MCM-41-N-propylsulfamic acid: An efficient catalyst for one-pot synthesis of 1-amidoalkyl-2-naphtols

Article abstract of DOI:10.1016/j.apcata.2013.11.002

An efficient, one-pot three-component condensation of aromatic aldehydes, acetamide and 2-naphtol in the presence of catalytic amounts of MCM-41-N-propylsulfamic acid under thermal solvent-free conditions is described for the preparation of 1-amidoalkyl-2

Full text of DOI:10.1016/j.apcata.2013.11.002

Accepted Manuscript
Title: MCM-41-N-propylsulfamic acid: An efficient catalyst
for one-pot synthesis of 1-amidoalkyl-2-naphtols
Author: Maryam Hajjami Farshid Ghorbani Fariba Bakhti
PII:
S0926-860X(13)00682-0
DOI:
Reference:
http://dx.doi.org/doi:10.1016/j.apcata.2013.11.002
APCATA 14557
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Applied Catalysis A: General
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31-10-2013
1-11-2013
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MCM-41-N-propylsulfamic acid: An efficient catalyst for one-pot synthesis of
1-amidoalkyl-2-naphtols
Maryam Hajjami,a, Farshid Ghorbanib and Fariba Bakhtia
a Department of Chemistry, Faculty of Science, Ilam University, P.O. Box 69315516, Ilam, Iran
b Department of Environment, Faculty of Natural Resource, University of Kurdistan, P.O. 66177-15177, Sanandaj, Iran
ABSTRACT
An efficient, one-pot three-component condensation of aromatic aldehydes, acetamide and 2-naphtol in the presence of catalytic amounts of
MCM-41-N-propylsulfamic acid under thermal solvent-free conditions is described for the preparation of 1-amidoalkyl-2-naphtols in good to
excellent yields. In this work, MCM-41-N-propylsulfamic acid was prepared by reaction of propylamine functionalized MCM-41 and
chlorosulfonic acid and characterized by FTIR, XRD and TGA.
Keywords: 1-Amidoalkyl-2-naphtols, MCM-41, MCM-41-N-propylsulfamic acid, Solvent-free, Multicomponent reaction.
1. Introduction
One of the principal problems of organic chemistry in recent years is the creation of structurally complex organic compounds from simple
substrates [1]. The first and most important method used for this purpose is multicomponent reaction (MCR). Multicomponent reactions are
performed without need to isolate any intermediate during the reaction, which reduces the amount of time and energy used [2]. There have been
tremendous developments in three or four component reactions. Condensation of 2-naphtol, aldehydes and amides in the presence of various
catalysts for the synthesis of 1-amidoalkyl-2-naphtol is an example of MCR. 1-Amidoalkyl-2-naphthol derivatives have attracted considerable
interest because of their biological and pharmacological activities [3]. Also these compounds can be converted into important biological active 1-
aminoalkyl-2-naphthol derivatives by amide hydrolysis [3,4]. In addition, 1-amidoalkyl-2-naphthols can be converted to 1,3-oxazines [5]. 1,3-
Oxazines have analgesic [6] and antirheumatic properties [7]. Preparation of 1-amidoalkyl-2-naphtols carried out in the presence of Lewis or
Bronsted acid catalysts. Therefore, some methods using various homogeneous or heterogeneous catalysts including Montmorillonite K10 [8],
iodine [9], sulphamic acid [10], silica supported perchloric acid [11], silica sulfuric acid [12], polymer supported sulfunic acid [13], ionic liquids
[14], graphite supported perchloric acid [15], tris(triphenylphosphine) ruthenium(II) dichloride [4], zinc benzenesulfonate [16], cation exchanged
resins [17], Silica gel–supported polyphosphoric acid [18] and Trityl Chloride [19] have been reported. However, many of these reported
methods suffer from one or more drawbacks such as long reaction times, poor yields, the use of toxic organic solvents, the use of expensive or
toxic metal salts as catalysts, and tedious work-up procedures. Therefore, search for finding an efficient, general and environmentally gentle
method and milder catalysts for the synthesis of 1-amidoalkyl-2-naphthols have been under permanent attention. In recent years, mesoporous
materials such as MCM-41 have attracted the attention of many scientists [20]. They enable to carrying high dosages of a variety of drugs in their
mesopores, called drug delivery vehicles [21]. Furthermore mesoporous silica containing specific functional groups have high specific surface
areas and porosities that opened a wide field of applications in removal of toxic metal ions from waste-water and natural-waters [22,23]. Thus
they provide a suitable approach to the development of green chemistry principles. Because of the availability of a large number of free silanol

Address correspondence to M. Hajjami, Department of Chemistry, Faculty of Science, Ilam University, P.O. Box 69315516, Ilam, Iran;
Tel/Fax: +98 841 2227022; E-mail address: mhajjami@yahoo.com or m.hajjami@ilam.ac.ir
1
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groups on the surface of MCM-41, modification by reaction of the surface silanol groups can occur and inorganic-organic hybrid mesoporous
materials have been developed [24]. These modified mesoporous could be applied as catalysts for different types of reactions such as nitration of
phenols [25], epoxidation of styrene [26] and reduction of p-nitrophenol to p-aminophenol [27] or could be used for environmental purification.
The present investigation reports the synthesis, characterization and catalytic properties of functionalized MCM-41 (MCM-41-N-propylsulfamic
acid) in the multicomponent synthesis of 1-amidoalkyl-2-naphtols. In this study, one-pot condensation reaction of aromatic aldehydes, 2-naphtol
and acetamide in the presence of catalytic amounts of MCM-41-N-propylsulfamic acid under solvent-free conditions at 130 0C carried out to
afford 1-amidoalkyl-2-naphtol derivatives.
2. Experimental
2.1. Chemicals
Analytical grade hexadecyltrimethylammonium bromide (CTAB), acetic acid, hydrochloric acid (37%), sodium hydroxide (NaOH), aldehydes, 2-
naphtol and acetamide were all purchased from Aldrich and Merck and used without further purification. Deionized distilled water was used in
the preparation of all solutions. The known products were characterized by comparison of their spectral (1H NMR, and 13CNMR, Bruker NMR-
Spectrometer FX 400Q) and physical data with those of authentic samples. Unknown compounds were identified by their 1H and 13CNMR
spectra and elemental analysis.
2.2. Synthesis of MCM-41-N-propylsulfamic acid
MCM-41 was synthesized according to the literature method [28] by the reaction of tetraethyl orthosilicate (TEOS) as the source of silica (1
mmol) and cetyltrimethylammonium bromide (CTAB, 0.1 mmol), in basic solution of 0.3 mmol NaOH: 60 mL H2O. The gel mixture was then
crystallized under hydrothermall treatment at 110 ˚C for 60 h in a Teflon lined autoclave. After cooling to room temperature the resultant solid
was recovered by filtration, washed with deionized water and dried in air. The collected product was calcined at 550 ˚C for 12 h to remove the
polymeric surfactants and CTAB. This mesoporous material is designated as MCM-41. In the next step, according to the literature [29] 27 mmol
of 3-Aminopropyl trimethoxysilane (APTMS) was stirred with MCM-41 (4.8 g) in n-hexane (96 mL) at 80 ˚C for 24 h under nitrogen
atmosphere. The resulting solid NH2-(CH2)3-MCM-41 was filtered, washed several times with n-hexane and dried in vacuum. Finally for
synthesis of MCM-41-N-propylsulfamic acid, to a solution of propylamine functionalized MCM-41 (2 g) in n-hexane (10 mL), Et3N (0.83 mL)
was added. The mixture was stirred for 10 min. Chlorosulfonic acid (0.266 mL) was added dropwise. HCl gas evolved from the reaction vessel
immediately. The mixture was stirred for next 3 h for completing the reaction. Afterwards, the residue was filtered and washed with n-hexane.
Then the resulting product was washed with ethanol and then water to afford crystalline MCM-41-N-propylsulfamic acid (scheme 1).
Si(OMe)3
2) ClSO3H, Et3N
H2N
1)
NHSO3H
Si
O
OHOH
OH
O
O
Scheme 1. Synthesis of MCM-41-N-propylsulfamic acid
2
Page 2 of 14

2.3. Catalyst characterization
The crystalline structure of synthesized samples was examined by X-ray diffraction using GBC-Difftech MMA diffractometer. The nickel filtered
Cu Kα (λ= 1.54A˚) radiation was used at acceleration voltage of 35 kV and current of 34.2 mA. The diffraction angle was scanned from 1˚ to 10˚,
2θ at a rate of 1˚/min. In order to determine the textural properties, the nitrogen adsorption–desorption isotherms were measured using a BEL
sorp-mini II volumetric adsorption analyzer in order to determine the textural properties. All of the samples were degassed at 100 ˚C under an
argon gas flow for 3 h before analysis. The specific surface area of the synthesized materials was evaluated using the BET method, and the pore
size distribution was calculated by the BJH method. Fourier transform infrared spectroscopy (FTIR) analyses were carried out on FTIR,
spectrophotometer (Bruker, Germany) Vertex 70 in the range of 400–4000 cm−1. A thermogravimetric analysis (TGA) was carried out
(PerkinElmer Pyris Diamond, U.K.) from an ambient temperature to 840 ˚C, using a ramp rate of 10˚C/min.
2.4. General procedure for the synthesis of 1-amidoalkyl-2-naphtols
In a typical reaction, to a mixture of 2-naphthol (1 mmol), aldehydes (1 mmol) and acetamide (1.5mmol), catalyst (0.1 gr) was added. The
mixture was stirred at 125 ˚C in an oil bath as indicated by thin-layer chromatography (TLC) for a complete reaction. After the completion of the
reaction, the mixture was cooled to room temperature, then the solid residue was solved in boiling EtOH and the mixture was stirred for 10
minutes. Catalyst was filtered, and the solution was concentrated under reduced pressure to obtain the product. The product was crystallized from
ethanol (Scheme 2). The products were characterized by IR, 13C NMR and 1H NMR, and values were compared with the literature data of known
products.
O
CH3
Ar
NH
OH
MCM-41-N-propylsulfamic acid
NH2COCH3
ArCHO
OH
solvent-free, 1300C
NHSO3H
Si
Cat. =
O
O
O
MCM-41
Scheme 2. One-pot synthesis of 1-amidoalkyl-2-naphthols
N-[(4-chloro-phenyl)-(2-hydroxy-napthalen-1-yl)-methyl]-acetamide (entry 2, table 3):
mp: 235-237 °C; 1H NMR (400 MHz, DMSO-d6): δH= 2.02 (s, 3H), 7.14 (d, J = 8, 1H), 7.19 (d, J = 8.4 1H), 7.29 (m, 3H), 7.4 (t, J = 7.2, 1H),
7.81 (m, 3H), 7.71 (d, J = 8.8, 1H), 8.51 ( d, J = 8, 1H), 10.1 (s, 1H) (ppm). 13C-NMR (100 MHz, DMSO): δC= 23.1, 56.6, 118.9, 119, 123, 123.6,
127, 128.4, 128.9, 129.1, 130, 131.1, 132.7, 142.3, 153.7, 170 (ppm).
N-[(4-hydroxy-phenyl)-(2-hydroxy-napthalen-1-yl)-methyl]-acetamide (entry 6, table 3):
mp: 233-234 °C; 1H NMR (400 MHz, DMSO-d6): δH= 1.98 (s, 3H), 6.67 (d, J = 8.4, 2H), 6.99 (d, J = 8, 2H), 7.06 (d, J = 8.4, 1H), 7.38 (t, J =
6.4, 1H), 7.78 (m, 2H), 7.88 (s, 1H), 8.42 ( d, J = 8.4, 1H), 9.24 (s, 1H), 9.99 (s, 1H) (ppm). 13C-NMR (100 MHz, DMSO): δC= 23.2, 48, 115.3,
119, 119.6, 122.8, 123.8, 126.6, 127.8, 129, 129.5, 132.8, 133, 153.5, 156.2, 169.5 (ppm).
N-[(3-hydroxy-phenyl)-(2-hydroxy-napthalen-1-yl)-methyl]-acetamide (entry 7, table 3):
mp: 227-228 °C; 1H NMR (400 MHz, DMSO-d6): δH= 1.99 (s, 3H), 6.56 (s, 1H), 6.58 (d, J = 8, 1H), 6.61 (d, J = 8.4, 1H), 6.63 (d, J = 6.4, 1H),
7.1 (m, 1H), 7.22 (m, 1H), 7.28 ( d, 1H), 7.77 (d, 1H), 7.81 (d, J = 8.4,1H), 8.39 ( s, 1H), 8.42 (s, 1H), 9.99 (s, 1H) (ppm). 13C-NMR (100 MHz,
DMSO): δC= 22.6, 40.1, 47.6, 113.1, 116.7, 118.4, 118.9, 122.3, 123.3, 123.4, 126.2, 128.4, 128.9, 129.1, 132.4, 144.1, 153.1, 157.1, 169.2
3
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(ppm).
N-[(4-ethoxy-phenyl)-(2-hydroxy-napthalen-1-yl)-methyl]-acetamide (entry 9, table 3):
mp: 213-217 °C; 1H NMR (400 MHz, DMSO-d6):δH= 1.29 (t, J = 6.8, 3H), 2 (s, 3H), 3.94 (q, J = 6.8, 2H), 6.82 (d, J = 8.8, 2H), 7.11 (t, J = 8.4,
3H), 7.27 (t, J = 8, 2H), 7.38 (m, 2H), 7.89 (s, 1H), 8.47 (d, J = 8.4, 1H), 10.04 (s, 1H) (ppm). 13C-NMR (100 MHz, DMSO): δC= 23.2, 48, 56.6,
63.4, 114.4, 119, 119.5, 122.8, 123.8, 126.7, 127.7, 129, 129.6, 132.8, 134.7, 153.6, 157.4, 169.6 (ppm).
N-[(3-nitro-phenyl)-(2-hydroxy-napthalen-1-yl)-methyl]-acetamide (entry 10, table 3):
mp: 251-253 °C; 1H NMR (400 MHz, DMSO-d6): δH= 2.04 (s, 3H), 7.27 (m, 3H), 7.43 (t, J = 7.2, 1H), 7.57 (m, 2H), 7.86 (m, 3H), 8.03 (s, 1H)
8.06 (m, 1H), 8.65 (d, J = 8, 1H), 10.17 (s, 1H) (ppm). 13C-NMR (100 MHz, DMSO): δC= 23, 48.1, 118.3, 118.9, 120.9, 121.7, 123.1, 123.3,
127.3, 128.9, 129.2, 130.1, 130.4, 132.6, 133.3, 145.9, 148.2, 153.8, 170.2 (ppm).
3. Results and discussion
3.1. Structural features of catalyst
The XRD pattern of MCM-41 and functionalized catalyst (NH2-(CH2)3-MCM-41 and MCM-41-N-propylsulfamic acid) is presented in Fig 1.
These spectra (Figure1.a) revealed that one-dimensional hexagonal mesoporous structure of MCM-41 was obtained. As shown, the MCM-41
pattern exhibits very sharp (1 0 0) diffraction peak at 2.24 and two additional high order peaks (1 1 0 and 2 0 0) with lower intensities at 3.91 and
4.5, respectively [30]. The values of d-spacing for these XRD peaks appear at 39.38, 22.58 and 19.60 ˚A, respectively. A unit cell parameter, a0,
of 45.50 ˚A was obtained using the following equation [31].
a0=2d100/√3
(1)
For NH2-(CH2)3-MCM-41 and MCM-41-N-propylsulfamic acid, a considerable decrease in the XRD peaks intensity was observed
(Figure 1.b). It should be noted that the intensity decreases in the (1 0 0) peak for functionalized MCM-41 providing further evidence of
functionalization occurring mainly inside the mesopore channels. Collectively, the XRD pattern of the functionalized MCM-41 also suggest not
only a significant degree of short range ordering of the structure and well-formed hexagonal pore arrays of the samples, but also the maintenance
of the structural order of the synthesized materials after functionalization. Also, used catalyst XRD diagram revealed that mesopore channels
during catalytic reaction was stable as physical structure damage has not been observed.
100
16000
100
10000
8000
6000
4000
2000
0
14000
12000
10000
8000
6000
4000
2000
0
MCM-41
Top: NH2-(CH2)3-MCM-41
Middle: Propylsulfamic acid-N-MCM-41
Bottom: used catalyst
110 200
110
200
2
4
6
8
10
Diffraction angle, 2
2
4
6
8
10
Diffraction angle, 2
110
(a)
(b)
Fig. 1. Low-angle XRD patterns of: a) MCM-41. b) NH2-(CH2)3-MCM-41, MCM-41-N-propylsulfamic acid and Used catalyst
4
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Physical parameters of nitrogen isotherms for the Barret-Joyner-Halenda average pore diameter (DBJH), the Brunauer-Emmett-Teller surface area
(SBET) and the total pore volumes (Vtotal) of the calcined MCM-41 and NH2-(CH2)3-MCM-41 are summarized in table 1.
Table 1. Textural properties of MCM-41and NH2-(CH2)3-MCM-41.
Sample
SBET (m2.g-1) DBJH (nm) Vtotal (cm3.g-1)
MCM-41
986.16
694.98
3.65
3.30
0.711
0.340
NH2-(CH2)3-MCM-41
Nitrogen adsorption/desorption isotherms of on MCM-41 show the typical type IV isotherm based on the IUPAC nomenclature for MCM-41
(Figure 2.a). The isotherms indicate that, at a relative pressure (P/P0) between 0.047-0.26, nitrogen adsorption takes place as a thin layer on the
walls (monolayer coverage). A sharp inflection at 0.26–0.33 is related to the capillary condensation and confirms the existence of uniform pores
[31]. Pore size distribution (ADS) of MCM-41 according to BJH methods is presented in Fig.2.b. After functionalization, a decrease in the SBET
and DBJH average pore diameter was observed that can be easily interpreted due to the fact that the presence of pendant group on the surface that
partially blocks the adsorption of nitrogen molecules.
5
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Fig. 3. FT-IR spectra of NH2-(CH2)3-MCM-41, MCM-41-N-propylsulfamic acid and used catalyst.
The thermograms of the synthesized mesoporous silica are presented in Figure 4. The thermogram of the calcined MCM-41 shows two steps of
weight loss. The weight loss is 4.16% in the first step from 25 ˚C to 120 ˚C that is associated with desorption of water [36] and in the second step
(120-840 ˚C), the weight loss (1.67%) is mainly due to water loss formed by the condensation of silanol groups [37]. The thermogram of the
amino-functionalized MCM-41 shows a gradual weight loss up to 840 ˚C. The TGA curve of the NH2-(CH2)3-MCM-41 shows four steps of
weight loss (25-120 ˚C, 120-340 ˚C, 340 ˚C -600 ˚C and >600 ˚C). The weight loss is 7.9% in the first step and is due to desorption of
physisorbed water held in the pores. The weight losses in the second and third steps (10.47%) are mainly associated with oxidative decomposition
of organic functional groups. In the final step, the weight loss (1.67%) is due to the dehydroxylation of the silicate networks. On the basis of
elemental analysis, the amount of functional groups of APTMS was calculated to be 0.58 mmol.g-1 of MCM-41. The TGA curve of the
Propylsulfamic acid-N-MCM-41 shows four steps of weight loss (25-135 ˚C, 135-370 ˚C, 370 ˚C -640 ˚C and >640 ˚C). The weight loss is 5.2%
in the first step and is due to desorption of water. The weight losses in the second and third steps (20.82%) are mainly associated with oxidative
decomposition of organic functional groups. So, the amount of functional groups of Propylsulfamic acid was calculated to be 0.090 mmol.g-1 of
MCM-41. In the final step, the weight loss (0.26%) is due to the dehydroxylation of the silicate networks.
Fig. 4. Thermograms of MCM-41,NH2-(CH2)3-MCM-41 and MCM-41-N-propylsulfamic acid.
6
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3.2. Reactions
Herein, we wish to report a novel protocol for the synthesis of a variety of biologically significant 1-amidoalkyl-2-naphthols using a
catalytic amount of MCM-41-N-propylsulfamic acid under solvent-free conditions. To find the optimum conditions, a model reaction of 4-
chlorobenzaldehyde (1 mmol), 2-naphthol (1 mmol), and acetamide (1.5 mmol) in the presence of different amounts of MCM-41-N-
propylsulfamic acid was performed under solvent-free conditions at 130 ˚C (Table 2). In the absence of any catalyst, desirable product was
obtained in very low yield (entry 1), whereas best result was obtained in the presence of 0.1 g of catalyst (entry 5). A slight excess of the
acetamide was found to be advantageous for yields of 1-amidoalkyl-2-naphthols and hence the molar ratio of aromatic aldehydes, 2-naphthol and
acetamide was kept at 1:1:1.5.
Table 2. Optimization of MCM-41-N-propylsulfamic acid as catalyst for synthesis of N-[(4-
chloro-phenyl)-(2-hydroxy-napthalen-1-yl)-methyl]-acetamide at 130 oCa
Entry Catalyst (g) Time (hr) Yield (%)b
1
2
3
4
5
-
24
8
5
3
1.75
17
33
45
63
95
0.02
0.05
0.08
0.1
a
Reaction conditions: 4-Chlorobenzaldehyde (1 mmol), 2-naphtol (1 mmol), acetamide (1.5
mmol). b Crude yields.
Furthermore, during the optimization of the reaction condition, the relation between the yields of the model reaction with temperature
was also studied. We carried out the reaction at temperatures ranging from 25 ˚C to 140 ˚C (Figure 5). As seen, the yield of the product increased
with increasing of temperature from 25 ˚C until it reaches a maximum at 130 ˚C, and decreases again after that. Therefore, the best suited
reaction conditions for this three-component reaction were obtained in the presence of 0.1 gr of MCM-41-N-propylsulfamic acid at 130 ˚C under
solvent-free condition.
7
Page 7 of 14

or ethoxy) or electron-withdrawing groups (such as nitro or halide) reacted successfully in the presence of MCM-41-N-propylsulfamic acid as
catalyst.
Table 3. MCM-41-N-propylsulfamic acid -catalyzed synthesis of 1-amidoalkyl-2-naphtolsa
Mp
Time
(min)
Yield
(%)b
Ref.
[38]
Entry
1
Aldehyde
Product
(lit. mp)
NHCOCH3
OH
238-240
(242-244)
120
97
CHO
Cl
NHCOCH3
235-237
(229-230)
2
3
4
105(300)c
95(80)c
[14a]
[14a]
[11]
Cl
CHO
CHO
OH
Br
NHCOCH3
OH
228-230
(229-231)
190
87
Br
F
NHCOCH3
OH
226-228
(230-232)
150
180
90
86
95
98
F
CHO
H3C
NHCOCH3
OH
218-222
(221-223)
5
6
[38]
H3C
CHO
HO
NHCOCH3
OH
233-234
227-228
-
HO
HO
CHO
OH
NHCOCH3
OH
7
8
105
240
98
86
-
CHO
H3CO
NHCOCH3
OH
178-180
(181-183)
[38]
H3CO
CHO
8
Page 8 of 14

H3CH2CO
NHCOCH3
OH
9
240
160
98
56
213-217
-
H3CH2CO
CHO
NO2
O2N
251-253
(241-242)
NHCOCH3
OH
10
[38]
CHO
NO2
NO2
NHCOCH3
OH
216-218
(218-219)
11
12
210
270
93
35
[39]
[40]
CHO
NHCOCH3
OH
198-201
(181-183)
CHO
a Reaction conditions: Aldehydes (1 mmol), 2-naphtol (1 mmol), acetamide (1.5 mmol), MCM-41-N-propylsulfamic acid ( 0.1 g), 130 ˚C b Crude
yields. c Reaction performed in the presence of recovered catalyst.
The proposed mechanism for this acid catalysis condensation reaction via in situ generation of ortho-quinone methides (o-QMs) is
presented in Scheme 3. First nucleophilic addition of 2-naphtol to the activated aldehydes by catalyst have been occurred to afford intermediate 1.
After dehydration of 1, the resultant o-QMs have been reacted with acetamide via conjugate addition to form intermediate 2. Finally this
intermediate will aromatize to produce 1-amidoalkyl-2-naphtols as desirable products.
H
H
O
Ar
Ar
OH
Ar
H
H
O
OH
O
Cat.
O
Ar
H
-H2O
1
o-QMs
NHSO3H
NH2COCH3
Cat.=
O
Si
O
Ar
NHCOCH3
OH
O
Ar
O
H
2
Scheme 3. Proposed mechanism for synthesis of 1-amidoalkyl-2-naphthols
To show the merit of MCM-41-N-propylsulfamic acid in comparison with other reported catalysts, we summarize several results for
the preparation of N-[phenyl (2-hydroxynaphthalen-1-yl) methyl] acetamide from benzaldehyde, 2-naphthol, and acetamide in table 4. It is
obvious that MCM-41-N-propylsulfamic acid showed good reaction time and higher yield than other catalysts used in literature.
9
Page 9 of 14

Table 4. Comparison results of MCM-41-N-propylsulfamic acid with other catalysts for the synthesis of N-[phenyl-(2-
hydroxy-napthalen-1-yl)-methyl]
Entry
Catalyst (mol %)
Montmorillonite K10 clay (0.1 g)
I2 (5)
Silica sulfuric acid (0.02 g)
Graphite-HClO4 (7.5)
SiO2- HClO4 (0.6)
Polymer supported sulphonic acid (0.17 g)
Indion-130 resin (0.25 g)
PPA-SiO2 (0.03 g)
Time
1.5 h
4.5 h
2 h
2 h
40 min
5 h
20 min
7 min
2h
Yield (%)
Ref.
[8]
[9]
[12]
[15]
[11]
[13]
[17]
[18]
This work
1
2
3
4
5
6
7
8
9
89
87
85
81
89
96
81
84
97
MCM-41-N-propylsulfamic acid (0.1 g)
4. Conclusion
Briefly, this is the first time that application of MCM-41-N-propylsulfamic acid as an efficient and heterogeneous catalyst for the
multicomponent one-pot synthesis of a variety of 1-amidoalkyl-2-naphthols under solvent-free conditions have reported. This simple procedure
reported here offers several significant advantages, such as high yields, easy handling, good reaction times, operational simplicity and easy
workup. The XRD pattern of the MCM-41-N-propylsulfamic acid also suggests not only a well-formed hexagonal pore arrays of the samples, but
also the maintenance of the structural order of the synthesized materials after functionalization. Also, used catalyst XRD diagram and IR revealed
that mesopore channels were stable during catalytic reaction.
Acknowledgments
Financial support to this work by the Ilam University, Ilam, Iran is gratefully acknowledged.
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Graphical abstract:
MCM-41-N-propylsulfamic acid: An efficient catalyst for one-pot synthesis of
1-amidoalkyl-2-naphtols
Maryam Hajjami,* Farshid Ghorbani and Fariba Bakhti
O
CH3
OH
Ar
NH
OH
MCM-41-N-propylsulfamic acid
NH2COCH3
ArCHO
solvent-free, 1300C
NHSO3H
Si
Cat. =
O
O
O
MCM-41
An efficient, one-pot three-component condensation of aromatic aldehydes, acetamide and 2-naphtol in the presence
of catalytic amounts of MCM-41-N-propylsulfamic acid under thermal solvent-free conditions is described for the
preparation of 1-amidoalkyl-2-naphtols.
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Highlights
 MCM-41-N-propylsulfamic acid was synthesized and characterized.
 Synthesis of 1-amidoalkyl-2-naphthols catalyzed by MCM-41-N-propylsulfamic acid.
 Used catalyst XRD and IR revealed mesopore channels was stable during reaction.
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