One-pot, three-component uncatalyzed quantitative synthesis of new aminonaphthols (Betti bases) in water

Article abstract of DOI:10.1080/00397910802279860

One-pot, three-component reaction of 2-naphthol, aromatic aldehyde, and heteroaryl amine in water at room temperature leads to the formation of the corresponding aminonaphthols (Betti bases). Reaction details and study of enantiomeric resolution of 1-(p-m

Full text of DOI:10.1080/00397910802279860

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One-Pot, Three-Component
Uncatalyzed Quantitative
Synthesis of New
Aminonaphthols (Betti Bases)
in Water
Mehdi Ghandi a , Abolfazl Olyaei b & Saeed
Raoufmoghaddam a
a School of Chemistry, University College of Science,
University of Tehran, Tehran, Iran
b Department of Chemistry, Payame Noor University
of Qazvin, Qazvin, Iran
Published online: 31 Oct 2008.
To cite this article: Mehdi Ghandi , Abolfazl Olyaei & Saeed Raoufmoghaddam
(2008) One-Pot, Three-Component Uncatalyzed Quantitative Synthesis of New
Aminonaphthols (Betti Bases) in Water, Synthetic Communications: An International
Journal for Rapid Communication of Synthetic Organic Chemistry, 38:23, 4125-4138,
DOI: 10.1080/00397910802279860
To link to this article: http://dx.doi.org/10.1080/00397910802279860
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Synthetic Communications1, 38: 4125–4138, 2008
Copyright # Taylor & Francis Group, LLC
ISSN: 0039-7911 print=1532-2432 online
DOI: 10.1080/00397910802279860
One-Pot, Three-Component Uncatalyzed
Quantitative Synthesis of New Aminonaphthols
(Betti Bases) in Water
Mehdi Ghandi,1 Abolfazl Olyaei,2 and Saeed Raoufmoghaddam1
1School of Chemistry, University College of Science,
University of Tehran, Tehran, Iran
2Department of Chemistry, Payame Noor University of Qazvin,
Qazvin, Iran
Abstract: One-pot, three-component reaction of 2-naphthol, aromatic aldehyde,
and heteroaryl amine in water at room temperature leads to the formation of
the corresponding aminonaphthols (Betti bases). Reaction details and study
of enantiomeric resolution of 1-(p-methylphenyl (2-pyrazinylamino) methyl)
1
naphthalene-2-ol with the aid of H NMR spectroscopy using chiral europium
shift reagent is presented.
Keywords: Aminonaphthol, Betti base, 2-naphthol, shift reagent
INTRODUCTION
Study of the chemistry of the Betti bases started at the beginning of the
20th century, when Betti,[1] a pioneer of asymmetric synthesis, reported
that condensation of 2-naphthol, benzaldehyde, and ammonia gave a
product with the ratio of 1:2:1 respectively. The product was identified
as 1,3-diphenyl-2,3-dihydro-1H-naphth[1,2-e][1,3]oxazine (1). Subsequ-
ent treatment of 1 with HCl, followed by addition of KOH to the
Received May 18, 2008.
Address correspondence to Mehdi Ghandi, School of Chemistry, University
College of Science, University of Tehran, Tehran, Iran. E-mail: ghandi@khayam.
ut.ac.ir
4125

4126
M. Ghandi, A. Olyaei, and S. Raoufmoghaddam
Scheme 1. Synthesis of Betti base 2.
ammonium salt, yielded 1-(a-aminobenzyl)-2-naphthol (2), the so-called
Betti base (Scheme 1).[2]
Preparation of the substituted Betti base derivatives via the modified
Mannich reaction has subsequently become of considerable importance
because of C–C bond formation under mild experimental conditions.
In recent years, attention has been paid to the Betti reaction, and a simi-
lar reaction, can be performed by either using other naphthols[3] or qui-
nolinols[4,5] or by replacing ammonia with alkyl amines.[6–9] In addition, a
variety of racemic structures related to the Betti bases have recently been
prepared by addition of naphthols to the preformed imminium salts.[10]
Traditionally, the Betti base derivative synthesis is carried out in organic
solvents such as EtOH, MeOH, and Et2O at room temperature for long
times or thermally under solventless conditions. As such, utilization of
environmentally friendly water as solvent not only provides the product
in an easy workup procedure (vide infra) but also is in accord with green
sustainable chemistry principles.
The racemic Betti bases have been used for transformation into pro-
ducts with antibacterial activity. Betti base derivatives have also provi-
ded convenient access to many useful synthetic building blocks via the
amino and phenolic hydroxy functional groups.[11,12] Optically active
Betti bases have been used as ligands complexed to dialkyl zinc for
enantioselective addition to aryl aldehydes. These ligands show highly
efficient asymmetric induction to give the corresponding alcohols up to
99% ee yields.[7,8,13–15] Moreover, condensation of Betti base derivatives
with aldehydes leads to the formation of the corresponding 1,3-
oxazines[9,16] with varied biological properties.[16,17]

New Aminonaphthol Synthesis in Water
RESULTS AND DISCUSSION
4127
As part of a continuous effort to develop new N,O-ligand derivatives
relevant to Betti bases, we report a fast, simple, and highly efficient
method for the synthesis of new aminonaphthols with heteroaryl amines
in water at ambient temperature in almost quantitative yields. The pro-
mising advantages such as removal of organic solvent, no need for cata-
lyst, easy product separation, and short reaction time are discussed in this
presentation. Our literature survey showed that heteroaryl amines have
not previously been used for the synthesis of Betti base derivatives. As
the model reaction, we initially examined the one-pot reaction of benzal-
dehyde, 2-aminopyridine, and 2-naphthol in CH3CN in the presence of
formic acid as catalyst at room temperature. It was found that at least
24 h is needed for reaction to be completed. On the other hand, the same
reaction was completed during 2 h under reflux conditions (see Table 1).
When this reaction was carried out in refluxing H2O, to our surprise,
the reaction proceeded to completion in the absence of acid catalyst during
10 min. At room temperature, 45 min was needed to obtain the comparable
product yield (Table 1). Therefore, we decided to examine the other reac-
tions in H2O at room temperature in the absence of acid catalyst.
One-pot, three-component reaction of 2-naphthol, heteroaryl amines
3a–d, and aromatic aldehydes 4a–c in water at room temperature in the
appropriate time (see Table 1) directly afforded aminonaphthols 5a–l in
excellent yields (Scheme 2). To see the effect of solvent, reactions were
carried out in CH3CN and H2O. The results are presented in Table 1.
To gain insight into the reaction mechanism, we initially studied the
reaction of 2-naphthol with aldehyde. 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 reac-
tion conditions, the corresponding Betti base derivative was obtained. In
our one-pot reaction, it might be concluded that imine generated in situ
from reaction of amine and aldehyde reacts with 2-naphthol, affording
the aminonaphthol.
Identification of 5a–l was carried out on the basis of spectroscopic
1
information. The H NMR spectra of compounds 5a–l show a sharp
singlet for the hydroxyl group at about d 10 ppm. CH3-Ph appears as
singlet at about d 2.2 ppm. The pyrimidinyl moieties in compounds 5a,
d, g, and i are exhibited as two well-resolved AB2 spin systems at about
d 6.6 and 8.3 ppm. The pyrazinyl protons of 5b, e, h, and k appear as two
doublets at about d 7.7 and 8.3 and a doublet of doublet at d 7.9 ppm.
With the exception of 5d, e, and f, 4-substituted phenyl protons show
two well-resolved AB spin systems near d 7.0–7.2 and 7.1–7.4 ppm. In

4128
M. Ghandi, A. Olyaei, and S. Raoufmoghaddam
Table 1. Reaction times, yields, and melting points of the products 5 in CH3CN
and H2O
CH3CNa
(reflux)b
H2Oc (rt)
Time Yield Time Yield
(min) (%) (min) (%)
Mp
(ꢀC)
Products
Ar0
Ar
5a
90
90
85
89
30
35
95
97
241–242
5b
196–198
5c
5d
120
90
91
80
45
35
98
95
184–185
242–243
5e
120
90
40
98
196–198
194–196
5f
60
60
88
88
40
25
98
97
5g
189–190
(Continued )

New Aminonaphthol Synthesis in Water
4129
Table 1. Continued
CH3CNa
(reflux)b
H2Oc (rt)
Time Yield Time Yield
(min) (%) (min) (%)
Mp
(ꢀC)
Products
Ar0
Ar
5h
120
89
40
98
196–198
5i
5j
360
60
90
85
65
25
98
96
173–175
242–243
5k
5l
60
90
85
25
50
98
96
199–201
204–205
120
aIn the presence of formic acid as catalyst.
bReaction times of 24 to 48 h were needed for reactions to be completed at
room temperature.
cReaction times of 5 to 15 min were needed for comparable yields under reflux
conditions.
the case of 5d, e, and f, similar phenyl protons are mixed with the aro-
matic protons. Upon addition of D2O into the NMR tube in the samples
of 5a–c, the hydroxyl signals disappear. In addition, reduction of one
proton in the region of aromatic on the basis of integration indicates
the disappearance of the NH group that resonates in this zone. Methine

4130
M. Ghandi, A. Olyaei, and S. Raoufmoghaddam
Scheme 2. Synthesis of aminonaphthol derivatives 5.
proton is expected to be seen as a doublet. Because the decoupling effect
of NH proton omission in D2O is not seen in nonaromatic regions, the
methine proton should have appeared in aromatic region. The OH and
NH absorptions are observed at 3250–3500 cmꢁ1 in IR spectra. Com-
pounds 5a–l exhibit the expected parent ions with medium intensity in
mass spectra.
As is known, chiral aminonaphtols complexed to dialkylzinc reagents
have extensively been used as chiral auxiliaries for chiral induction.
Therefore, separation and spectroscopic identification of pure enantio-
mers of new aminonaphtols obtained in this work seems worthy although
tedious work. High-performance liquid chromatography (HPLC) on
chiral stationary phase (CSPs) as an effective tool for the resolution of
chiral enantiomers has been used for enantioseparation of Betti base deri-
1
vatives.[18] In addition, H NMR and 13C NMR both provide the most
simple and common tools for determination of enantiomer purities by
using chiral shift reagents. The chiral NMR shift reagents function via
the Eu3þ, Pr3þ, Yt3þ, or La3þ Lewis acidic sites binding to the hetero
atom Lewis basic sites present in aminonaphtols.[19–22] This leads to the
formation of diasteromeric shift reagent–substrate complexes in which
resonances of the substrates may exhibit different shifts.
As a model reaction, identification of enantiomers was carried out on
5h by 1H NMR using europium tris[3-(heptafluoropropylhydroxymethy-
lene)-(ꢁ)-camphorate] chiral shift reagent. Spectra of the 1H NMR
obtained from eight samples containing 0.00, 0.05, 0.10, 0.20, 0.40,
0.60, 0.80, and 1.00 equivalent of chiral reagent relative to racemic com-
pound 5h in CDCl3 are presented in Fig 1. As is seen, methyl protons,
which appear at 2.36 ppm in the absence of shift reagent, start shifting
to lower fields in the presence of chiral shift reagent. Moreover, the

New Aminonaphthol Synthesis in Water
4131
Figure 1. CH3-Ph part of 1H NMR spectrum of rac-5h in CDCl3(0.042 M) at
298 K in the presence of 0.00 to 1.00 equiv of Eu(hfc)3 chiral shift reagent.
integration of methyl areas shows the concentration equalities of the
racemic mixture. Therefore, one can use methyl signal with the acceptable
1
resolution with 0.10 equiv of shift reagent present in H NMR tube to
evaluate enantiomeric purity following the diastereomeric separation of
aminonaphthol-chiral carboxylic acid salt.
In conclusion, we have successfully developed a quick, convenient,
and efficient method for the synthesis of new aminonaphthol (Betti base)
derivatives. Compared to other previously reported procedures in litera-
ture, the present method with the advantages such as omitting organic
solvent, generality and simplicity of procedure, lower reaction time,
and obtaining excellent yields merits recommendation to the users. More-
1
over, enantiomeric resolution of compound 5h by H NMR using euro-
pium shift reagent with the minimum equivalent concentration of shift
reagent seems promising. With reference to the importance of chiral ami-
nonaphthol almost in pure form complexed to dialkylzinc as chiral aux-
iliaries for chiral induction, utilization of different chiral carboxylic acids
for the synthesis of distereoisomeric salts is currently under investigation
in our laboratory.
EXPERIMENTAL
All commercially available chemicals and reagents were used without
further purification. Melting points were determined with an Electrother-
mal model 9100 apparatus and are uncorrected. IR spectra were recorded
1
on a Shimadzu 4300 spectrophotometer. The H and 13C NMR spectra
were recorded in DMSO-d6 and CDCl3 on Bruker DRX-500 Avance
spectrometers. Chemical shifts (d) are reported in parts per million and

4132
M. Ghandi, A. Olyaei, and S. Raoufmoghaddam
are referenced to the NMR solvent. 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).
General Procedure for the Synthesis of 1-(Y-Substituted
Phenyl(heteroarylamino)methyl)naphthalene-2-ols (5a–l)
To a stirring suspension of 2-naphthol (1.44 g, 10 mmol) in water
(15 mL), the appropriate aromatic aldehyde (10 mmol) and heteroaryl
amine (10 mmol) were added. The reaction mixture was stirred at ambi-
ent temperature for the appropriate times (see Table 1). Water was then
decanted, and the white precipitated product was separated upon addi-
tion of ethanol (10 mL) to the mixture with stirring, while cooling at
0–5 ꢀC. The precipitate was filtered, washed with cold EtOH, dried,
and purified by recrystallization from EtOH.
1-(Phenyl(2-pyrimidinylamino)methyl)naphthalene-2-ol (5a)
Colorless crystals; IR (KBr): 3400, 3080, 1625, 1566, 1269, 1055,
1
813 cmꢁ1; H NMR (500 MHz, DMSO-d6): d 6.63 (t, J ¼ 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 ¼ 4.8 Hz, 2H, pyrimidine-H4 and
1
H6), 10.24 (s, 1H, OH) ppm; H NMR (500 MHz, DMSO-d6 þ D2O):
d 6.62 (t, J ¼ 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 ¼ 4.8 Hz, 2H,
pyrimidine-H4 and H6) ppm; 13C NMR (125 MHz, DMSO-d6): d 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 ppm; MS
(EI): m=z 327 (Mþ), 231, 202, 166, 115, 97. Anal. calcd. for C21 H17N3O:
C, 77.06; H, 5.19; N, 12.84. Found: C, 77.01; H, 5.17; N, 12.80.
1-(Phenyl(2-pyrazinylamino)methyl)naphthalene-2-ol (5b)
Colorless crystals; IR (KBr): 3390, 3080, 1629, 1593, 1433, 1295, 1205,
1
810 cmꢁ1; H NMR (500 MHz, DMSO-d6): d 7.13–7.38, 7.76–7.81, 7.98
(m, 12H, Ph-H, NPh-H, and methine-H), 7.67 (br, 1H, NH), 7.68 (d,
1H, J ¼ 2.8 Hz, pyrazine-H5), 7.92 (dd, J ¼ 1.3, 2.8 Hz, 1H, pyrazine-
H6), 8.27 (d, J ¼ 1.3 Hz, 1H, pyrazine-H3), 10.05 (s, 1H, OH) ppm;
1H NMR (500 MHz, DMSO-d6 þ D2O): d 7.12–7.34, 7.73–7.78, 7.94
(m, 12H, Ph-H, NPh-H, and methine-H), 7.65 (d, 1H, J ¼ 2.8 Hz,

New Aminonaphthol Synthesis in Water
4133
pyrazine-H5), 7.90 (dd, J ¼ 1.3, 2.8 Hz, 1H, pyrazine-H6), 8.19 (d,
J ¼ 1.3 Hz, 1H, pyrazine-H3) ppm; 13C NMR (125 MHz, DMSO-d6): d
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 ppm; MS (EI): m=z 327 (Mþ), 231, 202,182, 144, 115, 95. Anal.
calcd. for C21 H17 N3 O: C, 77.06; H, 5.19; N, 12.84. Found: C, 76.98;
H, 5.18; N, 12.78.
1-(Phenyl(2-pyridinylamino)methyl)naphthalene-2-ol (5c)
Colorless crystals; IR (KBr): 3365, 3020, 1606, 1568, 1512, 1274, 1160,
1
810 cmꢁ1; H NMR (500 MHz, DMSO-d6): d 6.51 (m, 1H, pyridine-H),
6.82 (d, J ¼ 8.4 Hz, 1H, pyridine-H), 7.12–7.41 (m, 11H, Ph-H, NPh-H,
pyridine-H, methine-H and NH), 7.74–8.01 (m, 4H, NPh-H), 10.23 (s,
1
1H, OH) ppm; H NMR (500 MHz, DMSO-d6 þ D2O): d 6.52 (m, 1H,
pyridine-H), 6.73 (d, J ¼ 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)
ppm; 13C NMR (125 MHz, DMSO-d6): d 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 ppm; MS (EI):
m=z 326 (Mþ), 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-pyrimidinylamino)methyl)naphthalene-2-ol (5d)
Colorless crystals; IR (KBr): 3425, 3022, 1631, 1595, 1271, 1174, 808 cmꢁ1
;
1H NMR (500 MHz, DMSO-d6): d 6.65 (t, J ¼ 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 ¼ 4.8 Hz, 2H, pyrimidine-H4 and H6), 10.27 (s, 1H,
OH) ppm; 13C NMR (125 MHz, DMSO-d6): d 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 ppm; MS (EI): m=z 361
(Mþ), 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-Chlorophenyl(2-pyrazinylamino)methyl)naphthalene-2-ol (5e)
Colorless crystals; IR (KBr): 3251, 3047, 1627, 1591, 1431, 1292, 1203,
817 cmꢁ1 1H NMR (500 MHz, DMSO-d6): d 7.22–7.39, 7.72–7.93
;
(m, 12H, Ph-H, NPh-H, methine-H, and NH), 7.71 (d, 1H, J ¼ 2.8 Hz,
pyrazine-H5), 7.94 (dd, J ¼ 1.3, 2.8 Hz, 1H, pyrazine-H6), 8.28 (d,

4134
M. Ghandi, A. Olyaei, and S. Raoufmoghaddam
J ¼ 1.3 Hz, 1H, pyrazine-H3), 10.10 (s, 1H, OH) ppm; 13C NMR
(125 MHz, DMSO-d6): d 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 ppm; MS (EI): m=z 361 (Mþ), 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.
1-(p-Chlorophenyl(2-pyridinylamino)methyl)naphthalene-2-ol (5f)
Colorless crystals; IR (KBr): 3408, 3060, 1614, 1568, 1515, 1274, 1155,
1
819 cmꢁ1; H NMR (500 MHz, DMSO-d6): d 6.52 (m, 1H, pyridine-H),
6.82 (d, J ¼ 8.4 Hz, 1H, pyridine-H), 7.19–7.41 (m, 10H, Ph-H, NPh-H,
pyridine-H, methine-H, and NH), 7.75–7.98 (m, 4H, NPh-H), 10.21 (s,
1H, OH) ppm;13C NMR (125 MHz, DMSO-d6): d 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 ppm; MS (EI): m=z 360 (Mþ), 265, 231, 202, 144, 115, 94, 79.
Anal. calcd. for C22 H17ClN2O: C, 73.23; H, 4.71; N, 7.76. Found: C,
73.27; H, 4.65; N, 7.78.
1-(p-Methylphenyl(2-pyrimidinylamino)methyl)naphthalene-2-ol (5g)
Colorless crystals; IR (KBr): 3415, 3053, 1629, 1595, 1566, 1460, 1358,
1170, 1058, 850 cmꢁ1
1
;
H NMR (500 MHz, DMSO-d6): d 3.05 (s, 3H,
CH3), 6.62 (t, J ¼ 4.7 Hz, 1H, pyrimidine-H5), 7.04 (d, 2H, J ¼ 7.9 Hz,
Ph-H), 7.16 (d, 2H, J ¼ 7.9 Hz, Ph-H), 7.21–8.09 (m, 8H, NPh-H, NH
and methine-H), 8.32 (d, J ¼ 4.7 Hz, 2H, pyrimidine-H4 and H6), 10.22
(s, 1H, OH) ppm; 13C NMR (125 MHz, DMSO-d6): d 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 ppm; MS
(EI): m=z 341 (Mþ), 245, 231, 202, 144, 115. Anal. calcd. for C22
H19N3O: C, 77.42; H, 5.57; N, 12.31. Found: C, 77.39; H, 5.60; N, 12.30.
1-(p-Methylphenyl(2-pyrazinylamino)methyl)naphthalene-2-ol (5h)
Colorless crystals; IR (KBr): 3300, 3085, 1627, 1591, 1431, 1305, 1203,
1
806 cmꢁ1; H NMR (500 MHz, DMSO-d6): d 2.26 (s, 3H, CH3), 7.04
(d, 2H, J ¼ 8.0 Hz, Ph-H) 7.13 (d, 2H, J ¼ 8.0 Hz, Ph-H), 7.22–7.66,
7.75–7.80, 7.98 (m, 8H, NPh-H, methine-H and NH), 7.68 (d, 1H,
J ¼ 2.8 Hz, pyrazine-H5), 7.92 (dd, J ¼ 1.3, 2.8 Hz, 1H, pyrazine-H6),

New Aminonaphthol Synthesis in Water
4135
8.26 (d, J ¼ 1.3 Hz, 1H, pyrazine-H3), 10.02 (s, 1H, OH) ppm; 13C NMR
(125 MHz, DMSO-d6): d 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 ppm; MS (EI): m=z 341 (Mþ),
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-Methylphenyl(2-pyridinylamino)methyl)naphthalene-2-ol (5i)
Colorless crystals; IR (KBr): 3490, 3018, 1614, 1565, 1515, 1271, 1155,
1
811 cmꢁ1; H NMR (500 MHz, DMSO-d6): d 2.22 (s, 3H, CH3), 6.50
(m, 1H, pyridine-H), 6.80 (d, J ¼ 8.4 Hz, 1H, pyridine-H), 7.03 (d, 2H,
J ¼ 8.0 Hz, Ph-H) 7.14 (d, 2H, J ¼ 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) ppm; 13C NMR (125 MHz, DMSO-d6): d 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 ppm; MS (EI): m=z 340 (Mþ), 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-pyrimidinylamino)methyl)naphthalene-2-ol (5j)
Colorless crystals; IR (KBr): 3425, 3053, 1629, 1593, 1568, 1269, 1176,
1
806 cmꢁ1; H NMR (500 MHz, DMSO-d6): d 6.65 (t, J ¼ 4.8 Hz, 1H,
pyrimidine-H5), 7.22 (d, 2H, J ¼ 8.5 Hz, Ph-H) 7.44 (d, 2H, J ¼ 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 ¼ 4.8 Hz, 2H, pyrimidine-H4 and
H6), 10.27 (s, 1H, OH) ppm; 13C NMR (125 MHz, DMSO-d6): d 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 ppm; MS
(EI): m=z 405 (Mþ), 407 (Mþ), 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-(p-Bromophenyl(2-pyrazinylamino)methyl)naphthalene-2-ol (5k)
Colorless crystals; IR (KBr): 3240, 3120, 1625, 1591, 1429, 1309, 1203,
1068, 806 cmꢁ1 1H NMR (500 MHz, DMSO-d6): d 7.16 (d, 2H,
;
J ¼ 8.5 Hz, Ph-H), 7.43 (d, 2H, J ¼ 8.5 Hz, Ph-H), 7.20–7.40, 7.69,
7.77–7.92 (m, 8H, NPh-H, methine-H and NH), 7.71 (d, 1H, J ¼ 2.8 Hz,

4136
M. Ghandi, A. Olyaei, and S. Raoufmoghaddam
pyrazine-H5), 7.94 (dd, J ¼ 1.3, 2.8 Hz, 1H, pyrazine-H6), 8.28 (d,
J ¼ 1.3 Hz, 1H, pyrazine-H3), 10.09 (s, 1H, OH) ppm; 13C NMR
(125 MHz, DMSO-d6): d 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 ppm; MS (EI): m=z 405 (Mþ), 407 (Mþ),
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-(p-Bromophenyl(2-pyridinylamino)methyl)naphthalene-2-ol (5 l)
Colorless crystals; IR (KBr): 3400, 3057, 1614, 1568, 1515, 1272, 1155,
1
817 cmꢁ1; H NMR (500 MHz, DMSO-d6): d 6.52 (m, 1H, pyridine-H),
6.82 (d, J ¼ 8.4 Hz, 1H, pyridine-H), 7.17 (d, 2H, J ¼ 8.5 Hz, Ph-H),
7.42 (d, 2H, J ¼ 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)
ppm; 13C NMR (125 MHz, DMSO-d6): d 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 ppm; MS (EI):
m=z 404 (Mþ), 406 (Mþ), 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
Procedure for H NMR Shift Experiment for 5h
The spectrum of 5h in CDCl3 (0.042 M) was initially recorded. Europium
tris [3-heptafluoropropylhydroxymethylene)-(ꢁ)-camphorate] (0.00 to
0.10 equiv) was then added to the sample, and the spectrum of the result-
ing complexes was subsequently recorded.
ACKNOWLEDGMENT
The authors thank the Research Council of the University of Tehran and
Payame Noor University of Qazvin for financial support.
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