers were used in most cases, except molecular
oxygen was adopted as the oxidant in one single report.[14b] All
reactions were carried out in organic solvents. From the
environmental and industrial points of view, the development of
a green and versatile catalytic method for the synthesis of 1,2-
benzisothiazol-3(2H)-one compounds still remains a challenge
and is highly desired.
sulfonamides,[12]
2,2-dithiodibenzoate,[13]
N-substituted
thiosalicylate,[14] and sulfinyl substituted carboxamides[15] with
H2O2, hypervalent iodine reagent, (Cl3COO)2O or O2 as the
oxidizer. The conventional strategies accomplish the synthesis
of 1,2-Benzisothiazol-3(2H)-ones via intermolecular cyclization
by: 1) introducing sulfur reagents(S8, CS2, KSCN) into substrates
including 2-halobenzamides (CuHal as catalyst)[16] and
benzamide (Cu(OAc)2 as catalyst);[17] 2)introducing nitrogen
reagents (azide, primary amines) into substrates including 2-
mercaptobenzoic acid,[18] 2,2’-dithiodibenzoate,[19] 3H-1,2-
[a]
Liting Yang, Lijuan Song, Shanyu Tang, Longjia Li, Dr. Heng Li, Dr.
Bingxin Yuan, and Prof. Guanyu Yang
College of Chemistry and Molecular Engineering
Zhengzhou University
Recently, we reported the Co-catalyzed aerobic oxidation of
thiols with amines to synthesize sulfenamides.[22] Tetra-
substituted sulfonated cobalt phthalocyanine (CoPcS) showed
great catalytic ability to construct S-N bond with molecular
oxygen as the environment friendly oxidant and water as the
ideal green chemistry solvent. Inspired by that and our
continuous interest in green synthesis,[23] we intend to expend
100 Kexue Avenue, Zhengzhou, 450001
E-mail: bxyuan@zzu.edu.cn, yangguanyu@zzu.edu.cn
All authors contributed equally to this work.
[+]
Supporting information for this article is given via a link at the end of
the document.
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10.1002/ejoc.201801642
European Journal of Organic Chemistry
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this methodology to the synthesis of 1,2-benzisothiazol-3(2H)-
ones. Herein, we report the first example of Co-catalyzed
aerobic oxidation of N-substituted thiosalicylate to form
benzoisothiazolones in water (Figure 1).
different temperatures. Either decreasing the equivlant of CoPcS
(Entry 11, 12) or the reaction temperature (Entry 5) led to lower
Table 1. Optimization of reaction conditions. [a]
Results and Discussion
Initially, we attempted the intramolecular coupling of N-(t-butyl)-
Entry
1
2
3
4
5
6
7
8
Catalyst
Yield(%)[b]
2-mercaptobenzamide 1a to produce the corresponding
[22]
Co(OAc)2 ·2H2O
Co(acac)2
Mn(acac)2
Cu(acac)2
CoPcS
CuPcS
CoPcC
CoPc
Na[Co(EDTA)]·2H2O
–
23
29
18
46
benzoisothiazolone 2a with the similar procedure
as we
reported, in which 1 atm O2 was used as the oxidizing agent,
and water as the solvent. The attempt to use Co(OAc)2·2H2O as
catalyst only furnished the product in 23% yield (Table 1, Entry
1). Cu(acac)2 gave the best results among the metal-acac
complexes (Entry 2-4). By changing the ligand to
phthalocyanine-tetra-sodium sulfonate (PcS), the catalytic
performance was improved markedly owing to higher solubility
of MPcS in water (Entry 5, 6). However, the replacement of
sulfonate groups by carbonate lowered the product yield to 62%
(Entry 7). Na[Co(EDTA)]·2H2O only led to trace amount of
product. Additionally, the elimination of CoPcS resulted in no
product (Entry 10). These results illustrate the necessity of
CoPcS as the catalyst. The reaction was examined under
99(82[c]
78
)
62
Trace
Trace
0
49
10
9
10
11
12
13[d]
0.5 mol% CoPcS
0.1 mol% CoPcS
CoPcS
59
[a] Reaction conditions: 1a (0.2 mmol), catalyst (1 mol %), 2 mL H2O, 1
atm O2, 100 oC, 8 h. [b] Isolated yield. [c] 80 oC. [d] In air.
Table 2. Synthesis of 1,2-Benzisothiazol-3(2H)-one derivatives.[a], [b]
O
O
O
O
O
O
O
N
N
N
N
N
N
N
S
S
S
S
S
S
S
[c]
2a
99%
2b
2c
2e
95%
96%
95%
2d
2f
90%
90%
2g
93%
O
O
O
O
O
O
N
Cl
N
N
N
N
Br
I
NH2
N
O
S
S
S
S
S
S
2l
92%
2j
2m
95%
98%
2k
97%
2h
2i
96%
95%
O
O
O
O
O
O
N
CN
N
N
CF3
N
N
NO2
N
S
S
S
N
S
S
N
O
S
[d]
[d]
[d]
[d]
[d]
[d]
2n
2p
2q
2r
88%
85%
96%
O
86%
O
2o
2s
82%
92%
O
S
N
NH
O
N
O
N
S
N
S
S
N
N
S
Cl
S
[d], [e]
[d]
[d], [e]
[d], [e]
[d], [e]
2v
85%
2x
63%
2t
2u
2w
86%
80%
74%
[a] Reaction conditions: 1 (0.5 mmol), CoPcS (1 mol %), 1 atm O2, 5 mL H2O, 100 °C, 12 h. [b] Isolated yield. [c] 8 h. [d] 24 h. [e] 0.3 Mpa O2.
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10.1002/ejoc.201801642
European Journal of Organic Chemistry
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yields of 2a. The replacement of 1 atm O2 by air atmosphere
lowered the yield to 59%.
(Table 3). 1,2,4-Thiadiazole derivatives also are important sulfur-
containing heterocylclic moieties with various biological and
pharmaceutical properties.[24] 3-Aryl, alkyl, and N,N-
dimethylamino substituted 5-amino-1,2,4-thiadiazoles under the
optimal reaction conditions in quantitive yields, while the amion
group led to good yields. N-substituents of 3-substituted 1,2,4-
thiadiazoles showed no significant effect on the reaction.
To demonstrate the synthetic value of this protocol, a gram-
scale reaction of 1a was performed (Scheme 1). This reaction
could generate the desired product in an isolated yield of 98%.
With the optimal reaction conditions in hand, we continued to
screen the reaction scope of the CoPcS-catalyzed
intramolecular cyclization to synthesize a variety of N-substituted
1,2-benzisothiazol-3(2H)-one derivatives (Table 2). To be noted,
substrate 1a was found to be more reactive and the reaction
could complete in 8 h under 1 atm O2, however, for other
substrates 1b-m, the reaction time was extended to 12 h under
the same conditions. In general, all N-substituted alkyl and aryl
groups were well tolerated and furnished the desired 1,2-
benzisothiazol-3(2H)-ones 2a-x in excellent yields. The reaction
was not affected by electron-donating groups, such as methyl
(2f-h), methoxyl (2i), amino (2j), or electron-withdrawing groups,
such as halogen (2k-m), nitrile (2n), nitro (2o), trifluoromethyl
(2p), on the benzene ring. In addition, mercaptobenzamide 1f-h
bearing a methyl group at ortho-, meta- or para-position gave
the desired compounds 2f-h in similar yields. Substrates with
pyridyl, naphthyl, benzyl groups, 1-(2-chlorophenyl)ethyl, and 2-
(1H-indol-3-yl)ethyl groups on the nitrogen atom afforded the
desired products in good to modest yields (2q-w). The product
2x with two 1,2-benzisothiazol-3(2H)-one units was produced in
63% yield.
Scheme 1. The gram scale reaction.
With water as solvent, the work-up procedure for some certain
products was quite handy and convenient. Once completed, the
reaction mixture could be simply filtered and washed by H2O to
give pure desired products, implying promising application of this
Table 3. Synthesis of Substituted 1,2,4-Thiadiazoles. [a], [b]
synthetic
strategy
in
chemical
manufacturing
and
commercialization. Since there was nearly no byproduct, the
mother liquor containing CoPcS should be able to be recycled.
Therefore, the circulation of the mother liquor was performed
based on the substrate 1e (Table 4). The results showed that
the mother liquor could be circulated up to 6 times with a minor
loss in product yield.
O
S
N
S
N
S
N
N
N
N
N
N
N
H
H
Table 4. The circulation of mother liquor for the synthesis of 1,2-
benzisothiazol-3(2H)-one 2e. [a],
H
4a, 99%
4c, 98%
4b, 99%
O
S
N
S
N
S
N
N
N
H
N
N
H
N
N
H
4f, 99%
4e, 98%
Yield(%)[b]
4d, 98%
Time
1
2
3
4
5
6
94
92
89
85
81
76
O
S
N
S N
S
N
NH2
N
NH2
N
NH2
N
N
N
N
H
H
H
4g, 85%
4i, 83%
4h, 86%
O
[a] Reaction conditions: 1e (1 mmol), catalyst (1 mol %), 10 mL H2O, 1
atm O2, 100 oC, 12 h. [b] Isolated yield.
S
N
S
N
S
N
N
H
N
N
N
N
N
N
N
N
H
H
On the basis of our earlier study of aerobic dehydrogenative
coupling of intermolecular S-H/N-H, the reaction mechanism is
proposed as shown in Scheme 2. The interaction of CoPcS by
molecular oxygen generates Co(III) complex, which is able to
oxidize the thiyl group and result in the corresponding thiyl
radical. The nucleophilic attack on the sulfur atom by N-H with
the removal of H furnished the desired product.
4j, 98%
4l, 99%
4k, 99%
[a] Reaction conditions: 3 (0.5 mmol), catalyst (1 mol %), 5 mL H2O, 1 atm O2,
100 oC, 10 h. [b] Isolated yield.
Encouraged by the successful results, the reaction versatility
of intramolecular oxidative coupling of S-H/N-H was further
studied to synthesize 3-substituted 5-amino-1,2,4-thiadiazoles
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General Procedure B for the substrates 3a-f: A mixture of an amidine salt
(2.0 mmol), the corresponding isothiocyanate (2.2 mmol), and K2CO3
(414 mg, 3.0 mmol) in CH2Cl2 (10 mL) was stirred at room temperature
for 12 h, then quenched with H2O (10 mL), and extracted with CH2Cl2 (15
mL × 3). The combined organic layer was dried over anhydrous Na2SO4,
concentrated, and purified through silica gel column chromatography to
afford the substrates 3a-f.
General Procedure C for the substrates 3g-l: A mixture of an guanidine
salt (2.4 mmol), the corresponding isothiocyanate (2.0 mmol), and K2CO3
(553 mg, 4.0 mmol) in EtOH (10 mL) was stirred at 70 °C for 3 h, and
then concentrated under reduced pressure. The resulting residue was
treated with H2O (15 mL) and extracted with EtOAc (15 mL × 3). The
combined organic layer was dried over anhydrous Na2SO4, concentrated,
and purified through silica gel column chromatography to afford the
substrates 3g-l.
Scheme 2. Proposed Reaction Mechanism.
Conclusions
General procedure for the synthesis of product 2 and 4.
Conclusively, we have developed a versatile and green tool for
the synthesis of benzisothiazol-3(2H)-ones and 3-substituted 5-
amino-1,2,4-thiadiazoles. The protocol applied molecular oxygen
as the sole oxidant and avoids the usage of excess additives or
base. Water as solvent enables simple product purification and
mother liquor circulation. Such efficient and benign method for
working with chemical processes and product addresses the
challenges in green chemistry.
A 25 mL Schlenk tube was charged with 1 or 3 (0.5 mmol), CoPcS (4.5
mg, 0.005 mmol), H2O (5 mL), and 1 atm O2, and then the resulting
mixture was stirred at 100 °C for 8 h (for 3, 10 h was required). The
reaction mixture was extracted with ethyl acetate (3 × 10 mL) and then
dried over anhydrous Na2SO4 and filtered. After evaporation of the
solvent under vacuum, the residue was subjected to flash column
chromatography on silica gel to give the products 2 or 4.
The procedure for gram scale reaction.
Experimental Section
A 100 mL Schlenk tube was charged with 1a (1.04 g, 5.0 mmol), CoPcS
(45 mg, 0.05 mmol), H2O (50 mL), and 1 atm O2, and then the resulting
mixture was stirred at 100 °C for 18 h. The reaction mixture was
extracted with ethyl acetate (3 × 10 mL) and then dried over anhydrous
Na2SO4 and filtered. After evaporation of the solvent under vacuum, the
residue was subjected to flash column chromatography on silica gel to
give the products 2a.
General Information.
All materials and catalysts were purchased from general merchant. 1H
NMR and 13C NMR spectra were recorded at a Bruker Avance III HD
spectrometer (Bremen, Germany) at 600 MHz (400 MHz) for 1H NMR
and 150 MHz (100 MHz) for 13CNMR with CDCl3 or DMSO-d6 as the
solvent and TMS as the internal standard. High-resolution mass spectra
(HRMS) were measured with an Agilent 1290-6540 Q-TOF (Santa Clara,
CA). Low resolution mass spectra (LRMS) were recorded under electron
ionization (EI) conditions using a Shimadzu GCMS-QP2010 Plus mass
spectrometer (Kyoto, Japan). Infrared (IR) spectra were recorded on a
PerkinElmer Spectrum Two FT-IR spectrophotometer and are reported
as wave number (cm-1) (Massachusetts, USA).The melting points of the
products were determined using an X-4 micromelting point apparatus
(Beijing, China).
The procedure for recycling of mother liquor.
A
50 mL Schlenk tube was charged with 2-mercapto- N-phenyl
benzamide (0.23 g, 1 mmol), CoPcS (8.9 mg, 1 mol %), H2O (10 mL),
and 1 atm O2, and then the resulting mixture was stirred at 100 °C. After
12 h, the reaction mixture was filtered. The filter cake was dried and the
desired product 2e was obtained, giving the yield up to 94%. The filtrate
was reused directly as the solvent in the next run in which 2-mercapto-N-
phenylbenzamide (1 mmol) was added. The results are presented in
Table 4. We carried out the oxidation process successfully in 6 runs, with
the yields varying as follow: 94%, 92%, 89%, 85%, 81%, 76%.
Preparation of Substrates.
General Procedure A for the substrates 1: To a cooled (0 °C) solution of
amine (4.6 mmol) in CH2Cl2 (12 mL) was added a solution of AlMe3 in
toluene (1.6 M, 2.9 mL, 4.6 mmol). The reaction mixture was warmed to
room temperature and continued to stir for 30 min until the gas evolution
ceased. Then, methyl thiosalicylate (0.31 mL, 2.3 mmol) was added and
the solution was refluxed for 12 h. The reaction mixture was cooled in an
ice bath, and aq HCl (5%, 12 mL) was added carefully. The solution was
extracted with CH2Cl2 (3 × 20 mL), and the combined organic extracts
were washed with a saturated aq solution of NaHCO3 (20 mL) and brine
(20 mL) consequently. Then, the organic layer was dried over anhydrous
Na2SO4. After filtration and removal of the solvent under vacuum, the
residue was purified by using column chromatography to afford the
substrates 1.
Acknowledgments
Financial support provided by the National Natural Science
Foundation of China (No. 21502174 and 21801229), and Start-
up Research Fund of Zhengzhou University (No. 1411316005).
Keywords: Benzisothiazol-3(2H)-one • 1,2,4-Thiadiazole •
Aqueous reaction • Homogeneous catalysis • Oxidation •
Radical reaction •
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[1]
a) L. Craine, M. Raban, Chem. Rev. 1989, 89, 689-712; b) A. G.
Romero, W. H. Darlington, M. F. Piercey, R. A. Lahti, Bioorg. Med.
Chem. Lett. 1992, 2, 1703-1706; c) K. D. Combrink, H. B. Gülgeze, N.
A. Meanwell, B. C. Pearce, P. Zulan, G. S. Bisacchi, D. G. M. Roberts,
P. Stanley, S. M. Seiler, J. Med. Chem. 1998, 41, 4854-4860.
M. McKibben, E. W. McClelland, J. Chem. Soc., Trans. 1923, 123, 170-
173.
[14] a) A. Correa, I. Tellitu, E. Domínguez, R. SanMartin, Org. Lett. 2006, 8,
4811-4813; b) Z. Wang, Y. Kuninobu, M. Kanai, J. Org. Chem. 2013, 78,
7337-7342.
[15] S. W. Wright, M. M. Abelman, L. L. Bostrom, R. L. Corbett, Tetrahedron
Lett. 1992, 33, 153-156.
[2]
[3]
[16] a) V. Krasikova, M. Katkevics, Chem. Heterocycl. Com+. 2013, 48,
1684-1690; b) B. S. Bhakuni, S. J. Balkrishna, A. Kumar, S. Kumar,
Tetrahedron Lett. 2012, 53, 1354-1357; c) F. Wang, C. Chen, G. Deng,
C. Xi, J. Org. Chem. 2012, 77, 4148-4151; d) T. Li, L. Yang, K. Ni, Z.
Shi, F. Li, D. Chen, Org. Biomol. Chem. 2016, 14, 6297-6303; e) R.
Paul, T. Punniyamurthy, RSC Adv. 2012, 2, 7057-7060.
a) P. Zoumpoulakis, C. Camoutsis, G. Pairas, M. Soković, J. Glamočlija,
C. Potamitis, A. Pitsas, Bioorg. Med. Chem. 2012, 20, 1569-1583; b) P.
Borgna, M. L. Carmellino, M. Natangelo, G. Pagani, F. Pastoni, M.
Pregnolato, M. Terreni, Eur. J. Med. Chem. 1996, 31, 919-925; c) M. L.
Carmellino, G. Pagani, M. Pregnolato, M. Terreni, F. Pastoni, Eur. J.
Med. Chem. 1994, 29, 743-751.
[17] F.-J. Chen, G. Liao, X. Li, J. Wu, B.-F. Shi, Org. Lett. 2014, 16, 5644-
5647.
[4]
[5]
[6]
D. Dou, D. Alex, B. Du, K.-C. Tiew, S. Aravapalli, S. R. Mandadapu, R.
Calderone, W. C. Groutas, Bioorg. Med. Chem. 2011, 19, 5782-5787.
M. H. Norman, J. L. Kelley, E. B. Hollingsworth, J. Med. Chem. 1993,
36, 3417-3423.
[18] T. Chiyoda, K. Iida, K. Takatori, M. Kajiwara, Synlett 2000, 2000, 1427-
1428.
[19] a) J. P. Yevich, J. S. New, D. W. Smith, W. G. Lobeck, J. D. Catt, J. L.
Minielli, M. S. Eison, D. P. Taylor, L. A. Riblet, D. L. Temple, J. Med.
Chem. 1986, 29, 359-369; b) C. K. Jin, J.-K. Moon, W. S. Lee, K. S.
Nam, Synlett 2003, 2003, 1967-1968; c) P. Gopinath, K. Ramalingam,
K. M. Muraleedharan, D. Karunagaran, MedChemComm 2013, 4, 749-
752; d) A. Siegemund, K. Taubert, B. Schulze, Sulfur Rep. 2002, 23,
279-319; e) E. W. McClelland, A. J. Gait, J. Chem. Soc. 1926, 129,
921-925.
a) K.-C. Tiew, D. Dou, T. Teramoto, H. Lai, K. R. Alliston, G. H.
Lushington, R. Padmanabhan, W. C. Groutas, Bioorg. Med. Chem.
2012, 20, 1213-1221; b) H. Lai, D. Dou, S. Aravapalli, T. Teramoto, G.
H. Lushington, T. M. Mwania, K. R. Alliston, D. M. Eichhorn, R.
Padmanabhan, W. C. Groutas, Bioorg. Med. Chem. 2013, 21, 102-113.
K. H. Baggaley, P. D. English, L. J. A. Jennings, B. Morgan, B. Nunn, A.
W. R. Tyrrell, J. Med. Chem. 1985, 28, 1661-1667.
[7]
[8]
[9]
[20] W. Kim, J. Dannaldson, K. S. Gates, Tetrahedron Lett. 1996, 37, 5337-
5340.
W. L. Jorgensen, A. Trofimov, X. Du, A. A. Hare, L. Leng, R. Bucala,
Bioorg. Med. Chem. Lett. 2011, 21, 4545-4549.
[21] M. Shimizu, T. Shimazaki, T. Yoshida, W. Ando, T. Konakahara,
Tetrahedron 2012, 68, 3932-3936.
a) K. V. Thomas, Biofouling 2001, 17, 73-86; b) I. Gubelmann-Bonneau,
F. Pfammatter, C. Schlatter, M. Vogt, Pesticidal compositions. Google
Patents: 2002; c) A. Brand, J. Leitermann, R. Nyssen, K. Schubert, E.
Schuffenhauer, K. Wieser, H. Wigger, Aqueous pigment preparations.
Google Patents: 1999; d) R. E. Smith, E. S. Bensaid, Antimicrobial
mixtures of 1,3-bis(hydroxymethyl)-5,5-dimethylhydantoin and 1,2-
benzisothiazolin-3-one. Google Patents: 2000.
[22] Y. Dou, X. Huang, H. Wang, L. Yang, H. Li, B. Yuan, G. Yang, Green
Chem. 2017, 19, 2491-2495.
[23] a) L. Yang, S. Li, Y. Dou, S. Zhen, H. Li, P. Zhang, B. Yuan, G. Yang,
Asian J. Org. Chem. 2017, 6, 265-268; b) X. Huang, Y. Chen, S. Zhen,
L. Song, M. Gao, P. Zhang, H. Li, B. Yuan, G. Yang, J. Org. Chem.
2018, 83, 7331-7340; c) Y. Zong, L. Yang, S. Tang, L. Li, W. Wang, B.
Yuan, G. Yang, Catalysts 2018, 8, 48-57; d) Y. Dou, X. Huang, H.
Wang, L. Yang, H. Li, B. Yuan, G. Yang, Green Chem. 2017, 19, 2491-
2495; e) Y. Dou, L. Yang, L. Zhang, P. Zhang, H. Li, G. Yang, RSC Adv.
2016, 6, 100632-100635; f) L. Zhang, X. Huang, S. Zhen, J. Zhao, H. Li,
B. Yuan, G. Yang, Org. Biomol. Chem. 2017, 15, 6306-6309.
[24] a) T. Tim Fat, L.-T. Regis, L. Wanren, S. Michael, K. Khashayar, Mini-
Rev. Med. Chem. 2005, 5, 367-379; b) L. M. T. Frija, A. J. L. Pombeiro,
M. N. Kopylovich, Eur. J. Org. Chem. 2017, 2017, 2670-2682; c) K. M.
Dawood, T. A. Farghaly, Expert Opin. Ther. Pat. 2017, 27, 477-505; d)
Y. Li, J. Geng, Y. Liu, S. Yu, G. Zhao, ChemMedChem 2013, 8, 27-41;
e) K. Martin, V. Jarmila, Curr. Top. Med. Chem. 2016, 16, 2921-2952.
[10] J. F. Schwensen, M. D. Lundov, R. Bossi, P. Banerjee, E. Gimenez-
Arnau, J.-P. Lepoittevin, C. Lidén, W. Uter, K. Yazar, I. R. White, J. D.
Johansen, Contact Dermatitis 2015, 72, 127-138.
[11] W. G. Rice, J. G. Supko, L. Malspeis, R. W. Buckheit, D. Clanton, M.
Bu, L. Graham, C. A. Schaeffer, J. A. Turpin, J. Domagala, R. Gogliotti,
J. P. Bader, S. M. Halliday, L. Coren, R. C. Sowder, L. O. Arthur, L. E.
Henderson, Science 1995, 270, 1194-1197.
[12] a) M. Shimizu, Y. Sugano, T. Konakahara, Y. Gama, I. Shibuya,
Tetrahedron 2002, 58, 3779-3783; b) J. C. Grivas, J. Org. Chem. 1975,
40, 2029-2032.
[13] a) T. Sano, T. Takagi, Y. Gama, I. Shibuya, M. Shimizu, Synthesis 2004,
2004, 1585-1588; b) A. Henke, J. Srogl, Chem. Commun. 2010, 46,
6819-6821.
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10.1002/ejoc.201801642
European Journal of Organic Chemistry
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Sustainable Methodology
Liting Yang, Lijuan Song, Shanyu Tang,
Longjia Li, Heng Li, Bingxin Yuan,* and
Guanyu Yang*
Sustainable synthesis of 1,2-
benzisothiazol-3(2H)-ones and 1,2,4-
thiadiazoles via intramolecular S-N
bond formation were realized in
aqueous media with good to excellent
yields, which used tetra-sulfonated
cobalt phthalocyanine as a catalyst
and molecular oxygen as the
Page No. – Page No.
Co-Catalyzed Intramolecular S-N
Bond Formation in Water for 1,2-
Benzisothiazol-3(2H)-ones and 1,2,4-
Thiadiazoles Synthesis
environment friendly oxidant.
*one or two words that highlight the emphasis of the paper or the field of the study:
Sustainable Methodology
This article is protected by copyright. All rights reserved.