Discovery of an in situ carbocationic system using trityl chloride as a homogeneous organocatalyst for the solvent-free condensation of β-naphthol with aldehydes and amides/thioamides/alkyl carbamates in neutral media

Article abstract of DOI:10.1016/j.tet.2012.10.042

Trityl chloride (TrCl), efficiently catalyzes the one-pot multi-component condensation of β-naphthol with aromatic aldehydes and amides/thioamides/ carbamates such as acetamide, benzamide, nicotinamide, thioacetamide, and methylcarbamate under solvent-free and neutral conditions to afford 1-amido-alkyl-2-naphthols, 1-thioamido-alkyl-2-naphthols, and 1-carbamato-alkyl-2-naphthols in high yields and very short reaction times. Mechanistically, it is interesting that trityl chloride through the in situ generation of trityl carbocation with inherent instability is efficient as a reusable homogeneous organocatalyst in neutral media.

Full text of DOI:10.1016/j.tet.2012.10.042

Tetrahedron 69 (2013) 212e218
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Tetrahedron
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Discovery of an in situ carbocationic system using trityl chloride as
a homogeneous organocatalyst for the solvent-free condensation
of b-naphthol with aldehydes and amides/thioamides/alkyl
carbamates in neutral media
,
a
,
a,
*
b
Ardeshir Khazaei a , Mohammad Ali Zolfigol , Ahmad Reza Moosavi-Zare , Fereshteh Abi ,
Abdolkarim Zare b, Hamideh Kaveh b, Vahid Khakyzadeh a, Masoud Kazem-Rostami a, Abolfath Parhami b,
Hossein Torabi-Monfared b
*
*
a Faculty of Chemistry, Bu-Ali Sina University, Hamedan 6517838683, Iran
b Chemistry Department, Payame Noor University, 19395-4697 Tehran, Iran
a r t i c l e i n f o
a b s t r a c t
Article history:
Trityl chloride (TrCl), efficiently catalyzes the one-pot multi-component condensation of b-naphthol with
Received 23 May 2012
Received in revised form 25 September
2012
Accepted 15 October 2012
Available online 23 October 2012
aromatic aldehydes and amides/thioamides/carbamates such as acetamide, benzamide, nicotinamide,
thioacetamide, and methylcarbamate under solvent-free and neutral conditions to afford 1-amido-alkyl-
2-naphthols, 1-thioamido-alkyl-2-naphthols, and 1-carbamato-alkyl-2-naphthols in high yields and very
short reaction times. Mechanistically, it is interesting that trityl chloride through the in situ generation of
trityl carbocation with inherent instability is efficient as a reusable homogeneous organocatalyst in
neutral media.
Keywords:
Trityl chloride
Ó 2012 Elsevier Ltd. All rights reserved.
Multi-component condensation
1-Amido-alkyl-2-naphthol
1-Thioamido-alkyl-2-naphthol
1-Carbamato-alkyl-2-naphthol
Solvent-free
1. Introduction
1-Amidoalkyl-2-naphthol, 1-thioamidoalkyl-2-naphthol, and
1-carbamatoalkyl-2-naphthol derivatives are of importance as they
can be easily converted into biologically important compounds,
1-aminoalkyl-2-naphthols, which exhibit hypotensive and bradycar-
dic activities (Fig.1, A).1e3 Moreover,1-amidoalkyl-2-naphthols can be
converted in to 1,3-oxazine derivatives (Fig. 2, B).4 1,3-Oxazines have
potentially different biological activities including antibiotic,5e7 anti-
tumor,8e10 analgesic,11,12 anticonvulsant,13 antipsychotic,14 antimalar-
ial,15 antianginal,16 antihypertensive,17 and antirheumatic properties.18
Some new methods have been developed to improve the reaction
yield in the synthesis of 1-amidoalkyl-2-naphthols using catalysts such as
sulfonic acid functionalized imidazolium salt,19 PSePEGeOSO3H,20
H3þxPMo12ꢀxVxO40 heteropolyacid,21 methane sulphonic acid,22 [TEA]
[HSO4],23 silicagelsupported dual acidic ionic liquid,241-hexanesulphonic
Fig. 1. The general structures of 1-aminoalkyl-2-naphthols (A) and 1,3-oxazines (B).
acid sodium salt,25 hafnium (IV) bis(perfluorooctanesulfonyl)imide
complex,26 silica chloride,27 Ce(SO4)2,28 Fe(HSO4)3,29 and sulfamic acid/
ultrasound.30 1-Thioamidoalkyl-2-naphthols have been prepared by the
reaction between 2-naphthol, aldehydes, and thioamides using silica
sulfuric acid.31 This transformation has been scarcely studied in the lit-
erature. The most effective protocol, which has been utilized for the
synthesis of 1-carbamatoalkyl-2-naphthols involves the reaction of 2-
naphthol with aldehydes and alkyl carbamates in the presence of some
catalysts, such as 4-(1-imidazolium) butane sulfonate,32 silica-supported
NaHSO4,33 silica-supported Preyssler nano particle,34 and 1-butyl-3-
methylimidazolium bromide/p-toluene sulfonic acid.35 The synthesis of
this class of compounds has also been rarely reported.
* Corresponding authors. Fax: þ98 811 8272404; e-mail addresses:
Khzaei_1326@yahoo.com (A. Khazaei), mzolfigol@yahoo.com (M.A. Zolfigol),
moosavizare@yahoo.com (A.R. Moosavi-Zare).
0040-4020/$ e see front matter Ó 2012 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.tet.2012.10.042

A. Khazaei et al. / Tetrahedron 69 (2013) 212e218
213
Fig. 2. The structures of bis[1-amidoalkyl (or carbamatoalkyl)-2-naphthol] (compounds 4aec).
Development of organocatalytic processes in which the reactions
are catalyzed by organic molecules has become an area of importance
in currentorganic synthesis particularly froma green chemistry point
of view.36,37 With this issue in mind, we have employed triarylmethyl
chlorides (Ar3CCl) as novel neutral organic catalysts for the synthesis
of 12-aryl-8,9,10,12-tetrahydrobenzo[a]-xanthen-11-ones,38 bis(in-
dolyl) methanes,39 and N-sulfonyl imines.40 Furthermore, we have
recently synthesized 1-amidoalkyl-2-naphthols via the reaction of
under solvent-free conditions at temperature ranking between 60
and 80 ꢁC. The results are summarized in Table 1. As it can be seen in
Table 1, the best results were obtained when the reaction was
carried out using 10 mol % of TrCl at 70 ꢁC.
After optimization of the reaction conditions, the efficiency and
applicability of the method were studied by the reaction of b-naphthol
with arylaldehydes and different amide derivatives in the presence of
TrCl. The results are summarized in Table 2. As Table 2 indicates, using
this method, allaldehydes including benzaldehydeaswell as aromatic
aldehydes possessing electron-releasing substituents, electron-
withdrawing substituents, basic groups or halogens on their aro-
matic rings afforded the desired 1-amidoalkyl-2-naphthol derivatives
in high to excellent yields (88e98%) within relatively short reaction
times (3e25 min) (Table 2, compounds 1aem). Interestingly, the
method was highly efficient when thioamides or alkyl carbamates
were used instead of amides. In these cases, 1-thioamidoalkyl-2-
naphthol and 1-carbamatoalkyl-2-naphthol derivatives were ob-
tained in high to excellent yields (73e98%) and in relatively short re-
action times (4e30 min) (Table 2, compounds 2aed and 3aee).
b-naphthol with aromatic aldehydes and acetonitrile catalyzed by
trityl chloride (Ritter type reaction).41 However, this method was not
general; when we utilized aromatic nitriles instead of acetonitrile in
the reaction, the corresponding products were obtained in very low
yields. Changing the reaction times, temperature or the catalyst
amount did not improve theyields. The reaction times were also long.
Moreover, in that work,41 the preparation of 1-thioamidoalkyl-2-
naphthols and 1-carbamatoalkyl-2-naphthols has not been studied.
In this paper, we report our results on the rapid synthesis of 1-
amidoalkyl-2-naphthols, 1-thioamidoealkyl-2-naphthols, and 1-
carbamatoalkyl-2-naphthols by the condensation of
b-naphthol
with arylaldehydes and amides/thioamides/alkyl carbamates using
TrCl as a highly efficient, neutral, homogeneous, and reusable or-
ganic catalyst under solvent-free conditions at 70 ꢁC (Scheme 1).
Moreover, TrCl can catalyze the synthesis of bis(1-amidoalkyl-2-
Our method alsoworked well when b-naphthol was reacted with
bis-aldehydes (terephthaldehyde) and amides/alkyl carbamates in
the presence of 10 mol % of TrCl (Scheme 2). When 2.2 equiv of
b
-naphthol was reacted with 1 equiv of terephthaldehyde (a bis-
naphthol)s,
tioamidoalkyl-2-naphthol)s (Scheme 2).
bis(1-carbamatoalkyl-2-naphthol)s,
and
bis(1-
aldehyde) and 2.4 equiv of amides (or methylcarbamate) using 15%
mol of TrCl at 70 ꢁC in the absence of solvent, bis(1-amidoalkyl-2-
naphthol) derivatives 4a and 4b as well as bis(1-carbamatoalkyl-
2-naphthol) 4c were obtained in high yields (83e87%) and in rela-
tively short reaction times (15e20 min) (Fig. 2).
2. Results and discussion
In a plausible mechanism (Scheme 3), aldehyde was activated by
the trityl carbocation. Two resonance forms of activated aldehyde (I
and II) could be produced and converted together in a reversible
To optimize the reaction conditions, as a model, the reaction of
-naphthol with p-chlorobenzaldehyde and acetamide was exam-
ined in the presence of different amounts of triarylmethyl chlorides
b
Scheme 1. The synthesis and general structure of 1-amidoalkyl (carbamatoalkyl or thioamidoalkyl)-2-naphthols.

214
A. Khazaei et al. / Tetrahedron 69 (2013) 212e218
Scheme 2. The condensation between b-naphthol, terephthaldehyde and amides (or
alkyl carbamates).
Table 1
Effect of different triarylmethyl chlorides, their amounts, and temperature on the
reaction
Ar3CCl
Catalyst (mol %)
Temp (ꢁC)
Time (min)
Yielda (%)
TrCl
10
10
10
7.5
12.5
10
70
70
70
70
70
80
60
8
9
11
11
8
95
92
87
89
94
94
79
MMTClb
DMTClc
TrCl
TrCl
TrCl
TrCl
8
20
10
a
Isolated yield.
Ph2(p-MeOC6H4)CCl (monomethoxytrityl chloride).
Ph(p-MeOC6H4)2CCl (dimethoxytrityl chloride).
b
c
Table 2
The solvent-free synthesis of 1-aminoalkyl-2-naphthols, 1-thioamidoalkyl-2-
naphthol, and 1-carbamatoalkyl-2-naphthol using trityl chloride
Scheme 3. The plausible mechanism for the synthesis of 1-amidoalkyl (carbama-
toalkyl or thioamidoalkyl)-2-naphthols catalyzed by TrCl.
Compounds
R/R0
X
Time (min)
Yielda (%)
1H NMR (300 MHz, CDCl3):
d (ppm) of the aldehydic hydrogen
1a
1b
1c
1d
1e
1f
1g
1h
1i
H/Me
p-Me/Me
p-NO2/Me
m-NO2/Me
p-Cl/Me
O
O
O
O
O
O
O
O
O
O
O
O
O
S
S
S
S
O
O
O
O
O
8
9
11
8
8
9
16
8
25
3
7
8
10
12
30
30
30
7
8
7
4
8
94
92
88
96
95
91
90
92
92
98
95
94
96
78
73
82
80
96
98
97
98
95
(9.78) increased to 10.04 in the reaction mixture (Fig. 4).
UV spectra were another evidence to confirm of these forms (I
and II). The maxima of absorption for benzaldehyde appear at
240 nm and for trityl chloride at 222 nm. But lmax of the complexes
of aldehyde and trityl carbocation which formed by adding TrCl to
benzaldehyde was observed at 245 nm (Fig. 5).
p-Br/Me
p-CH3O/Ph
p-NO2/Ph
p-Cl/3-pyridyl
H/CH2CH
p-Me/CH2CH
p-OH/CH2CH
p-NO2/CH2CH
H/Me
I and II were introduced by Oikawa et al. as cationic in-
1j
1k
1l
termediates for the first time.42 Therefore, I and II act as an acti-
vated complex and then react with b-naphthol to provide III, which
1m
2a
2b
2c
2d
3a
3b
3c
3d
3e
converts into IV by proton transfer. Then, IV could be converted to V
by removing one molecule of triarylmethanol. Afterward, V or IV
reacts with amide to obtain VI. Intermediate VI reacts with triar-
ylmethanol to produce 1-amidoalkyl-2-naphthol and TrCl.28,41
The proposed mechanism is confirmed since the catalyst was
completely recovered unchanged and no TrOH could be identified
after the completion of the reaction. This matter was investigated by
adding petroleum ether (20 mL) tothe crude reaction mixture. It was
then refluxed, stirred, and filtered to separate the catalyst, which
could be recycled for other reactions. It means that TrCl is soluble in
petroleum ether and the products are insoluble in this solvent.
Therefore, the solvent was evaporated to give pure recycled TrCl.
As shown in Scheme 1, 1-thioamidoalkyl-2-naphthols were pre-
p-Me/Me
m-NO2/Me
p-Br/Me
H/CH3O
p-NO2/CH3O
m-NO2/CH3O
m-Cl/CH3O
p-Br/CH3O
a
Isolated yield.
reaction.38e41 To prove the formation of I and II, benzaldehyde was
reacted with trityl chloride at room temperature, and then IR, 1H, and
UV spectra of the aldehydic functional group in the benzaldehyde
were as follows:38,41 IR (Nujol): nmax (cmꢀ1) of C]O in benzaldehyde
(1705) decreased to 1697 in the reaction mixture (Fig. 3).
pared by the one-pot multi-component reaction between b-naphthol,
aldehydes, and thioacetamides in the presence of TrCl (compounds
2aed). The mixture was stirred for 12e30minat70ꢁC, which afforded

A. Khazaei et al. / Tetrahedron 69 (2013) 212e218
215
Fig. 3. IR spectra of benzaldehyde and mixture of benzaldehyde and TrCl.
1200 cmꢀ1, two strong peaks at about ca. 3142 cmꢀ1 and 3363 cmꢀ1
related to yOeH and yNeH stretching vibrations are important to the
identification of these compounds. In the 1H NMR spectra of them (for
samples in DMSO-d6 solution), the chemical shift of OH (phenolic
hydrogen), NH (amidic hydrogen), and CH3 (the hydrogens of methyl
group) appeared at about 10.4, 8.0, and 2.5, respectively. Moreover in
the 13C NMR spectra (for samples in DMSO-d6 solution), the chemical
shiftof thiocarbonyl group(C]S), aliphatic CH, and CH3 was displayed
at about 200.0, 55.9, and 33.4, respectively. These useful observations
helped us identify the structures of 1-thioamidoalkyl-2-naphthols
derivatives (Experimental section, 2aed).
3. Conclusions
In conclusion, we have developed a new method for the
preparation of 1-amidoalkyl (thioamidoalkyl or carbamatoalkyl)-2-
naphthol derivatives via the one-pot three-component of b-naph-
thol with aromatic aldehydes and different amides/thioamides/al-
kyl carbamates using trityl chloride as a homogenous and neutral
organic catalyst at 70 ꢁC under solvent-free conditions. The
advantages of the method are efficiency, generality, high yield,
short reaction time, cleaner reaction profile, and simplicity.
Fig. 4. Chemical shift of formyl hydrogen in 1H NMR spectra of benzaldehyde and
complexes of benzaldehyde and trityl cation (I and II) at room temperature in CDCl3.
4. Experimental
4.1. General
All chemicals were purchased from Merck or Fluka Chemical
Companies. The known products were identified by comparison of
their melting points and spectral data with those in the authentic
samples. The 1H NMR (250 or 300 MHz) and 13C NMR (62.5 or
75 MHz) were recorded on a Bruker Avance DPX-250 FT-NMR
spectrometer (d in parts per million). UV spectra were acquired on
a T8 UV/VIS Spectrometer PG Instruments Ltd. Melting points were
€
recorded on a Buchi B-545 apparatus in open capillary tubes.
Optical rotations were studied in spectral grade solvents using
a PerkineElmer 341 polarimeter.
Fig. 5. UV spectra of benzaldehyde, TrCl, and complexes of benzaldehyde and trityl
cation (I and II) at room temperature in hexane.
4.2. General procedure for the synthesis of 1-amidoalkyl
(carbamatoalkyl or thioamidoalkyl)-2-naphthols (Scheme 1)
the corresponding products in 73e82% yield. The structures of these
mentioned compounds were confirmed by the IR, 1H and 13C NMR,
mass and elemental analysis (Experimental section). In the IR spectra,
the absorbance of thiocarbonyl group (C]S) between 1050 and
To a well-ground mixture of
aldehyde (2 mmol) and amide derivatives (2.4 mmol) in a 10 mL
round-bottomed flask connected to a reflux condenser, was added
b-naphthol (0.288 g, 2 mmol),

216
A. Khazaei et al. / Tetrahedron 69 (2013) 212e218
TrCl (0.055 g, 0.2 mmol), and the resulting mixture was stirred in an
oil-bath (70 ꢁC) for the times reported in Table 2. Afterward, petro-
leum ether (20 mL) was added to the reaction mixture, refluxed, and
stirred for 3 min, and filtered (TrCl is soluble in petroleum ether;
however, the products are insoluble in this solvent). The filtrate
containing the catalyst was washed two times with 20 mL of 40% (w/
v) solution of NaHSO3 in H2O/EtOH (4:1) to extract the unreacted
aldehyde dissolved in the petroleum ether. The organic layer was
separated and dried with CaCl2; the solvent was evaporated to give
pure recycled TrCl. The solid residue was recrystallized from EtOH
(95%) to give the pure product (compounds 1aem, 2aed, and 3aee).
(lit.19 226e228 ꢁC); IR (KBr): 3467, 3339, 2966,1652,1598,1437 cmꢀ1
1H NMR (300 MHz, DMSO-d6):
¼1.98 (s, 3H), 6.98e7.34 (m, 8H),
7.61e7.67 (m, 2H), 7.86 (d, J¼10.1 Hz, 1H), 8.27 (d, J¼8.1 Hz,1H), 9.74(s,
1H) ppm; 13C NMR (75 MHz, DMSO-d6):
121.2, 122.4, 123.8, 126.9, 128.4, 128.7, 129.3, 130.2, 131.0, 133.2, 139.8,
152.6,168.4ppm;CHNanalysis:Anal. CalcdforC19H16BrNO2:C,61.64;
H, 4.36; N, 3.78. Found: C, 61.42; H, 4.44; N, 3.65.
;
d
d
¼23.7, 46.5, 117.8, 118.7,
4.2.7. N-[(2-Hydroxynaphthalen-1-yl)(4-methoxyphenyl)methyl]
benzamide (1g). Rf (EtOAc/n-hexane: 1:1)¼0.880; mp 202e204 ꢁC
(lit.44 208e210 ꢁC); IR (KBr): 3392, 3084,1651,1614,1517,1438,1336,
1066 cmꢀ1; 1H NMR (400 MHz, DMSO-d6):
d
¼3.69 (s, 3H), 6.86 (d,
J¼8.4 Hz, 2H), 7.24e7.34 (m, 5H), 7.47e7.57 (m, 4H), 7.80e7.89 (m,
4.2.1. N-[(2-Hydroxynaphthalen-1-yl)(phenyl)methyl]acetamide
4H), 8.12 (d, J¼8.4 Hz, 2H), 10.39 (s, 1H) ppm; 13C NMR (100 MHz,
(1a). Rf (EtOAc/n-hexane: 1:1)¼0.870; mp 238e240 ꢁC (lit.28
241e243 ꢁC); IR (KBr): 3407, 3248, 3007, 1642, 1582, 1371 cmꢀ1
;
DMSO-d6):
d
¼49.4, 55.5, 114.1, 118.9, 119.2, 123.2, 127.2, 127.6, 127.9,
1H NMR (250 MHz, DMSO-d6):
d
¼2.06 (s, 3H), 7.01e7.20 (m, 9H),
128.2,128.7,128.9,129.0,129.7,131.8,132.7,134.3,134.9,153.5,158.5,
166.0 ppm. CHN analysis: Anal. Calcd for C25H21NO3: C, 78.31; H,
5.52; N, 3.65. Found: C, 78.44; H, 5.62; N, 3.51.
7.65e7.73 (m, 3H), 8.11 (d, J¼7.7 Hz, 1H), 9.69 (s, 1H) ppm; 13C NMR
(62.5 MHz, DMSO-d6):
d
¼23.5, 41.3, 118.8, 120.2, 122.0, 123.9, 124.9,
125.7,127.6,128.1, 128.3, 128.5, 128.6, 134.2, 144.0,152.6,169.6 ppm;
CHN analysis: Anal. Calcd for C19H17NO2: C, 78.33; H, 5.88; N, 4.81.
Found: C, 78.18; H, 5.96; N, 4.69.
4.2.8. N-[(2-Hydroxynaphthalen-1-yl)(4-nitrophenyl)methyl]benza-
mide (1h). Rf (EtOAc/n-hexane: 1:1)¼0.770; mp 233e235 ꢁC (lit.44
237e239 ꢁC); IR (KBr): 3387, 3273, 1645, 1601, 1528, 1342 cmꢀ1; 1H
NMR (400 MHz, DMSO-d6):
d
¼7.27 (d, J¼8.8 Hz, 1H), 7.33 (t,
4.2.2. N-[(2-hydroxynaphthalen-1-yl)(p-tolyl)methyl]acetamide
(1b). Rf (EtOAc/n-hexane: 1:1)¼0.890; mp 221e223 ꢁC (lit.41
223e225 ꢁC); IR (KBr): 3421, 3316, 3059, 1621, 1598, 1514, 1466,
J¼7.2 Hz, 1H), 7.42 (d, J¼8.0 Hz, 1H), 7.48e7.59 (m, 6H), 7.86 (t,
J¼7.2 Hz, 2H), 7.92 (d, J¼7.2 Hz, 2H), 8.08 (d, J¼8.8 Hz, 1H), 8.18 (d,
J¼8.8 Hz, 2H), 9.09 (d, J¼8.4 Hz, 1H), 10.4 (s, 1H) ppm; 13C NMR
1389 cmꢀ1; 1H NMR (400 MHz, DMSO-d6):
d
¼2.0 (s, 3H), 2.24 (s, 3H),
(100 MHz, DMSO-d6):
d
¼49.5, 117.8, 119.0, 123.1, 123.2, 123.8, 127.4,
7.05e7.10 (m, 4H), 7.14 (d, J¼8.4 Hz, 1H), 7.24e7.29 (m, 2H), 7.37 (t,
127.9, 128.0, 128.9, 129.2, 130.4, 132.0, 132.7, 134.4, 146.6, 150.7,
153.9, 166.7 ppm; CHN analysis: Anal. Calcd for C24H18N2O4: C,
72.35; H, 4.55; N, 7.03. Found: C, 72.19; H, 4.63; N, 7.11.
J¼7.2 Hz, 1H), 7.76e7.82 (m, 2H), 7.87 (s, 1H), 8.45 (d, J¼8.4 Hz, 1H),
10.0 (s, 1H) ppm; 13C NMR (100 MHz, DMSO-d6):
d¼21.0, 23.1, 48.1,
118.9,119.5,122.8,123.8,126.4,126.7,129.0,129.1,129.6,132.8,135.5,
140.0, 153.5, 169.6 ppm. CHN analysis: Anal. Calcd for C20H19NO2: C,
78.66; H, 6.27; N, 4.59. Found: C, 78.42; H, 6.13; N, 4.71.
4.2.9. N-[(4-Chloro-phenyl)-(2-hydroxy-naphthalen-1-yl)-methyl]
nicotinamide
206e209 ꢁC (lit.19 206e209 ꢁC); IR (KBr): 3408, 3234, 3065, 1645,
1581, 1514, 1273 cmꢀ1; 1H NMR (300 MHz, DMSO-d6):
(1i). Rf
(EtOAc/n-hexane:
1:1)¼0.750;
mp
4.2.3. N-[(2-Hydroxynaphthalen-1-yl)(4-nitrophenyl)methyl]acet-
amide (1c). Rf (EtOAc/n-hexane: 1:1)¼0.760; mp 245e247 ꢁC (lit.19
246e248 ꢁC); IR (KBr): 3395, 3269, 2591, 1648, 1601, 1533, 1448,
d¼7.27e7.50
(m, 9H), 7.83 (d, J¼8.7 Hz, 2H), 8.10 (d, J¼8.4 Hz, 1H), 8.27 (d,
J¼7.8 Hz, 1H), 8.71 (d, J¼4.4 Hz, 1H), 9.12 (s, 1H), 9.35 (d, J¼7.6 Hz,
1347 cmꢀ1; 1H NMR (400 MHz, DMSO-d6):
d
¼2.04 (s, 3H), 7.21e7.32
1H), 10.38 (s, 1H) ppm; 13C NMR (75 MHz, DMSO-d6):
d¼49.4, 118.2,
(m, 3H), 7.43 (t, J¼7.6 Hz, 1H), 7.54e7.61 (m, 2H), 7.82e7.91 (m, 3H),
119.1, 123.1, 123.5, 123.9, 127.2, 128.6, 128.9, 129.2, 130.1, 130.4, 131.7,
132.8, 135.8, 141.2, 149.1, 152.4, 153.9, 165.4 ppm; CHN analysis:
Anal. Calcd for C23H17ClN2O2: C, 71.04; H, 4.41; N, 7.20. Found: C,
71.21; H, 4.53; N, 7.13.
8.07 (m, 2H), 8.66 (d, J¼8.0 Hz, 1H), 10.16 (s, 1H) ppm; 13C NMR
(100 MHz, DMSO-d6):
d
¼23.0, 48.0, 118.9, 120.9, 121.7, 123.1, 127.2,
128.9, 129.2, 130.0, 130.4, 132.6, 133.3, 145.9, 148.2, 153.8,
170.2 ppm; CHN analysis: Anal. Calcd for C19H16N2O4: C, 67.85; H,
4.79; N, 8.33. Found: C, 67.94; H, 4.66; N, 8.19.
4.2.10. N-[(2-Hydroxynaphthalen-1-yl)(phenyl)methyl]acrylamide
(1j). Rf (EtOAc/n-hexane: 1:1)¼0.840; mp 244e246 ꢁC (lit.43
247e249 ꢁC); IR (KBr): 3415, 3254, 1669, 1621 cmꢀ1 1H NMR
;
4.2.4. N-[(2-Hydroxynaphthalen-1-yl)(3-nitrophenyl)methyl]acet-
amide (1d). Rf (EtOAc/n-hexane: 1:1)¼0.700; mp 235e237 ꢁC (lit.19
238e240 ꢁC); IR (KBr): 3375, 3083, 2594, 1648, 1531, 1350 cmꢀ1; 1H
(300 MHz, DMSO-d6):
d
¼5.59 (1H, d, J¼10.2 Hz), 6.12 (1H, d,
J¼17.1 Hz), 6.59 (dd, J¼9.9, 16.5 Hz, 1H), 7.14e7.35 (m, 8H),
7.74e7.87 (m, 3H), 8.69 (d, J¼7.8, 1H), 10.01 (s, 1H) ppm; 13C NMR
NMR (250 MHz, DMSO-d6):
d
¼2.06 (s, 3H), 7.15e7.49 (m, 6H),
7.78e8.04 (m, 5H), 8.54 (d, J¼8.1 Hz, 1H), 10.12 (s, 1H) ppm; 13C
(75 MHz, DMSO-d6):
d
¼48.5, 118.9, 119.0, 122.8, 123.1, 123.7, 126.1,
NMR (62.5 MHz, DMSO-d6):
d
¼23.3, 48.1, 118.1, 118.7, 120.5, 122.3,
126.6, 126.8, 128.5, 128.9, 129.0, 129.8, 132.3, 132.8, 142.7, 153.7,
164.9 ppm; CHN analysis: Anal. Calcd for C20H17NO2: C, 79.19; H,
5.65; N, 4.62. Found: C, 79.35; H, 5.69; N, 4.51.
123.8, 125.7,127.3,128.4, 129.1,129.6, 130.8, 133.1, 134.1,144.5, 148.7,
152.9, 169.8 ppm; CHN analysis: Anal. Calcd for C19H16N2O4: C,
67.85; H, 4.79; N, 8.33. Found: C, 67.71; H, 4.69; N, 8.46.
4.2.11. N-[(2-Hydroxynaphthalen-1-yl)(p-tolyl)methyl]acrylamide
(1k). Rf (EtOAc/n-hexane: 1:1)¼0.870; mp 216e217 Cꢀ1(lit.45
ꢁ
4.2.5. N-[(2-Hydroxynaphthalen-1-yl)(4-chlorophenyl)methyl]acet-
1H
amide (1e).28 Rf (EtOAc/n-hexane: 1:1)¼0.840; IR (KBr): 3417, 3231,
214e216 ꢁC); IR (KBr): 3405, 3273, 2987, 1671, 1623 cm
;
2927, 1622, 1597, 1487 cmꢀ1; 1H NMR (250 MHz, DMSO-d6):
d
¼2.07
NMR (300 MHz, DMSO-d6):
d
¼2.21 (s, 3H), 5.59 (d, J¼9.6 Hz, 1H),
6.12 (d, J¼16.8 Hz, 1H), 6.59 (dd, J¼15.9, 10.2 Hz, 1H), 7.04e7.35 (m,
(s, 3H), 7.06 (m, 2H), 7.14e7.24 (m, 5H), 7.68e7.77 (m, 3H), 7.98 (d,
8H), 7.74e7.85 (m, 3H), 8.68 (d, J¼7.5 Hz, 1H), 10.00 (s, 1H) ppm; 13C
J¼7.4 Hz, 1H), 8.16 (d, J¼7.1 Hz, 1H), 9.90 (s, 1H) ppm; 13C NMR
NMR (75 MHz, DMSO-d6):
d
¼21.0, 49.5, 118.9, 119.1, 122.8, 123.8,
(62.5 MHz, DMSO-d6):
d
¼23.2, 47.6, 118.8, 119.8, 122.1, 123.7, 125.8,
126.0, 126.5, 126.8, 128.9, 129.3, 131.8, 132.3, 135.7, 139.6, 153.7,
164.9 ppm; CHN analysis: Anal. Calcd for C21H19NO2: C, 79.47; H,
6.03; N, 4.41. Found: C, 79.31; H, 6.14; N, 4.33.
126.9, 127.4, 128.3, 128.6, 129.3, 129.9, 134.0, 143.4, 152.5,
169.8 ppm; CHN analysis: Anal. Calcd for C19H16ClNO2: C, 70.05; H,
4.95; N, 4.30. Found: C, 70.23; H, 5.03; N, 4.17.
4.2.12. N-[(2-Hydroxynaphthalen-1-yl)(4-hydroxyphenyl)methyl]ac-
rylamide (1l). Rf (EtOAc/n-hexane: 1:1)¼0.790; mp 190e192 ꢁC; IR
4.2.6. N-[(2-Hydroxynaphthalen-1-yl)(4-bromorophenyl)methyl]
acetamide (1f). Rf (EtOAc/n-hexane: 1:1)¼0.850; mp 227e229 ꢁC

A. Khazaei et al. / Tetrahedron 69 (2013) 212e218
217
(KBr): 3398, 3231, 1642, 1604, 1482 cmꢀ1
DMSO-d6):
;
1H NMR (400 MHz,
200.6 ppm; CHN analysis: Anal. Calcd for C19H16BrNOS: C, 59.07; H,
d
¼5.61 (d, J¼10.0 Hz, 1H), 6.14 (d, J¼16.8 Hz, 1H), 6.59
4.17; N, 3.63. Found: C, 59.26; H, 4.31; N, 3.49; MS: m/z¼386 (Mþ).
(dd, J¼10.0, 16.8 Hz, 1H), 6.68 (d, J¼8.4 Hz, 2H), 7.0 (d, J¼8.0 Hz, 2H),
7.14 (d, J¼8.4 Hz, 1H), 7.24e7.29 (m, 2H), 7.39 (s, 1H), 7.76e7.82 (m,
2H), 7.91 (s,1H), 8.70 (d, J¼8.0 Hz,1H), 9.28 (s,1H), 9.99 (s,1H) ppm;
4.2.18. Methyl (2-hydroxynaphthalen-1-yl)(phenyl)methylcarbamate
(3a). Rf (EtOAc/n-hexane: 1:1)¼0.825; mp 220e222 ꢁC (lit.33
13C NMR (100 MHz, DMSO-d6):
d
¼48.2, 115.3, 119.0, 119.2, 122.8,
217e218 ꢁC); IR (KBr): 3421, 3196, 2967, 1678, 1607, 1436 cmꢀ1
;
123.8, 125.9, 126.7, 127.9, 128.9, 129.0, 129.5, 132.3, 132.6, 132.8,
153.6, 156.3, 164.7 ppm; CHN analysis: Anal. Calcd for C20H17NO3: C,
75.22; H, 5.37; N, 4.39. Found: C, 75.39; H, 5.29; N, 4.31; MS: m/
z¼319 (Mþ).
1H NMR (400 MHz, DMSO-d6):
d
¼3.59 (s, 3H), 6.90 (d, J¼8.8 Hz,1H),
7.17e7.19 (m, 1H), 7.24e7.30 (m, 6H), 7.41 (t, J¼7.6 Hz, 1H), 7.68 (d,
J¼5.6 Hz, 1H), 7.77e7.83 (m, 2H), 7.95 (d, J¼8.0 Hz, 1H), 10.14 (s,
1H) ppm; 13C NMR (100 MHz, DMSO-d6):
d
¼50.8, 52.1, 118.9, 119.3,
123.0, 126.5, 126.8, 127.0, 128.5, 128.8, 129.0, 129.7, 132.5, 142.8,
153.3, 157.0 ppm; CHN analysis: Anal. Calcd for C19H17NO3: C, 74.25;
H, 5.58; N, 4.56. Found: C, 74.41; H, 5.45; N, 4.64.
4.2.13. N-[(2-Hydroxynaphthalen-1-yl)(4-nitrophenyl)methyl]acryl-
amide (1m). Rf (EtOAc/n-hexane: 1:1)¼0.760; mp 218e220 ꢁC
(lit.45 223e225 ꢁC); IR (KBr): 3402, 3271, 1672, 1621, 1529,
1348 cmꢀ1
;
1H NMR (400 MHz, DMSO-d6):
d
¼5.66 (d, J¼10.4 Hz,
4.2.19. Methyl (2-hydroxynaphthalen-1-yl)(4-nitrophenyl)methyl-
carbamate (3b). Rf (EtOAc/n-hexane: 1:1)¼0.725; mp 202e203 ꢁC
(lit.33 205e207 ꢁC); IR (KBr): 3421, 3265, 2947, 1681, 1514, 1438, 1346,
1H), 6.22 (d, J¼16.8 Hz, 1H), 6.67 (dd, J¼10.4, 17.2 Hz, 1H), 7.22e7.33
(m, 3H), 7.44 (d, J¼8.8 Hz, 3H), 7.83e7.86 (m, 3H), 8.18 (d, J¼8.8 Hz,
2H), 8.89 (d, J¼8.0 Hz, 1H), 10.17 (s, 1H) ppm; 13C NMR (100 MHz,
1045 cmꢀ1
;
1H NMR (400 MHz, DMSO-d6):
d
¼3.62 (s, 3H), 6.99 (d,
DMSO-d6):
d
¼48.5, 118.0, 118.9, 123.1, 123.3, 123.7, 126.6, 127.2,
J¼8.4 Hz,1H), 7.24e7.32(m, 2H), 7.53(t, J¼8.0Hz,1H),7.50(d,J¼8.8Hz,
2H), 7.83 (t, J¼8.4 Hz, 2H), 7.88 (s, 1H), 7.93 (d, J¼6.4 Hz, 1H), 8.16 (d,
J¼8.8 Hz, 2H), 10.25 (s, 1H) ppm; 13C NMR (100 MHz, DMSO-d6):
127.6, 128.9, 129.1, 130.4, 131.8, 132.7, 146.4, 151.2, 153.9, 165.3 ppm.
CHN analysis: Anal. Calcd for C20H16N2O4: C, 68.96; H, 4.63; N, 8.04.
Found: C, 69.09; H, 4.56; N, 7.95.
d
¼50.7, 52.2, 118.4, 118.8, 123.1, 123.2, 123.8, 127.3, 127.6, 128.8, 129.1,
130.3,132.4,146.5,151.1,153.6,157.2ppm;CHNanalysis:Anal. Calcdfor
C19H16N2O5: C, 64.77; H, 4.58; N, 7.95. Found: C, 64.95; H, 4.44; N, 7.86.
4.2.14. N-[(2-Hydroxynaphthalen-1-yl)(phenyl)methyl]thio-
acetamide (2a). Rf (EtOAc/n-hexane: 1:1)¼0.889; mp 190e193 ꢁC;
IR (KBr): 3363, 3142, 3027, 1583, 1435, 1109 cmꢀ1
;
1H NMR
4.2.20. Methyl (2-hydroxynaphthalen-1-yl)(3-nitrophenyl)methyl-
carbamate (3c). Rf (EtOAc/n-hexane: 1:1)¼0.711; mp 247e250 ꢁC
(lit.34 253e255 ꢁC); IR (KBr): 3419, 3256, 2964,1675,1523,1437,1336,
(300 MHz, DMSO-d6):
J¼8.1 Hz, 1H), 7.79 (t, J¼8.7 Hz, 3H), 7.96 (d, J¼8.7 Hz, 1H), 10.39 (s,
1H) ppm; 13C NMR (75 MHz, DMSO-d6):
d¼2.54 (s, 3H), 7.11e7.28 (m, 8H), 7.40 (t,
d¼33.5, 55.9, 117.4, 119.0,
1064 cmꢀ1
;
1H NMR (400 MHz, DMSO-d6):
d
¼3.62 (s, 3H), 7.00 (d,
122.9, 123.3, 126.5, 126.9, 127.1, 128.4, 128.7, 129.0, 130.1, 133.2,
140.8, 154.2, 200.0 ppm; CHN analysis: Anal. Calcd for C19H17NOS:
C, 74.23; H, 5.57; N, 4.56. Found: C, 74.13; H, 5.68; N, 4.47; MS: m/
z¼307 (Mþ).
J¼8.4Hz,1H), 7.24e7.32(m, 2H),7.44(t,J¼7.2Hz,1H),7.55(t, J¼8.0Hz,
1H), 7.65 (d, J¼8.0 Hz,1H), 7.83 (t, J¼6.0 Hz, 2H), 7.94 (d, J¼8.0 Hz,1H),
7.99 (d, J¼8.0 Hz, 1H), 8.07 (d, J¼8.0 Hz, 1H), 8.15 (s, 1H), 10.29 (s,
1H) ppm; 13C NMR (100 MHz, DMSO-d6):
d¼50.5, 52.2, 118.3, 118.9,
120.9, 121.6, 121.9, 123.1, 127.3, 128.8, 129.1, 130.4, 132.4, 133.3, 133.9,
145.5, 148.2, 153.6, 157.2 ppm; CHN analysis: Anal. Calcd for
C19H16N2O5: C, 64.77; H, 4.58; N, 7.95. Found: C, 64.93; H, 4.69; N, 7.87.
4.2.15. N-[(2-Hydroxynaphthalen-1-yl)(p-tolyl)methyl]thio-
acetamide (2b). Rf (EtOAc/n-hexane: 1:1)¼0.895; mp 180e183 ꢁC;
IR (KBr): IR (KBr): 3354, 3163, 3024, 1596, 1121 cmꢀ1 1H NMR
;
(300 MHz, DMSO-d6):
d
¼2.21 (s, 3H), 2.53 (s, 3H), 7.02 (d, J¼3.9 Hz,
4.2.21. Methyl (3-chlorophenyl)(2-hydroxynaphthalen-1-yl) methyl-
carbamate (3d). Rf (EtOAc/n-hexane: 1:1)¼0.800; mp 197e199 ꢁC
(lit.34 196e198 ꢁC); IR (KBr): 3419, 3207, 2876, 1678, 1581, 1487,
4H), 7.18e7.28 (m, 3H), 7.37 (d, J¼7.2 Hz, 1H), 7.78 (t, J¼7.5 Hz, 3H),
7.96 (d, J¼8.4 Hz, 1H), 10.33 (s, 1H) ppm; 13C NMR (75 MHz, DMSO-
d6):
d
¼21.0, 33.5, 55.8, 117.6, 119.0, 119.4, 126.4, 127.0, 127.9, 128.7,
1065 cmꢀ1
;
1H NMR (400 MHz, DMSO-d6):
d
¼3.59 (s, 3H), 6.87 (d,
129.7, 130.1, 133.1, 136.2, 137.8, 154.0, 199.9 ppm; CHN analysis:
Anal. Calcd for C20H19NOS: C, 74.73; H, 5.96; N, 4.36. Found: C,
74.89; H, 5.79; N, 4.27; MS: m/z¼321 (Mþ).
J¼8.8Hz,1H),7.16(d,J¼7.2Hz,1H),7.21e7.32(m, 5H), 7.42(t, J¼8.0Hz,
1H), 7.77e7.84 (m, 3H), 7.93 (d, J¼8.4 Hz, 1H), 10.2 (s, 1H) ppm; 13C
NMR (100 MHz, DMSO-d6):
d
¼50.4, 52.2, 118.7, 118.8, 123.0, 123.3,
125.2, 126.2, 126.8, 127.1, 128.8, 129.1, 130.1, 130.5, 132.4, 133.3, 145.5,
153.4,157.1 ppm; CHN analysis: Anal. Calcd for C19H16ClNO3: C, 66.77;
H, 4.72; N, 4.10. Found: C, 66.83; H, 4.86; N, 4.03.
4.2.16. N-[(2-Hydroxynaphthalen-1-yl)(3-nitrophenyl)methyl]thio-
acetamide (2c). Rf (EtOAc/n-hexane: 1:1)¼0.750; mp 157e159 ꢁC;
IR (KBr): 3365, 3172, 3021, 1587, 1520, 1339, 1113 cmꢀ1 1H NMR
;
(400 MHz, DMSO-d6):
d
¼2.63 (s, 3H), 7.28 (d, J¼12.0 Hz, 1H), 7.31
4.2.22. Methyl (4-bromophenyl) (2-hydroxynaphthalen-1-yl) meth-
(t, J¼7.6 Hz, 1H), 7.49 (t, J¼7.6 Hz, 1H), 7.58 (d, J¼5.2 Hz, 2H),
7.81e7.90 (m, 3H), 7.98 (s, 1H), 8.03 (d, J¼8.4 Hz, 1H), 8.08e8.11
(m, 1H), 10.3 (s, 1H), 10.56 (d, J¼8.0 Hz, 1H) ppm; 13C NMR
ylcarbamate (3e). Rf (EtOAc/n-hexane: 1:1)¼0.850; mp 171e173 ꢁC;
IR (KBr): 3405, 3227, 1675, 1582, 1441 cmꢀ1 1H NMR (400 MHz,
;
DMSO-d6):
d
¼3.59 (s, 3H), 6.85 (d, J¼8.8 Hz, 1H), 7.19 (d, J¼8.0 Hz,
(100 MHz, DMSO-d6):
d
¼33.3, 35.3, 116.5, 118.9, 121.1, 122.0, 122.9,
1H), 7.23e7.31 (m, 2H), 7.41 (t, J¼8.0 Hz, 2H), 7.47 (d, J¼8.4 Hz, 2H),
123.2, 127.5, 128.7, 129.2, 130.1, 130.9, 133.0, 133.5, 143.5, 148.2,
145.3. 201.3 ppm; CHN analysis: Anal. Calcd for C19H16N2O3S: C,
64.76; H, 4.58; N, 7.95. Found: C, 64.91; H, 4.67; N, 7.83; MS: m/
z¼352 (Mþ).
7.72 (d, J¼5.2 Hz, 1H), 7.78e7.83 (m, 2H), 7.91 (d, J¼7.2 Hz, 1H),10.18
(s,1H) ppm; 13C NMR (100 MHz, DMSO-d6):
d
¼50.4, 52.1,118.8,118.9,
119.9,123.0,127.1,128.7,128.8,129.0,130.0,131.4,132.4,142.4,153.4,
157.1 ppm; CHN analysis: Anal. Calcd for C19H16BrNO3: C, 59.08; H,
4.18; N, 3.63. Found: C, 59.24; H, 4.11; N, 3.71; MS: m/z¼386 (Mþ).
4.2.17. N-[(4-Bromophenyl)(2-hydroxynaphthalen-1-yl)methyl]thio-
acetamide (2d). Rf (EtOAc/n-hexane: 1:1)¼0.885; mp 178e180 ꢁC;
4.3. General procedure for the condensation between 2-
naphthol, terephthaldehyde, and amides (or alkyl carba-
mates) (Scheme 2)
IR (KBr): 3351, 3147, 3029, 1595, 1107 cmꢀ1 1H NMR (400 MHz,
;
DMSO-d6):
d
¼2.59 (s, 3H), 7.09 (d, J¼8.4 Hz, 2H), 7.25 (d, J¼8.0 Hz,
1H), 7.31 (t, J¼7.2 Hz, 1H), 7.43e7.49 (m, 3H), 7.78e7.85 (m, 3H),
7.99 (d, J¼8.8 Hz, 1H), 10.20 (s, 1H), 10.40 (d, J¼8.0 Hz, 1H) ppm; 13C
To a well-ground mixture of
b-naphthol (0.576 g, 4 mmol),
NMR (100 MHz, DMSO-d6):
d¼33.4, 55.3, 117.0, 118.9, 120.0, 123.1,
terephthaldehyde (0.268 g, 2 mmol) and amide (or alkyl carba-
mate) (0.283 g, 4.8 mmol) in a 10 mL round-bottomed flask
123.2, 127.2, 128.7, 129.1, 130.4, 131.3, 131.4, 133.0, 140.4, 154.2,

218
A. Khazaei et al. / Tetrahedron 69 (2013) 212e218
connected to a reflux condenser, was added TrCl (0.083 g, 0.3 mmol,
15 mol %), and the resulting mixture was stirred in an oil-bath
(70 ꢁC) for the appropriate time. After completion of the reaction,
as monitored by TLC, the reaction mixture was cooled to room
temperature and triturated with hot EtOH (95%) (the impurities are
soluble in hot EtOH; however, the product isn’t soluble in this
solvent) to give pure bis[1-amidoalkyl (or carbamatoalkyl)-2-
naphthol] (compounds 4aec).
References and notes
1. Shen, A. Y.; Tsai, C. T.; Chen, C. L. Eur. J. Med. Chem. 1999, 34, 877e882.
2. Dingermann, T.; Steinhilber, D.; Folkers, G. Molecular Biology in Medicinal
Chemistry; Wiley-VCH: Weinheim, 2004.
3. Shen, A. Y.; Chen, C. L.; Lin, C. I. Chin. J. Physiol. 1992, 35, 45e54.
4. Damodiran, M.; Selvam, N. P.; Perumal, P. T. Tetrahedron Lett. 2009, 50
5474e4578.
5. Haneishi, T.; Okazaki, T.; Hata, T.; Tamura, C.; Nomura, M.; Naito, A.; Seki, I.;
Arai, M. J. Antibiot. 1971, 24, 797e799.
6. Sasaki, K.; Kusakabe, Y.; Esumi, S. J. Antibiot. 1972, 25, 151e154.
7. Kusakabe, Y.; Nagatsu, J.; Shibuya, M.; Kawaguchi, O.; Hirose, C.; Shirato, S. J.
Antibiot. 1972, 25, 44e47.
4.3.1. N,N0-[1,4-Phenylenebis((2-hydroxynaphthalen-1-yl)
methy-
lene)] diacetamide (4a). Rf (EtOAc/n-hexane: 1:1)¼0.210; mp
8. Wani, M. C.; Taylor, H. L.; Wall, M. E. J. Chem. Soc., Chem. Commun. 1973,
390e396.
277e279 ꢁC (lit.19 277e279 ꢁC); IR (KBr): 3402, 3192, 3059, 1644,
9. Jonson, P. Y.; Silver, R. B. J. Heterocycl. Chem. 1973, 10, 1029e1030.
10. Remillard, S.; Rebhun, L. I.; Howie, G. A.; Kupchan, S. M. Science 1975, 189,
1002e1005.
1583, 1478, 1275, 816 cmꢀ1. 1H NMR (300 MHz, DMSO-d6):
d
¼2.01
(s, 6H), 7.17e7.39 (m,12H), 7.77e7.93 (m, 6H), 8.53 (d, J¼8.2 Hz, 2H),
10.09 (s, 2H) ppm; 13C NMR (75 MHz, DMSO-d6):
ꢀ
11. Urbanski, T.; Ghrne, D.; Szczerek, I.; Modaski, M. Polish Patent 54, 007, 1967.
d¼23.1, 48.2,118.9,
12. Lesher, G. Y.; Surrey, A. R. J. Am. Chem. Soc. 1955, 77, 636e641.
13. Mosher, H. S.; Frankel, M. B.; Gregory, M. J. Am. Chem. Soc. 1953, 75, 5326e5328.
14. Peglion, J. L.; Vian, J.; Gourment, B.; Despaux, N.; Audinot, V.; Millan, M. Bioorg.
Med. Chem. Lett. 1997, 7, 881e886.
119.2, 122.8, 126.3, 126.8, 128.9, 129.0, 129.6, 132.7, 140.8, 140.9,
153.6, 169.7 ppm; CHN analysis: Anal. Calcd for C32H28N2O4: C,
76.17; H, 5.59; N, 5.55. Found: C, 75.97; H, 5.69; N, 5.42.
15. Ren, H.; Grady, S.; Gamenara, D.; Heinzen, H.; Moyna, P.; Croft, S.; Kendrick, H.;
Yardley, V.; Moyna, G. Bioorg. Med. Chem. Lett. 2001, 11, 1851e1854.
16. Benedini, F.; Bertolini, G.; Cereda, R.; Dona, G.; Gromo, G.; Levi, S.; Mizrahi, J.;
4.3.2. N,N0-[1,4-Phenylenebis ((2-hydroxynaphthalen-1-yl) methy-
lene)] dibenzamide (4b). Rf (EtOAc/n-hexane: 1:1)¼0.645; mp
260e263 ꢁC; IR (KBr): 3404, 3180, 1635, 1601, 1477 cmꢀ1; 1H NMR
ꢀ
Sala, A. J. Med. Chem. 1995, 38, 130e136.
17. Clark, R. D.; Caroon, J. M.; Kluge, A. F.; Repke, D. B.; Roszkowski, A. P.; Strosberg,
A. M.; Baker, S.; Bitter, S. M.; Okada, M. D. J. Med. Chem. 1983, 26, 657e661.
18. Matsuoka, H.; Ohi, N.; Mihara, M.; Suzuki, H.; Miyamoto, K.; Maruyama, N.;
Tsuji, K.; Kato, N.; Akimoto, T.; Takeda, Y.; Yano, K.; Kuroki, T. J. Med. Chem. 1997,
40, 105e111.
19. Zolfigol, M. A.; Khazaei, A.; Moosavi-Zare, A. R.; Zare, A.; Khakyzadeh, V. Appl.
Catal. A: Gen. 2011, 400, 70e81.
20. Quan, Z.-J.; Ren, R.-G.; Da, Y.-X.; Zhang, Z.; Wang, X.-C. Synth. Commun. 2011, 41,
3106e3116.
(400 MHz, DMSO-d6):
d
¼7.26e7.39 (m, 8H), 7.44e7.59 (m, 10H),
7.78e7.88 (m, 6H), 7.94 (d, J¼7.2 Hz, 2H), 8.13 (d, J¼8.4 Hz, 2H), 9.07
(d, J¼8.4 Hz, 2H), 10.39 (s, 2H) ppm; 13C NMR (100 MHz, DMSO-d6):
d¼49.7, 118.7, 119.2, 123.2, 127.0, 127.3, 127.8, 128.6, 128.9, 129.8,
130.3, 131.7, 132.7, 134.6, 135.3, 140.9, 153.6, 168.5 ppm; CHN anal-
ysis: Anal. Calcd for C42H32N2O4: C, 80.24; H, 5.13; N, 4.46. Found: C,
80.03; H, 5.23; N, 4.34; MS: m/z¼628 (Mþ), 523 (MþꢀPhCO), 418
(Mþꢀ2PhCO), 380 (MþꢀC17H12O2).
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4.3.3. Dimethyl
methylene] dicarbamate (4c). Rf (EtOAc/n-hexane: 1:1)¼0.250; mp
192e194 ꢁC; IR (KBr): 3421, 3244, 1695, 1603, 1477 cmꢀ1 1H NMR
(400 MHz, DMSO-d6):
4H), 7.17e7.20 (dd, J¼4.0, 9.2 Hz, 2H), 7.27 (t, J¼7.6 Hz, 2H), 7.37 (d,
J¼9.2 Hz, 2H), 7.61 (s, 2H), 7.75 (d, J¼8.8 Hz, 2H), 7.79 (d, J¼8.0 Hz,
2H), 7.91 (s, 2H), 10.08 (s, 2H) ppm; 13C NMR (100 MHz, DMSO-d6):
1,4-phenylenebis
[(2-hydroxynaphthalen-1-yl)
;
d
¼3.55 (s, 6H), 6.78 (d, J¼8.4 Hz, 2H), 7.13 (s,
d
¼50.7, 52.1, 118.9, 119.2, 122.9, 126.3, 126.7, 127.0, 128.8, 129.0,
129.7, 132.5, 140.9, 153.3, 156.9 ppm; CHN analysis: Anal. Calcd for
C32H28N2O6: C, 71.63; H, 5.26; N, 5.22. Found: C, 71.42; H, 5.38; N,
5.11; MS: m/z¼536 (Mþ).
34. Heravi, M. M.; Tavakoli-Hoseini, N.; Bamoharram, F. F. Green Chem. Lett. Rev.
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The authors gratefully acknowledge partial support of this work
by the Research Affairs Office of Bu-Ali Sina University (Grant
number 32-1716 entitled development of chemical methods, re-
agents and molecules) and Payame Noor University, and Center of
Excellence in Development of Chemical Method (CEDCM), Hame-
dan, I.R. Iran.
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Supplementary data
Supplementary data associated with this article can be found in
the online version, at http://dx.doi.org/10.1016/j.tet.2012.10.042.