Sulfonated polynaphthalene as an effective and reusable catalyst for the one-pot preparation of amidoalkyl naphthols: DFT and spectroscopic studies

Article abstract of DOI:10.1016/j.molstruc.2017.05.010

Sulfonated polynaphthalene (S-PNP) as a carbon-based solid acid efficiently catalyzed the one-pot three-component synthesis of amidoalkyl naphthols. The three-component process of substituted aryl aldehydes, 2-naphthol, and amide (benzamide and acetamide)

Full text of DOI:10.1016/j.molstruc.2017.05.010

Accepted Manuscript
Sulfonated polynaphthalene as an effective and reusable catalyst for the one-pot
preparation of amidoalkyl naphthols: DFT and spectroscopic studies
Seied Ali Pourmousavi, parvin moghimi, Fatemeh Ghorbani, Mehdi Zamani
PII:
S0022-2860(17)30592-6
10.1016/j.molstruc.2017.05.010
MOLSTR 23751
DOI:
Reference:
To appear in:
Journal of Molecular Structure
Received Date:
Revised Date:
Accepted Date:
26 December 2016
07 April 2017
04 May 2017
Please cite this article as: Seied Ali Pourmousavi, parvin moghimi, Fatemeh Ghorbani, Mehdi
Zamani, Sulfonated polynaphthalene as an effective and reusable catalyst for the one-pot
preparation of amidoalkyl naphthols: DFT and spectroscopic studies, Journal of Molecular Structure
(2017), doi: 10.1016/j.molstruc.2017.05.010
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Highlights
 The application of Sulfonated polynaphthalene (S-PNP) on the synthesis of
amidoalkyl naphthols was investigated.
 The thermochemical parameters of reactions were investigated.
 Optimized structure, molecular orbitals, electrostatic potential (ESP) map of three
amidoalkyl naphthol derivatives was studied.
1

FT-IR spectra and H nuclear magnetic resonance (NMR) spectra of selected
amidoalkyl naphthols were recorded and compared with the theoretical results.

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Sulfonated polynaphthalene as an effective and reusable catalyst for the
one-pot preparation of amidoalkyl naphthols: DFT and spectroscopic
studies
Seied Ali Pourmousavia, b*, Parvin Moghimia, Fatemeh Ghorbania, Mehdi Zamania
aSchool of Chemistry, Damghan University, Damghan, 36716-41167, Iran
b Institute of Biological Science, Damghan University, Damghan, 36716-41167, Iran
* Corresponding author: * pourmousavi@du.ac.ir ,Tel.: +98-233-522-0097

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Sulfonated polynaphthalene as an effective and reusable catalyst for the
one-pot preparation of amidoalkyl naphthols: DFT and spectroscopic
studies
Seied Ali Pourmousavia,b*, parvin moghimia, Fatemeh Ghorbania, Mehdi Zamania
aSchool of Chemistry, Damghan University, Damghan, 36715-364, Iran
b Institute of Biological Science, Damghan University, Damghan, 36716-41167, Iran
Abstract
Sulfonated polynaphthalene (S-PNP) as a carbon-based solid acid efficiently catalyzed the one-pot
three-component synthesis of amidoalkyl naphthols. The three-component process of substituted aryl
aldehydes, 2-naphthol, and amide (benzamide and acetamide) or urea in the presence of S-PNP under
thermal solvent-free conditions is described. Short reaction times, high yields and easy work-up are
the advantages of this protocol. Furthermore, the catalyst can be readily recycled and reused without
obvious significant loss of activity. Also, density functional theory (DFT) with the aid of M06-2X and
B3LYP methods was used for studying of the optimized structure, molecular orbitals, electrostatic
potential (ESP) map and spectroscopic analysis of some selected amidoalkyl naphthols. The
thermochemical parameters of reactions including enthalpy, internal energy, entropy and Gibbs free
1
energy were also investigated. The theoretically calculated infrared (IR) and H nuclear magnetic
resonance (NMR) spectra of title compounds were compared to the experimental data. Based on the
results, the synthesis of amidoalkyl naphthols is exothermic. A good consistency between the
calculated and observed spectral data was found.
Keywords: Amidoalkyl naphthols, Multicomponent reaction, Sulfonated
polynaphthalene, DFT, Thermochemistry.
Introduction
Since the first multicomponent process (MCP) was described by Strecker in 1850,1
multicomponent processes (MCPs) have been demonstrated to be a highly valuable tool for
the expedient creation of the numerous chemical compounds.2-7 Carrying out MCPs will be
one of the most suitable methods, which will be a significant component of green chemistry.8-
12 The Betti 3-component reaction (Betti-3CR) is one pot three-components reaction (3CR) in
the organic synthetic that generates 1-amido-2-naphthols via an MCR. Betti-3CR, a very
well-known process was introduced by Italian chemist Mario Betti in 1900.13 The Betti-3CR

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represents an efficient protocol to produce amidoalkyl naphthols, which are also named the
Betti base analogous (Fig. 1). Betti bases and the related molecules have attracted a lot of
attention due to applications in asymmetric synthesis.14 Computational studies on this field
were also reported in recent years.15
[Fig. 1.]
A variety of natural products containing 1,3-amino-oxygenated functional groups acts as
potential drugs, as antibiotic,16 antitumors,17 antimalarial,18 antianginal,19 antihypertensive,20
antirheumatic,21 and HIV protease inhibitors. The bradycardia effects of these motifs have
also been reported.22,23 Owing to the biological importance of 1-amidoalkyl-2-naphthol
derivatives, efforts have been made by various researchers in developing MCRs for the
synthesis of 1-amidoalkyl-2-naphthols from aldehydes, beta-naphthol, and amides or urea
under thermal or sonication conditions using various catalysts such as cellulose-SO3H,24
silica sulfuric acids,25 p-TSA,26 HClO4-SiO2,27 Fe(HSO4)3,28 sulfamic acid,29
heteropolyanion-based SO3H,30 saccarin sulfonic acid,31 pyridinium-based ionic liquid,32 N-
(4-sulfonic acid) butyl triethylammonium hydrogen sulfate ([TEBSA][HSO4]),33 2-
methylpyridinium trifluoromethanesulfonate ([2-MPyH]OTf),34 2,4,6-trichloro-1,3,5-triazine
(TCT),35 1,3-dibromo-5,5-dimethylhydantoin (DBH),36 N-bromophthalimide (NBPI),37 2-
Hydroxy-5-sulfobenzoic acid (2-HSBA).38 Although some of these methods have convenient
protocol with good to high yield, the majority suffer from at least one of the following
disadvantages: unsatisfactory yeilds, the use of toxic halogenated solvents or catalysts and
long reaction times. Despite these procedures, newer methodologies for the synthesis of
amidoalkyl naphthol derivatives are still in demand.
The development of heterogeneous catalyst in chemical synthesis have become a major
area of research. These catalyst have the potential to make the cleaner, safer, higher-yielding
and relatively inexpensive processes.39-42 In order to overcome to the problem associat of
toxicity and volatile nature of many organic solvents, the design of solvent-free reactions has
received significant attention in the area of green synthesis. The toxicity and volatile nature
of many organic solvents have posed a serious threat to the environment. Thus, design of
solvent free conditions and catalytic reaction has received tremendous attention in recent
times in the area of green synthesis. In addition, reactions performed in the absence of a
solvent typically require shorter reaction time and simpler work-up procedures.43,44

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During the course of our recent studies directed towards the development of practical and
environmentally procedures for the synthesis of organic compounds using reusable
catalysts,45,46 we investigated the application of a carbon-based solid acid (S-PNP) in the
preparation of amidoalkyl naphthols. According to reported method,47-50 this solid acid is
easily prepared by polymerization of naphthalene in the presence of FeCl3 and subsequent
sulfonation by chlorosulfonic acid and represents a potential catalyst for the synthesis of
amidoalkyl naphthols (Scheme 1).
[Scheme 1]
Experimental
General
The mid-IR spectrum was obtained using KBr pellets on a Perkin-Elmer RXI Fourier
Transform spectrophotometer. The ultraviolet absorption spectra were examined in the range
200–600 nm using Perkin-Elmer lambda 25 recording spectrophotometer equipped with a 10
mm quartz cell. The NMR Spectra were acquired at the ambient temperatures on a Brucker
AVANCE DRX 400. The development of reactions was monitored by thin layer
chromatography (TLC) on Merck pre-coated silica gel 60 F254 aluminum sheets, visualized
by UV light.
Preparation of PNP
To a solution of naphthalene (10.2 g, 80 mmol) in nitrobenzene (137 ml) was added FeCl3
(28.6 g, 176 mmol) with vigorous stirring at room temperature under nitrogen. The solution
was stirred at 90 °C for 1h and then at 150 °C for 24 h. The mixture was poured into
methanol (686 ml) containing a small amount of concentrate HCl (3 ml). The precipitate was
filtered and washed with methanol. It was dispersed in chloroform (200 ml). The precipitate
was filtered, washed with chloroform, and dried at 120 °C for 3 h under reduced pressure.
PNP (8.3 g, 83%) was obtained as the black powder (Scheme 2).
[Scheme 2]
Preparation of S-PNP by chlorosulfonic acid
A solution of chlorosulfonic acid (3.9 ml, 60 mmol) in dichloromethane (24 ml) was
slowly added to the mixture of the PNP (2.5 g, 15 mmol) in dichloromethane (60 ml) with
stirring under nitrogen. The mixture was stirred at 25 °C for 24 h. The precipitate was
collected by filtration and washed with dichloromethane. The precipitate was dispersed in 0.5
M NaOH solution (200 ml) and stirred at 80 °C for 4 h. The mixture was filtered and the

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precipitate was washed with distilled water. The precipitate was dispersed in 2M sulfuric acid
solution (200 ml) and stirred at room temperature for 1 h. The mixture was filtered and the
precipitate was washed with distilled water until the wash water reached a PH of 7. The
precipitate was dried at 150 °C for 3h under reduced pressure to give the sulfonated polymer
as the hygroscopic black powder. 50
General procedure for the synthesis of amidoalkyl naphthols
A mixture of 2-naphthol (1 mmol), an aromatic aldehyde (1 mmol), acetamide or
benzamide or urea (1 mmol), and S-PNP (0.05 g) was heated in oil bath at 80 °C for 10-70
min while monitoring the reaction process by TLC. Upon completion of the transformation,
next, hot ethyl acetate (15 ml) was added to the resulting mixture, the solid residue was
dissolved in EtOAc and the mixture filtered off. Then solvent was evaporated, the remained
solid product was recrystallized in EtOH (15 ml).
Spectral data:
1
N-[(2-Hydroxynaphthalen-1-yl) (phenyl) methyl] acetamide (4a): H NMR (500MHz,
DMSO-d6): δ 1.95 (s, 3H), 7.05-7.25 (m, 8H), 7.32 (t, 1H, J= 7.2 Hz), 7.73 (d, 1H, J= 8.8
Hz), 7.77 (d,1H, J=7.9 Hz), 7.81 (br, 1H), 8.40 (d, 1H, J= 8.3Hz), 9.95 (s, 1H).
1
N-[(4-chlorophenyl) (2-hydroxynaphthalen-1-yl) methyl] acetamide (4b): H NMR
(500 MHz, DMSO-d6): δ 1.99 (s, 3H), 7.10 (d, 1H, J=8.2 Hz), 7.16 (d, 2H, J= 8.3 Hz), 7.22
(d, 1H, J= 8.8 Hz), 7.25-7.35 (m, 3H), 7.38 (t, 1H, J=7.3 Hz), 7.78 (d, 1H, J= 8.8 Hz), 7.81 (a
doublet overlapped with a broad signal, 2H, J= 7.5 Hz), 8.46 (d, 1H, J= 8.2 Hz), 10.03 (s,
1H).
N-[(2-Hydroxynaphthalen-1-yl) (4-nitrophenyl) methyl] acetamide (4f): 1H NMR (500
MHz, DMSO-d6): δ 1.98 (s, 3H), 7.14 (d, 1H, J= 7.9 Hz), 7.19 (d, 1H, J=8.8 Hz), 7.25 (t, 1H,
J=7.5 Hz), 7.33-4.40 (m, 3H), 7.74-7.82 (m, 3H), 8.10 (d, 2H, J=8.8 Hz), 8.53 (d, 1H, J=7.9
Hz), 10.07(s, 1H).
1
N-[(2-Hydroxynaphthalen-1-yl) (phenyl) methyl] benzamide (4o): H NMR (500MHz,
DMSO-d6): δ 7.24-7.88 (m, 13H), 7.82 (m, 3H), 8.08 (d, 1H, J= 8.0 Hz), 9.03 (d, 1H, J= 8.0
Hz), 10.38 (s,1H).

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1
N-[(2-Hydroxynaphthalen-1-yl) (phenyl) methyl] urea (4w): H NMR (500MHz,
DMSO-d6): δ 5.86 (s,2H, NH2), 6.94 (s, 1H), 7.12-7.41 (m, 7H, Ar-H), 7.82 (d, 1H, NH),
7.75-7.83 (m, 3H, Ar-H), 9.97 (s, 1H, OH).
Computational details
Since the reactivity of the various derivatives of amidoalkyl naphthols are all quite similar,
it was only necessary to study some of them as representatives of these derivatives. Three
derivatives of amidoalkyl naphthols (compounds 1-3) (Scheme 4) were optimized through
recently developed M06-2X meta hybrid density functional and 6-311G (d, p) polarized basis
function. The vibrational frequencies were calculated to check the nature of the minima,
prediction of IR spectrum and calculation of thermochemical data for multicomponent
reactions of Scheme 3.
[Scheme 4]
M06-2X is one of the recommended density functional methods for the applications
involving main-group thermochemistry51 which was used in this article. The difference of the
sum of electronic energy and thermal enthalpy for the reactants and the products was used for
calculation of standard enthalpy of reactions (ΔrH°). The difference of the sum of electronic
energy and thermal energy for reactants and the products was used for the calculation of
internal energy of reactions (ΔrU°). The entropy of reactions (ΔrS°) was evaluated on the basis
of the thermodynamic functions obtained by vibrational analysis results and the statistical
thermodynamic method. The Gibbs free energy of reactions (ΔrG°) was calculated via
equation (1). These thermochemical data were calculated at ambient and reaction
temperatures (T = 298.15 and 353.15 K).
ΔrG° = ΔrH° − TΔrS°
(1)
1H NMR chemical shifts (δ, ppm) versus TMS were calculated by gauge-independent
atomic orbitals (GIAO) method, 52, 53 using more convenient B3LYP/6-311+G (2d, p) density
functional. All calculations were performed using Gaussian 09 program package.54
Results and discussion
Preparation and characterization of S-PNP catalyst:

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According to Tanemura method,50 S-PNP was prepared by oxidative coupling
polymerization of naphthalene in nitrobenzene by FeCl3 under heating conditions and then
sulfonation by chlorosulfonic acid in dichloromethane as solvent (Scheme 2).
The XRD pattern of catalyst exhibits a broad and a weak diffraction peaks (2θ = 15-35°)
attributable to amorphous carbon (Fig. 2).
[Fig. 2]
Synthesis of amidoalkyl naphthols using S-PNP catalyst
After characterization of the sulfonated CBSA we decided to examine the catalyst
efficacy in the preparation of amidoalkyl naphthols. Initially to find the best reaction
conditions, three-component condensation of 2-naphthol, benzaldehyde and acetamide was
employed as the template reaction. At first, screening trials were performed to optimize
various reaction parameters, including temperature, catalyst amount, solvent and molar ratio,
with the results summarized in Table 1.
[Table 1]
Among them, to check the effect of solvent on the yield of the product, the template
reaction was carried out in various solvents (Table 1). Markedly low yields were observed
when EtOH, CH3CN, CHCl3, THF, n-hexane were utilized as the reaction media (entries 12-
16), the reaction proceeded most readily to give the highest yield of the product under
solvent-free conditions. The best result was obtained when the reaction was conducted at 80
°C in the presence of 0.05 g of the catalyst under solvent-free conditions (Table1, entry 2). A
further increase in temperature and catalyst amount did not improve the product yield.
Encouraged by the remarkable results obtained with above reaction conditions, and to
show the generality and scope of this new protocol, a range of amidoalkyl naphthols were
prepared in the presence of S-PNP under optimized conditions, with the results shown in
Table 2.
[Table 2]
With the optimized reaction conditions in hand, the expediency of this method was well
evaluated using a variety of aryl aldehydes and amides, a series of compounds were
synthesized with this simple approach. Most of the reactions proceeded very efficiently and
no side-products were observed. As can be seen from Table 2, the nature and position of
functional groups on phenyl ring were not affected yields of products and reaction times,
aromatic aldehydes bearing either electron-donating groups such as –OCH3, -CH3, -OH or

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electron-withdrawing groups such as –NO2, -F, -Cl reacted successfully with 2-naphthol and
amide or urea to give the corresponding amidoalkyl naphthol products in high yields over
short reaction time. The results also show that the amides with electron-withdrawing
substituent react slowly and produce lower yields compared to amides without electron-with
drawing groups.
To further evaluate the overall utility of the current methodology, we compared our results
with those obtained using other techniques previously reported for the synthesis of
amidoalkyl naphthols. As show in Table 3, it is clear that our method both reduces the
required temperature and the reaction time and generates higher yields of the products.
[Table 3]
Also, in exploration to reusability of the catalyst after completion of the reaction, upon
completion of the transformation, next, hot ethyl acetate (15 ml) was added to the resulting
mixture, the solid residue was dissolved in EtOAc and the mixture filtered and the recovery
solid catalyst was applied as such for the consecutive runs in four series of the same model
reaction under the optimized conditions for up to four runs (1th use: 90%, isolated yield, 2th
use: 87% isolated yield, 3th use: 79% isolated yield, 4th use: 73% isolated yield) (Fig. 3).
Decreasing the yield is probably related to slight reduction in the catalytic activity of the
catalyst or decreasing the amount of catalyst recovery which is attributed to the handling.
[Fig. 3]
Structural, electronic, thermochemical and spectroscopic properties of amidoalkyl
naphthols
As shown in Scheme 3, a chiral center is generated during the reaction of β-naphthol,
benzaldehyde, and amides (acetamide or benzamide) or urea. Therefore, it is possible to have
two stereoisomers for these compounds with enantiomeric relationship. The product of
reactions is racemic mixture and optically inactive. The optimized structure and structural
parameters for selected amidoalkyl naphthols 1-3 (Scheme 4) calculated at M06-2X/6-
311G(d,p) level of theory are shown in Fig. 4. In all structures, the amidic -NH (acetamide,
benzamide or urea fragments) orients to the side of -OH group of β-naphthol to make favored
intramolecular hydrogen bond. The NH…O distances for compounds 1-3 are Å, 2.312, 2.261
and 2.252, respectively (Fig and Table. 4).
[Fig. 4]
[Table 4]

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Figure 5 displays the highest and the lowest molecular orbitals (HOMO and LUMO) and
the calculated HOMO-LUMO energy separation for amidoalkyl naphthols 1-3. As shown that
the HOMO and LUMO are localized on the naphthol part of molecules. The theoretically
estimated energy gap for these molecules is around 6.6 eV.
[Fig. 5]
The calculated electrostatic potential (ESP) map for amidoalkyl naphthols 1-3 are shown
in Fig. 6. The red and blue signs in the ESP maps indicate the most negative (the amidic
oxygen atoms) and the most positive (hydrogen bonded hydrogen atoms) electrostatic
potentials, respectively (unit for the legend is in Ha).
[Fig. 6]
Table 5 lists the calculated thermochemical data for the synthesis of amidoalkyl naphthols
1-3 through multi-component reaction of β-naphthol, benzaldehyde, and amides (acetamide
or benzamide) or urea (Scheme 4). The gas phase enthalpy (ΔrH°), internal energy (ΔrU°),
Gibbs free energy (ΔrG°) and entropy (ΔrS°) of reactions are calculated for 298.15 and 353.15
K via M06-2X/6-311G(d,p) level of theory. It is found that the enthalpy and internal energy
of reactions are negative (exothermic), i.e. -13 to -14 kcal/mol. The entropy of reactions is
also negative, i.e. -0.05 kcal/mol K. The decrease in entropy of reactions is due to the number
of product molecules is less than the number of molecules of starting material in the same
phase. Except for compound 3 at 298.15 K, the calculated Gibbs free energies of reactions are
positive, which indicate that the mentioned reactions cannot be occurred spontaneously. The
values of ΔrG° rise as temperature increases (Table 5).
[Table. 5]
The calculated and recorded IR spectrum for amidoalkyl naphthols 1-3 are shown in Fig.
7. More important vibrational modes compared to experimental data are listed in Table 6.
Due to the harmonic approximation, most of theoretical methods overestimate the vibrational
frequencies; therefore the scaling factors of 0.89 and 0.93 are used to improve the calculated
vibrational frequencies via M06-2X/6-311G(d,p) method for the modes above and below
2500 cm-1, respectively. The O-H stretching vibration of compounds 1-3 occurs at 3400, 3419
and 3446 cm-1, respectively. The N-H stretching modes of these compounds appear at 3249,
3021 and 3246 cm-1, respectively. Other peaks are assigned in Table 6.
[Table 6]

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Table 7 lists the 1H NMR chemical shifts (δ, ppm) for amidoalkyl naphthols 1-3 calculated
via B3LYP/6-311G(d,p) level of theory in the gas phase and in DMSO as solvent (versus
TMS). The observed spectra recorded in DMSO are shown in Fig. 8.
Conclusion
In conclusion, the synthesis of amidoalkyl naphthol derivatives is reported, via a one-pot
three-component condensation of β-naphthol, aryl aldehydes, and amides (acetamid or
benzamid) or urea in the presence of S-PNP as the catalyst under solvent-free conditions has
been developed. The reaction exhibited merits such as mild conditions, easy wok-up,
completion reaction in shorter reaction times, reuse of catalyst, safe, and no organic solvent is
from the ecologically point of view. The structural and spectroscopic properties of various
number of amidoalkyl naphthols with different substituents were investigated by calculation
of optimized geometry, frontier molecular orbitals, electrostatic potential map, IR vibrational
modes and H NMR chemical shifts. In all structures, the -NH group (acetamide, benzamide
or urea fragments) orients to the side of -OH group of β-naphthol to make favored
intramolecular hydrogen bond. The MO and ESP calculations show that the electronic and
surface properties of these compounds (with 6.6 eV energy gap) are quite similar. Based on
the thermochemical calculations, the formation of amidoalkyl naphthols is an exothermic
process with decrease in entropy. The changes of Gibbs free energy during the reactions
show that the formation of compound 3 with urea fragment is thermodynamically more
favored than compounds 1 and 2 with amidic fragments. Comparison between the calculated
ΔrG° values at different temperatures predicts that the reactions are less favorable with the
increasing temperature. The theoretically calculated infrared (IR) and 1H nuclear magnetic
resonance (NMR) spectra of title compounds confirm the experimental data about the
formation of amidoalkyl naphthols.
Acknowledgement
The authors are thankful to the Research Council of Damghan University.
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A.D. Daniels, M.C. Strain, O. Farkas, D.K. Malick, A.D. Rabuck, K. Raghavachari, J.B.
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Chemical Science Transactions. 2, 330-336 (2013).
Table 1. Synthesis of N-((2-hydroxynaphthalen-1-yl) (phenyl)methyl) acetamide as a
template under various conditions.
NHCOCH3
O
O
OH
S-PNP
OH
H
H2N
CH3
Entry
1
Catalyst Amount (g)
0.025
Solvent
-
T (
ͦ
C)
Time a(min)
50
Yield b%
60
80
2c
0.05
-
80
25
80
3
4
0.075
0.1
-
80
80
20
13
80
80
40
-
-
5
-
-
80
180
180
180
25
6
0.05
0.05
0.05
0.05
-
25
7
-
50
47
87
40
9
-
100
12
CH3CN
Reflux
120

ACCEPTED MANUSCRIPT
13
14
15
0.05
0.05
0.05
0.05
CHCl3
THF
Reflux
Reflux
Reflux
Reflux
60
75
60
90
20
30
20
40
EtOH
16
n-hexane
Reaction conditions: a well-ground mixture of 1-naphthol (1mmol), benzaldehyde (1mmol),
acetamide (1mmol), and the catalyst (S-PNP) under different conditions.
a Progress of the reaction monitored with TLC analysis.
b Isolated yields.
c Optimized conditions shown in bold.
Table 2. The solvent-free synthesis of 1-amidoalkyl-2-naphthols from β-naphthol, aromatic
aldehydes and amides derivatives using sulfonated polynaphthalene.
Ar
NHCOR
O
O
OH
OH
S-PNP (0.05 g)
Ar
H
+
R
NH2
+
Solvent-free, 80 oC
1a-w
R= CH3, CH2Cl, CHCl2, Ph
4a-w
0
Time
(min)
Yield
(%)
mp. C
Entry
Aldehyde
H
Amide
Product
(Ref.)
O
NHCOCH3
OH
232-233
(238-
1
CH3CONH2
25
30
35
90
240)55a
1a
4a
O
H
Cl
235-236
(237-
238)55b
NHCOCH3
OH
2
3
CH3CONH2
90
96
4b
Cl
H
1b
1c
Cl
O
194-196
(197-
199)55a
NHCOCH3
OH
Cl
CH3CONH2
4c

ACCEPTED MANUSCRIPT
Cl
Cl
O
H
NHCOCH3
OH
227-229
(228-
Cl
4
5
6
CH3CONH2
CH3CONH2
CH3CONH2
35
30
40
87
94
97
230)55c
Cl
1d
4d
NO2
O
H
240-242
(238-
240)55a
NHCOCH3
OH
NO2
1e
4e
O
H
O2N
240-242
(237-
238)55b
NHCOCH3
OH
4f
NO
H
2 1f
NO2
O
208-210
(218-
NHCOCH3
OH
NO2
7
8
CH3CONH2
CH3CONH2
40
30
86
78
219)55b
1g
4g
OMe
O
O
H
240-241
(241-
242)55b
NHCOCH3
OH
OMe
1h
4h
4i
H
MeO
180-181
(183-
185)55d
NHCOCH3
OH
9
CH3CONH2
CH3CONH2
35
40
96
81
OMe
1i
O
H
MeO
OMe
189-191
(190-
192)55c
NHCOCH3
OH
OMe
10
4j
OMe
O
1j
OMe
H
MeO
MeO
198-200
(192-
194)55c
NHCOCH3
OH
11
CH3CONH2
70
94
MeO
OMe
OMe
1k
4k

ACCEPTED MANUSCRIPT
OMe
MeO
O
H
233-234
(235-
237)55d
NHCOCH3
12
CH3CONH2
50
82
OH
OMe
OMe
H
4l
1l
O
HO
199-200
(205-
NHCOCH3
OH
13
14
CH3CONH2
36
18
81
89
207)55e
4m
OH
1m
H
O
F
225-227
(230-
232)55d
NHCOCH3
OH
CH3CONH2
4n
F
1n
O
H
234-236
(238-
NHCOPh
OH
15
16
PhCONH2
PhCONH2
PhCONH2
11
15
20
88
90
80
240)55b
1o
Cl
4o
Cl
O
H
224-226
(284-
285)55b
NHCOPh
OH
1p
4p
OMe
NHCOPh
OH
O
H
H
265-267
(266-
267)55b
OMe
17
18
1q
4q
O
NHCOCHCl2
OH
NH2COCHCl2
NH2COCH2Cl
45
25
75
76
227-229
1r
4r
4s
O
H
198-
200(206-
207)55b
NHCOCH2Cl
OH
19
1s

ACCEPTED MANUSCRIPT
O
O
H
HO
NHCOCH2Cl
20
21
NH2COCH2Cl
43
40
77
84
213-215
OH
4t
OH
1t
H
NO2
H
O2N
219-221
(217-
218)55b
NHCOCH2Cl
OH
NH2COCH2Cl
4u
1u
O
175-177
(172-176)
55a
NHCONH2
OH
22
NH2CONH2
60
80
1w
4w
Reaction condition: Aldehyde (1 mmol), beta-naphthol (1 mmol), amide-benzamide-2-
chloroacetamide-2,2-dichloroacetamide or urea (1 mmol) under thermal solvent-free
condition, oil bath 80 °C.
Table 3. Comparison results of S-PNP with recently reported catalyst in the synthesis of
amidoalkyl naphthols.
NHCOCH3
O
O
OH
S-PNP
OH
H
H2N
CH3
Entry
Catalyst
Conditions
Time
5 min
Yielda %
52
1
2
3
4
5
6
P2O5/SiO2
Solvent-free 100 °C
Solvent-free 125 °C
Solvent-free 120 °C
Solvent-free 125 °C
Solvent-free 120 °C
Solvent-free 100 °C
94
91
92
89
85
95
[2-MPyH]OTf 42
Succinic acid 53
45 min
38 min
1.5 h
Montmorillonite K10 clay 54
H-BEA 55
5-7 min
5 min
2-HSBA 38

ACCEPTED MANUSCRIPT
28
7
8
9
Fe(HSO4)3
Fe(HSO4)3
S-PNP
Solvent-free 85 °C
65 min
7 min
83
90
90
28
Microwave oven at 450W
Solvent-free 80°C
25 min
Reaction conditions: a well-ground mixture of 1-naphthol (1 mmol), benzaldehyde (1 mmol),
acetamide (1 mmol), and the catalyst (S-PNP) under different conditions
a Isolated yields
Table 4. The calculated bond lengths for amidoalkyl naphthols 1-3 at M06-2X/6-311G(d,p)
level of theory.
Compound 1
Bond length
C1-C2
(Å)
Bond length
C18-C20
C20-C21
C20-C29
C21-C23
C23-C25
C25-C27
C27-C29
(Å)
Bond length
C30-C36
C30-O35
C30-N15
N15-H16
(Å)
1.416
1.368
1.368
1.421
1.422
1.414
1.418
1.417
1.368
1.417
1.371
1.361
0.960
1.484
1.395
1.392
1.386
1.394
1.391
1.390
1.516
1.209
1.367
1.007
C1-C6
C2-C3
C3-C4
C4-C5
C4-C12
C5-C6
C5-C7
C7-C9
C9-C11
C11-C12
C11-O13
O13-H14
Compound 2
Bond length
C1-C2
(Å)
Bond length
(Å)
Bond length
C30-N15
(Å)
1.416
1.368
C18-C20
C20-C21
1.484
1.395
1.370
1.210
C1-C6
C30-O35

ACCEPTED MANUSCRIPT
C2-C3
1.368
1.421
1.422
1.414
1.418
1.417
1.368
1.417
1.371
1.361
0.960
C20-C29
C21-C23
C23-C25
C25-C27
C27-C29
1.392
1.386
1.394
1.391
1.390
C30-C36
C36-C37
C36-C38
C37-C39
C38-C41
C39-C43
C41-C43
N15-H16
1.503
1.394
1.393
1.390
1.388
1.390
1.392
1.008
C3-C4
C4-C5
C4-C12
C5-C6
C5-C7
C7-C9
C9-C11
C11-C12
C11-O13
O13-H14
Compound 3
Bond length
C18-C20
C20-C21
C20-C29
C21-C23
C23-C25
C25-C27
C27-C29
Bond length
C1-C2
(Å)
(Å)
Bond length
C30-N15
C30-N36
C30-O35
N36-H37
N36-H38
N15-H16
(Å)
1.416
1.368
1.368
1.421
1.422
1.414
1.418
1.417
1.368
1.417
1.371
1.361
0.960
1.484
1.395
1.392
1.386
1.394
1.391
1.390
1.385
1.385
1.207
1.008
1.008
1.008
C1-C6
C2-C3
C3-C4
C4-C5
C4-C12
C5-C6
C5-C7
C7-C9
C9-C11
C11-C12
C11-O13
O13-H14
Table 5. Thermochemical properties for multi-component reactions for synthesis of
amidoalkyl naphthols 1-3 (Scheme 1), calculated at M06-2X/6-311G(d,p) level of theory.
Property
Compound 1
Compound 2
Compound 3

ACCEPTED MANUSCRIPT
298.15 K 353.15 K 298.15 K 353.15 K 298.15 K 353.15 K
ΔrH° (kcal/mol)
ΔrU° (kcal/mol)
ΔrS° (kcal/mol K)
ΔrG° (kcal/mol)
-14.05
-13.46
-0.05
1.30
-13.83
-13.13
-0.05
4.11
-13.94
-13.35
-0.05
0.14
-14.00
-13.30
-0.05
2.61
-14.10
-13.51
-0.05
-13.85
-13.14
-0.05
2.54
-0.03
Table 6. Calculated and scaled vibrational frequencies for amidoalkyl naphthols 1-3 at M06-
2X/6-311G(d,p) level of theory in comparison to experimental data.
Compound 1
Compound 2
Compound 3
Exp. Cal Scal Assignm Exp Calc. Scal Assignme Exp Calc. Scal. Assignme
c. ent nt nt
.
.
.
.
3400 391 348 OH(Str) 341 3640 324 OH(Str)
344 3911 3481 OH(Str)
6
7
6
9
0
3249 364 324 NH(Str)
302 3639 323 NH(Str)
324 3609 3212 NH(Str)
6
4
3
1
9
1640 180 168 C=O(Str) 162 1788 166 C=O(Str) 340 3615 3217 NH2(Str)
6
0
2
3
5
1582 154 143 C=C(Str) 153 1531 142 C=C(Str)
320 3730 3320 NH2(Str)
6
1
3
2
4
1436 140 130 CH3(ben 822 838
d)
779 Ring1
(OOP)
1640 1827 1699 C=O(Str)
1
3
807 755 702 Ring1
(OOP)
751 759
706 Ring2
(OOP)
152 1538 1430 C=C(Str)
2
742 755 702 Ring2
(OOP)
696 684
636 Ring2
(OOP)
814 822
746 758
698 680
764
705
632
Ring1
(OOP)
696 664 618 Ring2
(OOP)
Ring2
(OOP)
Ring2
(OOP)
1 Phenyl Ring
2 2-naphthole ring

ACCEPTED MANUSCRIPT
Table 7. Calculated 1H NMR chemical shifts (δ, ppm) for compounds 1-3 at the B3LYP/6-311 + G(2d,p) level of
theory, as well as the corresponding experimental data for these compounds
Compound 1
Compound 2
Compound 3
Atom
number
OH
Calc. Calc. Atom number
Calc.2 Atom number
Calc.2
Exp.
Exp. Calc.1
Exp. Calc.1
1
2
9.95 9.25 8.93 OH
8.40 8.14 8.11 NH
7.81 7.58 7.64 Ha
10.38 9.33
9.03 8.46
8.08 7.97
9.10
8.32
8.07
OH
NH
Ha
9.97 9.26
7.82 8.07
6.94 7.58
9.05
8.16
7.64
NH
Ha
2-
7.05- 7.29- 7.24- 2-naphthole
7.24- 7.64- 7.76- 2-naphthole
7.75- 7.29- 7.22-
naphthole 7.27 7.50 7.62 ring(Hb,Hc,Hd) 7.88
8
8.13
ring(Hb,Hc,Hd) 7.83 8.01
8.10
ring
(Hb,Hc,Hd)
Phenyl ring
7.11- 6.79- 6.76- (He,Hf)
7.12- 7.20- 7.29- Phenyl ring
7.12- 6.86- 7.06-
Phenyl
7.40 7.60
7.70
(He)
7.41 7.13
706-
7.18
6.62
ring(He)
7.16 7.17 7.19
NH2
5.86 6.51
Me
1.95 1.80 1.82
1 Gas phase
2 In DMSO
O
CHO
H2N
CH2X
Ph
NHCOCH2X
OH
OH
solven-free
80 °C
SO3H
SO3H
Scheme 1. One-pot 3C synthesis of 1-amidoalkyl-2-naphthols catalysis by S-PNP.

ACCEPTED MANUSCRIPT
FeCl3/ Nitrobenzene
N2 / T
Polynaphthalene (PNP)
SO3H
SO3H
CH2Cl2 / ClSO2OH
N2
Sulfonated Polynaphthalene (S-PNP)
Scheme 2. Preparation of PNP (top) and S-PNP (bottom).
Ar
NHCOR
OH
O
O
OH
S-PNP (0.05 g)
Ar
H
+
R
NH2
+
Solvent-free, 80 °C
1a-w
4a-w
R= CH3, CH2Cl, CHCl2, Ph, NH2
Scheme 3. Synthesis of 1-amidoalkyl-2-naphthols catalysis by S-PNP.
N-[(2-Hydroxynaphthalen-1-yl) (phenyl)methyl] acetamide (Compound 1)
Hc
H
a NHCOCH3
OH
Hb
Hd Hc
N-[(2-Hydroxynaphthalen-1-yl) (phenyl)methyl] benzamide (Compound 2)
He
O
Ha
Hf
CHN
OH
Hb
Hd Hc
N-[(2-Hydroxynaphthalen-1-yl) (phenyl)methyl] urea (Compound 3)

ACCEPTED MANUSCRIPT
He
Ha
H2NOCHN
OH
Hb
Hd Hc
Scheme 4. Three derivatives of amidoalkyl naphthols (compounds 1-3) (Scheme 4). were
optimized.
Figure captions:
Figure 1. General structure of Betti bases (A) and amidoalkylNaphthols (B).
Figure 2. The XRD pattern of S-PNP catalyst.
Figure 3. Reusability of S-PNP in the synthesis of amidoalkyl naphthol 1a
Figure 4. The optimized structure for amidoalkyl naphthols 1-3 at M06-2X/6-311G(d,p) level
of theory.
Figure 5. The calculated frontier molecular orbitals shape and energy for compounds 1-3
(from left to right, respectively).
Figure 6. The calculated ESP map for compounds 1-3 (from left to right, respectively).
Figure 7. Experimental (solid line) and calculated (dotted line) IR spectra for compounds 1-3.
Figure 8. Experimental 1H NMR spectra for compounds 1-3.
O
Ar(R)
NH
OH
R1
N
Ar
Ar
R2
OH
A
B
Figure 1.

ACCEPTED MANUSCRIPT
Figure 2.
Figure 3.

ACCEPTED MANUSCRIPT
Compound 1
Compound 2
Fig. 4. Continued
Compound 3

ACCEPTED MANUSCRIPT
Figure 4.
ELUMO= –7.07 eV
ELUMO= –7.07 eV
ELUMO= –7.00 eV
ΔE= 6.65 eV
ΔE= 6.66 eV
ΔE= 6.66 eV
EHOMO= –0.42 eV
EHOMO= –0.41 eV
Figure 5.
EHOMO= –0.34 eV
-7.249e-2
7.249e-2
-8.416e-2
8.416e-2
-9.111e-2
9.111e-2
Figure 6.

ACCEPTED MANUSCRIPT
Frequency (cm-1)
4000
3500
3000
2500
2000
1500
1000
500
0
Compound 1
Compound 2
Compound 3
Figure 7.
2 In DMSO