Microwave-assisted solvent-free synthesis of quinolines using N-bromosulfonamides

Article abstract of DOI:10.1080/10426500902787732

Quinolines were readily prepared under new convenient conditions using poly(N,N'-dibromo-N,N'-dimethylenebenzene-1,3-disulfonamide) (PBBS) or N,N,N',N'-tetra bromo benzene-1,3-disulfonamide (TBBDA) as efficient reagents from 2-aminobenzophenones and keton

Full text of DOI:10.1080/10426500902787732

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Phosphorus, Sulfur, and Silicon and the
Related Elements
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Microwave-Assisted Solvent-Free
Synthesis of Quinolines Using N-
Bromosulfonamides
a
a
Ramin Ghorbani-Vaghei & Somayeh Akbari-Dadamahaleh
a
Department of Organic Chemistry, Faculty of Chemistry , Bu-Ali
Sina University , Hamedan, Iran
Published online: 03 Feb 2010.
To cite this article: Ramin Ghorbani-Vaghei & Somayeh Akbari-Dadamahaleh (2010) Microwave-
Assisted Solvent-Free Synthesis of Quinolines Using N-Bromosulfonamides, Phosphorus, Sulfur, and
Silicon and the Related Elements, 185:2, 319-324
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Phosphorus, Sulfur, and Silicon, 185:319–324, 2010
Copyright ꢀ
Taylor & Francis Group, LLC
C
ISSN: 1042-6507 print / 1563-5325 online
DOI: 10.1080/10426500902787732
MICROWAVE-ASSISTED SOLVENT-FREE SYNTHESIS
OF QUINOLINES USING N-BROMOSULFONAMIDES
Ramin Ghorbani-Vaghei and Somayeh Akbari-Dadamahaleh
Department of Organic Chemistry, Faculty of Chemistry, Bu-Ali Sina University,
Hamedan, Iran
ꢀ
Quinolines were readily prepared under new convenient conditions using poly(N,N -
ꢀ
ꢀ
ꢀ
dibromo-N,N -dimethylenebenzene-1,3-disulfonamide) (PBBS) or N,N,N ,N -tetra bromo
benzene-1,3-disulfonamide (TBBDA) as efficient reagents from 2-aminobenzophenones and
ketones or phenylacetylene under microwave/solvent-free conditions in good to excellent
yields.
Keywords Acetylacetone; 2-aminobenzophenone; PBBS; quinolines; TBBDA
INTRODUCTION
High-throughput screening has created a critical demand to develop practical routes
for rapid chemical synthesis of natural product-like molecules. To secure such practice,
the discovery and invention of new synthetic methods for accessing some natural product
1
–8
entities in more efficient ways has been a fertile area of organic synthesis. The quinoline
nucleus is a backbone of many natural products and pharmacologically significant com-
9
,10
pounds displaying a broad range of biological activity. They are found to possess a wide
spectrum of biological activities and are used as antimalarial, antibacterial, antiasthmatic,
1
1–13
antihypertensive, and tyrosine kinase inhibiting agents.
In addition to the medicinal importance, polyquinolines derived from quinolines are
found to undergo hierarchical self-assembly into a variety of nano- and mesostructures
1
4–17
with enhanced electronic and photonic functions.
Consequently, various methods such
as Skraup, Doebner–von Miller, Friedlander, and Combes methods have been developed
1
8–25
29
26
for the preparation of quinoline derivatives.
In recent years, iodine ; Lewis acids
27
28
such as AuCl3, Bi(OTf)3, and Ag3PW12O40 ; a combination of acidic catalysts and mi-
3
0,31
32
33
34
crowave irradiation
; ionic liquids ; chlorotrimethylsilane ; dodecylphosphonic acid ;
and 1-methylimidazolium trifluoroacetate35 have also been utilized to be effective for this
synthesis. However, many of these procedures also suffer from harsh reaction conditions,
Received 19 December 2008; accepted 30 January 2009.
We are thankful to Bu-Ali Sina University, Center of Excellence and Development of Chemical Methods
(
CEDCM), for financial support.
Address correspondence to Ramin Ghorbani-Vaghei, Department of Organic Chemistry, Faculty of Chem-
istry, Bu-Ali Sina University, 65174 Hamedan, Iran. E-mail: rgvaghei@yahoo.com
3
19

320
R. GHORBANI-VAGHEI AND S. AKBARI-DADAMAHALEH
long reaction times, low yields, difficult workup, and the use of stoichiometric and/or
relatively expensive reagents.
RESULTS AND DISCUSSION
In continuation of our studies towards the development of new environmentally
ꢁ
ꢁ
friendly synthesis of quinolines through N-halo reagents, we now report N,N,N ,N -tetra
ꢁ
ꢁ
bromobenzene-1,3-disulfonamide (TBBDA) and poly(N,N -dibromo-N,N -dimethylene
benzene-1,3-disulfonamide) (PBBS)3
6–40
as efficient reagents for the preparation of
quinolines from 2-aminobenzophenones and different ketones or phenylacetylene under
microwave/solvent-free conditions (Scheme 1).
R2
R4
O
R2
R1
R4
R3
Ph
R3
N
O
TBBDA or PBBS
Solvent-free/MW
R1
+
or
or
NH2
R2
R1
N
Ph
Br
N
Br
N Br
Br
N
Br
N
Br
(
H C
S
S
CH2) n
S
O
S
2
O
O O
O O
O O
TBBDA
PBBS
Scheme 1
Quinoline derivatives were prepared from different 2-aminobenzophenones and
various α-methylene carbonylic compounds or phenylacetylene. Several 2-aminobenzo
phenones were converted to quinolines using TBBDA or PBBS with good to high yields
without byproducts. The results are presented in Table I. For chemoselectivity, a reaction
was inserted between 2-aminobenzophenone and either ethylacetoacetate and methylace-
toactate, but no obvious product was obtained.
For the optimization of reaction conditions, 2-amino-5-chlorobenzophenone and
acetylacetone were selected as model substrates because the other substances have al-
most the same characteristics. It was found that, in the absence of solvent, the reaction is
completed in the presence of 0.45 mmol of TBBDA and irradiation by microwave for 9 min.
The product was obtained in 94% yield (Table I, entry 4). To demonstrate the generality
of the method, we next extended the scope of this reaction to other model compounds, the
results of which are summarized in Table I. As is obvious from Table I, this method is
equally effective for both cyclic and acyclic ketones.

SYNTHESIS OF QUINOLINES USING N-BROMOSULFONAMIDES
321
Table I Synthesis of various quinolines by TBBDA and PBBS under microwave/solvent-free conditions
TBBDA
PBBS
2
-Aminoaryl
ketone
Ketone or
Acetylene
Time[min]
Yield (%)
Time[min]
Yield (%)
a
a
Entry
1
Product
Ref.
34
5
6
8
97
95
94
9
93
90
91
Ph
O
O
O
Ph
O
NH2
N
2
3
8.5
10
34
34
Ph
O
O
Ph
NH2
N
Ph
O
O
Ph
NH2
N
4
5
9
9
94
93
13
16
88
87
34
34
Ph
O
O
O
Ph O
Cl
Cl
Cl
Cl
NH2
N
Ph
O
O
Ph
NH2
N
6
7
8
15
17
11
88
86
91
20
20
13
83
80
86
29
29
31
O
O
O
Cl
Cl
Cl
Cl
Cl
Cl
O
N
NH2
O
Cl
Cl
O
N
NH2
Ph
O
C CH
NH2
N
9
16
90
19
87
31
Ph
C CH
Cl
O
Cl
NH2
N
(
Continued on next page)

322
R. GHORBANI-VAGHEI AND S. AKBARI-DADAMAHALEH
Table I Synthesis of various quinolines by TBBDA and PBBS under microwave/solvent-free conditions
(
Continued)
TBBDA
PBBS
2
-Aminoaryl
ketone
Ketone or
Acetylene
Time[min]
Yield (%)
Time[min]
Yield (%)
a
a
Entry
Product
Ref.
31
1
0
20
90
24
85
C CH
Cl
Cl
Cl
Cl
O
NH2
N
1
1
1
2
12
10
—b
—b
12
15
—b
—b
—b
Ph
O
O
O
O
Ph
COOEt
COOMe
OEt
NH2
N
–b
Ph
O
O
Ph
OMe
NH2
N
aProducts were characterized by their physical properties, comparison with authentic samples, and by spectro-
scopic methods.
b
No reaction.
Also, this reaction is very clean and free from side reactions, such as self-condensation
of ketones, which are normally observed under basic conditions.
As shown in Table I, this method is effective for phenylacetylene. 2-Aminoaryl
ketones such as 2-aminobenzophenone, 2-amino-5-chlorobenzophenone, and 2-amino-
ꢁ
2
,5-dichlorobenzophenone reacted smoothly with phenylacetylene to produce a range
of quinoline derivatives in good to excellent yields.
Since TBBDA and PBBS contain halogen atoms, which are attached to nitrogen
+
atoms, it is very possible that they release X in situ, which in turn can act as a catalyst in
the reaction medium.3
6–40
Therefore, the mechanism shown in Scheme 2 can be suggested
for the reaction of phenyl acetylene with 2-amino acetophenone derivatives.
31
CONCLUSIONS
In conclusion, we now report TBBDA and PBBS as efficient reagents for the prepa-
ration of quinolines from o-aminoarylketones and different ketones or phenylacetylene
under solvent-free/microwave irradiation conditions. This method not only provides an
excellent complement to quinoline synthesis, but also avoids the use of hazardous and
environmentally unfriendly acids or bases.
TBBDA and PBBS are inexpensive and nonhazardous reagents. They work under
heterogeneous conditions, and can conveniently be handled and removed from the reaction
mixture by simple filtration.
EXPERIMENTAL
2
-Amino-5-chlorobenzophenone (0.23 g, 1 mmol), acetophenone (0.6 g, 5 mmol)
ꢁ
ꢁ
or phenylacetylene (0.82 g, 8 mmol), and N,N,N ,N -tetrabromobenzene-1,3-disulfonamide

SYNTHESIS OF QUINOLINES USING N-BROMOSULFONAMIDES
323
R2
R2
Br
N
Br
N
Br
Br
N
Br
N
O
O
+
R1
Br
Br
R1
Br
+
S
O
S
S
O
S
NH
2
O
O O
NH
2
O
O O
1
2
3
4
Ph
H
5
R2
R2
BrO
Br
Br
N
Br
N
R1
O
R1
H
Br
Ph
+
Ph
S
O
S
NH
2
NH
2
O
O O
8
7
6
3
R2
Br
R1
O
3
NH
2
3
R2
H
N
H
N
R1
Ph
H
H
O
2
S
S
NH
O
O
O O
9
1
1
+
R2
R2
N
R1
N
Ph
R1
1
0
Ph
1
0
Scheme 2
(
0.25 g, 0.45 mmol) or PBBS (0.25 g, 0.60 mmol) were mixed together and irradiated
under microwave conditions at a power output of 900 W (LG Co. microwave, 230v
50 Hz, RF output 900 W). After completion of the reaction [Table I, monitored by TLC
5:1, n-hexane:acetone)], CH2Cl2 (10 mL) was added, and the sulfonamide was removed
∼
(
by filtration. Evaporation of the solvent under reduced pressure followed by purification
using preparative thin layer chromatography afforded the pure product.
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