Convenient and efficient method for the synthesis of n-heteroaryl aminonaphthols under solvent-free conditions

Article abstract of DOI:10.1002/cjoc.201090153

A convenient, efficient and green synthesis of N-heteroaryl aminonaphthols has been developed by one-pot, three-component condensation of β-naphthol, heteroaryl amines and substituted benzaldehydes under solvent-free conditions at elevated temperature. The advantages of these reactions are simplicity of the reaction procedure, short reaction times, simple work-up, catalyst-free conditions and pure products in good to excellent yields.

Full text of DOI:10.1002/cjoc.201090153

FULL PAPER
Convenient and Efficient Method for the Synthesis of
N-Heteroaryl Aminonaphthols under Solvent-Free Conditions
Olyaei, Abolfazl*,a
Raoufmoghaddam, Saeedb
Ebadzadeh, Behruza
Sadeghpour, Mahdiehc
a Department of Chemistry, Payame Noor University (PNU), Qazvin, Iran
b School of Chemistry, University College of Science, University of Tehran, Tehran, Iran
c Department of Chemistry, Islamic Azad University, Takestan Branch, Qazvin, Iran
A convenient, efficient and green synthesis of N-heteroaryl aminonaphthols has been developed by one-pot,
three-component condensation of β-naphthol, heteroaryl amines and substituted benzaldehydes under solvent-free
conditions at elevated temperature. The advantages of these reactions are simplicity of the reaction procedure, short
reaction times, simple work-up, catalyst-free conditions and pure products in good to excellent yields.
Keywords β-naphthol, Betti base, solvent-free, heteroaryl amine, aminonaphthol
Introduction
addition to aryl aldehydes. These ligands show highly
efficient asymmetric induction to give the
corresponding alcohols up to 99% ee yields.20-22 We
now wish to describe the synthesis of Betti base deriva-
tives via a facile three-component and one-pot method
for aminoalkylation of 2-naphthol using aromatic alde-
hydes and heteroaryl amines in the absence of catalyst,
short reaction time and solvent-free conditions. As such,
utilization of environmental friendly (absence of organic
solvent) not only provides the product in an easy
work-up procedure, but also is in accord with green
sustainable chemistry principles.
Organic reactions under solvent-free or so-called
solventless conditions have gained in popularity in re-
cent years. The solid-state reaction has many advantages:
reduced pollution, shorter reaction time, simpler reac-
tors, low cost, simplicity in process and efficient work
up procedures. Moreover, these factors are especially
important in industry.
The Mannich reaction (aminoalkylation) is an exam-
ple of multi-component condensation between a
non-enolizable aldehyde, an amine (1 or 2) and an eno-
lizable carbonyl compound.1 Direct aminoalkylation has
great interest in synthetic organic chemistry and consid-
erable importance for the synthesis of drugs, pesticides
and natural products.2
Many methods of aminoalkylation of electron rich
aromatic compounds have been studied to date.
Katritzky et al.3 have reported an improved aminoalky-
lation of 2-naphthol and phenol derivatives with prefor
med iminium salts derived from aromatic aldehydes, in
a two-step sequence with 26%—92% yields. Moreover,
aminoalkylation of electron rich aromatic compounds
such as 2-naphthol for the synthesis of Betti base de-
rivatives4-14 in the presence of LiClO4, Sc(OTf)3,
Yb(OTf)3, La(OTf)3, YbCl3, TiCl4 and Me3SiCl as cata-
lysts has been reported.15-17
The racemic aminonaphthols (Betti bases) have been
used for transformation into products with anti bacterial
activity. Betti base derivatives have also provided
convenient access to many useful synthetic building
blocks via the amino and phenolic hydroxy functional
groups.18,19 Optical active Betti bases have been used as
ligands complexed to dialkyl zinc for enantioselective
Results and discussion
We have previously reported a facile synthesis of
aminonaphthols (Betti bases) with heteroaryl amines in
24
water at ambient temperature23 and 50 ℃ in almost
quantitative yields. In this paper, we decided to synthe-
size these aminonaphthols cleanly and efficiently under
solventless conditions.
As the model reaction, we initially examined the
one-pot, three-component, Mannich reaction of
2-naphthol, 2-aminopyrimidine and benzaldehyde in
solvent-free conditions at 100—150 ℃ in the absence
of acid catalyst. Our investigation demonstrated that the
best result was obtained when temperature was fixed at
125 ℃ at which the reaction was completed in 1 min.
Under the optimized reaction conditions, we decided to
examine the other reactions in catalyst and solvent-free
conditions at 125 ℃.
One-pot, three-component reaction of 2-naphthol,
aromatic aldehydes 1a—1h (benzaldehyde, 4-chloro-
benzaldehyde, 3-chlorobenzaldehyde, 4-methyl benzal-
*
E-mail: Olyaei_a@pnu.ac.ir; Tel.: 0098-281-3336366; Fax: 0098-281-3344081
Received September 15, 2009; revised November 2, 2009; accepted December 14, 2009.
Chin. J. Chem. 2010, 28, 825— 832
© 2010 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
825

Olyaei et al.
FULL PAPER
dehyde, 4-bromobenzaldehyde, 3-bromobenzaldehyde,
4-nitrobenzaldehyde and 3-nitrobenzaldehyde) and het-
eroaryl amines 2a—2d (2-aminopyrimidine, 2-amino-
pyrazine, 2-aminopyridine and 3-aminopyridine) in
solvent-free conditions at 125 ℃ in appropriate time
(Table 1) directly afforded aminonaphthols 3a—3s in
good to excellent yields (Scheme 1).
These reactions require neither solvent nor inert at-
mosphere conditions. Each compound was isolated by
the addition of ethanol to the reaction mixture and filtra-
tion of the resulting precipitate. The results of the above
mentioned reactions are shown in Table 1. As indicated
in Table 1, the reactions proceeded slowly with 3-
aminopyridine with respect to the previously mentioned
Table 1 Synthesis of N-heteroaryl aminonaphthols under solvent-free conditions at 125 ℃
Entry
1
Amine
Aldehyde
Product
3
Time/min
Yield/%
90
3a
1
2
3
3b
3c
2
3
92
92
4
5
6
3d
3e
3f
2
3
4
91
94
90
7
3g
4
89
826
www.cjc.wiley-vch.de
© 2010 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Chin. J. Chem. 2010, 28, 825— 832

Convenient and Efficient Method for the Synthesis of N-Heteroaryl Aminonaphthols
Continued
Yield/%
Entry
8
Amine
Aldehyde
Product
3
Time/min
3h
6
93
91
90
9
3i
3j
6
5
10
11
3k
5
93
12
13
14
15
3l
3m
3n
3o
4
87
90
92
15
20
15
89
Chin. J. Chem. 2010, 28, 825— 832
© 2010 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.cjc.wiley-vch.de
827

Olyaei et al.
FULL PAPER
Continued
Entry
Amine
Aldehyde
Product
3
Time/min
20
Yield/%
16
3p
91
89
94
90
17
18
19
3q
3r
3s
25
20
25
Scheme 1 Synthesis of N-heteroaryl aminonaphthols 3
action of amine and aldehyde in the first step. Then, in
the second step imine reacts with 2-naphthol affording
the corresponding aminonaphthol. As a result, negative
charge on the nitrogen in the intermediate, was stabi-
lized with 2-aminopyrimidine, 2-aminopyrazine and
2-aminopyridine with very electron poor nature,
whereas 3-aminopyridine with partially less electron
deficiency was not able to stabilize the negative charge.
To make insight into the reaction mechanism, we
initially studied the reaction of 2-naphthol with alde-
hyde. No reaction progress was observed during several
hours. When the Schiff base product obtained from
amine condensation with aldehyde was treated with
2-naphthol under the reaction conditions, the corre-
sponding Betti base derivative was obtained.
heteroaryl amines. However, we proposed the mecha-
nism for the formation of 1-[substituted phenyl (het-
eroarylamino)methyl] naphthalene-2-ols in Scheme 2.
Scheme 2 Proposed reaction mechanism
Conclusion
In conclusion, we have successfully developed a
quick, convenient, efficient and uncatalyzed method for
the synthesis of N-heteroaryl aminonaphthols (Betti
bases) by condensation reaction of 2-naphthol, alde-
hydes and heteroaryl amines in catalyst and solvent-free
conditions. The present method has advantages such as
no organic solvent, generality and simplicity of proce-
dure, lower reaction time, simple work-up, catalyst-free
conditions and low cost procedure for the synthesis of
these products in good to excellent yields.
In this mechanism, imine generated in situ from re-
828
www.cjc.wiley-vch.de
© 2010 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Chin. J. Chem. 2010, 28, 825— 832

Convenient and Efficient Method for the Synthesis of N-Heteroaryl Aminonaphthols
Experimental
and H6), 10.22 (s, 1H, OH); 13C NMR (DMSO-d6, 125
MHz) δ: 21.39, 50.82, 111.70, 119.60, 120.45, 123.45,
126.90, 127.60, 129.22, 129.46, 129.48 129.50, 129.97,
133.120, 136.11, 140.89, 153.86, 159.08, 162.73; IR
(KBr) ν: 3415, 3053, 1629, 1595, 1566, 1460, 1358,
All commercially available chemicals and reagents
were used without further purification. Melting points
(uncorrected) were determined by an Electrothermal
engineering LTD 9100 apparatus. IR spectra were re-
＋
－1
1170, 1058, 850 cm ; MS (EI) m/z: 341 (M ), 245, 231,
202, 144, 115. Anal. calcd for C22H19N3O: C 77.42, H
5.57, N 12.31; found C 77.39, H 5.60, N 12.30.
1
corded on a Perkin-Elmer model 543, the H NMR and
13C NMR spectra were obtained using BRUKER
AVANCE DRX 300 apparatus at 298 K. Chemical
shifts (δ) are referenced to the NMR solvent peak. Pro-
gress of the reactions was monitored by TLC using
precoated sheets of silica gel Merck 60 F254 on alu-
minium. Mass spectra of the products were obtained
with a HP (Agilent technologies) 5937 Mass Selective
Detector. Elemental analyses were carried out by a
CHN-O-Rapid Heraeus elemental analyzer (Wellesley,
MA).
1-[p-Bromophenyl(2-pyrimidinylamino)methyl]naph-
thalene-2-ol (3d)
Colorless crystals; 1H NMR (DMSO-d6, 500 MHz) δ:
6.65 (t, J＝4.8 Hz, 1H, pyrimidine-H5), 7.22 (d, 2H,
J＝8.5 Hz, Ph-H) 7.44 (d, 2H, J＝8.5 Hz, Ph-H), 7.24,
7.33, 7.45—7.50 (m, 5H, NPh-H, methine-H and NH),
7.78—8.09 (m, 3H, NPh-H), 8.33 (d, J＝4.8 Hz, 2H,
pyrimidine-H4 and H6), 10.27 (s, 1H, OH); 13C NMR
(DMSO-d6, 125 MHz) δ: 50.63, 111.95, 119.55, 119.87,
120.17, 123.38, 123.55, 127.78, 129.22, 129.25, 129.55,
130.31, 131.80, 133.03, 143.51, 153.97, 159.12, 162.66;
IR (KB－r) ν: 3425, 3053, 1629, 1593, 1568,＋1269, 1176,
1-(Phenyl(2-pyrimidinylamino)methyl)naphthalene-
2-ol (3a)
Colorless crystals; 1H NMR (DMSO-d6, 500 MHz) δ:
6.63 (t, J＝4.8 Hz, 1H, pyrimidine-H5), 7.14—7.49 (m,
10H, Ph-H, NPh-H, methine-H and NH), 7.77—8.12 (m,
3H, NPh-H), 8.33 (d, J＝4.8 Hz, 2H, pyrimidine-H4
and H6), 10.24 (s, 1H, OH); 1H NMR (DMSO-d6＋D2O,
500 MHz) δ: 6.62 (t, J＝4.8 Hz, 1H, pyrimidine-H5),
7.12—8.08 (m, 9H, Ph-H, NPh-H and methine-H),
7.75—8.08 (m, 3H, NPh-H), 8.30 (d, J＝4.8 Hz, 2H,
pyrimidine-H4 and H6); 13C NMR (DMSO-d6, 125
MHz) δ: 51.02, 111.77, 119.61, 120.38, 123.49, 123.52,
126.95, 127.10, 127.67, 128.93, 129.24, 129.51, 130.07,
133.16, 143.95, 153.92, 153.10, 162.76; IR (KBr) ν:
＋
1
806 cm ; MS (EI) m/z: 405 (M ), 407 (M ), 311, 231,
202, 144, 115, 95. Anal. calcd for C21H16BrN3O: C
62.06, H 3.94, N 10.34; found C 61.98, H 3.97, N 10.31.
1-[Phenyl(2-pyrazinylamino)methyl]naphthalene-2-
ol (3e)
Colorless crystals; 1H NMR (DMSO-d6, 500 MHz) δ:
7.13—7.98, (m, 12H, Ph-H, NPh-H and methine-H),
7.67 (br, 1H, NH), 7.68 (d, J＝2.8 Hz, 1H, pyrazine-H5),
7.92 (dd, J＝1.3, 2.8 Hz, 1H, pyrazine-H6), 8.27 (d, J＝
1.3 Hz, 1H, pyrazine-H3), 10.05 (s, 1H, OH); 1H NMR
(DMSO-d6＋D2O, 500 MHz) δ: 7.12—7.34, 7.73—7.78,
7.94 (m, 12H, Ph-H, NPh-H and methine-H), 7.65 (d,
J＝2.8 Hz, 1H, pyrazine-H5), 7.90 (dd, J＝1.3, 2.8 Hz,
1H, pyrazine-H6), 8.19 (d, J＝1.3 Hz, 1H, pyrazine-H3);
13C NMR (DMSO-d6, 125 MHz) δ: 50.19, 119.37,
120.30, 123.27, 124.52, 126.87, 127.09, 127.13, 128.85,
129.44, 129.51, 130.12, 132.43, 133.28, 134.83, 142.25,
143.96, 153.97, 155.67; IR (KBr)－ν: 3390, 3080, 1629,
－1
3400, 3080, 1625, 1566, 1269, 1055, 813 cm ; MS (EI)
m/z: 327 (M＋), 231, 202, 166, 115, 97. Anal. calcd for
C21H17N3O: C 77.06, H 5.19, N 12.84; found C 69.98, H
5.17, N 12.80.
1-[p-Chlorophenyl(2-pyrimidinylamino)methyl]naph-
thalene-2-ol (3b)
Colorless crystals; 1H NMR (DMSO-d6, 500 MHz) δ:
6.65 (t, J＝4.8 Hz, 1H, pyrimidine-H5), 7.22—7.50 (m,
9H, Ph-H, NPh-H, methine-H and NH), 7.78—8.09 (m,
3H, NPh-H), 8.33 (d, J＝4.8 Hz, 2H, pyrimidine-H4
and H6), 10.27 (s, 1H, OH); 13C NMR (DMSO-d6, 125
MHz) δ: 50.59, 111.94, 119.57, 119.93, 123.39, 123.55,
127.77, 128.83, 128.88, 129.26, 129.55, 130.30, 131.73,
133.05, 143.05, 153.97, 159.11, 162.68; IR (KBr) ν:
1
1593, 1433, 1295, 1205, 810 cm ; MS (EI) m/z: 327
(M＋), 231, 202, 182, 144, 115, 95. Anal. calcd for
C21H17N3O: C 77.06, H 5.19, N 12.84; found C 69.95, H
5.18, N 12.78.
1-[p-Chlorophenyl(2-pyrazinylamino)methyl]naphth-
alene-2-ol (3f)
－1
Colorless crystals; 1H NMR (DMSO-d6, 500 MHz) δ:
7.22—7.93 (m, 12H, Ph-H, NPh-H, methine-H and NH),
7.71 (d, J＝2.8 Hz, 1H, pyrazine-H5), 7.94 (dd, J＝1.3,
2.8 Hz, 1H, pyrazine-H6), 8.28 (d, J＝1.3 Hz, 1H,
pyrazine-H3), 10.10 (s, 1H, OH); 13C NMR (DMSO-d6,
125 MHz) δ: 49.77, 119.33, 119.86, 123.35, 124.33,
127.30, 128.76, 128.78, 128.93, 129.50, 130.36, 131.41,
132.60, 133.15, 134.93, 142.23, 143.18, 153.98, 155.57;
IR (KBr) ν: 3251, 3047, 1627, 1591, 1431, 1292, 1203,
3425, 3022, ＋1631, 1595, 1271, 1174, 808 cm ; MS (EI)
m/z: 361 (M ), 265, 231, 202, 144, 115, 95. Anal. calcd
for C21H16ClN3O: C 69.71, H 4.42, N 11.61; found C
69.75, H 4.40, N 11.63.
1-(p-Methylphenyl(2-pyrimidinylamino)methyl)naph-
thalene-2-ol (3c)
Colorless crystals; 1H NMR (DMSO-d6, 500 MHz) δ:
3.05 (s, 3H, CH3), 6.62 (t, J ＝ 4.7 Hz, 1H,
pyrimidine-H5), 7.04 (d, J＝7.9 Hz, 2H, Ph-H), 7.16 (d,
J＝7.9 Hz, 2H, Ph-H), 7.21—8.09 (m, 8H, NPh-H, NH
and methine-H), 8.32 (d, J＝4.7 Hz, 2H, pyrimidine-H4
＋
－1
817 cm ; MS (EI) m/z: 361 (M ), 265, 231, 202, 144,
115, 95. Anal. calcd for C21H16ClN3O: C 69.71, H 4.42,
N 11.61; found C 69.70, H 4.45, N 11.59.
Chin. J. Chem. 2010, 28, 825— 832
© 2010 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.cjc.wiley-vch.de
829

Olyaei et al.
FULL PAPER
NPh-H), 10.21 (s, 1H, OH); 13C NMR (DMSO-d6, 125
MHz) δ: 50.12, 109.91, 113.18, 119.55, 120.68, 123.31,
124.47, 127.17, 128.67, 128.96, 129.43, 129.54, 130.13,
131.22, 133.16, 137.70, 143.88, 148.13, 153.99, 159.18;
IR (KBr) ν: 3408, 3060, 1614, 1568, 1515, 1274, 1155,
819 cm ; MS (EI) m/z: 360 (M ), 265, 231, 202, 144,
115, 94, 79. Anal. calcd for C22H17ClN2O: C 73.23, H
4.71, N 7.76; found C 73.27, H 4..65, N 7.78.
1-[p-Methylphenyl(2-pyrazinylamino)methyl]naphth-
alene-2-ol (3g)
Colorless crystals; 1H NMR (DMSO-d6, 500 MHz) δ:
2.26 (s, 3H, CH3), 7.04 (d, 2H, J＝8.0 Hz, Ph-H), 7.13
(d, 2H, J＝8.0 Hz, Ph-H), 7.22—7.98 (m, 8H, NPh-H,
methine-H and NH), 7.68 (d, J ＝ 2.8 Hz, 1H,
pyrazine-H5), 7.92 (dd, J＝1.3, 2.8 Hz, 1H, pyrazine-
H6), 8.26 (d, J＝1.3 Hz, 1H, pyrazine-H3), 10.02 (s, 1H,
OH); 13C NMR (DMSO-d6, 125 MHz) δ: 21.41, 50.00,
119.36, 120.38, 123.22, 124.57, 127.02, 127.05, 129.41,
129.43, 129.51, 130.01, 132.35, 133.25, 134.76, 135.80,
140.87, 142.23, 153.89, 155.65; IR (KBr) ν: 3300, 3085,
＋
－1
1-[p-Methylphenyl(2-pyridinylamino)methyl]naphth-
alene-2-ol (3k)
Colorless crystals; 1H NMR (DMSO-d6, 500 MHz) δ:
2.22 (s, 3H, CH3), 6.51—6.49 (m, 1H, pyridine-H), 6.80
(d, J＝8.4 Hz, 1H, pyridine-H), 7.03 (d, 2H, J＝8.0 Hz,
Ph-H) 7.14 (d, 2H, J＝8.0 Hz, Ph-H), 7.19—7.40 (m,
6H, NPh-H, pyridine-H, methine-H and NH), 7.73—
7.99 (m, 4H, NPh-H), 10.25 (s, 1H, OH); 13C NMR
(DMSO-d6, 125 MHz) δ: 21.42, 50.51, 109.74, 113.00,
119.72, 121.28, 123.21, 124.73, 126.95, 127.06, 129.37,
129.40, 129.61, 129.84, 133.25, 135.68, 137.76, 141.43,
148.07, 154.02, 159.29; IR (KBr)－ν: 3490, 3018, 1614,
1565, 1515, 1271, 1155, 811 cm
－1
1627, 1＋591, 1431, 1305, 1203, 806 cm ; MS (EI) m/z:
341 (M ), 245, 231, 202, 144, 115, 95. Anal. calcd for
C22H19N3O: C 77.42, H 5.57, N 12.31; found C 77.46, H
5.59, N 12.28.
1-[p-Bromophenyl(2-pyrazinylamino)methyl]naphth-
alene-2-ol (3h)
Colorless crystals; 1H NMR (DMSO-d6, 500 MHz) δ:
7.16 (d, 2H, J＝8.5 Hz, Ph-H), 7.43 (d, 2H, J＝8.5 Hz,
Ph-H), 7.20—7.92 (m, 8H, NPh-H, methine-H and NH),
7.71 (d, J＝2.8 Hz, 1H, pyrazine-H5), 7.94 (dd, J＝1.3,
2.8 Hz, 1H, pyrazine-H6), 8.28 (d, J＝1.3 Hz, 1H,
pyrazine-H3), 10.09 (s, 1H, OH); 13C NMR (DMSO-d6,
125 MHz) δ: 49.76, 119.30, 119.79, 119.82, 123.35,
124.30, 127.30, 129.32, 129.49, 130.37, 130.40, 131.68,
132.59, 133.12, 134.92, 142.22, 143.64, 153.96, 155.54,;
IR (KBr) ν: 3－240, 3120, 1625, 1591, 1429, 1309＋, 1203,
1; MS (EI) m/z: 340
(M＋), 245, 231, 202, 195, 144, 115, 94, 79. Anal. calcd
for C23H20N2O: C 81.17, H 5.88, N 8.23; found C 81.12,
H 5.59, N 8.20.
1-[p-Bromophenyl(2-pyridinylamino)methyl]naph-
thalene-2-ol (3l)
Colorless crystals; 1H NMR (DMSO-d6, 500 MHz) δ:
6.53—6.51 (m, 1H, pyridine-H), 6.82 (d, J＝8.4 Hz, 1H,
pyridine-H), 7.17 (d, 2H, J＝8.5 Hz, Ph-H), 7.42 (d, 2H,
J ＝ 8.5 Hz, Ph-H), 7.20 — 7.40 (m, 6H, NPh-H,
pyridine-H, methine-H and NH), 7.75—7.98 (m, 4H,
NPh-H), 10.20 (s, 1H, OH); 13C NMR (DMSO-d6, 125
MHz) δ: 50.16, 109.91, 113.18, 119.52, 119.65, 120.63,
123.30, 124.46, 127.18, 129.37, 129.42, 129.53, 130.13,
131.57, 133.15, 137.67, 144.36, 148.13, 153.97, 159.17;
IR (KB－r) ν: 3400, 3057, 1614, 1568, 1515,＋1272, 1155,
＋
1
1068, 806 cm ; MS (EI) m/z: 405 (M ), 407 (M ), 311,
231, 202, 144, 115. Anal. calcd for C21H16BrN3O: C
62.06, H 3.94, N 10.34; found C 62.01, H 3.92, N 10.38.
1-[Phenyl(2-pyridinylamino)methyl]naphthalene-2-
ol (3i)
Colorless crystals; 1H NMR (DMSO-d6, 500 MHz) δ:
6.52—6.50 (m, 1H, pyridine-H), 6.82 (d, J＝8.4 Hz, 1H,
pyridine-H), 7.12—7.41 (m, 11H, Ph-H, NPh-H, pyri-
dine-H, methine-H and NH), 7.74 — 8.01 (m, 4H,
NPh-H), 10.23 (s, 1H, OH); 1H NMR (DMSO-d6＋D2O,
500 MHz) δ: 6.53—6.51 (m, 1H, pyridine-H), 6.73 (d,
J＝8.4 Hz, 1H, pyridine-H), 7.11—7.40 (m, 10H, Ph-H,
NPh-H, pyridine-H and methine-H), 7.72—7.99 (m, 4H,
NPh-H); 13C NMR (DMSO-d6, 125 MHz) δ: 50.57,
109.77, 113.02, 119.62, 121.14, 123.22, 124.64, 126.71,
126.99, 127.08, 128.75, 129.36, 129.55, 129.89, 133.24,
137.73, 144.55, 148.09, 153.99, 159.27; IR (KBr)－ν:
＋
1
817 cm ; MS (EI) m/z: 404 (M ), 406 (M ), 311, 231,
202, 144, 115, 94, 79. Anal. calcd for C22H17BrN2O: C
65.18, H 4.19, N 6.91; found C 65.14, H 4.22, N 6.88.
1-[Phenyl(3-pyrimidinylamino)methyl]naphthalene-
2-ol (3m)
Colorless crystals; 1H NMR (DMSO-d6, 500 MHz) δ:
6.55 (d, J＝6.6 Hz, 1H, methine-H), 6.72 (d, J＝6.6 Hz,
1H, NH), 7.00—8.15 (m, 15H, NPh-H, Ph-H and Pyri-
dine-H), 10.25 (s, 1H, OH); 1H NMR (DMSO-d6＋D2O,
500 MHz) δ: 6.57 (s, 1H, methine-H), 7.01—8.09 (m,
15H, NPh-H, Ph-H and Pyridine-H); 13C NMR
(DMSO-d6, 125 MHz) δ: 53.39, 119.08, 119.17, 119.56,
123.26, 124.34, 124.94, 126.91, 127.32, 127.59, 129.06,
129.45, 129.70, 130.19, 133.08, 136.73, 138.11, 143.11,
1
3365, 3020, 1606, 1568, 1512, 1274, 1160, 810 cm ;
MS (EI) m/z: 326 (M＋), 284, 157,101, 144, 88. Anal.
calcd for C22H18N2O: C 80.98, H 5.52, N 8.58; found C
80.94, H 5.55, N 8.61.
1-[p-Chlorophenyl(2-pyridinylamino)methyl]naphtha-
alene-2-ol (3j)
145.44, 153.8－8; IR (KBr) ν: 3394, 3068, 2900, 1625,
Colorless crystals; 1H NMR (DMSO-d6, 500 MHz) δ:
6.53—6.51 (m, 1H, pyridine-H), 6.82 (d, J＝8.4 Hz, 1H,
pyridine-H), 7.19—7.41 (m, 10H, Ph-H, NPh-H, pyri-
dine-H, methine-H and NH), 7.75 — 7.98 (m, 4H,
＋
1
1240, 804 cm ; MS (EI) m/z: 326 [M ], 231, 202, 94.
Anal. calcd for C22H18N2O: C 80.98, H 5.52, N 8.58;
found C 80.87, H 5.60, N 8.49.
830
www.cjc.wiley-vch.de
© 2010 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Chin. J. Chem. 2010, 28, 825— 832

Convenient and Efficient Method for the Synthesis of N-Heteroaryl Aminonaphthols
1-[4-Chlorophenyl(3-pyrimidinylamino)methyl]naph-
6.68 (d, J＝6.3 Hz, 1H, methine-H), 6.81 (d, J＝6.3 Hz,
thalene-2-ol (3n)
1H, NH), 7.06—8.19 (m, 14H, NPh-H, Ph-H and Pyri-
dine-H), 10.35 (s, 1H, OH); 13C NMR (DMSO-d6, 125
MHz) δ: 53.29, 119.08, 119.11, 119.14, 119.37, 123.47,
124.28, 124.44, 127.37, 128.69, 129.58, 129.64, 130.76,
132.92, 136.86, 138.53, 145.17, 147.01, 151.70, 153.93;
IR (KBr) ν: 3406, 3087, 2916, 1627, 1514, 1346, 1244,
Colorless crystals; 1H NMR (DMSO-d6, 500 MHz) δ:
6.60 (d, J＝6.6 Hz, 1H, methine-H), 6.72 (d, J＝6.6 Hz,
1H, NH), 7.02—8.12 (m, 14H, NPh-H, Ph-H and Pyri-
dine-H), 10.25 (s, 1H, OH); 13C NMR (DMSO-d6, 125
MHz) δ: 52.86, 119.07, 119.21, 119.26, 123.33, 124.36,
124.69, 127.08, 128.99, 129.42, 129.51, 129.66, 130.39
131.83, 132.95, 136.76, 138.26, 142.27, 145.27, 153.85;
－1
＋
827 cm ; MS (EI) m/z: 371 [M ], 260, 231, 202, 144,
94. Anal. calcd for C22H17N3O3: C 71.16, H 4.58, N
11.32; found C 71.20, H 4.57, N 11.22.
－1
IR (KBr) ν: 3373, 3051, 2917, 1627, 1299, 806 cm ;
MS (EI) m/z: 360 [M＋], 265, 231, 202, 144, 94. Anal.
calcd for C22H17ClN2O: C 73.23, H 4.71, N 7.76; found
C 73.19, H 4.64, N 7.80.
1-[3-Nitrophenyl(3-pyrimidinylamino)methyl]naph-
thalene-2-ol (3s)
Colorless crystals; 1H NMR (DMSO-d6, 500 MHz) δ:
6.71 (d, J＝6.7 Hz, 1H, methine-H), 6.93 (d, J＝6.7 Hz,
1H, NH), 7.10—8.23 (m, 14H, NPh-H, Ph-H and Pyri-
dine-H), 10.40 (s, 1H, OH); 13C NMR (DMSO-d6, 125
MHz) δ: 53.01, 118.75, 119.21, 120.07, 122.09, 122.46,
123.49, 124.22, 124.71, 127.45, 129.59, 129.64, 130.60,
130.80, 132.91, 134.32, 136.07, 137.90, 145.28, 145.81,
148.71, 154.10; IR (KBr) －ν: 3390, 3078, 2925, 1622,
1-[3-Chlorophenyl(3-pyrimidinylamino)methyl]naph-
thalene-2-ol (3o)
Colorless crystals; 1H NMR (DMSO-d6, 500 MHz) δ:
6.57 (d, J＝6.8 Hz, 1H, methine-H), 6.74 (d, J＝6.8 Hz,
1H, NH), 7.02—8.13 (m, 14H, NPh-H, Ph-H and Pyri-
dine-H), 10.28 (s, 1H, OH); 13C NMR (DMSO-d6, 125
MHz) δ: 52.97, 119.10, 119.17, 119.24, 123.39, 124.37,
124.52, 126.29, 127.15, 127.23, 127.32, 129.55, 129.61,
130.48, 130.96, 132.93, 133.81, 136.77, 138.35, 145.16,
145.95, 153.90; IR (KBr) ν: 3404, 3051, 2906, 1625,
＋
1
1527, 1348, 1236, 804 cm ; MS (EI) m/z: 371 [M ],
276, 260, 231, 202, 144, 94. Anal. calcd for C22H17N3O3:
C 71.16, H 4.58, N 11.32; found C 71.11, H 4.50, N
11.25.
＋
－1
1292, 815 cm ; MS (EI) m/z: 360, [M ], 265, 231, 216,
202, 144, 94. Anal. calcd for C22H17ClN2O: C 73.23, H
4.71, N 7.76; found C 73.16, H 4.68, N 7.72.
Acknowledgments
The authors wish to thank the Research Council of
the Payame Noor University of Qazvin for financial
supports.
1-[4-Bromophenyl(3-pyrimidinylamino)methyl]naph-
thalene-2-ol (3p)
Colorless crystals; 1H NMR (DMSO-d6, 500 MHz) δ:
6.53 (d, J＝6.3 Hz, 1H, methine-H), 6.71 (d, J＝6.3 Hz,
1H, NH), 7.02—8.12 (m, 14H, NPh-H, Ph-H and Pyri-
dine-H), 10.26 (s, 1H, OH); 13C NMR (DMSO-d6, 125
MHz) δ: 52.93, 119.10, 119.25, 120.33, 123.35, 124.38,
124.60, 124.72, 127.10, 129.52, 129.67, 129.82, 130.41,
131.91, 132.96, 136.78, 138.28, 142.75, 145.29, 153.87;
References
1
Arend, M.; Westermann, B.; Risch, N. Angew. Chem., Int.
Ed. 1998, 37, 1044.
2
3
Tramontini, M.; Angionili, L. Tetrahedron 1990, 46, 1791.
Katritzky, A. R.; Abdel-Fattah, A. A. A.; Tymoshenko, D.
O.; Belyakov, S. A.; Ghiviriga, I.; Steel, P. J. J. Org. Chem.
1999, 64, 6071.
－1
IR (KBr) ν: 3373, 30＋51, 2915, 1627, 1249, 806 cm ;
MS (EI) m/z: 404 [M ], 406 [M＋], 311, 231, 202, 144,
94. Anal. calcd for C22H17BrN2O: C 65.18, H 4.19, N
6.91; found C 65.21, H 4.11, N 6.89.
4
5
6
7
8
9
Betti, M. Gazz. Chim. Ital. 1900, 30, 310.
Betti, M. Org. Synth. Coll. 1941, I, 381.
Szatmari, I.; Fulop, F. Curr. Org. Synth. 2004, 1, 155.
Pirrone, F. Gazz. Chim. Ital. 1940, 70, 520.
Phillips, J. P.; Barrall, E. M. J. Org. Chem. 1956, 21, 692.
Phillips, J. P. Chem. Rev. 1956, 56, 271.
1-[3-Bromophenyl(3-pyrimidinylamino)methyl]naph-
thalene-2-ol (3q)
Colorless crystals; 1H NMR (DMSO-d6, 500 MHz) δ:
6.59 (d, J＝6.3 Hz, 1H, methine-H), 6.75 (d, J＝6.3 Hz,
1H, NH), 7.02—8.15 (m, 14H, NPh-H, Ph-H and Pyri-
dine-H), 10.32 (s, 1H, OH); 13C NMR (DMSO-d6, 125
MHz) δ: 52.96, 119.10, 119.15, 119.25, 122.51, 123.39,
124.37, 126.67, 127.21, 129.55, 129.60, 130.13, 130.21,
130.48, 131.25, 131.90, 132.94, 136.78, 138.36, 145.16,
146.19, 153.94; IR (KBr) ν: 3394, 3053,＋2923, 1625,
10 Brode, W. R.; Littman, J. B. J. Am. Chem. Soc. 1930, 52,
1655.
11 Wang, Y.; Li, X.; Ding, K. Tetrahedron: Asymmetry 2002,
13, 1291.
12 Cardellicchio, C.; Ciccarella, G.; Naso, F.; Perna, F.;
Tortorella, P. Tetrahedron 1999, 55, 14685.
13 Szatmari, I.; Tamas, A. M.; Lazar, L.; Fulop, F.
Tetrahedron 2003, 59, 2877.
14 Grumbach, H. J.; Arend, M.; Risch, N. Synthesis 1996, 883.
15 Mojtahedi, M. M.; Sharifi, A.; Mohsenzadeh, F.; Saidi, M.
R. Synth. Commun. 2000, 30, 69.
＋
－1
1238, 817 cm ; MS (EI) m/z: (%) 404 [M ], 406 [M ],
311, 231, 202, 144, 95. Anal. calcd for C22H17BrN2O: C
65.18, H 4.19, N 6.91; found C 65.14, H 4.16, N 6.97.
1-[4-Nitrophenyl(3-pyrimidinylamino)methyl]naph-
thalene-2-ol (3r)
16 Saidi, M. R.; Azizi, N.; Naimi-jamal, M. R. Tetrahedron
Lett. 2001, 42, 8111.
Colorless crystals; 1H NMR (DMSO-d6, 500 MHz) δ:
Chin. J. Chem. 2010, 28, 825— 832
© 2010 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.cjc.wiley-vch.de
831

Olyaei et al.
FULL PAPER
17 Huang, T.; Li, C. J. Tetrahedron Lett. 2000, 41, 6715.
18 Szatmari, I.; Heteny, A.; Lazar, L.; Fulop, F. J. Heterocyclic
Chem. 2004, 41, 367.
19 Heydenreich, M.; Koch, A.; Klod, S.; Szatmari, I.; Fulop, F.;
Kleinpeter, E. Tetrahedron 2006, 62, 11081.
22 Lu, J.; Xu, X.; Wang, C.; He, J.; Hu, Y.; Hu, H.
Tetrahedron Lett. 2002, 43, 8367.
23 Ghandi, M.; Olyaei, A.; Raoufmoghaddam, S. Synth. Com-
mun. 2008, 38, 4125.
24 Ghandi, M.; Olyaei, A.; Raoufmoghaddam, S. J. Heterocyc-
lic Chem. 2009, 46, 914.
20 Palmieri, G. Tetrahedron: Asymmetry 2000, 11, 3361.
21 Ma, F.; Shen, L. Ai, X.; Zhang, C. Org. Lett. 2007, 9, 125.
(E0909152 Sun, H.; Lu, Z.)
832
www.cjc.wiley-vch.de
© 2010 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Chin. J. Chem. 2010, 28, 825— 832