Multicomponent synthesis of 1-[aryl(p-tolylsulfanyl)methyl]naphthalen-2-ols using p-toluenesulfonic acid as a catalyst

Article abstract of DOI:10.3184/174751913X13599036993960

Three-component reaction between 2-naphthol, an aromatic aldehyde and thiols catalysed by p-toluene sulfonic acid (p-TSA) provided a simple and efficient one-pot route for the synthesis of 1-[aryl(arylsulfanyl)methyl] naphthalen-2-ol derivatives in excell

Full text of DOI:10.3184/174751913X13599036993960

1
52 RESEARCH PAPER
MARCH, 152–154
JOURNAL OF CHEMICAL RESEARCH 2013
Multicomponent synthesis of 1-[aryl(p-tolylsulfanyl)methyl]naphthalen-2-
ols using p-toluenesulfonic acid as a catalyst
Alireza Hassanabadi*
Department of Chemistry, Islamic Azad University, Zahedan Branch, PO Box 98135-978, Zahedan, Iran
Three-component reaction between 2-naphthol, an aromatic aldehyde and thiols catalysed by p-toluene sulfonic acid
(
p-TSA) provided a simple and efficient one-pot route for the synthesis of 1-[aryl(arylsulfanyl)methyl]naphthalen-2-ol
derivatives in excellent yields.
Keywords: 2-naphthol, aromatic aldehydes, thiols, three-component reaction, p-toluene sulfonic acid
Multi-component reactions are useful and efficient methods
in organic synthesis. The major advantages of these reactions
are a single purification step, higher yields than stepwise
assembly, the use of simple and diverse precursors to construct
complex molecules and the use of only a single promoter or
catalyst. Thus, the development of new multi-component reac-
tions is a popular area of research in organic chemistry and
same conditions, but no product was isolated from the reaction
mixtures.
Products 4a–h were all new compounds and their structures
were deduced from their elemental analyses and spectral data.
The mass spectrum of compound 4a showing a molecular ion
peak at 342 confirmed that compound 4a is a triadduct of
1
2-naphthol, benzaldehyde and thiol. The H NMR spectrum of
1
–3
from a green chemistry point of view.
Ortho-quinone methides have been employed in many
compound 4a displayed a sharp single signal at δ = 5.46 ppm
for methine proton, along with charactristic signals at δ =
7.15–7.83 ppm for the aromatic protons.A singlet was observed
4
–6
tandem processes, but there are only a few reports on their
7
–9
at δ = 10.21 ppm, disappeared by addition of D O, for OH
2
13
reactions with nucleophiles. There are some recent reports
from the three-component reaction between 2-naphthol,
aromatic aldehydes and nucleophiles such as amides or
proton. C NMR spectrum of compound 4a showed 19 distinct
signals in agreement with the proposed structure.
1
0–13
A possible mechanism for the formation of 1-[aryl(arylsulfa
nyl)methyl]naphthalen-2-ols 4a–h has been proposed in
ureas using different catalysts.
These reactions have been
reported to proceed by the nucleophilic addition of amide
or urea derivative on the intermediate ortho-quinone methides.
In continuation of our previous work on three-component
reactions between an aldehyde, an enolic system, such as
substituted 2-naphthols, 4-hydroxycoumarin or 2-hydroxy-3-
1
3,18–20
Scheme 3. As reported in the literature,
the reaction of
2
-naphthol with aromatic aldehydes in the presence of an acid
catalyst is known to give orthoquinone methides. The same
orthoquinone methides, generated in situ, have been reacted
with thiol via conjugate addition to form 1-[aryl(arylsulfanyl)
methyl]naphthalen-2-ol derivatives.
1
4–17
naphthoic acid and a nucleophile,
here we describe the
three-component reaction between 2-naphthol, aromatic
aldehydes and thiols in the presence of catalytic amounts of
p-toluene sulfonic acid (p-TSA).
In conclusion, we report here a simple and efficient one-
pot synthesis of 1-[aryl(arylsulfanyl)methyl]naphthalen-2-ol
derivatives by three-component reaction between 2-naphthol,
an aromatic aldehyde and thiols catalysed by p-toluenesulfonic
acid. The advantages of this method are available starting
materials, short reaction times, easy and clean work-up, and
excellent yields.
Results and discussion
Thus, reaction between 2-naphthol, benzaldehyde and thiol in
the presence of p-TSA in refluxing 1,2-dichloroethane after
2
h afforded 1-[phenyl(phenylsulfanyl)methyl]naphthalen-2-ol
(
4a) in 90% yield (Scheme 1).
To determine the optimum quantity of p-TSA the reaction
Experimental
All melting points are uncorrected. Elemental analyses were
performed at the analytical laboratory of Science and Research Unit
of the Islamic Azad University. Mass spectra were recorded on a
FINNIGAN-MAT 8430 mass spectrometer operating at an ionisation
potential of 70 eV. IR spectra were recorded on a Shimadzu IR-470
of 2-naphthol (1 equiv.), benzaldehyde (1 equiv.), and thiol
1 equiv.) was carried out under the above conditions using
different quantities of catalyst. The use of 5 mol% of catalyst
resulted in the highest yield in 2 h. We prepared a range of
(
1
13
spectrometer. H and C NMR spectra were recorded on Bruker DRX-
00 Avance spectrometer at solution in DMSO using TMS as internal
standard. The chemicals used in this work were purchased from Fluka
Buchs, Switzerland) and were used without further purification.
1
-[aryl(arylsulfanyl)methyl]naphthalen-2-ols 4 under the
5
optimised reaction conditions: 2-naphthol 1 (1 mmol), aryl
aldehydes 2 (1 mmol), and thiols 3 (1 mmol) in the presence
of p-TSA (0.05 mmol). In all cases, aromatic aldehydes with
either electron-donating or electron-withdrawing groups gave
the desired products in 85–92% yields. (Scheme 2)
(
General procedure
A magnetically stirred solution of thiols (1mmol), 2-naphthol (1 mmol),
aldehyde (1 mmol) and p-TSA (0.05 mmol) in 15 mL 1,2-dichloroeth-
ane was refluxed for 2 h. The mixture was poured into water (50 mL).
We also examined the reaction between 2-naphthol, aro-
matic aldehydes and thiol in the absence of p-TSA in the
Scheme 1 Condensation of benzaldehyde, 2-naphthol and thiol catalysed by p-TSA.
Correspondent. E-mail: ar_hasanabadi@yahoo.com
*

JOURNAL OF CHEMICAL RESEARCH 2013 153
Scheme 2 Three-component reaction between aromatic aldehydes, 2-naphthol and thiols catalysed by p-TSA.
Scheme 3 Suggested mechanism for formation of compounds 4a–h.
3
The solid product was filtered and recrystallised from ethyl acetate/
haxane mixture to give the pure product.
s, CH), 7.24–7.32 (3H, m, 3CH naphthol moiety), 7.34 (1H, d, J
=
HH
3
8 Hz, CH naphthol moiety), 7.74 (1H, d, J = 8 Hz, CH naphthol
moiety), 7.76 (1H, d, J = 8 Hz, CH naphthol moiety), 7.22–7.45
(8H, m, 8CH phenyl moieties), 10.27 (1H, broad s, OH) ppm.
NMR (125.8 MHz, d -DMSO): δ 47.36 (CH), 119.54, 119.82, 123.32,
123.88, 127.42, 129.65, 130.22, 130.76, 132.95 and 153.38 (naphthol
moiety), 126.27, 127.19, 127.76, 128.44, 128.90 130.37, 142.13 and
143.16 (phenyl moieties) ppm.
1-[2-Chlorophenyl(phenylsulfanyl)methyl]naphthalen-2-ol (4d):
White solid, m.p. 150–152 °C, IR (KBr) (νmax cm ): 3462, 1590,
HH
3
1
-[Phenyl(phenylsulfanyl)methyl]naphthalen-2-ol (4a): White solid,
HH
−
1
13
m.p. 143–145 °C, IR (KBr) (νmax cm ): 3465, 1593, 1511. Anal. Calcd
for C H OS: C, 80.67; H, 5.30. Found: C, 80.60; H, 5.34%. MS (m/z,
): 342 (10). H NMR (500 MHz, d -DMSO): δ 5.46 (1H, s, CH),
C
23
18
6
1
%
7
6
3
.28–7.32 (3H, m, 3CH naphthol moiety), 7.38 (1H, d, J = 8 Hz,
HH
3
CH naphthol moiety), 7.78 (1H, d, J = 8 Hz, CH naphthol moiety),
HH
3
7
.83 (1H, d, J = 8 Hz, CH naphthol moiety), 7.15–7.39 (10H,
m, 10CH phenyl moieties), 10.21 (1H, broad s, OH) ppm. C NMR
125.8 MHz, d -DMSO): δ 46.82 (CH), 118.85, 119.50, 123.48,
HH
13
−1
(
1504. Anal. Calcd for C H ClOS: C, 73.30; H, 4.55. Found: C, 73.35;
H, 4.62%. MS (m/z, %): 376 (7). H NMR (500 MHz, d -DMSO):
δ 5.58 (1H, s, CH), 7.23–7.35 (3H, m, 3CH naphthol moiety), 7.61
6
23 17
1
1
24.11, 127.15, 129.38, 129.31, 130.19, 133.02 and 153.78 (naphthol
moiety), 126.81, 127.24, 127.72, 128.30, 128.86 130.35, 141.76 and
43.27 (phenyl moieties) ppm.
-[4-Chlorophenyl(p-tolylsulfanyl)methyl]naphthalen-2-ol (4b):
6
3
3
1
(1H, d, J = 8 Hz, CH naphthol moiety), 7.75 (1H, d, J = 8 Hz,
HH HH
3
1
CH naphthol moiety), 7.80 (1H, d, J = 8 Hz, CH naphthol moiety),
HH
−
1
White solid, m.p. 156–158 °C, IR (KBr) (νmax cm ): 3460, 1590,
505. Anal. Calcd for C H ClOS: C, 73.74; H, 4.90. Found: C, 73.79;
7.20–7.42 (9H, m, 9CH phenyl moieties), 10.08 (1H, broad s, OH)
ppm. C NMR (125.8 MHz, d -DMSO): δ 47.38 (CH), 118.04,
119.71, 123.53, 124.62, 127.15, 129.18, 130.24, 130.60, 133.52 and
154.37 (naphthol moiety), 125.93, 127.18, 127.90, 128.35, 128.97
130.44, 131.04 133.06, 140.32, and 143.19 (phenyl moieties) ppm.
1-[3-Nitrophenyl(p-tolylsulfanyl)methyl]naphthalen-2-ol (4e): White
13
1
24
19
6
1
H, 4.76%. MS (m/z, %): 390 (4). H NMR (500 MHz, d -DMSO):
6
δ 2.28 (3H, s, CH ), 5.63 (1H, s, CH), 7.21–7.33 (3H, m, 3CH
3
3
naphthol moiety), 7.35 (1H, d, J = 8 Hz, CH naphthol moiety), 7.74
HH
3
3
(
1H, d, J = 8 Hz, CH naphthol moiety), 7.79 (1H, d, J = 8 Hz,
H
H
H
H
−
1
CH naphthol moiety), 7.18–7.48 (8H, m, 8CH phenyl moieties), 10.24
solid, m.p. 161–163 °C, IR (KBr) (νmax cm ): 3466, 1594, 1500. Anal.
Calcd for C H NO S: C, 71.80; H, 4.77; N, 3.49%. Found: C, 71.85;
1
3
(
(
1H, broad s, OH) ppm. C NMR (125.8 MHz, d -DMSO): δ 21.53
6
24 19
3
1
CH ), 47.38 (CH), 118.75, 119.47, 123.40, 124.22, 127.28, 129.37,
H, 4.70; N, 3.61. MS (m/z, %): 401 (8). H NMR (500 MHz,
3
3
1
1
29.42, 130.35, 133.06 and 153.75 (naphthol moiety), 126.15, 127.16,
27.82, 128.33, 128.92 130.44, 142.07 and 143.28 (phenyl moieties)
d -DMSO): δ 2.32 (3H, s, CH ), 5.66 (1H, s, CH), 7.31 (1H, t, J
=
HH
6
3
3
8 Hz, CH naphthol moiety), 7.48 (1H, d, J = 8 Hz, CH naphthol
moiety), 7.52 (1H, t, J = 8 Hz, CH naphthol moiety), 7.64 (1H,
HH
3
ppm.
-[4-Bromophenyl(phenylsulfanyl)methyl]naphthalen-2-ol (4c): White
HH
3
3
1
d, J = 8 Hz, CH naphthol moiety), 7.83 (1H, d, J = 8 Hz, CH
HH HH
3
−
1
solid, m.p. 129–131 °C, IR (KBr) (νmax cm ): 3457, 1582, 1501. Anal.
naphthol moiety), 7.86 (1H, d, J = 8 Hz, CH naphthol moiety),
HH
Calcd for C H BrOS: C, 65.56; H, 4.07. Found: C, 65.42; H, 4.15%.
7.19–8.12 (8H, m, 8CH phenyl moieties), 10.35 (1H, broad s, OH)
23
17
1
13
MS (m/z, %): 421 (5). H NMR (500 MHz, d -DMSO): δ 5.65 (1H,
ppm. C NMR (125.8 MHz, d -DMSO): δ 21.62 (CH ), 47.73 (CH),
6
6
3

1
54 JOURNAL OF CHEMICAL RESEARCH 2013
1
1
1
18.53, 119.24, 123.50, 124.08, 127.65, 129.28, 129.72, 130.54,
33.60 and 154.27 (naphthol moiety), 121.24, 122.17, 127.18, 128.98
30.42, 130.82, 132.90, 143.21 146.12 and 148.51, (phenyl moieties)
d -DMSO): δ 21.58 (CH ), 47.67 (CH), 55.64 (OCH ), 119.30, 119.71,
6 3 3
123.16, 124.26, 126.85, 129.24, 130.12, 130.80, 133.16 and 153.85
(naphthol moiety), 111.60, 120.42, 127.22, 128.27, 128.61, 128.96,
129.16, 130.61, 143.17 and 157.32 (phenyl moieties) ppm.
ppm.
-[4-Nitrophenyl(p-tolylsulfanyl)methyl]naphthalen-2-ol (4f): White
solid, m.p. 155–157 °C, IR (KBr) (νmax cm ): 3465, 1592, 1503. Anal.
Calcd for C H NO S: C, 71.80; H, 4.77; N, 3.49%. Found: C, 71.85;
H, 4.70; N, 3.61. MS (m/z, %): 401 (4). H NMR (500 MHz,
d -DMSO): δ 2.30 (3H, s, CH ), 5.64 (1H, s, CH), 7.40–7.45 (3H, m,
1
−
1
Received 13 December 2012; accepted 7 January 2013
Paper 1201678 doi: 10.3184/174751913X13599036993960
Published online: 12 March 2013
24
19
3
1
6
3
3
3
7
8
1
CH naphthol moiety), 7.34 (1H, d, J = 8 Hz, CH naphthol moiety),
HH
3 3
.80 (1H, d, J = 8 Hz, CH naphthol moiety), 7.83 (1H, d, JHH
=
References
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1
2
3
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13
0.36 (1H, broad s, OH) ppm. C NMR (125.8 MHz, d -DMSO):
6
δ 21.60 (CH ), 47.69 (CH), 118.52, 119.31, 123.54, 124.05, 127.63,
3
1
1
29.22, 129.76, 130.50, 133.62 and 154.21 (naphthol moiety), 114.92,
27.12, 127.56, 128.84, 130.36, 143.16 146.47 and 150.85 (phenyl
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5
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-[4-Methoxyphenyl(phenylsulfanyl)methyl]naphthalen-2-ol (4g):
1
996, 74, 465.
1
−
1
6
7
8
9
0
G. Desimon and G. Tecconi, Chem. Rev., 1975, 75, 65.
White solid, m.p. 166–168 °C, IR (KBr) (νmax cm ): 3474, 1599,
508. Anal. Calcd for C H O S: C, 77.39; H, 5.41. Found: C, 77.50;
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1
24
20
2
1
H, 5.45%. MS (m/z, %): 372 (9). H NMR (500 MHz, d -DMSO):
δ 3.62 (3H, s, OCH ), 5.32 (1H, s, CH), 7.21–7.35 (3H, m, 3CH
naphthol moiety), 7.30 (1H, d, J = 8 Hz, CH naphthol moiety), 7.75
6
3
1
M.M. Khodaei, A.R. Khosropour and H. Moghanian, Synlett, 2006, 916.
3
HH
11 B.P. Sachin, R.S. Pankajkumar, P.S. Mandar and D.S. Shriniwas, Ultrason.
3
3
(
1H, d, J = 8 Hz, CH naphthol moiety), 7.81 (1H, d, J = 8 Hz,
H
H
H
H
Sonochem., 2007, 14, 515.
12 B.P. Sachin, R.S. Pankajkumar, P.S. Mandar and D.S. Shriniwas, Synth.
Commun., 2007, 37, 1659.
CH naphthol moiety), 7.23–7.58 (9H, m, 9CH phenyl moieties), 10.38
13
(
(
1H, broad s, OH) ppm. C NMR (125.8 MHz, d -DMSO): δ 47.62
CH), 55.82 (OCH ), 119.54, 119.82, 123.32, 123.88, 127.42, 129.62,
6
13 D. Biswanath, K. Laxminarayana, B. Ravikanth and R.B. Rama, J. Mol.
3
1
1
29.92, 130.78, 133.02 and 154.25 (naphthol moiety), 114.52, 127.19,
28.58, 128.93, 129.07, 133.42, 143.12 and 146.05 (phenyl moieties)
Cat. A: Chem., 2007, 261, 180.
1
1
1
1
4
5
6
7
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ppm.
-[2-Methoxyphenyl(p-tolylsulfanyl)methyl]naphthalen-2-ol (4h):
1
−
1
White solid, m.p. 163–165 °C, IR (KBr) (νmax cm ): 3470, 1596,
507. Anal. Calcd for C H O S: C, 77.69; H, 5.74. Found: C, 77.60;
1
25
22
2
1
H, 5.63%. MS (m/z, %): 386 (7). H NMR (500 MHz, d -DMSO):
δ 2.27 (3H, s, CH ), 3.36 (3H, s, OCH ), 5.37 (1H, s, CH), 6.95–7.30
6
M. Anary-Abbasinejad, M. Akhavan, A. Hassanabadi, J. Chem. Res., 2009,
3
3
33, 143.
3
(
3H, m, 3CH naphthol moiety), 7.32 (1H, d, J = 8 Hz, CH naphthol
HH
3
18 A.R. Khosropour, M.M. Khodaei, H. Moghanian, Synlett, 2005, 955.
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moiety), 7.50 (1H, d, J = 8 Hz, CH naphthol moiety), 7.64 (1H, d,
HH
3
JHH = 8 Hz, CH naphthol moiety), 7.21–7.45 (8H, m, 8CH phenyl
13
moieties), 9.96 (1H, broad s, OH) ppm. C NMR (125.8 MHz,

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