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

DOI: 10.1016/j.molstruc.2017.05.010

Reference: MOLSTR 23751

To appear in: Journal of Molecular Structure

Received Date: 26 December 2016

Revised Date: 07 April 2017

Accepted Date: 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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 ACCEPTED MANUSCRIPT

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.
 FT-IR spectra and 1H nuclear magnetic resonance (NMR) spectra of selected
amidoalkyl naphthols were recorded and compared with the theoretical results.
 ACCEPTED MANUSCRIPT

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: * [email protected] ,Tel.: +98-233-522-0097

 ACCEPTED MANUSCRIPT

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
energy were also investigated. The theoretically calculated infrared (IR) and 1H 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
 ACCEPTED MANUSCRIPT

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:
N-[(2-Hydroxynaphthalen-1-yl) (phenyl) methyl] acetamide (4a): 1H 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).

N-[(4-chlorophenyl) (2-hydroxynaphthalen-1-yl) methyl] acetamide (4b): 1H 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).

N-[(2-Hydroxynaphthalen-1-yl) (phenyl) methyl] benzamide (4o): 1H 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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N-[(2-Hydroxynaphthalen-1-yl) (phenyl) methyl] urea (4w): 1H 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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Table 1. Synthesis of N-((2-hydroxynaphthalen-1-yl) (phenyl)methyl) acetamide as a

template under various conditions.

NHCOCH3
O
O OH
OH S-PNP
H
H 2N CH3

Entry Catalyst Amount (g) Solvent T (ͦ C) Time a(min) Yield b%

1 0.025 - 80 50 60

2c 0.05 - 80 25 80

3 0.075 - 80 20 80

4 0.1 - 80 13 80

5 - - 80 180 40

6 0.05 - 25 180 -

7 0.05 - 50 180 47

9 0.05 - 100 25 87

12 0.05 CH3CN Reflux 120 40

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13 0.05 CHCl3 Reflux 60 20

14 0.05 THF Reflux 75 30

15 0.05 EtOH Reflux 60 20

16 0.05 n-hexane Reflux 90 40

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
1a-w Solvent-free, 80 oC
4a-w
R= CH3, CH2Cl, CHCl2, Ph

Time Yield mp. 0C

Entry Aldehyde Amide Product
(min) (%) (Ref.)

O H
NHCOCH3 232-233
1 CH3CONH2 25 90 (238-
OH
240)55a
1a 4a

O H Cl
NHCOCH3 235-236
2 CH3CONH2 30 90 (237-
OH
238)55b
Cl 4b
1b

Cl
O H
NHCOCH3 194-196
3 Cl CH3CONH2 35 96 (197-
OH
199)55a
1c
4c
 ACCEPTED MANUSCRIPT

Cl Cl
O H
NHCOCH3 227-229
Cl
4 CH3CONH2 OH 35 87 (228-
230)55c
Cl 1d
4d

NO2
O H
240-242
NHCOCH3
5 CH3CONH2 30 94 (238-
OH 240)55a
NO2 1e
4e

O H O2 N
NHCOCH3 240-242
6 CH3CONH2 40 97 (237-
OH
238)55b
NO2 1f 4f

NO2
O H
NHCOCH3 208-210
7 NO2 CH3CONH2 40 86 (218-
OH
1g 219)55b
4g

OMe
O H
NHCOCH3 240-241
8 OMe CH3CONH2 30 78 (241-
OH
242)55b
1h
4h

O H MeO
NHCOCH3 180-181
9 CH3CONH2 OH
35 96 (183-
185)55d
OMe 1i 4i

O H MeO OMe

OMe NHCOCH3 189-191

10 CH3CONH2 40 81 (190-
OH
192)55c
OMe 1j 4j

O H OMe
MeO
198-200
NHCOCH3
11 CH3CONH2 MeO 70 94 (192-
MeO OMe OH
OMe
194)55c
1k 4k
 ACCEPTED MANUSCRIPT

O H OMe
MeO
233-234
NHCOCH3
12 CH3CONH2 50 82 (235-
OH
OMe 237)55d
OMe 1l 4l

O H HO
NHCOCH3 199-200
13 CH3CONH2 36 81 (205-
OH
207)55e
OH 1m 4m

O H F
NHCOCH3 225-227
14 CH3CONH2 18 89 (230-
OH
232)55d
F 4n
1n

O H
NHCOPh 234-236
15 PhCONH2 OH
11 88 (238-
240)55b
1o
4o

Cl
O H
NHCOPh 224-226
16 Cl PhCONH2 15 90 (284-
OH
285)55b
1p
4p

OMe
O H
NHCOPh 265-267
17 OMe PhCONH2 20 80 (266-
OH
267)55b
1q
4q

O H
NHCOCHCl2
18 NH2COCHCl2 OH 45 75 227-229

1r 4r

O H
NHCOCH2Cl 198-
19 NH2COCH2Cl OH 25 76 200(206-
207)55b
1s 4s
 ACCEPTED MANUSCRIPT

O H HO
NHCOCH2Cl
20 NH2COCH2Cl 43 77 213-215
OH

OH 1t 4t

O H
O2 N
NHCOCH2Cl 219-221
21 NH2COCH2Cl OH
40 84 (217-
218)55b
NO2 1u 4u

O H
NHCONH2 175-177
22 NH2CONH2 OH
60 80 (172-176)
55a
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
OH S-PNP
H
H 2N CH3

Entry Catalyst Conditions Time Yielda %

1 P2O5/SiO2 52 Solvent-free 100 °C 5 min 94

2 [2-MPyH]OTf 42 Solvent-free 125 °C 45 min 91

3 Succinic acid 53 Solvent-free 120 °C 38 min 92

4 Montmorillonite K10 clay 54 Solvent-free 125 °C 1.5 h 89

5 H-BEA 55 Solvent-free 120 °C 5-7 min 85

6 2-HSBA 38 Solvent-free 100 °C 5 min 95

 ACCEPTED MANUSCRIPT

7 Fe(HSO4)3 28 Solvent-free 85 °C 65 min 83

8 Fe(HSO4)3 28 Microwave oven at 450W 7 min 90

9 S-PNP Solvent-free 80°C 25 min 90

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 (Å) Bond length (Å) Bond length (Å)

C1-C2 1.416 C18-C20 1.484 C30-C36 1.516

C1-C6 1.368 C20-C21 1.395 C30-O35 1.209

C2-C3 1.368 C20-C29 1.392 C30-N15 1.367

C3-C4 1.421 C21-C23 1.386 N15-H16 1.007

C4-C5 1.422 C23-C25 1.394

C4-C12 1.414 C25-C27 1.391

C5-C6 1.418 C27-C29 1.390

C5-C7 1.417

C7-C9 1.368

C9-C11 1.417

C11-C12 1.371

C11-O13 1.361

O13-H14 0.960

Compound 2

Bond length (Å) Bond length (Å) Bond length (Å)

C1-C2 1.416 C18-C20 1.484 C30-N15 1.370

C1-C6 1.368 C20-C21 1.395 C30-O35 1.210

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C2-C3 1.368 C20-C29 1.392 C30-C36 1.503

C3-C4 1.421 C21-C23 1.386 C36-C37 1.394

C4-C5 1.422 C23-C25 1.394 C36-C38 1.393

C4-C12 1.414 C25-C27 1.391 C37-C39 1.390

C5-C6 1.418 C27-C29 1.390 C38-C41 1.388

C5-C7 1.417 C39-C43 1.390

C7-C9 1.368 C41-C43 1.392

C9-C11 1.417 N15-H16 1.008

C11-C12 1.371

C11-O13 1.361

O13-H14 0.960

Compound 3

Bond length (Å) Bond length (Å) Bond length (Å)

C1-C2 1.416 C18-C20 1.484 C30-N15 1.385

C1-C6 1.368 C20-C21 1.395 C30-N36 1.385

C2-C3 1.368 C20-C29 1.392 C30-O35 1.207

C3-C4 1.421 C21-C23 1.386 N36-H37 1.008

C4-C5 1.422 C23-C25 1.394 N36-H38 1.008

C4-C12 1.414 C25-C27 1.391 N15-H16 1.008

C5-C6 1.418 C27-C29 1.390

C5-C7 1.417

C7-C9 1.368

C9-C11 1.417

C11-C12 1.371

C11-O13 1.361

O13-H14 0.960

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) -14.05 -13.83 -13.94 -14.00 -14.10 -13.85

ΔrU° (kcal/mol) -13.46 -13.13 -13.35 -13.30 -13.51 -13.14

ΔrS° (kcal/mol K) -0.05 -0.05 -0.05 -0.05 -0.05 -0.05

ΔrG° (kcal/mol) 1.30 4.11 0.14 2.61 -0.03 2.54

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)
7 6 9 0 6
3249 364 324 NH(Str) 302 3639 323 NH(Str) 324 3609 3212 NH(Str)
4 3 1 9 6
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)
1 3 2 4 6
1436 140 130 CH3(ben 822 838 779 Ring1 1640 1827 1699 C=O(Str)
1 3 d) (OOP)
807 755 702 Ring1 751 759 706 Ring2 152 1538 1430 C=C(Str)
(OOP) (OOP) 2
742 755 702 Ring2 696 684 636 Ring2 814 822 764 Ring1
(OOP) (OOP) (OOP)
696 664 618 Ring2 746 758 705 Ring2
(OOP) (OOP)
698 680 632 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 Calc. Calc. Atom number Calc.2 Atom number Calc.2
Exp. Exp. Calc.1 Exp. Calc.1
number 1 2

OH 9.95 9.25 8.93 OH 10.38 9.33 9.10 OH 9.97 9.26 9.05

NH 8.40 8.14 8.11 NH 9.03 8.46 8.32 NH 7.82 8.07 8.16
Ha 7.81 7.58 7.64 Ha 8.08 7.97 8.07 Ha 6.94 7.58 7.64
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 7.12- 7.20- 7.29- Phenyl ring 7.12- 6.86- 7.06-
Phenyl 7.11- 6.79- 6.76- (He,Hf) 7.40 7.60 7.70 (He) 7.41 7.13 706-
ring(He) 7.16 7.17 7.19 7.18
NH2 5.86 6.51 6.62
Me 1.95 1.80 1.82
1 Gas phase
2 In DMSO

O CHO

H2N CH 2X
Ph NHCOCH 2X

OH OH

solven-f ree
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)

SO 3H SO 3H

CH2Cl2 / ClSO 2OH

N2

Sulf onated Polynaphthalene (S-PNP)

Scheme 2. Preparation of PNP (top) and S-PNP (bottom).

Ar NHCOR
O O
OH OH
S-PNP (0.05 g)
Ar H + + R NH2
1a-w Solvent-free, 80 °C
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
Ha
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.

R1 O Ar(R)
Ar N Ar NH
R2
OH 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 EHOMO= –0.34 eV

Figure 5.

-8.416e-2 8.416e-2 -7.249e-2 7.249e-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
Transmittance

Compound 2

Compound 3

Figure 7.
2 In DMSO
ACCEPTED MANUSCRIPT

(Compound 1)

(Compound 2)

(Compound 3)

Figure. 8.