SbCl3-SiO 2 catalyzed simple and efficient one-pot synthesis of 1-amidoalkyl-2-naphthols under solvent-free conditions

Article abstract of DOI:10.1080/15533174.2011.609860

Silica-supported antimony trichloride (SbCl₃-SiO₂) was found to be an inexpensive and effective catalyst for the one-pot three-component synthesis of 1-amidoalkyl-2-naphthols in high yields. The main advantages of the present approac

Full text of DOI:10.1080/15533174.2011.609860

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SbCl -SiO Catalyzed Simple and Efficient One-Pot
3
2
Synthesis of 1-Amidoalkyl-2-Naphthols Under Solvent-
Free Conditions
a
b
b
Farid Moeinpour , Arezoo Sardashti-Birjandi , Nadieh Dorostkar-Ahmadi , Amir
b
c
Khojastehnezhad & Fatemeh S. Mohseni-Shahri
a
Department of Chemistry, Bandar Abbas Branch, Islamic Azad University, Bandar Abbas, I.
R. Iran
b
Department of Chemistry, Mashhad Branch, Islamic Azad University, Mashhad, I. R. Iran
c
Department of Chemistry, Faculty of Sciences, Ferdowsi University of Mashhad, Mashhad, I.
R. Iran
Published online: 23 Mar 2012.
To cite this article: Farid Moeinpour , Arezoo Sardashti-Birjandi , Nadieh Dorostkar-Ahmadi , Amir Khojastehnezhad &
Fatemeh S. Mohseni-Shahri (2012) SbCl -SiO Catalyzed Simple and Efficient One-Pot Synthesis of 1-Amidoalkyl-2-Naphthols
3
2
Under Solvent-Free Conditions, Synthesis and Reactivity in Inorganic, Metal-Organic, and Nano-Metal Chemistry, 42:2,
78-281, DOI: 10.1080/15533174.2011.609860
2
To link to this article: http://dx.doi.org/10.1080/15533174.2011.609860
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Synthesis and Reactivity in Inorganic, Metal-Organic, and Nano-Metal Chemistry, 42:278–281, 2012
Copyright ꢀC Taylor & Francis Group, LLC
ISSN: 1553-3174 print / 1553-3182 online
DOI: 10.1080/15533174.2011.609860
SbCl -SiO Catalyzed Simple and Efficient One-Pot
3
2
Synthesis of 1-Amidoalkyl-2-Naphthols Under Solvent-Free
Conditions
1
2
2
Farid Moeinpour, Arezoo Sardashti-Birjandi, Nadieh Dorostkar-Ahmadi,
2
3
Amir Khojastehnezhad, and Fatemeh S. Mohseni-Shahri
1
Department of Chemistry, Bandar Abbas Branch, Islamic Azad University, Bandar Abbas, I. R. Iran
Department of Chemistry, Mashhad Branch, Islamic Azad University, Mashhad, I. R. Iran
Department of Chemistry, Faculty of Sciences, Ferdowsi University of Mashhad, Mashhad, I. R. Iran
2
3
HClO4/SiO2, cyanuric chloride, K5CoW12O40.3H2O, silica-
3 2
Silica-supported antimony trichloride (SbCl -SiO
) was found supported molybdophosphoric acid, copper p-toluenesulfonate
to be an inexpensive and effective catalyst for the one-pot three- (p-TSA), silica chloride, and hexanesulfonic acid sodium
component synthesis of 1-amidoalkyl-2-naphthols in high yields.
The main advantages of the present approach are short reaction
times, clean reaction profiles, and simple experimental and work-
up procedures.
[12]
salt.
However, the major problems associated with these
reactions in most of the published procedures are that high
catalyst loading, long reaction times, unsatisfactory yields,
harsh reaction conditions, expensive catalysts, and tedious
work-up procedure. Therefore, the development of a suitable
Keywords 1-amidoalkyl-2-naphthols, heterogeneous catalyst, one-
pot reaction, silica-supported antimony trichloride method using additional reagents and catalysts for the efficient
(
SbCl
3
-SiO
2
), solvent-free
synthesis of 1-amidoalkyl-2-naphthols remains an attractive
field to researchers. Recently, solid-supported reagents, such
as silica gel–supported acids, have gained considerable interest
in organic synthesis because of their unique properties of the
INTRODUCTION
1-amidoalkyl-2-naphthols have received much attention reagents such as high efficiency caused by more surface area,
because of their easy transformation to 1-aminoalkyl-2- more stability and reusability, low toxicity, greater selectivity
naphthols as an important class of bioactive compounds, by and ease of handling.[ In recent years, antimony trichloride
13]
amide hydrolysis reaction. 1-aminoalkyl-2-naphthols have has been used as catalyst in many important organic reactions,
been regularly used as hypotensive and bradycardiac agents.[
1]
because this compound not only is commercially available and
1
-Amidoalkyl-2-naphthols can be also converted to 1,3-oxazine inexpensive, but also is easier to handle than other metal halides
[
2]
[14]
derivatives. 1,3-oxazines have potentially different biological such as InCl3,GdCl3, and TiCl4.
activities such as antibiotic, antitumor, analgesic, anti- work on new synthetic methodologies, we wish to report an
In continuation of our
[
3]
[4]
[5]
[15]
[
6]
[7]
[8]
[9]
convulsant, antipsychotic, antimalarial, antianginal,
efficient method for the synthesis of 1-amidoalkyl-2-naphthols
antihypertensive,[10] and antirheumatic properties. Synthesis in high yields in the presence SbCl3-SiO2 as heterogeneous and
of 1-amidoalkyl-2-naphthols is usually done via one-pot reusable catalyst under solvent free conditions (Scheme 1).
three-component condensation of arylaldehydes, 2-naphthol
[11]
and amide derivatives, or acetonitrile. Several Lewis and
Brønsted acids have been used for this reaction including
EXPERIMENTAL
All chemicals were commercially available and used with-
Ce(SO4)2, Montmorillonite K-10, iodine, cation-exchanged
out further purification. All yields refer to isolated products after
resins, NaHSO4.H2O, Fe(HSO4)3, sulfamic acid/ultrasound,
purification. All the products were characterized by comparison
of spectroscopic data (IR, H NMR spectra) and melting points
1
with authentic samples. The catalyst was synthesized according
Received 29 June 2011; accepted 29 July 2011.
to the literature.[ Melting points were recorded on an elec-
16]
The corresponding author gratefully acknowledges the financial
support from the Research Council of the Islamic Azad University,
Bandar Abbas Branch.
Address correspondence to Farid Moeinpour, Department of Chem-
istry, Bandar Abbas Branch, Islamic Azad University, Bandar Abbas
trothermal type 9100 melting point apparatus. 1-amidoalkyl-
2-naphthols were prepared according to the following general
procedure: A mixture of 2-naphthol 1 (1 mmol), aromatic alde-
hyde 2a-k (1 mmol), acetamide 3 (1 mmol), and SbCl3-SiO2
◦
7
915893144, Iran. E-mail: f.moeinpour@gmail.com
(0.08 g) was heated on the oil bath at 120 C for 3–8 min. The
278

SbCl3-SiO2 CATALYZED 1-AMIDOALKYL-2-NAPHTHOL SYNTHESIS
279
SCH. 1.
reaction was monitored by TLC. After the completion of the
TABLE 1
reaction, the reaction mixture was cooled to room temperature
and ethyl acetate was added. The solid residue was dissolved
in ethyl acetate and mixture stirred for 5 min. The catalyst was
filtered off and the crude product was collected from the filtrate
after evaporation of the solvent and recrystallized from ethanol
to give compounds 4a-k in high yields. All the 1-amidoalkyl-
Synthesis of 1-amidoalkyl-2-naphthol 4a in the presence of
SbCl3-SiO2 (0.08 g) in different solvents and optimization of
temperature in solvent-free conditions
◦
∗
Entry Solvent Temperature ( C) Time (min) Yield (%)
1
2
3
4
5
6
7
MeOH
EtOH
CH3CN
H2O
Solvent-free
Solvent-free
Solvent-free
64
78
81
100
100
120
130
300
300
300
300
7
Trace
73
60
63
80
2-naphthols are known and were identified by comparison of
their physical and spectroscopic data (IR, NMR) with those of
authentic samples.[
12]
The spectral data of some representative amidoalkyl naph-
thols are the following:
7
7
91
91
N-[(2-Hydroxynaphthalen-1-yl)(4-chlorophenyl)methyl]ac-
−
1
etamide (4c): IR (KBr, cm ): 3418, 3316, 3070, 1621, 1595,
∗
The yields were calculated based on benzaldehyde and refer to the
pure isolated product.
1
561, 1515, 1467, 1392, 1281, 1201, 1141, 1051, 939, 884,
1
784, 744, 714. H NMR (500 MHz, DMSO-d6): δ (ppm) 3.16
(
7
7
s, 3H), 7.09 (d, J = 8.1 Hz, 1H), 7.15 (d, J = 8.0 Hz, 2H),
.21 (d, J = 8.8 Hz, 1H), 7.27–7.31 (m, 3H), 7.38 (brd, 1H), ried out under the previously mentioned conditions using differ-
◦
.76–7.81 (m, 3H), 8.46 (d, J = 8.1 Hz, 1H), 10.03 (s, 1H). N- ent quantities of catalyst at 120 C. The use of 0.08 g of catalyst
[
(
(2-Hydroxynaphthalen-1-yl)(4-nitrophenyl)methyl]acetamide resulted in the highest yield in 7 min (Table 2).
−
1
4f): IR (KBr, cm ): 3391, 3267, 2593, 1648, 1603, 1522,
Thus, we prepared a range of 1-amidoalkyl-2-naphthols un-
438, 1063, 825, 739, 447. H NMR (500 MHz, DMSO-d6): δ der the optimized reaction conditions. In all cases, aromatic
ppm) 2.02 (s, 3H), 7.19 (d, J = 8.0 Hz, 1H), 7.21 (d, J = 8.8 aldehydes with substituents carrying either electron-donating
1
1
(
Hz, 1H), 7.28 (t, J = 7.47 Hz, 1H), 7.40 (t, J = 7.34 Hz, 1H), or electron-withdrawing groups reacted successfully and gave
7
8
1
.54–7.57 (m, 2H), 7.88 (t, J = 9.38 Hz, 2H), 7.89 (brd, 1H), the expected products in excellent yields and short reaction
.13 (d, J = 8.0 Hz, 2H), 8.57 (d, J = 8.0 Hz, 1H), 10.11 (s, times. The kind of aldehyde has no significant effect on the
H).
reaction. The results are shown in Table 3. It was showed that
both electron-rich and electron-deficient aldehydes reacted well,
mostly leading to high yields of products.
RESULTS AND DISCUSSION
For our investigations, SbCl3-SiO2 was prepared according
TABLE 2
[
16]
to the literature procedure. The synthesis of 1-amidoalkyl-2-
naphthols was achieved by the one-pot, three-component con-
densation of aryl aldehydes, 2-naphthol, and acetamide in the
presence of SbCl3-SiO2 as a heterogeneous catalyst (Scheme Entry
Optimization of the amount of catalyst in the preparation of
∗
1
-amidoalkyl-2-naphthol 4a
∗∗
Yield (%)
Catalyst (g)
Time (min)
1
). To optimize the reaction conditions, the reaction of ben-
1
2
3
4
5
6
None
0.03
0.05
0.08
0.09
0.1
120
7
7
7
7
No reaction
zaldehyde (1 mmol), 2-naphthol (1 mmol), and acetamide (1
mmol) in the presence of SbCl3-SiO2 (0.08 g) was selected as
a model. The reaction was carried out in various solvents and
under solvent-free conditions. As shown in Table 1, in com-
parison with conventional methods, the yields of the reaction
under solvent-free conditions are greater and the reaction time
60
81
91
92
92
7
is shorter. The shortest time and best yield were achieved at
1
∗
1 mmol 2-naphthol, 1 mmol acetamide, and 1 mmol benzaldehyde
20 C. Next, to find the optimum quantity of SbCl3-SiO2, the at 120 C. The yields were calculated based on benzaldehyde and
◦
◦
∗∗
reaction of benzaldehyde, 2-naphthol, and acetamide was car- refer to the pure isolated product.

280
F. MOEINPOUR ET AL.
TABLE 3
∗
Preparation of 1-amidoalkyl-2-naphthols using SbCl3-SiO2 (0.08g) as catalyst
∗
∗
◦
Entry
1
Ar
Phenyl
Time/min
7
Product
Yield /%
91
m.p. (Lit. m.p)/ C (12)
4a
241–243
(245–246)
226–229
(227–229)
224–226
(224–227)
179–181
(180–182)
235–237
(236–237)
246–248
(248–250)
183–185
(184–186)
221–223
(222–223)
201–203
(203–205)
196–198
(194–196)
196–198
(198–199)
2
3
4
5
6
7
8
9
4-Br-phenyl
4-Cl-phenyl
6
5
3
4
3
8
5
6
8
4
4b
4c
4d
4e
4f
89
90
90
92
90
89
90
88
85
90
2-NO2-phenyl
3-NO2-phenyl
4-NO2-phenyl
4-OMe-phenyl
4-Me-phenyl
4-F-phenyl
4g
4h
4i
1
0
1
2-Cl-phenyl
4j
1
2,4-Cl2-phenyl
4k
∗
◦
∗∗
1
mmol 2-naphthol, 1 mmol acetamide, and 1 mmol aryl aldehyde at 120 C under solvent-free conditions. The yields were calculated
based on aryl aldehyde and refer to the pure isolated products.
The recyclability of the catalyst in the reaction of benzalde- cooled to room temperature and ethyl acetate was added. The
hyde (10 mmol), 2-naphthol (10 mmol), and acetamide (10 solid residue was dissolved in ethyl acetate and mixture stirred
mmol) in the presence of SbCl3-SiO2 (0.8 g) was also checked. for 5 min. The catalyst was separated by simple filtration, dried
◦
After the completion of the reaction, the reaction mixture was at 100 C under vacuum for 2 h and reused for the similar
FIG. 1. Recycling experiment for SbCl3-SiO2 (color figure available online).

SbCl3-SiO2 CATALYZED 1-AMIDOALKYL-2-NAPHTHOL SYNTHESIS
281
TABLE 4
∗
Comparison results of SbCl3-SiO2 with other catalysts reported in the literature
Entry
Condition
Catalyst
Time/min
Yield%
1
2
3
4
5
6
7
8
Under reflux
Solvent-free, 125 C
Solvent-free, 125 C
Solvent-free, 125 C
Solvent-free, 125 C
Solvent-free, 110 C
Solvent-free, 125 C
Solvent-free, 120 C
Ce(SO4)2
Montmorillonite K-10 clay
Iodine
K5CoW12O40 – 3H2O
p-TSA
Cation-exchanged resins
HClO4- SiO2
2160
90
330
120
300
20
72
89
85
90
88
81
89
91
◦
◦
◦
◦
◦
◦
◦
40
7
SbCl3-SiO2
∗
Based on 1 mmol 2-naphthol, 1 mmol acetamide, and 1 mmol benzaldehyde.
reaction. As it is shown in Figure 1, the catalyst could be reused
at least three times without significant loss of activity.
6. Mosher, H.S.; Frankel, M.B.; Gregory, M. J. Am. Chem. Soc. 1953, 75,
326.
5
7. Peglion, J.L.; Vian, J.; Gourment, B.; Despaux, N.; Audinot, V.; Millan, M.
Bioorg. Med. Chem. Lett. 1997, 7, 881.
To show the merit of the present work in comparison with
reported results in the literature, we compared reactions of
SbCl3-SiO2 with Ce(SO4)2, montmorillonite K-10 clay, io-
dine, K5CoW12O40, 3H2O, copper p-toluenesulfonate (p-TSA),
cation-exchanged resins, and HClO4-SiO2 (12) in the synthesis
of 1-amidomethyl-2-naphthol derivatives. As shown in Table 4,
SbCl3-SiO2 can act as high-efficiency catalyst with fast time
and high yields of the obtained products.
8
. Ren, H.; Grady, S.; Gamenara, D.; Heinzen, H.; Moyna, P.; Croft, S.;
Kendrick, H.; Yardley, V.; Moyna, G. Bioorg. Med. Chem. Lett. 2001, 11,
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9
. Benedini, F.; Bertolini, G.; Cereda, R.; Don a´ , G.; Gromo, G.; Levi, S.;
Mizrahi, J.; Sala, A. J. Med. Chem. 1995, 38, 130.
1
1
1
0. Clark, R.D.; Caroon, J.M.; Kluge, A.F.; Repke, D.B.; Roszkowski, A.P.;
Strosberg, A.M.; Baker, S.; Bitter, S.M.; Okada, M.D. J. Med. Chem. 1983,
2
6, 657.
1. Matsuoka, H.; Ohi, N.; Mihara, M.; Suzuki, H.; Miyamoto, K.; Maruyama,
N.; Tsuji, K.; Kato, N.; Akimoto, T.; Takeda, Y.; Yano, K.; Kuroki, T. J.
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CONCLUSION
In conclusion, we report on a new simple catalytic method for
the synthesis of 1-amidoalkyl-2-naphthols by one-pot conden-
sation reaction of 2-naphthols, acetamide, and aryl aldehydes
using SbCl3-SiO2 as an efficient, reusable, and green heteroge-
neous catalyst under solvent-free conditions. The catalyst could
be recycled after a simple work-up, and reused at least three
runs without appreciable reduction in its catalytic activity. High
yields, short reaction times, easy work-up, and absence of any
volatile and hazardous organic solvents are some advantages of
this protocol.
(
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