N,2-Dibromo-6-chloro-3,4-dihydro-2H-benzo[e][1,2,4]thiadiazine-7-sulfonamide 1,1-dioxide: An efficient and homogeneous catalyst for one-pot synthesis of 4H-pyran, pyranopyrazole and pyrazolo[1,2-b]phthalazine derivatives under aqueous media

Article abstract of DOI:10.1039/c5ra10730j

N,2-Dibromo-6-chloro-3,4-dihydro-2H-benzo[e][1,2,4]thiadiazine-7-sulfonamide 1,1-dioxide (DCDBTSD) as a highly efficient and homogeneous catalyst was successfully applied for the synthesis of 4H-pyran, pyranopyrazole and pyrazolo[1,2-b]phthalazine derivat

Full text of DOI:10.1039/c5ra10730j

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ARTICLE
N,2-dibromo-6-chloro-3,4-dihydro-2H-benzo[e][1,2,4] thiadiazine-
7-sulfonamide 1,1-dioxide: An efficient and homogeneous catalyst
for one-pot synthesis of 4H-pyran , pyranopyrazole and
pyrazolo[1,2-b] phthalazine derivatives under aqueous media
Received 00th January 20xx,
Accepted 00th January 20xx
DOI: 10.1039/x0xx00000x
Ardeshir Khazaei,*a Mohammad Ali Zolfigol,*a Fatemeh Karimitabar,a Iraj Nikokarb and Ahmad
Reza Moosavi-Zarec
www.rsc.org/
N,2-dibromo-6-chloro-3,4-dihydro-2H-benzo[e][1,2,4] thiadiazine-7-sulfonamide 1,1-
dioxide (DCDBTSD) as a highly efficient and homogeneous catalyst was successfully
applied for the synthesis of 4H-pyran , pyranopyrazole and pyrazolo[1,2-b] phthalazine
derivatives by the one-pot multi-component reaction (MCR) in water. The described
method has some advantages such as mild and neutral reaction media, high yields, short
reaction times, cleaner and easier reaction profiles and compliance with green chemistry
protocols.
Introduction
anticonvulsant, cardiotonic, and vasorelaxant.8 Various catalysts
Water as an available, inexpensive, nonflammable, nonhazardous, including dodecylphosphonic acid,9a Ce(SO4)2,9b heteropolyacids,9c
nontoxic, uniquely redoxstable solvent in enormous quantities, can Mg(HSO4)2,9d silica sulfuric acid9e and p-TSA9f have been used for
accelerate the rate of organic reactions even for water-insoluble the synthesis of these compounds.
reactants as well as product isolation by straightforward filtration.1 However, some reported methods for the synthesis of mentioned
Thus, the development of synthetically useful and convergent compounds suffer from one or more of disadvantages such as using
multicomponent reactions (MCRs) using water as a green reaction toxic, corrosive, expensive and/or large amount of catalysts, long
medium is more demand.1 Multi-component reactions (MCRs) play reaction time, toxic and corrosive solvents and strong acidic media.
an important role in combinatorial chemistry because of the ability Because of the importance of these compounds, the investigation
to preparation of target compounds with greater efficiency and for a milder, more eco-friendly under green, neutral and aqueous
atomic economy by generating structural complexity in a single step conditions and faster method with higher yields is still needed.
from three or more reactants.2
A large group of compounds generically called N-halo reagents that
The preparation of tetrahydrobenzo[b]pyrans are important due to are used as potentially reactive intermediates. These compounds
their significant anti-coagulant, diuretic, spasmolytic, anti-cancer, are widely used in organic synthesis and in the chemistry of natural
antihypertensive, calcium antagonists spasmolytic, pharmaceuticals compounds. Some specific features of N-halo reagents such as high
and anti-anaphylactic properties.3 Several methods have been activity of the N-X bond and the various modes of splitting of this
introduced for the synthesis of tetrahydro-4H-benzopyran bond cause their wide application in organic transformations.10-12
derivatives using different catalyst such as [cmmim]Br,4a Having above facts and in continuation of our previous studies on
hexadecyldimethylbenzyl ammonium bromide (HDMBAB),4b the applications of N-halo reagents in organic synthesis,13–21 we
Na2SeO4,4c [Pyridine–SO3H]Cl,4d magnesium oxide,4e (S)-proline.4f
have
recently
used
N,2-dibromo-6-chloro-3,4-dihydro-2H-
Pyranopyrazoles are fused heterocyclic compounds, which are benzo[e][1,2,4]thiadiazine-7-sulfonamide 1,1-dioxide (DCDBTSD)
important because of their biological properties such as fungicidal,5a (Figure 1) as an efficient and homogeneous catalyst for the
bactericidal,5b vasodilatory activities5c and they act as anticancer synthesis of 4H-pyran and pyrazolo[1,2-b] phthalazine and
agents.5d Some catalysts have been used to promote this reaction pyranopyrazole derivatives.
such as imidazole,6 [Dsim]AlCl4,7a Silicotungstic acid,7b L-Proline,7c
isonicotinic acid.7d
2H-indazolo[2,1-b]phthalazine-triones,
as
N-heterocycles
compounds, show biological and pharmacological activities such as
Figure 1. The structure of N,2-dibromo-6-chloro-3,4-dihydro-2H-benzo [e]
[1,2,4] thiadiazine-7-sulfonamide 1,1-dioxide (DCDBTSD).
Results and discussion
a.Faculty of Chemistry, Bu-Ali Sina University, Hamedan 6517838683, Iran.
b Department of Medical Biotechnology, Guilan University of Medical Sciences,
Rasht, Iran.
c Department of Chemistry, University of Sayyed Jamaleddin Asadabadi, Asadabad,
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 1
6541835583, Iran.
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N,2-dibromo-6-chloro-3,4-dihydro-2H-benzo[e][1,2,4]thiadiazine-7-
sulfonamide 1,1-dioxide (DCDBTSD) was prepared via a simple
1
procedure and fully characterized by IR, UV, H and 13C NMR, XRD,
TG/DTG as well as mass spectra and used as an efficient catalyst for Scheme 1. The synthesis of 4H-Pyrans.
the preparation of 4,40-(arylmethylene)-bis(3-methyl-1-phenyl-1H- Table 2. The preparation of 4H-pyran derivatives by the reaction of
pyrazol-5-ol)s via one-pot pseudo five component condensation chroman-2,4-dione, aldehydes and malononitrile using DCDBTSD.
reaction of phenylhydrazine, acetoacetate derivatives and
arylaldehydes.13
In order to expand the application, efficacy and the scope of
DCDBTSD in the synthesis of heterocyclic compound, initially, the
Entry
Product
Yielda
Time
(min)
M.p. (Lit)Ref
synthesis of 4H- pyran derivatives via the one-pot condensation
reaction of reactive α-methylene group with aromatic aldehydes
and malononitrile was studied.
In order to optimize the reaction conditions, the reaction of 4-
hydroxycoumarine (1) (1 mmol), 4-nitrobenzaldehyde (2) (1 mmol)
and malononitrile (3) (1.2 mmol) as model reaction was
investigated in the variation of reaction parameters, such as
catalyst quantity, reaction temperature and kinds of solvents. The
results are summarized in Table 1.
1
95
20
263–265 (262-264)22
2
90
30
260–262 (258-260)22
As it is shown at Table 1, 10 mol% of DCDBTSD (0.0455 g) in water
was the best reaction condition for the described reaction (Table 1,
entry 3). Notably, no product was observed in the absence of
catalyst (Table 1, entry 1) which further requires the use of
DCDBTSD in this transformation. To optimize the reaction
temperature, we also performed several experiments in water at
25, 60, and 80 °C. It was found that the excellent yield of product
was achieved at 80 °C (Table 1, entry 3).
3
4
85
82
25
15
286-288(289–290)23
Also, the reaction could be efficiently done in all the tested solvents
(Table 1, entries 3 and 7-9). The reaction using water as the solvent
lead to higher yields and shorter reaction time than those using
methanol, ethanol and acetonitrile as solvent. Thus, water, which
additionally is an available, low-cost, safe, harmless, was chosen as
the solvent for all further reactions.
250–252 (247-249)23
5
6
80
85
40
60
257–259 (256-258)22
Table 1. Optimization of reaction conditions for the preparation of 4H-pyran
derivatives.a
Entry
Solvent
Temp.
Time
(min)
Yelidb
Amount of
catalyst/mol%
269-271(266–268)14
1
2
3
4
-
H2O
H2O
H2O
H2O
80
80
80
80
240
70
Trace
82
5
10
20
30
88
30
88
5
6
7
8
9
10
10
10
10
10
10
10
H2O
H2O
MeOH
EtOH
CH3CN
neat
60
r.t
80
80
80
80
60
150
60
40
60
60
79
40
70
85
78
68
7
85
80
30
80
253-254 (251-252)14
aModel reactions: 4-hydroxycoumarine 1 (1 mmol), 4-nitrobenzaldehyde 2
(1 mmol), malononitrile 3 (1 mmol) and DCDBTSD.
b Isolated yield.
9
223-224 (223-224)24
With the optimized conditions in hand, to outline this approach, the
scope and generality of this protocol was next examined by
employing a good range of aromatic aldehydes possessing a
reactive α-methylene group and malononitrile (Scheme 1).
All the reactions proceeded efficiently under the optimized
conditions (Tables 2 and 3).
a Isolated yield.
Table 3. The preparation of 4H-pyran derivatives by the reaction of
naphthalen-1-ol, aldehydes and malononitrile using DCDBTSD.
2 | J. Name., 2012, 00, 1-3
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Ar
CN
CN
9
OH
NH2
290-292(291-292)13b
4q
40
85
O
4i-n
NH2
O
CN
(DCDBTSD) 10%
Water, 80 o
H
O
or
or
O
C
CN
Ar
OH
NH2
CN
Cl
4r
CN
10
85
216–218 (214-215)24
Ar
22
NH2
4o-u
O
Entry
Product
Yielda
Time
(min)
M.p. (Lit)Ref
O2N
4s
CN
92
186–188 (187-189)27
30
NH2
1
85
247–248 (247-248)24
11
12
13
20
O
Br
4t
CN
NH2
238–240 (238-240)27
30
35
2
3
92
86
246–248 (243-244)24
207–209 (207-209)24
91
25
O
CN
NH2
4u
84
30
271-274(273-275)14
O
a Isolated yield.
211–212(213-214)24
Aromatic aldehydes with bearing both electron-withdrawing
and electron-donating groups in ortho, meta and para
positions of the aromatic ring were converted into favorite
products in good to excellent yields.
4
15
91
Moreover, the presented methodology was used successfully
for various carbonyl compounds which have a reactive
α-methylene group, and corresponding desired products were
obtained in good to excellent yields without observing any by-
products.
5
6
25
25
83
87
258–261 (259-260)25
We also compared the result of the present DCDBTSD with
other catalysts reported in the literature such as
triethylbenzylammonium Chloride (TEBA), PEI@Si–MNPs,
Hexamethylenetetramine (HMT) and TiO2 nanowires (TiO2
NWs) for preparation of 4H-Pyran derivatives (Table 4). Table 4
obviously demonstrates that DCDBTSD is effective catalysts in
terms of reaction time and yield of obtained product relative
to other reported catalysts.
NH2
CN
4n
225–227 (222-223)24
O
OEt
OH
NC
4o
CN
Table 4. Comparison of the results of with other catalysts reported in
literature with DCDBTSD in the synthesis of 4H-Pyran derivatives.
NH2
7
8
79
25
280–282(284-286) 25
O
Entry
Catalyst
Conditions
Time
(min)
Yielda
Ref.
1
2
3
4
TEBA
H2O, 90 oC
600
50
88
96
95
90
95
28
3
Cl
CN
PEI@Si–MNPs
HMT
H2O, Reflux
NH2
4p
90
20
236-239 (237-238)26
EtOH, Reflux
EtOH/H2O(1/1), Reflux
H2O, 80 oC
40
23
29
O
TiO2 NWs
DCDBTSD
40
b
5
20
-
a
Yields refer to isolated pure products. Based on the reaction of 4-
hydroxycoumarine 1 (1 mmol), 3-nitrobenzaldehyde
malonitrile 3 (1 mmol) in corresponding condition.
b The presented work.
2 (1 mmol),
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Indole holds
a noticeable ability among the various
Heterocycles containing pyrazole rings are important target
compounds in synthetic and medicinal chemistry because the
ring is a key moiety in various biologically active compounds.38
Pyrazole derivatives have been widely studied in the
development of insecticides, acaricides, fungicides, herbicides,
dyes, and reagents because of their efficiency, low toxicity,
heterocyclic systems because it is present as a core unit in a
number of compounds having a wide spectrum of biological
activates.30
It has been reported that the spiro-oxindole heterocyclic
framework is an important structural motif in biologically
relevant compounds as natural products and pharmaceuticals,
unique reaction mechanisms, safety, lack of cross-resistance,
and other characteristics.38,
e.g., surugatoxin, horsfiline, spirotryprostatin
A and B,
41
elacomine, gelsemine, alstonisine and strychnofoline.31-37
The development of efficient and convenient syntheses of
novel bioactive organic compounds, such as spirooxindoles is
an important current research area, with MCRs considered the
most efficient method of preparing spirooxindoles.38 To
further expand the scope of the reaction, it was meaningful
thought to replace aromatic aldehydes with N-alkyl isatin
derivatives in order to show the versatility of this protocol
(Scheme 2).
Being inspired by the above
results and also in continuation of our interests to extend the
scope of the N-bromo sulfonamide reagent in the synthesis of
heterocyclic compounds, we investigated the three-
component reaction of aromatic aldehydes possessing a 3-
methyl-1-phenyl-2-pyrazolin-5-one and molonitrile in the
present of DCDMTSD. (Scheme 3).
Ar
CN
NH2
N
N
O
N
O
N
CN
CN
(DCDMTSD) 10 %
H2O, 80 o
O
Scheme 2. Synthesis of spiro[2-amino-4H-pyran-oxindoles].
+
+
H
Ar
C
8a-k
3
Scheme 3. Synthesis2of 1,4-dihydropyrano[2,3-c]pyrazoles.
7
As can be seen from Table 6, for precursors bearing either
electron-donating or electron-withdrawing, the reactions all
proceeded very smoothly to provide the desired products. The
property of the electronic character of substituents on the
aromatic ring of the aldehyde did not exert an obvious effect
on the reaction yields. All desired products were obtained in
high yields and in short reaction times.
At first, N-alkyl isatin derivatives were prepared by the
reaction of isatin with K2CO3 and alkyl halide(Scheme 3).39
To our surprise, N-alkyl isatin derivatives were easily
transformed into the desired products in excellent yields
(Table 5).
Table 6. The preparation of 1,4-dihydropyrano[2,3-c]pyrazole
derivatives.
Table 5. The preparation of spiro[2-amino-4H-pyran-oxindole]
derivatives.
Entry
1
Product
Yielda
Time (min)
M.p. (Lit)Ref
Entry
Structure
Yielda
Time
(min)
M.p. (Lit)Ref
80
25
198–200
(197–199)42a
1
95
40
45
296-298
(303)40a
277-279
(278-
280)40b
2
3
90
2
92
25
230–232
(
233–235)42b
95
95
30
35
270-272
268-270
3
95
20
194–196
(192–195)42a
4
a Isolated yield.
a Isolated yield.
4 | J. Name., 2012, 00, 1-3
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Table 6. Continued.
prepare 3-amino -1H-pyrazolo[1,2-b]phthalazine-5,10-dione by
three-component reaction of aromatic aldehydes or N-alkyl
Entry
Product
Yielda
Time (min)
M.p. (Lit)Ref
isatin derivatives possessing
a 2,3-dihydrophthalazine-1,4-
dione and malonitrile (scheme 4).
4
83
30
173-175
(170-171)43
Scheme 4. Synthesis of 1H-pyrazolo[1,2-b]phthalazine-5,10-diones.
As is it shown in Table 7, the presented procedure provides an
efficient and green approach for the synthesis of 3-amino -1H-
pyrazolo[1,2-b]phthalazine-5,10-dione derivatives. According
to the obtained results (Table 7), DCDBTSD could be applicable
for the synthesis of various types of nitrogen-containing
heterocyclic compounds.
5
79
30
173-175
(172–174)29
Table 7. The preparation of 1H-pyrazolo[1,2-b]phthalazine-5, 10-dione
derivatives.
6
80
35
159-162 (159-
160)43
Entry
1
Product
Yielda
Time (min)
M.p. (Lit)Ref
7
88
20
184–185
184–185)42b
(
80
30
271-273
(276–278)38
8
78
30
183-185
(188–191)29
2
93
15
271–273
(270–272)51
9
80
40
166-168
(169-170)30
3
95
15
229–230
(228–229)52
10
81
30
212–214
(210–212)29
4
82
25
250-252
(253–255)38
a Isolated yield.
5
85
35
154–156
(152–154)52
Heterocyclic having bridgehead hydrazine have been studied
for over century owing to their pharmacological
a
characteristics and clinical applications.38, 44, 45 Thus, more and
more research briefs have been reported in the past five
decades.46-50 In order to expand the application of DCDBTSD in
the synthesis of heterocyclic compounds, we decided to
a Isolated yield.
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Table 7. Continued.
Entry
b]phthalazine]-2,5',10'-trione(12a-d) derivatives in the
presence of DCDMTSD
Product
Yielda
Time (min)
M.p. (Lit)Ref
.
As Table 8 Table 9, indicates that the desired products were
obtained in all cases with excellent yields. Our effort to use
N-Substituted isatins as a starting material with active carbonyl
functional group in the above mentioned MCR was also
successful verifying to the flexibility of the existing procedure.
Table 8. The preparation of spiro[pyrano[2,3-c]pyrazoles] derivatives.
10f
6
80
20
250–252 (248–
250)53
O
O
N
N
CN
NH2
O
Br
10g
7
87
20
264–266 (263–
265)53
O
N
N
CN
NH2
O
Yielda
M.p. (Lit)Ref
Time (min)
Entry
Structure
10h
8
87
20
268–268 (266–
267)53
O
NO2
1
N
CN
N
237-238
(236-237) 55
94
30
NH2
O
OH
10i
9
80
35
271–273 (270–
272)54
O
2
3
228-230
N
90
35
(232–234) 56
CN
NH2
N
O
10j
Br
10
81
15
274–276 (271–
273)53
O
N
89
40
210-212
198-200
CN
NH2
N
O
O
4
87
40
10k
84
20
275–277 (276–
278)51
N
N
a Isolated yield.
11
CN
NH2
Table
9.
The
preparation
spiro[indoline-3,1'-pyrazolo[1,2-
O
b]phthalazine] derivatives.
a Isolated yield.
To evaluate the generality and versatility of our catalyst for the
preparation of bioactive compounds, we decided synthesis of
spiro[indoline-3,40-pyrano [2,3-c]pyrazole] derivatives and 3'-
aminospiro[indoline-3,1'-pyrazolo [1,2-b]phthalazine]-2,5',10'-
trione using DCDBTSD (scheme 7). For this purpose, we have
examined the reaction of N-Substituted isatins, 3-methyl-1-
phenyl-2-pyrazolin-5-one or 2,3-dihydrophthalazine-1,4-dione
with malononitrile (scheme 5).
Entry
1
Structure
Yielda
Time (min)
M.p. (Lit)Ref
92
20
263–265
(260–261)
44
O
N
O
O
N
NH
N
NH2
N
N
2
90
20
260-263
(265-266) 57
NH
O
O
N
NH2
CN
O
9
CN
CN
7
O
CN
O
+
N
R
H2O, 80 0C, Cat.
H2O, 80 0C, Cat.
N
O
O
N
R
R
5
12a-d
3
11a-d
Scheme 5. Synthesis of spiro[indoline-3,4’-pyrano[2,3-
c]pyrazole] (11a-d) and spiro[indoline-3,1'-pyrazolo[1,2-
6 | J. Name., 2012, 00, 1-3
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A mixture of aromatic aldehyde 2 (1 m mol), malonitrile 3 (1.2
m mol), 3-methyl-1-phenyl-2-pyrazolin-5-one 7 (1mmol) and
DCDBTSD (0.0455 g, 10 mol%) were added to 2 mL water and
the reaction mixture was stirred at 80 °C for the appropriate
time as mentioned in Table 6. After completion of the
reaction, as monitored by TLC, the reaction mixture was
cooled to room temperature and the solid product was
obtained by simple filtration and the solid residue was finally
recrystallized from EtOH.
3
86
87
25
25
218--220
210-212
4
a Isolated yield.
Experimental
Materials
General procedure for the synthesis of 10a-k
A mixture of aromatic aldehyde 2 (1 m mol), malonitrile 3 (1.2
mmol), 2,3-dihydrophthalazine-1,4-dione
9 (1 mmol) and
DCDBTSD (0.0455 g, 10 mol%) were added to 2 mL water and
the reaction mixture was stirred at 80 °C for the appropriate
time as mentioned in Table 7. After completion of the
reaction, as monitored by TLC, the reaction mixture was
cooled to room temperature and the solid product was
obtained by simple filtration and the solid residue was finally
recrystallized from EtOH.
All chemicals were purchased from Merck or Fluka Chemical.
The known products were identified by comparison of their
physical properties such as melting points and spectral data
with those reported in the literature.
General procedure for the synthesis of DCDBTSD
General procedure for the synthesis of 11a-d
A solution of sodium hydroxide (6 mol.Lit-1, 1mL) was added
dropwise to a stirring round bottomed flask (50 mL) containing
hydrochlorothizide (0.6 g, 2 mmol) in distillated water (2 mL)
over a period of 10 min at room temperature. After the addition
was completed, the reaction mixture was stirred for 20 min.
After this time, to the stirring solution of hydrochlorothiazide,
bromine (0.08 mL, 3 mmol) was slowly added over a period of
15 min at 0 °C. The insoluble brominated catalyst was removed
A mixture of isatin 5 (1 mmol), malonitrile 3 (1.2 mmol), 3-
methyl-1-phenyl-2-pyrazolin-5-one 7 (1mmol) and DCDBTSD
(0.0455 g, 10 mol%) were added to 2 mL water and the
reaction mixture was stirred at 80 °C for the appropriate time
as mentioned in Table 8. After completion of the reaction, as
monitored by TLC, the reaction mixture was cooled to room
temperature and the solid product was obtained by simple
filtration and the solid residue was finally recrystallized from
EtOH.
by filtration and washed with H2O (10 mL) to give
N,2-
dibromo-6-chloro-3,4-dihydro-2H-benzo[e][1,2,4]thiadiazine-
7-sulfonamide 1,1-dioxide (DCDBTSD) in 90 % of yield (0.82
g).13
General procedure for the synthesis of 12a-d
A mixture of isatin 5 (1 mmol), malonitrile 3 (1.2 mmol), 2,3-
dihydrophthalazine-1,4-dione
9 (1 mmol) and DCDBTSD
(0.0455 g, 10 mol%) were added to 2 mL water and the
reaction mixture was stirred at 80 °C for the appropriate time
as mentioned in Table 9. After completion of the reaction, as
monitored by TLC, the reaction mixture was cooled to room
temperature and the solid product was obtained by simple
filtration and the solid residue was finally recrystallized from
EtOH.
General procedure for the synthesis of 4a-u
Carbonyl compounds possessing
a reactive α-methylene
group1 (1 mmol), aromatic aldehyde 2 (1 mmol), malonitrile 3
(1.2 mmol) and DCDBTSD (0.0455 g, 10 mol%) were added to 2
mL water and the reaction mixture was stirred at 80 °C for the
appropriate time as mentioned in Tables 2 and 3. After
completion of the reaction, as monitored by TLC, the reaction
mixture was cooled to room temperature and the solid
product was obtained by simple filtration and the solid residue
was finally recrystallized from EtOH.
Conclusions
In conclusion, we demonstrated that N,2-dibromo-6-chloro-
3,4-dihydro-2H-benzo[e][1,2,4]thiadiazine-7-sulfonamide 1,1-
dioxide (DCDBTSD), was a remarkably effective homogeneous
catalyst for the one-pot construction of the 4H-pyran,
pyranopyrazole, pyrazolo[1,2-b] phthalazine and spiro-
oxindoles derivatives in aqueous media from commercially
available starting materials. The most noticeable feature
within the study was that water used both as a reaction
medium as well as a medium for synthesis of the catalyst.
Moreover the aqueous conditions, outstanding yields, simple
experimental procedure, environmentally proceeds and
elimination of hazardous organic solvents are several
advantages of this protocol.
General procedure for the synthesis of 6a-d
4-hydroxy-2H-chromen-2-one1 (1 mmol), isatin 5 (1 mmol),
malonitrile 3 (1.2 mmol) and DCDBTSD (0.0455 g, 10 mol%)
were added to 2 mL water and the reaction mixture was
stirred at 80 °C for the appropriate time as mentioned in Table
5. After completion of the reaction, as monitored by TLC, the
reaction mixture was cooled to room temperature and the
solid product was obtained by simple filtration and the solid
residue was finally recrystallized from EtOH.
General procedure for the synthesis of 8a-k
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J. Name., 2013, 00, 1-3 | 7
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ARTICLE
Journal Name
7.120 (dd, J=2.4 Hz, 1H, ArH), 7.288-7.353 (m, 3H, ArH), 7.430-
7.448 (d, J=7.2 Hz, 2H, ArH), 7.467-7.496 (1H, ArH ), 7.538-7.576 (t,
J=7.6 Hz, 1H, ArH), 7.637-7.657 (d, J=8 Hz, 2H, ArH), 7.699 (br s, 2H,
NH2, D2O exchangeable), 7.759-7.822 (m, 4H, ArH), 7.902-7.922(d,
J=8 Hz, 1H, ArH), 7.958-7.977 (d, J=7.6 Hz, 1H, ArH). 13C NMR
(400MHz, DMSO-d6): 23.948, 24.188, 26.387, 57.140, 67.391,
67.675, 101.726, 107.150, 117.165, 118.614, 119.225, 123.099,
123.184, 123.812, 123.909, 123.996, 126.120, 126.759, 126.830,
127.107, 127.953, 128.868, 129.571, 129.676, 132.855, 134.793,
146.983, 152.533, 155.664, 156.830, 156.994, 158,744, 176.089
Acknowledgements
The authors acknowledge the Bu-Ali Sina university research
council and Center of Excellence in Development of
Environmentally Friendly Methods for Chemical Synthesis
(CEDEFMCS) for providing support to this work.
Spectral data analysis of compounds
Spiro[pyrano[2,3-c]pyrazole] (11a, Table 8). White powder; mp 237-
238 °C (lit: 236-237 °C). IR (KBr) (ʋmax, cm-1): 3410, 3287, 3124,
1
Spiro[2-amino-4H-pyran-oxindole] (6a, Table 5). White powder; mp 2202, 1692, 1655, 1526, 1132. H NMR (400 MHz, DMSO-d6) δppm
:
292-294 °C (lit: 303 °C). IR (KBr) (ʋmax, cm-1): 3361, 3297, 3197,
1.560(s, 3H, CH3),6.955-6.974 (d, J=7.6 Hz, 1H, ArH), 7.03-7.067 (t,
J=7.6 Hz, 1H, ArH ), 7.190-7.208 (d, J=7.2 Hz, 1H, ArH), 7.286-7.324
(t, J=7.6 Hz ,2H, ArH), 7.353-7.390 (t, J=7.2 Hz ,1H, ArH), 7.516-7.556
(t, J=8.4 Hz 2H, ArH), 7.612 (s, 2H, NH2, D2O exchangeable), 7.796-
7.815 (d, J = 7.6 Hz 2H, ArH) 10.774 (s,1H, NH). 13C NMR (400MHz,
DMSO-d6): δppm 12.17, 48.24, 56.62, 96.82, 110.32, 118.40, 118.43,
120.60, 123.12, 125.38, 127.05, 129.76, 129.94, 132.60, 137.71,
142.07, 144.42, 145.40, 161.46, 161.50, 177.98.
1
2206, 1734, 11712, 1675, 1360. H NMR (400 MHz, DMSO-d6) δppm
:
6.869-6889 (d, 1H, J=8 Hz, ArH), 6.938-6.976 (t, 1H, J=7.6 Hz ArH),
7.225-7.241 (d, J=6.4 Hz, 2H, ArH), 7.502-7.582 (m, 2H, ArH), 7.707
(s, 2H, NH2, D2O exchangeable), 7.768-7.806 (t, J=7.2 Hz, 1H, ArH),
7.954-7.973 (d, J=7.6 Hz, 1H, ArH), 10.717 (s, 1H, NH). 13C NMR
(400MHz, DMSO-d6): δppm 48.074, 57.494, 101.89, 109.973,
112.929, 117.138, 117.441, 122.524, 123.137, 124.600, 125.482,
129.390, 133.520, 134.140, 142.657, 152.51, 155.542, 158.741,
158.906, 177.615
Spiro[pyrano[2,3-c]pyrazole] (11b, Table 8). Pale yellow powder; mp
228-230 °C (lit: 232–234°C). IR (KBr) (ʋmax, cm-1): 3390, 3314, 3191,
2904, 2200, 2208, 1701, 1662, 1396, 746. 1H NMR (400 MHz,
DMSO-d6) δppm:1.368 (s, 3H, CH3), 4.943-5.096 (AB-q, 2H, CH2),
7.094-7.130 (t, J=7.6 Hz, 2H, ArH), 7.276-7.399 (m, 6H, ArH), 7.444-
7.462 (d, J=7.2 Hz, 2H, ArH), 7.523-7.563 (t, J=7.6 Hz, 2H, ArH),
7.697 (s, 2H, NH2, D2O exchangeable), 7.801-7.821 (d, J=8 Hz, 2H,
ArH). 13C NMR (400MHz, DMSO-d6): δppm 12.19, 43.79, 47.98, 56.33,
96.58, 110.00, 118,42, 120.67, 123.93, 125.33, 127.13, 128.08,
129.06, 129.83, 129.95, 131.82, 136.51, 137.67, 142.60, 144.33,
145.46, 161.59, 161.63, 161.67, 176.61.
Spiro[2-amino-4H-pyran-oxindole] (6b, Table 5). White powder; mp
278-280 °C (lit: 278-280 °C). IR (KBr) (ʋmax, cm-1): 3451, 3452, 3166,
2946, 2880, 2196, 1695, 1673, 1611, 1505, 1466, 1360, 762, 746. 1H
NMR (400 MHz, DMSO-d6) δppm: 2.066-2.128 (m, 2H, CH2), 3.841-
3.976 (m, 2H, CH2-N), 4.032-4.048 (d, 2H, J=6.4 Hz, CH2-O), 6.941-
6.971 (m, 2H, ArH), 6.989-7.026 (t, J=7.6 Hz, 1H, ArH),7.101 -7.145
(m, 3H, ArH), 7.268-7.319 (m, 2H, ArH), 7.504-7.524(d, J=8 Hz, 1H,
ArH), 7.553-7.591 (t, J=7.6 Hz, 1H, ArH), 7.771-7.816(m, 3H, NH2 and
ArH D2O exchangeable), 7.962-7.980 (d, J=7.2 Hz, 1H, ArH). 13C
,
NMR (400MHz, DMSO-d6): δppm 27.27, 37.123, 47.616, 57.132,
65.708, 101.669, 108.970, 112.919, 116.127, 116.207, 116.287,
116.354, 117.184, 117.389, 123.186, 124.588, 125.539, 129.577,
132.739, 134.238, 143.346, 152.524, 155.246, 155.694, 155.753,
158.095, 158.825, 158.985, 176.109.
Spiro[pyrano[2,3-c]pyrazole] (11c, Table 8). Yellow powder; mp
210-212 °C. IR (KBr) (ʋmax, cm-1): 3401, 3380, 3021, 2890, 2870,
1
2238, 1702, 1691, 1610, 1515, 1450, 1341, 1203,755. H NMR (400
MHz, DMSO-d6) δppm: 1.516(s, 3H, CH3), 2.152-2.303 (m, 2H,CH2),
3.933-4.06 (m, 2H, CH2N), 4.189-4.213(t, J=7.6 Hz, 2H, CH2O), 7.079-
7.135 (t, J=7.6 Hz, 1H, ArH), 7.168-7.304 (m, 4H, ArH), 7.344-7.393
(m, 3H, ArH), 7.444-7.480 (t, J=7.2 Hz, 1H, ArH), 7.518-7.558 (t,
J=7.6 Hz, 1H, ArH), 7.697 (s, 2H, NH2, D2O exchangeable), 7.797-
7.859(m, 5H, ArH). 13C NMR (400MHz, DMSO-d6): δppm 12.30, 26.94,
37.37, 37.63, 47.87, 56.47, 96.49,107.23, 101.45, 118.65, 119.23,
120.65, 123.80, 124.06, 126.84, 127.11, 127.16, 127.99, 128.99,
129.76, 129.94, 132.02, 134.71, 137.68, 142,68, 144.34, 145.48,
156.78, 161.46, 161.46, 161.50, 176.33.
Spiro[2-amino-4H-pyran-oxindole] (6c, Table5). White powder; mp
270-272 °C. IR (KBr) (ʋmax, cm-1): 3482, 3452, 3166, 2946, 2880,
2196, 1695, 1673, 1611, 1505, 1466, 1360, 762, 746. 1H NMR (400
MHz, DMSO-d6) δppm: 2.066-2.113 (t, 2H, J=6.4 Hz, CH2-O), 3.841-
3.976 (m, 2H, CH2), 4.032-4.048 (d, 2H, J=6.4 Hz, CH2-N), 6.926-
6.960 (m, 2H, ArH), 6.989-7.026 (t, J=7.6 Hz, 1H, ArH),7.08 -7.131
(m, 3H, ArH), 7.253-7.305 (m, 2H, ArH), 7.490-7.511(d, J=8.4 Hz, 1H,
ArH), 7.540-7.577 (t, J=7.6 Hz, 1H, ArH), 7.751-7.802(m, 3H, NH2 and
ArH), 7.944-7.966 (dd, J=1.2 Hz, 1H, ArH). 13C NMR (400MHz,
DMSO-d6): δppm 27.27, 37.123, 47.616, 57.132, 65.708, 101.669,
108.970, 112.919, 116.127, 116.207, 116.287, 116.354, 117.184,
117.389, 123.186, 124.588, 125.539, 129.577, 132.739, 134.238,
143.346, 152.524, 155.246, 155.694, 155.753, 158.095, 158.825,
158.985, 176.109.
Spiro[pyrano[2,3-c]pyrazole] (11d, Table 8). Yellow powder; mp
198-200 °C. IR (KBr) (ʋmax, cm-1): 3370, 3329, 3181, 2944, 2875,
2207, 1699, 1662, 1601, 1552, 1467, 1395, 1359, 1219,751, 652. 1H
NMR (400 MHz, DMSO-d6) δppm
:
1.504(s, 3H, CH3), 1901(br s,
4H,CH2), 3.881-3.911(t, J=6 Hz 2H, CH2N), 4.151-4.179(t, J=6.4 Hz
2H, CH2O), 7.112-7.189(m, 2H, ArH), 7.251-7.287(t, J=7.2 Hz, 2H,
ArH), 7.329-7.406(m, 4H, ArH), 7.439-7.476(t, J=7.6 Hz, 1H, ArH),
7.520-7.60(t, d, J=7.2 Hz, 2H, ArH), 7.647(s, 2H, NH2), 7.798-
7.837(m, 5H, ArH); 13C NMR (400MHz, DMSO-d6): δppm 12.28, 18.99,
19.04, 24.40, 26.55, 47.87, 56.39, 96.56, 107.16, 109.55, 118.23,
Spiro[2-amino-4H-pyran-oxindole] (6d, Table 5). Pale yellow
powder; mp 268-270 °C. H NMR (400 MHz, DMSO-d6) δppm: 1.839-
1.873 (br s, 4H, CH2), 3.794-3.824 (t, J=6 Hz, 2H, CH2N), 4.127-4.155
(t, J=5.6 Hz, 2H, CH2O), 7.002-7.039 (t, J=7.6 Hz, 1H, ArH), 7.091-
1
8 | J. Name., 2012, 00, 1-3
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119.20, 120.64, 123.72, 123.97, 125.31, 126.82, 127.13, 127.96,
128.91, 129.73, 129.94, 131.96, 134.79, 137.68, 142.86, 144.31,
145.49, 156.98, 161.49. 161.54, 176.34.
Khojasteh, Z. Asgari, V. Khakyzadeh, A. Khalafi-Nezhad,
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Spiro[indoline-3,1'-pyrazolo[1,2-b]phthalazine] (12b, Table 9).
Yellow powder; mp 260-263 °C (lit: 265-266 °C). IR (KBr) (ʋmax, cm-1):
3310, 3270, 3020, 2895, 2229, 1720, 1666, 1662, 1593, 1494, 1349,
1083, 791, 759. 1H NMR (400 MHz, DMSO-d6) δH: 4.957(s, 2H, CH2),
7.062-7.082(d, J=8 Hz, 1H, ArH), 7.191-7.231(t, J=8 Hz, 1H, ArH),
7.306-7.348(m, 1H, ArH), 7.367-7.441 (m, 4H, ArH), 7.582-7.620 (t,
J=7.6 Hz, 1H, ArH), 7.892-7.925 (m, 3H, ArH), 7.962-7.981 (d, J=7.6
Hz, 1H, ArH), 8.091(br s, 3H, NH2 and ArH). 13C NMR (400MHz,
DMSO-d6): δppm 43.47, 82.12, 111.43, 111.99, 113.44, 118.72,
124.06, 125.61, 126.16, 127.88, 128.20, 129.19, 133.08, 135.70,
137.98, 146.57, 150.05, 163.12.
Spiro[indoline-3,1'-pyrazolo[1,2-b]phthalazine] (12c, Table 9).
Yellow powder; mp 218-220 °C. IR (KBr) (ʋmax, cm-1): 3434, 3434,
3029, 2926, 2870, 2228, 1727, 1661, 1628, 1613, 1597, 1470, 1371,
1259, 1180, 837, 762, 748. 1H NMR (400 MHz, DMSO-d6) δppm
:
2.136- 2.184 (m, 2H, CH2), 3.917-3.951 (t, J=6.8 Hz, 2H, CH2N),
4.164-4.193( t, J=5.6 Hz, 2H, CH2O), 7.094- 7.122(dd, J=2.4 Hz, 1H,
ArH), 7.170-7.208(t, J=7.6 Hz, 1H, ArH), 7.241-7.261 (m, 2H, ArH),
7.332-7.372 (m, 1H, ArH), 7.439-7.480 (m, 1H, ArH), 7.439-7.480(m,
1H, ArH), 7.588-7.629 (m, 1H, ArH), 7.762-7.787 (d, J=8 Hz 1H, ArH),
7.809-7.884 (m, 2H, ArH), 7.892-7.956(m, 5H, ArH), 8.090 (br s, 2H,
NH2); 13C NMR (400MHz, DMSO-d6): δppm 26.93, 37.37, 37.63, 65.51,
81.50, 107.23, 111.08, 111.91, 113.43, 118.65, 119.06, 123.80,
124.06, 125.58, 126.10, 126.87, 127.11, 127.99, 128.96, 129.74,
133.10, 134.66, 138.11, 147.10, 150.30, 156.64, 163.00.
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Spiro[indoline-3,1'-pyrazolo[1,2-b]phthalazine] (12d, Table 9).
Yellow powder; mp 210-212 °C. IR (KBr) (ʋmax, cm-1): 3430, 3401,
3180, 2931, 2870, 2221, 1720, 1668, 1610, 1603, 1590, 1470, 1370,
1240, 1110, 768, 750, 718. 1H NMR (400 MHz, DMSO-d6) δppm:1.846
(br s, 4H, 2CH2), 3.784-3.816 (t, J=7.6 Hz, 2H, CH2N), 4.115-4.147 (t,
J=6.8 Hz, 2H, CH2O), 7.098-7.126 (dd, J=2.4 Hz, 1H, ArH), 7.188-
7.226 (t, J=7.6 Hz, 1H, ArH),7.249-7.268 (d, J=8 Hz, 1H, ArH), 7.289-
7.298 (d, J=2 Hz, 1H, ArH), 7.327-7.363(t, J=7.2 Hz, 1H, ArH), 7.439-
7.475( t, J=7.2 Hz, 1H, ArH), 7.645-7.683 (t, J=7.6 Hz, 1H, ArH),
7.782-7.831 (m, 3H, ArH), 7.889-7.921 (m , 3H, ArH), 8.089 (br s, 2H,
NH2); 13C NMR (400MHz, DMSO-d6): δppm 23.97, 26.40, 37.35, 37.60,
67.39, 81.61, 107.15, 111.13, 111.94, 113.37, 118.59, 119.11,
123.82, 124.01, 125.58, 126.12, 126.84, 127.12, 127.97, 128.88,
129.73, 133.08, 134.73, 138.11, 146.96, 150.10, 156.80, 162.93.
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10 | J. Name., 2012, 00, 1-3
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Graphical Abstract
N,2-dibromo-6-chloro-3,4-dihydro-2H-benzo[e][1,2,4] thiadiazine-7-
sulfonamide 1,1-dioxide: An efficient and homogeneous catalyst for
one-pot synthesis of 4H-pyran , pyranopyrazole and pyrazolo[1,2-b]
phthalazine derivatives under aqueous media
Ardeshir Khazaei,* Mohammad Ali Zolfigol,* Fatemeh Karimitabar, Iraj Nikokar and Ahmad
Reza Moosavi-Zare
O Ar
CN
Ar
O
O
CN
O
NH2
CN
O NH2
NH2
Ar
O
Ar
O
O
O
S
O O
S
HN
R
CN
N
Br
Br
N
N
O
O
N
NH2
O
CN
NH2
Cl
N
H
O
N
NH2
N
N
O
O
O
N
Ar
NH2
CN
O
CN
O
N
N
CN
NH2
O
N
R
N
R
DCDBTSD was successfully applied for the synthesis of 4H-pyran , pyranopyrazole and pyrazolo[1,2-b]
phthalazine derivatives by the one-pot multi-component reaction in water.