Synthesis of 4,8-dihydro-1: H -pyrazolo[3,4- e] [1,4]thiazepin-7(6 H)-one derivatives by solid acid-catalyzed multi-component reaction in water

Article abstract of DOI:10.1039/c6ra24310j

A solid acid functionalized with polyvinyl alcohol and hydroxyethylsulfuric acid is found to efficiently catalyze the one-pot three-component condensation of substituent-pyrazoles, aldehydes, and thioglycollic acid to afford a wide range of 4,8-dihydro-1H

Full text of DOI:10.1039/c6ra24310j

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Synthesis of 4,8-dihydro-1H-pyrazolo[3,4-e][1,4]thiazepin-7(6H)-
one derivatives by solid acid-catalyzed multi-component reaction
in water
Received 00th January 20xx,
Accepted 00th January 20xx
Furen Zhang,* Chunmei Li and Chenze Qi*
DOI: 10.1039/x0xx00000x
A solid acid functionalized with polyvinyl alcohol and hydroxyethylsulfuric acid is found to efficiently catalyze the one-pot
three-component condensation of substituent-pyrazoles, aldehydes, and thioglycollic acid to afford a wide range of 4,8-
dihydro-1H-pyrazolo[3,4-e][1,4]thiazepin-7(6H)-one derivatives with good to excellent yields. The using of recyclable
heterogeneous solid acid catalyst makes this procedure mild, simple, efficient, and sustainable.
www.rsc.org/
Tackling the current increasing environmental concerns,
sustainability has become a watchword for modern society.10
Heterogeneous catalysis has a rich history of facilitating energy
Introduction
The nitrogen-containing heterocycles comprising 1,4-oxazepines,
1,4-thiazepines, morpholines, and thiomorpholines are some of the
most important pharmacophores,1 which have been widely used for
the synthesis of pharmaceutical agents and biologically active
compounds.2 Besides, pyrazole skeletons constitute the core
structural element in both natural and synthetic bioactive
compounds, which show many pharmacological properties such as
anxiolytic,3 inhibitors of A1 adenosine receptors,4 inhibitors of
xanthine oxidases,5 treatment of Alz-heimer’s disease,6 kinase
inhibitors,7 inhibitors in immune and inflammatory cells.8 In view of
the versatile bioactivities of the above mentioned skeletons, we
reasoned that the combination of pyrazole scaffold with 1,4-
thiazepine segment might result in the discovery of unknown drug
intermediates with enhanced or new bioactivities. However,
compared with the vast attentions and numerous synthetic
methods to 1,4-thiazepines and pyrazoles, the design and synthesis
of 1,4-thiazepine compounds with pyrazole frameworks has been
less recognized and only very few literatures involved the synthesis
of such compounds.9 The previous methods employing pyrazole
were reported by Tu9b and Maheshwari9d, respectively, but those
procedures suffered from one or more shortcomings, such as
particular conditions (microwave irradiation or sonication), high
temperature, especially, the limited substrate scopes. Therefore,
the development of a facile approach for 1,4-thiazepine derivatives
implanted with pyrazole with structural diversity is still highly
desirable and valuable for medicinal chemistry and drug discovery
(Scheme 1).
efficient selective molecular transformations and contributes to
chemical manufacturing processes and industrial products.11 As a
traditional heterogeneous catalysis, solid acids are usually used in
the transes-terification and esterification of oils.12 Since some
carbonaceous materials solid acids were found owned high catalysis
activity in organic synthesis, more and more new solid acids were
synthesized and used to induce organic synthesis reaction.13 Liang
group synthesized
a series of novel sulfuric acid groups
functionalized carbonaceous materials,14 many of them showed
high catalytic activities in organic synthesis reactions. As the
continued effort of diversity synthesis of heterocyclic skeletons,15
we would like to report a green chemistry approach for the
synthesis 4,8-dihydro-1H-pyrazolo[3,4-e][1,4]thiazepin-7(6H)-one
derivatives using sulfuric acid groups functionalized carbonaceous
material (C-SO3H)14b of polyvinyl alcohol and hydroxyethylsulfuric
acid as heterogeneous catalysis.
a.School of Chemistry and Chemical Engineering, Zhejiang Key Laboratory of
Alternative Technologies for Fine Chemicals Process, Shaoxing University,
Shaoxing, Zhejiang Province 312000, China. E-mail: frzhang@usx.edu.cn (F. R.
Zhang) qichenze@usx.edu.cn (C. Z. Qi); Fax: +8657588345682; Tel:
+8657588345682
Electronic Supplementary Information (ESI) available: [details of any
supplementary information available should be included here]. See
DOI: 10.1039/x0xx00000x
Scheme 1 Strategies for the synthesis of pyrazolo[3,4-e][1,4]
thiazepines.
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performed at certain temperature catalyzed by C-SO3H (10 mg)
in different solvents including dichloromethane (CH2Cl2),
Results and discussion
The choice of a suitable catalyst is very important for
successful preparation of target product. Firstly, we started
from the reaction of 3-methyl-1-phenyl-1H-pyrazol-5-amine
trichloromethane
(CHCl3),
acetonitrile
(CH3CN),
tetrahydrofuran (THF), toluene, methanol (MeOH), ethanol
(EtOH) and water (H2O) (Table 2, entries 2-9). We found that
the protonation ability of the solvents had an obvious impact
on the yield of 4a. The aprotic solvents with different polarity
such as dichloromethane (CH2Cl2), trichloromethane (CHCl3),
acetonitrile (CH3CN), tetrahydrofuran (THF), and toluene only
gave poor yields of goal product (Table 2 entries 2-6). However,
the protic solvents such as methanol (MeOH), ethanol (EtOH)
and water (H2O) gave obvious high yields of product (Table 2,
entries 7-9). Taking into account economy, efficiency, as well
as sustainability, we chose water as the optimum reaction
medium. Then, to screen the optimum reaction temperature,
the model reaction was carried out at a temperature ranging
from 20 oC to 100 oC under above optimized reaction
conditions. As can be seen from Table 2, we found that the
yield of 4a improved obviously as the temperature increased
(
1a), benzaldehyde (2a), and thioglycollic acid (3) with
equimolar quantity for catalyst screening at 80 oC in water.
As shown in Table 1, no goal product was given even after 24 h
at 80 oC in the absence of catalyst (Table 1, entry 1). Then,
zeolite (HY) and Amberlyst-15 were used as a catalyst for the
model reaction respectively, yet the reaction did not occur and
gave no target compound (Table 1, entries 2-3). However,
when sulfonated solid acid14a synthesized with furaldehyde
and hydroxyethylsulfonic acid was used, the goal product was
obtained with 59% yield (Table 1, entry 4). Gratifyingly, when
the sulfonated solid acid14a was replaced with C-SO3H, the
target product was obtained smoothly with even excellent
yield (Table 1, entry 5). Subsequently, different Brønsted acid
such as H2SO4, TFA, PTSA, and HOAc and Lewis acids such as
AlCl3, and TiCl4 were used to catalyze the model reaction
respectively. Unfortunately, only 10-56% yields of 3-methyl-
1,4-diphenyl-4,8-dihydro-1H-pyrazolo[3,4-e][1,4]thiazepin-
7(6H)-one were obtained (Table 1, entries 6-11). From above
results it is obvious that C-SO3H shows a superior catalytic
advantage not only in promoting the reaction but also in
isolation procedure, and the best yield was obtained (Table 1,
entry 5). The subsequent results demonstrate C-SO3H (10 mg)
is enough to promote this reaction. Thus, C-SO3H (10 mg) was
employed as the catalyst for the following reactions.
o
o
from 20 C to 80 C (Table 2, entries 9-12). However, the yield
reached
a plateau when the temperature was further
increased from 80 oC to 100 oC (Table 2, entries 12-13).
o
Therefore, 80 C was chosen as reaction temperature for the
following synthesis of compound 4.
Table 2 Optimization of the solvent and temperature for the synthesis of
compound 4.a
Table 1 Screening of the catalyst for synthesis of compound 4.a
Entry
1
Solvent
-
T (oC)
80
Yield (%)b
56
2
3
4
5
6
7
8
9
CH2Cl2
CH2Cl3
CH3CN
THF
Toluene
EtOH
MeOH
H2O
reflux
reflux
80
reflux
80
reflux
reflux
80
18
36
47
41
53
81
61
87
Entry
1
2
3
4
5
6
7
8
Catalyst (mg)
-
Time (h)
Yield (%)b
24
24
24
6
6
6
6
6
6
6
0
0
0
Zeolite (HY) (10)
Amberlyst-15 (10)
Sulfonated carbon (10)c
C-SO3H (10)
H2SO4 (10)
59
87
56
43
20
34
21
10
63
88
10
11
12
13
H2O
H2O
H2O
H2O
20
40
60
100
0
20
45
89
TFA (10)
PTSA (10)
HOAc (10)
AlCl3 (10)
TiCl4 (10)
C-SO3H (5)
C-SO3H (20)
a Reaction conditions: 1a (1.0 mmol), 2a (1.0 mmol), 3 (1.0 mmol ) and C-
SO3H (10 mg) at selected temperature in different solvents. b Isolated
yields.
9
10
11
12
13
6
6
6
a Reaction conditions: 1a (1.0 mmol), 2a (1.0 mmol), 3 (1.0 mmol ) and
different catalyst at 80 oC in water. b Isolated yields. c The catalyst was
synthesized according to the methods in refs [14a].
With the above optimized reaction conditions, we then used 3-
methyl-1-phenyl-1H-pyrazol-5-amine (1a) and thioglycollic acid (3)
as model substrates and invesgated the scope of aldehydes by
using various aromatic aldehydes and aliphatic aldehydes. In all
these cases, the multi-component reaction proceeded smoothly to
give corresponding 3-methyl-1-phenyl-4,8-dihydro-1H-pyrazolo[3,4-
e][1,4]thiazepin-7(6H)-one derivatives with good to excellent yields
(Table 3, entries 1-14). Meanwhile, we also noted that the
To search for the optimal reaction media, the model
reaction was firstly carried out without using any solvent, only
middle yield of product 4a was obtained (Table 2, entry 1). To
further choose the optimum solvent, the same reaction was
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electronic nature and position of the substituents bearing the product in 72% (Table 3, entry 10). Furthermore, the 1-
aromatic rings had slight effects on the yields. The strongly electron naphthaldehyde (2k) and the heterocyclic aldehydes such as
donating 4-methoxybenzaldehyde (2f) afforded the highest yield thiophene-2-carbaldehyde (2l) still displayed high reactivities and
(Table 3, entry 6). However, the aldehydes with electron gave desired products with 81-82% yield correspondingly (Table 3,
withdrawing group universally gave slight low yields of product, and entries 11-12). In addition, it is worth mentioning that the aliphatic
the 4-nitrobenzaldehyde gave the lowest yield (Table 3, entry 5). At aldehydes such as 3-methylbutanal and nonanal also proceeded this
the same time, the position of substituents on the phenyl ring of 2 transformation and gave corresponding 3-methyl-4,8-dihydro-1H-
also affects the conversion of the reaction, ortho-substituted pyrazolo[3,4-e][1,4]thiazepin-7(6H)-one derivatives (Table 3, entries
aromatic aldehydes only give corresponding product in 72-81% 13-14).
yield and the 2,6-dichlorobenzaldehyde (2j) gave the lowest yield of
Table 3 Substrate scope of the multi-component reaction.a
Entry
1
2
3
4
5
6
7
8
R1
R2
4
4a
4b
4c
4d
4e
4f
4g
4h
4i
4j
4k
4l
4m
4n
4o
4p
4q
4r
Time (h)
Yield (%)b
87
C6H5 (1a)
C6H5 (1a)
C6H5 (1a)
C6H5 (1a)
C6H5 (1a)
C6H5 (1a)
C6H5 (1a)
C6H5 (1a)
C6H5 (1a)
C6H5 (1a)
C6H5 (1a)
C6H5 (1a)
C6H5 (1a)
C6H5 (1a)
H (1b)
C6H5 (2a)
4-FC6H4 (2b)
6
6
6
6
6
6
6
6
6
6
6
6
6
6
5
5
5
5
5
86
86
83
80
90
75
76
81
72
82
81
81
77
83
85
89
4-ClC6H4 (2c)
4-BrC6H4 (2d)
4-NO2C6H4 (2e)
4-OMeC6H4 (2f)
2-NO2C6H4 (2g)
3-NO2C6H4 (2h)
2,4-Cl2C6H3 (2i)
2,6-Cl2C6H3 (2j)
1-Naphthal (2k)
2-Thienyl (2l)
i-Butyl (2m)
9
10
11
12
13
14
15
16
17
18
19
n-Octyl (2n)
4-ClC6H4 (2c)
4-Me C6H4 (2o)
4-OMe C6H4 (2f)
1-Naphthal (2k)
2-Thienyl (2l)
H (1b)
H (1b)
H (1b)
H (1b)
80
81
4s
a Reaction conditions: 1 (1.0 mmol), 2 (1.0 mmol), 3 (1.0 mmol ) and C-SO3H (10 mg) at 80 oC in water. b Isolated yields.
To further expand the scope of the substrate, 3-methyl-1H-
pyrazol-5-amine (1b) was employed to react with representative
aldehydes (2) and thioglycollic acid (3). Similar to above multi-
component processes, the present reaction was compatible with
various aromatic aldehydes including different electronic feature
and
gave
4-aryl-3-methyl-4,8-dihydro-1H-pyrazolo[3,4-
e][1,4]thiazepin-7(6H)-one derivatives with good yields (Table 3,
entries 16-19). Subsequently, attempts to replace the methyl-1-
phenyl-1H-pyrazol-5-amine (1a) with 2,6-diaminopyrimidin-4(3H)- Scheme 2. Three-component reaction for unexpected product 5.
one (1c) resulted in a failure in directional transformation (Scheme
2). Instead, product 5 was obtained with good yield (80%), which
Additionally, in our continued study, it was also found that ethyl
probable because of the poor reactivity of -NH2 group bearing in 2-(((5-amino-3-methyl-1-phenyl-1H-pyrazol-4-yl)(argio)methyl)thio)
2,6-diaminopyrimidin-4(3H)-one (1c).
acetate derivatives 7 were obtained easily in good yields under the
similar reactions, when additional substrate ethanol was added to
react with 3-methyl-1-phenyl-1H-pyrazol-5-amine (1a), aldehydes (2)
and thioglycollic acid (3) (Scheme 3). As we anticipated, ethyl-2-
mercaptoacetate was formed firstly, which hampered the following
cyclization and the four-component product was given successfully.
To the best of our knowledge, the ethyl 2-(((5-amino-3-methyl-1-
phenyl-1H-pyrazol-4-yl)(argio)methyl)thio) acetate derivatives 7,
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which are not studied and no corresponding compounds were derivatives in good to excellent yields employing solid acid (10 mg)
reported in the literature, may be the potential pharmacological as catalyst. The major advantages of this strategy include the mild
molecules with enhanced or unknown bioactivities.
conditions, high catalytic efficiency and recyclable of catalyst, using
clean, cheap, and sustainable water as reaction media, and the
structural diversity of products. Thus, the procedure constitutes a
straightforward of various biologically active targets without
metallic contaminants.
Experimental
General
All commercially available chemicals were used without further
purification, unless otherwise stated. Analytical thin layer
chromatography (TLC) was performed using Merck silica gel GF254
plates. IR spectra were taken on a FT-IR-Tensor 27 spectrometer in
KBr pellets and reported in cm−1. NMR-data were recorded on
Bruker Avance 400 Spectrometer. 1H- and 13C-spectra were
referenced to the residue solvent signals in the deuterated solvent.
1H NMR spectra were recorded on a 400 MHz instrument. Chemical
shifts (δ) are given in ppm relative to TMS as the internal reference,
with coupling constants (J) in Hz. 13C NMR spectra were recorded at
100 MHz. Chemical shift were reported in ppm with the internal
chloroform signal at 77.0 ppm as a standard. HRMS (ESI) was
measured with a Bruker Daltonics APEXII instrument.
Scheme 3. Four-component reaction for products 7.
The solid acid catalyst was easily separated by filtered and reused
after activation by drying in vacuum oven at 100 oC for 4 h. The
catalytic reactivity of the recovered catalyst was verified in the
reaction
of
3-methyl-1-phenyl-1H-pyrazol-5-amine
(1a),
benzaldehyde (2a) and thioglycollic acid (3). The yield of product
4a was 87% using fresh solid acid, while the recovery catalyst
gave the yield of 86%, 84%, and 83% in the following three
cycles respectively. We contributed the slight reduction of
catalytic activity to the loss and contamination of the recovered
catalyst.
General procedure for synthesis of 4,8-dihydro-1H-pyrazolo [3,4-
e][1,4]thiazepin-7(6H)-one derivatives (4)
3-Methyl-1H-pyrazol-5-amine (1, 1.0 mmol) was added to a 10-mL
reaction vial in water (3.0 mL), to the resulting solution were
sequentially added aldehydes (2, 1.0 mmol), thioglycollic acid (3,
1.0 mmol), and C-SO3H (10 mg). The mixture was stirred at the
indicated temperature until TLC showed that the conversion of the
substrates was complete about 5-6 h. Then, the mixture was cooled
to room temperature and the solid was filtered. The result solid was
resolved in hot ethanol, filtered, and the mother liquor was
concentrated and recrystallized to give goal products (4).
General procedure for synthesis of 2-((argio(2,4-diamino-6-oxo-
1,6-dihydropyrimidin-5-yl)methyl)thio)acetic acid (5)
Scheme 4 Proposed mechanism for the formation of product 4a.
2,6-Diaminopyrimidin-4(3H)-one (1c, 1.0 mmol) was added to a
10-mL reaction vial in water (3.0 mL), to the resulting solution
were sequentially added 4-methylbenzaldehyde (2o, 1.0 mmol),
thioglycollic acid (3, 1.0 mmol), and C-SO3H (10 mg). The mixture
was stirred at the indicated temperature until TLC showed that the
conversion of the substrates was complete about 6 h. Then, the
mixture was cooled to room temperature and the solid was filtered.
The result solid was resolved in hot ethanol, filtered, and the
mother liquor was concentrated and recrystallized to give goal
product (5).
The reaction mechanism of this cyclization is proposed in
Scheme 4. Under the effect of solid acid, intermediate A was
formed by nucleophilic addition of active aldehyde and 3-
methyl-1-phenyl-1H-pyrazol-5-amine
underwent the dehydration to give intermediate B.
Subsequently, intermediate was formed by nucleophilic
which
successively
C
function of thioglycollic acid to intermediate B, which could be
seperated successfully. Finally, the goal product 4a was
obtained by intramolecular dehydration of intermediate C.
General procedure for synthesis of ethyl 2-(((5-amino-3-methyl -1-
phenyl-1H-pyrazol-4-yl)(aryl)methyl)thio)acetate (7)
Conclusions
3-Methyl-1-phenyl-1H-pyrazol-5-amine (1a, 1.0 mmol) was added
to a 10-mL reaction vial in water (3.0 mL), to the resulting
solution were sequentially added aromatic aldehydes (2, 1.0
In conclusion, we have described an efficient synthesis of 3-
methyl-4,8-dihydro-1H-pyrazolo[3,4-e][1,4]thiazepin-7(6H)-one
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mmol), thioglycollic acid (3, 1.0 mmol), ethanol (6, 3.0 mmol), and 3-methyl-4-(2-nitrophenyl)-1-phenyl-4,8-dihydro-1H-pyrazolo[3,4-
C-SO3H (10 mg). The mixture was stirred at the indicated e][1,4]thiazepin-7(6H)-one (4g)
Yellow solid, mp: 88-90 oC, IR (KBr, ν, cm-1): 3272, 1691, 1577,
temperature until TLC showed that the conversion of the substrates
1295, 1144, 1035, 907, 809, 733cm-1; 1H NMR (400 MHz, CDCl3):
was complete about 6 h. Then, the mixture was cooled to room
temperature and the solid was filtered. The result solid was
δ
= 8.06 (d, 2H, J = 8.0 Hz, ArH), 7.58-7.55 (m, 3H, ArH), 7.52-7.47
resolved in hot ethanol, filtered, and the mother liquor was
concentrated. The residue was purified by column chromatography
on silica gel using petroleum ether/ethyl acetate as eluent (ethyl
acetate/petroleum ether = 1:20~1:4) to provide desired product (7).
(m, 4H, ArH), 7.37 (br, s, 1H, NH), 7.23 (d, 1H, J = 7.2 Hz, ArH), 6.25
(s, 1H, CH), 3.30 (d, 1H, J = 15.2 Hz, CH2), 3.17 (d, 1H, J = 15.2 Hz,
CH2), 1.94 (s, 3H, CH3); 13C NMR (100 MHz, CDCl3):
δ = 170.0, 147.9,
134.7, 129.9, 129.7, 128.9, 125.5, 105.7, 67.1, 40.5, 33.5, 12.7;
HRMS (ESI): m/z [M + H]+ calcd for C19H17N4O3S+: 381.1016; found:
381.1019.
3-methyl-1,4-diphenyl-4,8-dihydro-1H-pyrazolo[3,4-
e][1,4]thiazepin-7(6H)-one (4a)9c
Yellow solid, mp: 74-76 oC, 1H NMR (400 MHz, CDCl3):
δ = 7.58-7.54
3-methyl-4-(3-nitrophenyl)-1-phenyl-4,8-dihydro-1H-pyrazolo[3,4-
e][1,4]thiazepin-7(6H)-one (4h) 9b
(m, 2H, ArH), 7.50-7.47 (m, 3H, ArH), 7.39-7.36 (m, 2H, ArH), 7.33-
7.29 (m, 4H, ArH+NH), 5.27 (s, 1H, CH), 3.37 (d, 1H, J = 15.2 Hz, CH2),
3.27 (d, 1H, J = 15.6 Hz, CH2), 1.92 (m, 3H, CH3).
1
Yellow solid, mp: 83-85 oC, H NMR (400 MHz, CDCl3):
δ = 8.20-8.18
(m, 2H, ArH), 7.66 (d, 1H, J = 7.6 Hz, ArH), 7.59-7.55 (m, 3H, ArH),
7.52-7.48 (m, 3H, ArH), 7.38 (br, s, 1H, NH), 5.37 (s, 1H, CH), 3.42 (d,
1H, J = 15.2 Hz, CH2), 3.18 (d, 1H, J = 15.2 Hz, CH2), 1.93 (s, 3H, CH3);
4-(4-fluorophenyl)-3-methyl-1-phenyl-4,8-dihydro-1H-
pyrazolo[3,4-e][1,4]thiazepi-7(6H)-one (4b)9d
13C NMR (100 MHz, CDCl3):
δ = 169.6, 157.7, 143.4, 135.0, 134.0,
Yellow crystal, mp: 94-96 oC, 1H NMR (400 MHz, CDCl3):
δ = 7.57-
130.2, 129.8, 129.3, 125.7, 123.0, 122.9, 105.8, 42.5, 31.8, 12.9.
7.53 (m, 2H, ArH), 7.50-7.45 (m, 3H, ArH), 7.43 (br, s, 1H, NH), 7.29-
7.25 (m, 2H, ArH), 7.05 (t, 1H, J = 8.4 Hz, ArH), 5.27 (s, 1H, CH), 3.38
(d, 1H, J = 15.2 Hz, CH2), 3.21 (d, 1H, J = 15.2 Hz, CH2), 1.92 (s, 3H,
4-(2,4-dichlorophenyl)-3-methyl-1-phenyl-4,8-dihydro-1H-
pyrazolo[3,4-e][1,4]thiazepin-7(6H)-one (4i)9b
CH3); 13C NMR (100 MHz, CDCl3):
δ = 170.2, 148.2, 136.9, 134.7,
o
1
Pale yellow crystal, mp: 219-221 C, H NMR (400 MHz, CDCl3):
δ =
130.1, 129.8, 129.2, 125.7, 115.8, 115.6, 106.9, 72.8, 42.5, 31.8,
12.8.
7.58-7.50 (m, 2H, ArH), 7.49-7.46 (m, 4H, ArH), 7.40 (br, s, 1H, NH),
7.24-7.21 (m, 1H, ArH), 7.02 (d, 1H, J = 8.4 Hz, ArH), 5.59 (s, 1H, CH),
3.36-3.25 (m, 2H, CH2), 1.86 (s, 3H, CH3).
4-(4-chlorophenyl)-3-methyl-1-phenyl-4,8-dihydro-1H-
pyrazolo[3,4-e][1,4]thiazepi-7(6H)-one (4c)9b
4-(2,6-dichlorophenyl)-3-methyl-1-phenyl-4,8-dihydro-1H-
pyrazolo[3,4-e][1,4]thiazepin-7(6H)-one (4j)
1
Yellow crystal, mp: 99-100 oC, H NMR (400 MHz, CDCl3):
δ = 7.57-
Pale yellow crystal, mp: 239-241 oC, IR (KBr, ν, cm-1): 3222, 1684,
1586, 1390, 1252, 1138, 909, 811, 753 cm-1; 1H NMR (400 MHz,
7.54 (m, 2H, ArH), 7.50-7.46 (m, 3H, ArH), 7.43 (br, s, 1H, NH), 7.35-
7.33 (m, 2H, ArH), 7.23 (d, 2H, J = 8.4 Hz, ArH), 5.24 (s, 1H, CH), 3.37
(d, 1H, J = 15.2 Hz, CH2), 3.20 (d, 1H, J = 15.2 Hz, CH2), 1.92 (s, 3H,
CH3).
CDCl3):
δ = 7.54-7.50 (m, 2H, ArH), 7.46-7.42 (m, 5H, ArH), 7.29 (br,
s, 1H, NH), 7.21 (t, 1H, J = 8.0 Hz, ArH), 6.38 (s, 1H, CH), 3.70 (d, 1H,
J = 14.8 Hz, CH2), 3.18 (dd, 1H, J = 14.8, 2.0 Hz, CH2), 1.80 (s, 3H,
4-(4-bromophenyl)-3-methyl-1-phenyl-4,8-dihydro-1H-
pyrazolo[3,4-e][1,4]thiazepi-7(6H)-one (4d) 9b
CH3); 13C NMR (100 MHz, CDCl3):
δ = 169.4, 148.2, 136.0, 135.3,
132.8, 130.2, 129.9, 129.4, 128.9, 126.3, 125.8, 37.7, 31.5, 12.6;
HRMS (ESI): m/z [M + H]+ calcd for C19H16Cl2N3OS+: 404.0386; found:
404.0395.
Yellow solid, mp: 101-102 oC, 1H NMR (400 MHz, CDCl3):
δ = 7.58-
7.54 (m, 2H, ArH), 7.50-7.46 (m, 5H, ArH), 7.32 (br, s, 1H, NH), 7.17
(d, 2H, J = 8.4 Hz, ArH), 5.22 (s, 1H, CH), 3.37 (d, 1H, J = 15.6 Hz,
CH2), 3.20 (d, 1H, J = 15.6 Hz, CH2), 1.93 (s, 3H, CH3).
3-methyl-4-(naphthalen-1-yl)-1-phenyl-4,8-dihydro-1H-
pyrazolo[3,4-e][1,4]thiazepin-7(6H)-one (4k)
3-methyl-4-(4-nitrophenyl)-1-phenyl-4,8-dihydro-1H-pyrazolo[3,4-
e][1,4]thiazepin-7(6H)-one (4e)9b
Yellow solid, mp: 238-240 oC, IR (KBr, ν, cm-1): 3169, 1682, 1588,
1492, 1254, 1138, 905, 738, 723 cm-1; 1H NMR (400 MHz, CDCl3):
Yellow solid, mp: 97-98 oC, 1H NMR (400 MHz, CDCl3):
δ = 8.24 (d,
δ
= 8.30 (d, 1H, J = 8.4 Hz, ArH), 7.95 (d, 1H, J = 7.6 Hz, ArH), 7.84 (d,
2H, J = 8.8 Hz, ArH), 7.60-7.55 (m, 2H, ArH), 7.53-7.47 (m, 5H, ArH),
7.33 (br, s, 1H, NH), 5.32 (s, 1H, CH), 3.41 (d, 1H, J = 15.2 Hz, CH2),
3.19 (d, 1H, J = 15.2 Hz, CH2), 1.93 (s, 3H, CH3).
1H, J = 8.4 Hz, ArH), 7.69-7.65 (m, 1H, ArH), 7.61-7.56 (m, 3H, ArH),
7.54-7.50 (m, 3H, ArH), 7.46 (br, s, 1H, NH), 7.41 (t, 1H, J = 7.2 Hz,
ArH), 7.12 (d, 1H, J = 6.4 Hz, ArH), 6.00 (s, 1H, CH), 3.39-3.29 (m, 2H,
CH2), 1.83 (s, 3H, CH3); 13C NMR (100 MHz, CDCl3):
δ = 169.9, 148.3,
4-(4-methoxyphenyl)-3-methyl-1-phenyl-4,8-dihydro-1H-
pyrazolo[3,4-e][1,4]thiazepin-7(6H)-one (4f) 9b
135.4, 134.5, 130.2, 129.3, 129.2, 129.0, 126.7, 126.2, 125.9, 124.9,
124.8, 123.0, 106.7, 39.2, 32.2, 12.6; HRMS (ESI): m/z [M + H]+ calcd
for C23H20N3OS+: 386.1322; found: 386.1328.
o
1
Yellow crystal, mp: 103-104 C, H NMR (400 MHz, CDCl3):
δ = 7.57-
7.53 (m, 2H, ArH), 7.50-7.46 (m, 3H, ArH), 7.32 (br, s, 1H, NH), 7.21-
7.19 (m, 2H, ArH), 6.90-6.87 (m, 2H, ArH), 5.25 (s, 1H, CH), 3.82 (s,
3H, OMe), 3.36 (d, 1H, J = 15.2 Hz, CH2), 3.25 (d, 1H, J = 15.2 Hz,
3-methyl-1-phenyl-4-(thiophen-2-yl)-4,8-dihydro-1H-pyrazolo[3,4-
e][1,4]thiazepin-7(6H)-one (4l)
CH2), 1.93 (s, 3H, CH3); 13C NMR (100 MHz, CDCl3):
δ = 170.3, 159.1,
Brown oil, IR (KBr, ν, cm-1): 3175, 1683, 1584, 1492, 1252, 1138,
148.3, 137.0, 134.6, 132.7, 130.1, 129.3, 129.1, 125.8, 114.0, 107.2,
905, 743, 718 cm-1; 1H NMR (400 MHz, CDCl3):
δ = 7.57-7.53 (m,
55.3, 42.6, 31.8, 12.8.
2H, ArH), 7.50-7.45 (m, 3H, ArH), 7.38 (br, s, 1H, NH), 7.31-7.29 (m,
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ARTICLE
Journal Name
1H, ArH), 6.95-6.93 (m, 1H, ArH), 6.84 (d, 1H, J = 3.2 Hz, ArH), 5.45 White solid, mp: 234-236 oC, IR (KBr, ν, cm-1): 3171, 1681, 1589,
(s, 1H, CH), 3.39 (s, 2H, CH2), 2.09 (s, 3H, CH3); 13C NMR (100 MHz, 1493, 1256, 1137, 905, 737, 721 cm-1; 1H NMR (400 MHz, CDCl3):
CDCl3):
δ
= 169.8, 148.1, 146.1, 134.2, 130.1, 129.2, 127.2, 126.7,
δ = 12.30 (br, s, 1H, NH), 10.05 (s, 1H, NH), 8.35 (d, 1H, J = 8.0 Hz,
126.1, 125.8, 107.4, 38.3, 31.9, 12.6; HRMS (ESI): m/z [M + H]+ calcd ArH), 7.95-7.93 (m, 1H, ArH), 7.82 (d, 1H, J = 8.4 Hz, ArH), 7.60-7.52
+
for C17H16N3OS2 : 342.0729; found: 342.0732.
(m, 2H, ArH), 7.38 (t, 1H, J = 7.6 Hz, ArH), 7.04 (d, 1H, J = 6.8 Hz,
ArH), 6.23 (s, 1H, CH), 3.21 (d, 1H, J = 15.2 Hz, CH2), 3.08 (d, 1H, J =
14.8 Hz, CH2), 1.66 (s, 3H, CH3); 13C NMR (100 MHz, CDCl3):
δ = 171.1,
4-isobutyl-3-methyl-1-phenyl-4,8-dihydro-1H-pyrazolo[3,4-
e][1,4]thiazepin-7(6H)-one (4m)
137.7, 134.2, 130.4, 129.2, 128.4, 126.6, 126.3, 126.1, 125.5, 124.2,
106.3, 38.7, 32.4, 10.4; HRMS (ESI): m/z [M + H]+ calcd for
C17H16N3OS+: 310.1009; found: 310.1015.
Yellow solid, mp: 97-98 oC, IR (KBr, ν, cm-1): 3124, 1680, 1591, 1393,
1157, 939, 809, 741, 729 cm-1; 1H NMR (400 MHz, CDCl3):
δ = 7.52-
7.48 (m, 2H, ArH), 7.44-7.40 (m, 3H, ArH), 7.07 (br, s, 1H, NH), 4.09-
4.05 (m, 1H, CH), 3.49 (d, 1H, J = 14.0 Hz, CH2), 3.13 (d, 1H, J = 13.6
Hz, CH2), 2.31 (s, 3H, CH3), 1.87-1.80 (m, 2H, CH2), 1.76-1.71 (m, 1H,
CH), 0.97 (d, J = 6.0 Hz, CH3); 13C NMR (100 MHz, CDCl3):
3-methyl-4-(thiophen-2-yl)-4,8-dihydro-1H-pyrazolo[3,4-
e][1,4]thiazepin-7(6H)-one (4s)
δ
= 170.8, Brown solid, mp: 249-250 oC, IR (KBr, ν, cm-1): 3177, 1682, 1585,
147.0, 137.3, 133.6, 129.8, 128.5, 124.7, 112.1, 46.7, 36.2, 31.0, 1492, 1250, 1137, 905, 746, 720 cm-1; 1H NMR (400 MHz, CDCl3):
25.5, 23.1, 21.5, 12.7; HRMS (ESI): m/z [M + H]+ calcd for
C17H22N3OS+: 316.1478; found: 316.1483.
δ = 12.32 (br, s, 1H, NH), 9.91 (s, 1H, NH), 7.41-7.38 (m, 1H, ArH),
6.94-6.89 (m, 2H, ArH), 5.71 (s, 1H, CH), 3.28 (d, 1H, J = 14.4 Hz,
CH2), 2.97 (d, 1H, J = 14.8 Hz, CH2), 1.94 (s, 3H, CH3); 13C NMR (100
3-methyl-4-octyl-1-phenyl-4,8-dihydro-1H-pyrazolo[3,4-
e][1,4]thiazepin-7(6H)-one (4n)
MHz, CDCl3): δ = 170.9, 148.1, 127.1, 126.3, 126.2, 107.5, 66.8, 37.3,
+
32.2, 10.3; HRMS (ESI): m/z [M + H]+ calcd for C11H12N3OS2 :
Yellow oil, IR (KBr, ν, cm-1): 3131, 1681, 1590, 1397, 1155, 939, 806,
740, 725 cm-1; 1H NMR (400 MHz, CDCl3):
δ = 7.54 (t, 2H, J = 7.2 Hz,
266.0416; found: 266.0421.
2-(((2,4-diamino-6-oxo-1,6-dihydropyrimidin-5-yl)(p-
ArH), 7.49-7.43 (m, 3H, ArH), 4.94 (t, 1H, J = 7.2 Hz, CH), 4.44 (br, s,
tolyl)methyl)thio)acetic acid (5)
1H, NH), 3.38-3.25 (m, 2H, CH2), 2.27-2.23 (m, 2H, CH2), 2.14-2.09
(m, 5H, CH3 + CH2), 1.34-1.26 (m, 10H, CH2), 0.88 (t, 3H, J = 6.4 Hz, White solid, mp: 150-152 oC, 1H NMR (400 MHz, CDCl3):
δ
= 10.07
CH3); 13C NMR (100 MHz, CDCl3):
δ = 170.3, 131.4, 130.1, 129.1, (br, s, 1H, NH), 7.26 (d, 2H, J = 8.0 Hz, ArH), 7.07 (d, 2H, J = 8.0 Hz,
125.9, 44.3, 31.8, 31.7, 31.0, 29.8, 29.4, 29.2, 29.1, 28.2, 22.7, 14.1, ArH), 6.21 (s, 2H, NH2), 5.77 (s, 2H, NH2), 5.64 (s, 1H, CH), 3.12 (d,
12.6; HRMS (ESI): m/z [M + H]+ calcd for C21H30N3OS+: 372.2104; 2H, J = 2.0 Hz, CH2), 2.23 (s, 3H, CH3).
found: 372.2108.
ethyl
2-(((5-amino-3-methyl-1-phenyl-1H-pyrazol-4-yl)(4-
4-(4-chlorophenyl)-3-methyl-4,8-dihydro-1H-pyrazolo[3,4-
e][1,4]thiazepin-7(6H)-one (4o) 9c
chlorophenyl)methyl)thio)acetate (6a)
Yellow solid, mp: 146-148 oC, IR (KBr, ν, cm-1): 3219, 1688, 1616,
= 12.32 1492, 1250, 1036, 906, 808, 741, 727cm-1; 1H NMR (400 MHz,
White solid, mp: 287-288 oC, 1H NMR (400 MHz, CDCl3):
δ
(br, s, 1H, NH), 9.92 (s, 1H, NH), 7.37-7.33 (m, 2H, ArH), 7.24-7.22 CDCl3): δ = 7.57 (d, 2H, J = 7.2 Hz, ArH), 7.56-7.50 (m, 2H, ArH), 7.47-
(m, 2H, ArH), 5.47 (s, 1H, CH), 3.25 (dd, 1H, J = 14.8, 4.8 Hz, CH2), 7.44 (m, 2H, ArH), 7.37 (d, 1H, J = 7.6 Hz, ArH), 7.34-7.31 (m, 2H,
2.98 (dd, 1H, J = 14.8, 4.8 Hz, CH2), 1.80 (s, 3H, CH3); 13C NMR (100 ArH), 5.44 (s, 1H, CH), 4.41 (s, 2H, NH2), 4.21-4.13 (m, 2H, CH2),
MHz, CDCl3):
10.4.
δ = 171.3, 142.3, 132.0, 130.1, 128.8, 106.5, 41.4, 31.9, 3.25-3.15 (m, 2H, CH2), 2.12 (s, 3H, CH3), 1.30 (t, 3H, J = 7.2 Hz, CH3);
13C NMR (100 MHz, CDCl3):
δ = 170.5, 137.6, 133.3, 129.6, 128.8,
127.4, 123.9, 61.6, 44.1, 33.6, 14.2, 12.4; HRMS (ESI): m/z [M + H]+
3-methyl-4-(p-tolyl)-4,8-dihydro-1H-pyrazolo[3,4-e][1,4]thiazepin-
7(6H)-one (4p) 9c
calcd for C21H23ClN3O2S+: 416.1194; found: 416.1188.
White solid, mp: >300 oC, 1H NMR (400 MHz, CDCl3):
1H, NH), 9.88 (s, 1H, NH), 7.09 (s, 4H, ArH), 5.40 (s, 1H, CH), 3.25 (d,
δ
= 12.30 (br, s,
ethyl
2-(((5-amino-3-methyl-1-phenyl-1H-pyrazol-4-yl)(p-
tolyl)methyl)thio)acetate (6b)
1H, J = 14.8 Hz, CH2), 2.98 (d, 1H, J = 14.8 Hz, CH2), 2.25 (s, 3H, CH3), Red brown oil, IR (KBr, ν, cm-1): 3179, 1681, 1586, 1492, 1250,
1.78 (s, 3H, CH3); 13C NMR (100 MHz, CDCl3):
129.4, 128.2, 106.9, 42.0, 32.1, 21.1, 10.4.
δ δ = 7.63 (d,
= 171.4, 140.0, 136.7, 1137, 907, 739, 721 cm-1; 1H NMR (400 MHz, CDCl3):
2H, J = 8.0 Hz, ArH), 7.59-7.53 (m, 2H, ArH), 7.48 (d, 1H, J = 8.0 Hz,
ArH), 7.37 (d, 2H, J = 8.0 Hz, ArH), 7.19 (d, 2H, J = 8.0 Hz, ArH), 5.43
(s, 1H, CH), 4.21-4.15 (m, 2H, CH2), 3.21 (s, 2H, CH2), 2.36 (s, 3H,
CH3), 2.23 (s, 3H, CH3), 1.30 (t, 3H, J = 7.2 Hz, CH3); 13C NMR (100
4-(4-methoxyphenyl)-3-methyl-4,8-dihydro-1H-pyrazolo[3,4-
e][1,4]thiazepin-7(6H)-one (4q) 9c,9d
Pale yellow solid, mp: 278-280 oC, 1H NMR (400 MHz, CDCl3):
δ =
MHz, CDCl3):
δ = 170.5, 129.8, 129.3, 124.3, 114.1, 61.6, 55.3, 44.0,
33.7, 29.7, 14.2; HRMS (ESI): m/z [M + H]+ calcd for C22H26N3O2S+:
12.31 (br, s, 1H, NH), 9.87 (s, 1H, NH), 7.12 (d, 2H, J = 8.4 Hz, ArH),
6.85 (d, 2H, J = 8.8 Hz, ArH), 5.40 (s, 1H, CH), 3.71 (s, 3H, OMe), 3.25
(d, 1H, J = 14.8 Hz, CH2), 2.97 (d, 1H, J = 14.4 Hz, CH2), 1.77 (s, 3H,
396.1740; found: 396.1735.
CH3); 13C NMR (100 MHz, CDCl3):
δ = 171.5, 158.6, 134.8, 129.4,
ethyl
2-(((5-amino-3-methyl-1-phenyl-1H-pyrazol-4-yl)(4-
methoxyphenyl)methyl)thio)acetate (6c)
114.2, 107.1, 66.8, 55.5, 41.9, 32.2, 10.5.
Red brown oil, IR (KBr, ν, cm-1): 3218, 1680, 1608, 1390, 1070,
900, 842, 722 cm-1; 1H NMR (400 MHz, CDCl3):
δ = 7.61 (d, 2H, J =
3-methyl-4-(naphthalen-1-yl)-4,8-dihydro-1H-pyrazolo[3,4-
e][1,4]thiazepin-7(6H)-one (4r)
8.0 Hz, ArH), 7.53 (t, 2H, J = 7.6 Hz, ArH), 7.42 (d, 3H, J = 8.8 Hz,
6 | J. Name., 2012, 00, 1-3
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DOI: 10.1039/C6RA24310J
Journal Name
ARTICLE
R. Singh, J. Joshi and S. Maheshwari, Res. Chem. Intermed.,
2015, 41, 4213-4226.
10 A. F. Lee and K. Wilson, Catal. Today, 2015, 242, 3-18.
11 (a) J. M. Thomas, Proc. R. Soc. A: Math. Phys. Eng. Sci., 2012,
468, 1884-1903. (b) G. A. Somorjai, H. Frei and J. Y. Park, J.
Am. Chem. Soc., 2009, 131, 16589-16605.
ArH), 6.90 (d, 2H, J = 8.8 Hz, ArH), 5.42 (s, 1H, CH), 4.71 (s, 2H, NH2),
4.22-4.13 (m, 2H, CH2), 3.82 (s, 3H, OMe), 3.24-3.16 (m, 2H, CH2),
2.19 (s, 3H, CH3), 1.30 (t, 3H, J = 7.2 Hz, CH3); 13C NMR (100 MHz,
CDCl3):
δ = 170.5, 130.1, 129.6, 127.9, 124.7, 61.5, 44.3, 33.5, 29.7,
18.9, 14.1; HRMS (ESI): m/z [M + H]+ calcd for C22H26N3O3S+:
12 (a) K. Narasimharao, D. R. Brown, A. F. Lee, A. D. Newman, P.
F. Siril, S. J. Tavener and K. Wilson, J. Catal., 2007, 248, 226-
234; (b) K. Suwannakarn, E. Lotero, K. Ngaosuwan and J. G.
Goodwin Jr., Ind. Eng. Chem. Res., 2009, 48, 2810-2818; (c)
M. Kouzu, A. Nakagaito and J.-S. Hidaka, Appl. Catal. A: Gen.,
2011, 405, 36-44; (d) E. Lotero, Y. Liu, D. E. Lopez, K.
Suwannakarn, D. A. Bruce and J. G. Goodwin, Ind. Eng. Chem.
Res., 2005, 44, 5353-5363.
412.1689; found: 412.1694.
ethyl 2-(((5-amino-3-methyl-1-phenyl-1H-pyrazol-4-yl)(thiophen-2-
yl)methyl)thio)acetate (6d)
Brown oil, IR (KBr, ν, cm-1): 3177, 1680, 1585, 1491, 1259, 1134,
909, 745, 720 cm-1; 1H NMR (400 MHz, CDCl3):
δ = 7.56 (d, 2H, J =
8.0 Hz, ArH), 7.50-7.47 (m, 2H, ArH), 7.37-7.33 (m, 1H, ArH), 7.27-
7.24 (m, 1H, ArH), 7.08-7.06 (m, 1H, ArH), 5.65 (s, 1H, CH), 4.30 (s,
2H, NH2), 4.21-4.13 (m, 2H, CH2), 3.28-3.20 (m, 2H, CH2), 2.20 (s, 3H,
CH3), 1.30 (t, 3H, J = 7.2 Hz, CH3); 13C NMR (100 MHz, CDCl3):
13 (a) R. H. Vekariya, K. D. Patel and H. D. Patel, RSC
Adv., 2015, 5, 90819-90837; (b) S. S. Kauthale, S. U. Tekale, A.
B. Rode, S. V. Shinde, K. L. Ameta and R. P. Pawar, Heterog.
Catal., 2015, 133-162; (c) G. Mohammadi Ziarani, N. Lashgari
and A. Badiei, J. Mol. Catal. A: Chem., 2015, 397, 166-191; (d)
M. B. Gawande, R. Hosseinpour and R. Luque, Curr. Org.
Synth., 2014, 11, 526-544; (e) P. Gholamzadeh, G.
Mohammadi Ziarani, N. Lashgari, A. Badiei and P.
Asadiatouei, J. Mol. Catal. A: Chem., 2015, 391, 208-222; (f)
M. K. Patil, A. N. Prasad and B. M. Reddy, Curr. Org.
Chem., 2011, 15, 3961-3985.
δ =
170.5, 148.3, 143.7, 143.5, 129.6, 127.4, 126.9, 125.9, 125.4, 123.9,
99.2, 61.6, 40.0, 33.6, 14.2, 12.3; HRMS (ESI): m/z [M + H]+ calcd for
+
C19H22N3O2S2 : 388.1148; found: 388.1156.
Acknowledgements
14 (a) X. Z. Liang, M. F. Zeng and C. Z. Qi, Carbon, 2010, 48
,
We thank the Natural Science Foundation of Zhejiang Province
(No. LY16B020007) and the Foundation of Education
Department of Zhejiang Province (No. Y201533906) for
financial support.
1844-1848; (b) X. Z. Liang, H. Q. Xiao, Y. M. Shen and C. Z. Qi,
Mater. Lett., 2010, 64, 953-955; (c) X. Z. Liang, Chem. Eng. J.,
2015, 264, 251-257; (d) X. Z. Liang, H. Q. Xiao and C. Z. Qi,
Fuel Process. Technol., 2013, 110, 109-113; (e) X. Z. Liang, Ind.
Eng. Chem. Res., 2013, 52, 6894-6900; (f) X. Z. Liang and J. G.
Yang, Green Chem., 2010, 12, 201-204; (g) X. Z. Liang, S. Gao,
J. G. Yang and M. Y. He, Catal. Lett., 2008, 125, 396-400.
15 (a) C. M. Li, X. Z. Liang, F. R. Zhang and C. Z. Qi, Catal.
Commun., 2015, 62, 6-9; (b) F. R. Zhang, C. M. Li, C. Wang
and C. Z. Qi, Org. Biomol. Chem., 2015, 13, 5022-5027; (c) Z.
Chen, Y. X. Shi, Q. Q. Shen, H. X. Xu and F. R. Zhang,
Tetrahedron Lett., 2015, 56, 4749-4752; (d) C. M. L and F. R.
Notes and references
1
2
(a) M. D. Ghooghe, T. Vanlangendonck, K. W. THrnroos and N.
De Kimpe, J. Org. Chem., 2006, 71, 4678-4681; (b) R. Pedrosa,
C. AndrIs, P. MendiguchJa and J. Nieto, J. Org. Chem., 2006,
71, 8854-8863; (c) B. A. Lanman and A. G. Myers, Org. Lett.,
2004,
(a) B. Zaleska, D. Ciez, J. Grochowski, P. Serda and W. Winnik,
Liebigs Ann., 1996, , 211-215; (b) P. G. Sammers, Chem. Rev.,
6, 1045-1047.
Zhang, RSC Adv., 2016, 6, 75359-75364.
2
1976, 76, 113-155; (c) S. A. Matlin and L. Chan, Chem.
Commun., 1980, 798-799; (d) A. Levai, J. Ott and G. Snatzke,
Monatsh. Chem., 1992, 123, 919-930; (e) J. Bohrisch, H. Faltz,
M. Patzel and J. Liebscher, Tetrahedron, 1994, 50, 10701-
10708.
3
4
B. A. Meiners and A. I. Salama, Eur. J. Pharmacol., 1982, 78,
315-322.
F. Manetti, S. Schenone, F. Bondavalli, C. Brullo, O. Bruno, A.
Ranise, L. Mosti, G. Menozzi, P. Fossa, M. L. Trincavelli, C.
Martini, A. Martinelli, C. Tintori and M. Botta, J. Med. Chem.,
2005, 48, 7172-7185.
5
6
7
B. Lynck, M. Khan, H. Teo and F. Pedrotti, Can. J. Chem., 1988,
66, 420-428.
Y. L. Chen, WO9534563 A1, 1995; Chem. Abstr., 1995, 124
232447.
,
L. Revesz, E. Blum, F. E. Di Padova, T. Buhl, R. Feifel, H. Gram,
P. Hiestand, U. Manning, U. Neumann and G. Rucklin, Bioorg.
Med. Chem. Lett., 2006, 16, 262-266.
8
9
J. N. Hamblin, T. D. R. Angell, S. P. Ballantine, C. M. Cook, A.
W. J. Cooper, J. Dawson, C. J. Delves, P. S. Jones, M. Lindvall,
F. S. Lucas, C. J. Mitchell, M. Y. Neu, L. E. Ranshaw, Y. E.
Solanke, D. O. Somers and J. O. Wiseman, Bioorg. Med. Chem.
Lett., 2008, 18, 4237-4241.
(a) S.-J. Tu, X.-D. Cao, W.-J. Hao, X.-H. Zhang, S. Yan, S.-S. Wu,
Z.-G. Han and F. Shi, Org. Biomol. Chem., 2009, 7, 557-563; (b)
F. Shi, X.-N. Zeng, X.-D. Cao, S. Zhang, B. Jiang, W.-F. Zheng
and S.-J. Tu, Bioorg. Med. Chem. Lett., 2012, 22, 743-746; (c)
R. Abonia, Curr. Org. Synth., 2014, 11, 773-786; (d) A. Dandia,
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DOI: 10.1039/C6RA24310J
Synthesis of 4,8-dihydro-1H-pyrazolo[3,4-e][1,4]thiazepin
-7(6H)-one derivatives by solid acid-catalyzed
multi-component reaction in water