AgI nanoparticles as a remarkable catalyst in the synthesis of (amidoalkyl)naphthol and oxazine derivatives: An eco-friendly approach

Article abstract of DOI:10.1007/s00706-014-1184-y

AgI nanoparticles were discovered to be an effectual heterogeneous nanocatalyst for the preparation of (amidoalkyl)naphthol and oxazine derivatives under solvent-free conditions. The advantages of the present approach are short reaction times, moderate te

Full text of DOI:10.1007/s00706-014-1184-y

Monatsh Chem
DOI 10.1007/s00706-014-1184-y
ORIGINAL PAPER
AgI nanoparticles as a remarkable catalyst in the synthesis
of (amidoalkyl)naphthol and oxazine derivatives: an eco-friendly
approach
•
Javad Safaei Ghomi Safura Zahedi
•
Mohammad Ali Ghasemzadeh
Received: 29 August 2013 / Accepted: 13 February 2014
Ó Springer-Verlag Wien 2014
Abstract AgI nanoparticles were discovered to be an
effectual heterogeneous nanocatalyst for the preparation of
(amidoalkyl)naphthol and oxazine derivatives under sol-
vent-free conditions. The advantages of the present
approach are short reaction times, moderate temperature,
premier yields, eco-friendly reaction conditions, simple
purification and good reusability of the catalyst.
economical and mild reagent for the synthesis of highly
functionalized oxazines [19].
Compounds containing 1,3-amino-oxygenated func-
tional groups have been found in various important natural
products and potent drugs including a number of nucleo-
side antibiotics and HIV protease inhibitors, such as
ritonavir and lipinavir [20]. As well, 1-(amidoalkyl)-2-
naphthols can be converted to 1-(aminomethyl)-2-naph-
thols by an amide hydrolysis reaction, which displays
depressor and bradycardia effects in humans [21, 22].
Multicomponent condensation of aldehydes, 2-naphthol
and acetonitrile or different amides affords 1-(amidoalkyl)-
2-naphthols in the presence of Lewis or Brønsted acids
such as dodecylphosphonic acid (DPA) [23], H2NSO3H
[24], oxalic acid [25], Fe(HSO4)3 [26], Sr(OTf)2 [27], I2
[28], K5CoW12O40Á3H2O [29], HPMo [30], Yb(OTf)3 in
ionic liquid [31], Indion-130 [32], montmorillonite K10
[33], TMSCl/NaI [34], Al2O3-HClO4 [35], InCl3 [36],
2,4,6-trichloro-1,3,5-triazine [37], CuPW and CuPMo [38],
FeCl3/SiO2 [39], H4SiW12O40 [40], CPTS [41], TrCl [42],
boric acid [43] and POCl3/Na2B4O7 [44].
Keywords Nanoparticles Á 2-Naphthol Á
Solvent-free conditions Á Oxazine Á
Multicomponent reactions
Introduction
In recent years, oxazines have been considered because of
their various ranges of biological properties such as antibi-
otic [1], antitumor agent [2], analgesic [3] and anticonvulsant
[4]. In addition, benzo-1,3-oxazines are biologically active
as anti-malarial [5], antianginal [6], antihypertensive [7] and
potent antirheumatic agents [8]. Recently, some procedures
have been reported for the preparation of naphtha-oxazine
derivatives using various catalysts such as p-TSA [9],
[bmim]Br [10], TMSCl/NaI [11], HClO4/SiO2 [12], ZnO
nanoparticles [13], Cu nanoparticles [14], TMSCl [15], thi-
amine hydrochloride [16], I2 [17] and montmorillonite [18].
In addition, the Vilsmeier-Haack reagent is an efficient,
According to the above-mentioned importance of oxa-
zines and (amidoalkyl)-2-naphthols, synthesis of oxazine
and (amidoalkyl)-2-naphthol derivatives based on safety
procedures is of principal interest for generating these
products under mild conditions endured by sensitive
functional groups from both synthetic and environmental
points of view.
In modern science, one of the growing and important
fields is nanotechnology. Because of different physical and
chemical properties of nano-sized catalysts in comparison
with bulk material, they attract interest from different
researcher areas. Since the particles are in small size, the
surface area exposed to the reactant is maximized, thus
allowing more reactions to occur at the same time; hence,
J. Safaei Ghomi (&) Á M. A. Ghasemzadeh
Department of Chemistry, Qom Branch, Islamic Azad
University, Qom, Islamic Republic of Iran
e-mail: safaei@kashanu.ac.ir
S. Zahedi
Department of Organic Chemistry, Faculty of Chemistry,
University of Kashan, 51167 Kashan, Islamic Republic of Iran
123

J. Safaei Ghomi et al.
the process is speeded up. Among various metal nano-
structures, silver nanoparticles have received significant
attention owing to their unusual properties and potential
applications in diverse fields [45]. In particular, advantages
of silver iodide nanoparticles are available, including mild
reaction conditions to produce high yields of products in
short reaction times compared to traditional catalysts, and
they can also be recycled [46]. Recently, catalysis by AgI
nanoparticles (NPs) and related compounds as nanocata-
lysts has become a field of increasing importance.
Then, the prepared (amidoalkyl)naphthols were reacted
with Vilsmeier reagent in the presence of AgI NPs to give
highly substituted functionalized oxazine derivatives
(Scheme 1).
Results and discussion
For initiating optimization of the reaction conditions, we
selected model reactions. Model 1: one-pot three-compo-
nent condensation of acetamide, benzaldehyde and
2-naphthol; model 2: reaction of 2-naphthol, benzaldehyde
and urea; model 3: cyclization of N-[(phenyl)(2-hydroxy-
naphthalen-1-yl)methyl]acetamide (Scheme 2).
In order to achieve more efficient synthetic processes,
minimize by-products and decrease the number of separate
reaction steps, we have tried to develop a clean and envi-
ronment-friendly approach to the synthesis of
(amidoalkyl)naphthol and oxazine derivatives with high
yields using AgI NPs as catalyst. The treatment of
2-naphthol, aldehyde and urea provided the synthesis of
naphtho[1,2-e][1,3]oxazinones and 2-naphthol, aldehyde
and acetamide resulted in 1-(amidoalkyl)-2-naphthols.
To test the efficiency of the catalytic activity, we choose
to focus our initial studies on the above-mentioned model
reactions in the presence of different nanocatalysts, such as
AgBr, CuCl, NiO, bulk AgI and AgI NPs (Table 1). As
indicated in Table 1, AgI was selected as the interesting
Scheme 1
Scheme 2
CHO
H
N
O
O
OH
Model (1)
+
+
O
H2N
NH2
4a
CHO
CHO
H
O
NHAc
OH
N
Model (2)
OH
Model (3)
CHO
+
+
H3C
NH2
O
6a
7a
123

AgI nanoparticles as a remarkable catalyst
Table 1 Comparison of
Product
Catalyst
Time/min
Yielda/%
catalytic activity of various
catalysts in model reactions
None
AgI
120
30
60
75
65
5
0
77
68
59
62
89
NHAc
OH
AgBr
NiO
CuCl
AgI NPs
6a
4a
None
AgI
120
45
67
80
74
8
0
74
66
55
59
90
H
N
O
AgBr
NiO
O
CuCl
AgI NPs
None
AgI
180
44
65
59
50
20
86
79
69
63
73
88
CHO
CHO
H
N
AgBr
NiO
O
CuCl
AgI NPs
7a
a
Yields refer to isolated
products
catalyst because when it was used replacing bulk AgI, the
yield of the desired product was maximized.
stretching vibration of SDS (sodium dodecyl sulfonate) can
be seen at 2,923 cm-1. The appearance of this peak suggests
that a trace amount of SDS has been coated on the surface of
AgI nanoparticles.
Characterization of the AgI NPs structure was gained by
SEM, XRD and FT-IR spectra. The SEM images of AgI
nanoparticles are depicted in Fig. 1. These results show
that spherical AgI nanoparticles were obtained from
AgNO3 and KI with particle size in the range of 40–50 nm
under ultrasound power.
In another effort, we have investigated the effect of
different solvents and also solvent-free conditions for the
preparation of products 4a and 6a. Afterwards, it was
concluded that solvent-free conditions were the best choice
for the synthesis of these organic compounds. As nanoAgI
was preferred as the most suitable catalyst for these reac-
tions under solvent-free conditions, we then tried to
optimize the amount of catalyst for the model reactions.
Our optimization studies disclosed that the yields increased
smoothly with catalyst load up to 0.03 g and then remained
unchanged to 0.05 g (Table 2). With these results, we
extended our work to various aldehydes, and all of the
results are shown in Tables 3 and 4.
The XRD pattern of AgI nanoparticles is shown in
Fig. 2. All reflection peaks in Fig. 2 can be readily indexed
to the pure cubic phase of AgI with the F-43 m space group
(JCDPS no. 78-0641). THe Debye–Scherrer equation
(D = Kk/bcosh) is used to calculate the crystallite size
diameter (D) of the AgI nanoparticles, where b (FWHM,
full-width at half-maximum or half-width) is in radian and
h is the position of the maximum of diffraction peak, K is
the so-called shape factor, which usually takes a value of
˚
about 0.9, and k is the X-ray wavelength (1.5406 A for Cu
Heterogeneous catalysts are useful because of the ability
to reuse of them to reduce waste. In order to study the
stability of our catalyst, the reaction was run successively
with the same catalyst in the same reaction. Figure 4 shows
the results of this survey in the model reaction 1 in the
presence of AgI NPs. After completion of the reaction, the
catalyst was washed well with chloroform and methanol
Ka). Crystallite size of AgI has been found to be 48 nm.
Figure 3 shows the FT-IR spectrum of AgI nanoparticles.
The broad peak at 3,436 and 1,628 cm-1 can be attributed to
the (OH) stretching and bending vibrations, respectively;
these peaks indicate the presence of physisorbed water
linked to nanoparticles. The peak corresponding to CH2
123

J. Safaei Ghomi et al.
Fig. 1 SEM image of AgI
nanoparticles
Fig. 2 The XRD pattern of
silver iodide nanoparticles
Fig. 3 FT-IR spectrum of AgI
nanoparticles
and dried at 70 °C for 10 h. Then the filtered catalyst was
used several times with a slightly decreased activity as
shown in Fig. 4. It could thus be concluded that AgI NPs
with high activity and good reusability could be a satisfy-
ing catalyst for these reactions.
Bruker 400 MHz spectrometer with CDCl3 or DMSO-d6 as
solvent and TMS as internal standard. CHN compositions
were measured by a Carlo ERBA Model EA 1108 analyzer.
Powder X-ray diffraction (XRD) was carried out on a
Philips diffractometer of the X’pert Company with mono-
˚
chromatized Cu Ka radiation (k = 1.5406 A). Microscopic
morphology of products was visualized by SEM (LEO
1455VP). The mass spectra were recorded on a Joel D-30
instrument at an ionization potential of 70 eV.
Experimental
All organic materials were purchased commercially from
Sigma-Aldrich and Merck and were used without further
purification. All melting points were determined in capil-
lary tubes on a Boetius melting point microscope. FT-IR
spectra were recorded with KBr pellets using a Magna-IR
spectrometer 550 Nicolet. NMR spectra were recorded on a
General procedure for the preparation of silver iodide
nanoparticles
A solution of 0.415 g KI (25 9 10-4 mol) in 25 cm3 dis-
tillated water was added dropwise to a solution of 0.425 g
123

AgI nanoparticles as a remarkable catalyst
precipitate was separated by centrifugation and washed
with distillated water and ethanol to remove impurities for
several times and then dried.
Table 2 Effect of solvent, temperature and catalyst load for prepa-
ration of products 4a, 6a and 7a
Product Catalyst/g Solvent
T/oC
Time/min Yielda/%
4a
0.05
0.05
0.05
0.05
0.01
0.02
0.03
0.03
0.03
0.03
0.03
0.05
0.05
0.05
0.01
0.02
0.03
0.03
0.03
0.05
0.03
0.05
0.05
0.05
0.01
0.02
0.03
0.05
0.03
EtOH
Reflux 150
Reflux 120
Reflux 100
48
General procedure for the preparation
CH3CN
CH2Cl2
53
of naphthooxazinones 4a-4i
42
Solvent-free 140
Solvent-free r.t.
Solvent-free 110
8
240
120
90
A mixture of b-naphthol (0.01 mol), aldehyde (0.01 mol),
urea (0.012 mol) and 0.03 g AgI NPs was finely ground
and heated with stirring at 140 °C in an oil bath. The
reaction was monitored by TLC. After cooling, the reaction
mixture was dissolved in ethyl acetate and the mixture
stirred for 5 min. The suspended solution was filtered and
the heterogeneous catalyst was recovered. The ethyl ace-
tate was evaporated and the crude product crystallized from
MeOH to afford the pure product.
No reaction
15
EtOH
Reflux 140
15
Solvent-free 110
Solvent-free 140
Solvent-free 140
Solvent-free 160
120
8
23
90
15
8
90
90
6a
EtOH
Reflux 150
Reflux 120
Reflux 100
54
CH3CN
CH2Cl2
66
44
General procedure for the synthesis
Solvent-free r.t.
Solvent-free 100
240
120
No reaction
of (amidoalkyl)naphthols 6a-6m
17
EtOH
Reflux 120
15
A mixture of 0.14 g b-naphthol (1 mmol), aldehyde
(1 mmol), 0.07 g acetamide (1.2 mmol) and 0.03 g AgI
NPs was finely ground and heated with stirring at 110 °C in
an oil bath, and the reaction was monitored by TLC. After
cooling, the reaction mixture was dissolved in hot ethanol
and the mixture stirred for 5 min. The reaction mixture was
filtered, and the heterogeneous catalyst was recovered.
Then the crude product was crystallized from EtOH (15 %)
to afford the pure product. The products were characterized
by comparison of their physical data with those of known
compounds unless otherwise mentioned.
Solvent-free 50
Solvent-free 110
Solvent-free 110
Solvent-free 140
Solvent-free r.t.
Solvent-free 40
Solvent-free 50
Solvent-free 60
Solvent-free 60
Solvent-free 70
Solvent-free 70
Solvent-free 80
120
5
35
89
5
89
5
89
7a
180
120
90
70
65
20
20
20
No reaction
33
55
69
73
88
88
88
General procedure for the synthesis of 1,3-oxazines
a
Isolated yields
7a-7m
Table 3 Preparation of naphthoxazine-3-one derivatives
Products Ar
Time/min Yielda/% M.p. [References]
To a solution of acetamidonaphthols 6 (1 mmol) in
DMF (1.2 equiv) and 0.03 g AgI NPs, POCl3 (0.8 eq-
iuv) was added dropwise (15 min) at 0 °C, and the
reaction mixture was allowed to reach room tempera-
ture. Then the reaction mixture was stirred at 70 °C for
20 min. After completion of the reaction, it was
allowed to cool to room temperature. The reaction
mixture was filtered, and the heterogeneous catalyst was
recovered. The filtrate was poured into crushed ice and
refrigerated overnight. The solution was neutralized
with sodium acetate, and the crude compound was
extracted with dichloromethane (3 9 10 cm3) and
washed with water (3 9 5 cm3). The organic layer was
dried over anhydrous sodium sulfate and concentrated
under reduced pressure. The crude product was purified
through crystallization from EtOH to afford the pure
product.
4a
4b
4c
4d
4e
4f
4g
4h
4i
C6H5
8
15
12
6
90
82
78
90
95
79
92
80
80
217–219 [14]
189–190 [13]
163–165 [13]
217–218 [14]
204–206 [14]
206–208
4-MeOC6H4
4-MeC6H4
4-BrC6H4
4-ClC6H4
3-MeC6H4
4-iPrC6H4
6
12
15
171–173 [11]
218–219
4-Me2NC6H4 20
Thiophen-2-yl
7
209–210 [12]
a
Yields refer to the pure isolated products
AgNO3 (25 9 10-4 mol) in 25 cm3 distillated water under
ultrasound power in the presence of 0.2 g sodium dodecyl
sulfate (SDS) as surfactant. The yellow as-synthesized
123

J. Safaei Ghomi et al.
Table 4 Synthesis of
(amidoalkyl)naphthols and 1,3-
oxazines
Entry Aldehyde (R)
6
Time/ Yielda/% M.p./°C
7
Time/ Yielda/% M.p./°C
min
min
[References]
1
C6H5
6a
6b
6c
6d
6e
6f
5
3
89
95
92
90
89
80
84
85
90
80
85
82
245-–246 [35] 7a 20
247–249 [33] 7b 20
178–180 [33] 7c 20
223–225 [33] 7d 20
200–202 [31] 7e 20
88
92
92
88
80
79
79
82
88
87
85
82
235–237
263–264
255–257
232–234
209–210
219–221
205–206
228–229
237–239
241–243
250–252
245–247
2
4-NO2C6H4
2-NO2C6H4
4-ClC6H4
2,4-Cl2C6H3
4-MeC6H4
4-MeOC6H4
4-iPrC6H4
4-BrC6H4
4-OHC6H4
3
4
4
4
5
5
6
10
222–223 [31] 7f
183–185 [31] 7g 20
220–222 7h 20
227–229 [27] 7j 20
7k 20
7l 20
7m 20
20
7
6g 15
6h 20
8
9
6j
6k 15
17
4
10
11
12
226–227
227–229
210–220
2,4-(MeO)2C6H3 6l
a
Yields refer to isolated
products
1-Naphthyl
6m 15
Ar–H), 7.95 (t, J = 7.6 Hz, 1H, Ar–H), 8.68 (s, 1H, NH)
ppm; 13C NMR (100 MHz, DMSO-d6): d = 31.5 (CH3),
53.9 (CH), 112.8, 115.1, 117.3, 123.1, 125.4, 126.4, 127.7,
128.1, 129.0, 130.3, 130.8, 130.9, 147.7, 150.0, 150.4 (CO)
ppm; MS (EI): m/z = 318 (M?).
100
80
60
40
20
0
N-[(2-Hydroxynaphthalen-1-yl)(4-isopropylphenyl)-
methyl]acetamide (6h, C22H23NO2)
IR (KBr): vꢀ = 3,405, 3,168, 3,058, 1,633, 1,515, 1,438, 1,370,
1,330, 1,275, 1,168, 986, 816, 744 cm-1; 1H NMR (400 MHz,
DMSO-d6): d = 1.14 (d, J = 7.0 Hz, 6H), 1.95 (s, 3H), 2.81
(m, J = 7.0 Hz, 1H), 7.06–7.11 (m, 5H), 7.19 (t, J = 7.2 Hz,
1H), 7.27 (t, J = 7.6 Hz, 1H), 7.36 (t, J = 7.6 Hz, 1H), 7.75
(d, J = 7.6 Hz, 1H), 7.80 (d, J = 7.8 Hz, 1H), 7.88 (d,
J = 7.8 Hz, 1H), 8.43 (d, J = 8.4 Hz, 1H), 9.96 (s, 1H) ppm;
13C NMR (100 MHz, DMSO-d6): d = 23.1, 24.4, 33.4, 48.3,
119.0, 119.4, 122.8, 123.0, 123.6, 126.3, 126.6, 126.7, 128.0,
128.9, 129.0, 129.5, 132.8, 140.3, 146.6, 153.5, 169.5 ppm;
MS (EI): m/z = 333 (M?).
1
2
3
4
5
6
7
Fig. 4 Recoverability of AgI nanoparticles
1,2-Dihydro-1-(3-methylphenyl)-3H-naphtho[1,2-e]-
[1,3]oxazine-3-one (4f, C19H15NO2)
IR (KBr): vꢀ = 3,264, 1,746, 1,515, 815, 745 cm-1
;
1H
N-[(2-Hydroxynaphthalen-1-yl)(4-hydroxyphenyl)-
methyl]acetamide (6k, C19H17NO3)
NMR (400 MHz, DMSO-d6): d = 2.21 (s, 3H, CH3), 6.12
(s, 1H, CH), 7.04–7.12 (m, 3H, Ar–H), 7.21 (t, 1H, Ar–H),
7.35–7.48 (m, 3H, Ar–H), 7.80 (d, J = 7.6 Hz, 1H, Ar–H),
7.93 (d, J = 7.6 Hz, 1H, Ar–H), 7.98 (d, J = 7.6 Hz, 1H,
Ar–H), 8.80 (s, 1H, NH) ppm; 13C NMR (100 MHz,
DMSO-d6): d = 21.5 (CH3), 54.3 (CH), 114.5, 115.0,
116.5, 117.3, 123.5, 124.6, 125.5, 127.8, 129.1, 129.2,
129.3, 130.7, 130.9, 138.6, 143.3, 147.9, 149.8 (CO) ppm;
MS (EI): m/z = 289 (M?).
IR (KBr): vꢀ = 3,406, 3,180, 3,052, 1,616, 1,514, 1,438, 1,370,
1,330, 1,275, 1,168, 986, 813, 738 cm-1; 1H NMR (400 MHz,
DMSO-d6): d = 1.97 (s, 3H), 7.04–7.09 (m, 5H), 7.19 (t,
J = 7.2 Hz, 1H), 7.25 (t, J = 7.2 Hz, 1H), 7.36 (t,
J = 7.6 Hz, 1H), 7.77 (d, J = 7.6 Hz, 1H), 7.80 (d,
J = 7.8 Hz, 1H), 7.88 (d, J = 7.8 Hz, 1H), 8.55 (d,
J = 8.4 Hz, 1H), 9.20 (s, 1H), 9.87 (s, 1H) ppm; 13C NMR
(100 MHz, DMSO-d6): d = 23.4, 48.5, 119.3, 120.1, 122.8,
123.0, 123.6, 126.3, 126.6, 126.7, 128.0, 128.9, 129.0, 129.5,
132.8, 140.3, 146.8, 153.2, 168.9 ppm; MS (EI): m/z = 307
(M?).
1,2-Dihydro-1-(4-dimethylaminophenyl)-3H-naphtho-
[1,2-e][1,3]oxazine-3-one (4h, C20H18N2O2)
IR (KBr): vꢀ = 3,224, 1,734, 1,600, 850, 730 cm-1 1H
;
N-[(2,4-Dimethoxyphenyl)(2-hydroxynaphthalen-1-yl)-
methyl]acetamide (6l, C21H21NO4)
NMR (400 MHz, DMSO-d6): d = 2.80 (s, 6H, CH3), 6.02
(s, 1H, CH), 6.62 (d, J = 7.8 Hz, 2H, Ar–H), 7.08 (d,
J = 7.8 Hz, 2H, Ar–H), 7.35 (d, J = 7.6 Hz, 2H, Ar–H),
7.45 (t, J = 7.6 Hz, 2H, Ar–H), 7.78 (d, J = 7.6 Hz, 1H,
IR (KBr): vꢀ = 3,406, 3,139, 1,646, 1,521, 1,506, 1,442,
1,400, 1,374, 1,329, 1,264, 1,242, 1,091, 1,068, 818, 764,
123

AgI nanoparticles as a remarkable catalyst
1
659 cm-1; H NMR (400 MHz, DMSO-d6): d = 1.90 (s,
7.88 (d, J = 7.8 Hz, 1H), 7.96 (d, J = 7.8 Hz, 1H), 10.01 (br
s, 2H, CHO), 12.26 (s, 1H) ppm; 13C NMR (100 MHz,
CDCl3): d = 48.9, 101.1, 113.7, 118.4, 123.3, 125.7, 127.3,
128.5, 128.9, 129.6, 130.4, 131.7, 131.8, 132.9, 134.5, 143.2,
144.5, 148.2, 162.3, 186.8 ppm; MS (EI): m/z = 374 (M?).
3H), 3.72 (s, 6H), 6.89–7.01 (m, 2H), 7.17 (d, J = 8.4 Hz,
1H), 7.29 (t, J = 7.2 Hz, 1H), 7.33–7.39 (m, 2H), 7.46 (d,
J = 8.4 Hz, 1H), 7.74-7.79 (m, 3H), 8.55 (d, J = 7.6 Hz,
1H), 9.98 (s, 1H) ppm; 13C NMR (100 MHz, DMSO-d6):
d = 23.3, 48.7, 55.2, 55.9, 110.4, 118.6, 118.8, 123.2,
126.9, 128.5, 129.1, 129.5, 129.7, 130.5, 131.6, 132.8,
144.9, 149.3, 153.7, 153.9, 170.2 ppm; MS (EI): m/
z = 351 (M?).
[1-(4-Chlorophenyl)-1,2-dihydro-3H-naphtho-
[1,2-e][1,3]oxazine-3-ylidene]malonaldehyde
(7d, C21H14ClNO3)
IR (KBr): vꢀ = 3,406, 1,627, 1,515, 1,453, 1,221,
;
831 cm-1 1H NMR (400 MHz, CDCl3): d = 6.21 (s,
N-[(1-Naphthyl)(2-hydroxynaphthalen-1-yl)methyl]-
acetamide (6m, C23H19NO2)
1H), 7.12–7.14 (d, J = 7.6 Hz, 2H), 7.19–7.25 (d,
J = 7.6 Hz, 2H), 7.46–7.49 (t, J = 7.7 Hz, 3H), 7.61 (d,
J = 7.8 Hz, 1H), 7.88 (d, J = 7.7 Hz, 1H), 7.96 (d,
J = 7.7 Hz, 1H), 10.01 (br s, 2H, CHO), 12.28 (s, 1H)
ppm; 13C NMR (100 MHz, CDCl3): d = 50.4, 101.1,
113.4, 117.9, 123.3, 125.7, 127.3, 128.5, 128.9, 129.6,
130.4, 131.7, 131.8, 132.9, 134.5, 143.6, 144.9, 148.4,
163.1, 186.7 ppm; MS (EI): m/z = 363 (M?).
IR (KBr): vꢀ = 3,412, 3,173, 3,060, 1,642, 1,572, 1,514,
1,437, 1,400, 1,374, 1,332, 1,274, 1,224, 1,172, 932, 813,
1
745 cm-1; H NMR (400 MHz, DMSO-d6): d = 1.90 (s,
3H), 7.22–7.29 (m, 3H), 7.39–7.44 (m, 4H), 7.61 (d,
J = 8.4 Hz, 1H), 7.70–7.80 (m, 3H), 7.91–8.03 (d,
J = 7.6 Hz, 3H), 8.70 (d, J = 7.6 Hz, 1H), 10.01 (s, 1H)
ppm; 13C NMR (100 MHz, DMSO-d6): d = 22.9, 47.4,
117.6, 118.7, 119.3, 122.8, 123.5, 123.9, 125.5, 125.7, 125.9,
126.5, 126.7, 127.9, 129.0, 129.2, 129.7, 131.5, 133.3, 134.0,
137.8, 153.8, 168.9 ppm; MS (EI): m/z = 341 (M?).
[1-(2,4-Dichlorophenyl)-1,2-dihydro-3H-naphtho-
[1,2-e][1,3]oxazine-3-ylidene]malonaldehyde
(7e, C21H13Cl2NO3)
(1,2-Dihydro-1-phenyl-3H-naphtho[1,2-e][1,3]-
IR (KBr): vꢀ = 3,409, 1,620, 1,510, 1,449, 1,220,
826 cm-1 1H NMR (400 MHz, CDCl3): d = 6.22 (s,
;
oxazine-3-ylidene)malonaldehyde (7a, C21H15NO3)
IR (KBr): vꢀ = 3,398, 1,629, 1,515, 1,453, 1,221, 828 cm-1
;
1H), 7.19–7.25 (d, J = 7.6 Hz, 2H), 7.49–7.62 (d,
J = 7.7 Hz, 2H), 7.65–7.70 (d, J = 7.7 Hz, 2H),
7.89–7.93 (d, J = 7.8 Hz, 2H), 8.11 (s, 1H), 10.03 (br s,
2H, CHO), 12.28 (s, 1H) ppm; 13C NMR (100 MHz,
CDCl3): d = 50.3, 101.3, 113.4, 117.2, 123.1, 124.3,
126.8, 128.8, 128.9, 129.6, 130.1, 131.7, 131.8, 131.9,
134.5, 143.0, 144.8, 148.6, 162.1, 186.7 ppm; MS (EI): m/
z = 397 (M?).
1H NMR (400 MHz, CDCl3): d = 6.24 (s, 1H), 7.13–7.15
(d, J = 7.6 Hz, 2H), 7.17–7.21 (d, J = 7.6 Hz, 2H), 7.48-
7.49 (t, J = 7.6 Hz, 3H), 7.76 (t, J = 7.8 Hz, 2H), 7.90 (d,
J = 7.8 Hz, 1H), 7.97 (d, J = 7.8 Hz, 1H), 10.04 (br s, 2H,
CHO), 12.33 (s, 1H) ppm; 13C NMR (100 MHz, CDCl3):
d = 50.6, 101.1, 113.6, 118.3, 123.2, 124.7, 127.3, 128.8,
129.6, 130.4, 131.7, 132.9, 134.5, 143.6, 144.9, 148.4, 162.3,
186.9 ppm; MS (EI): m/z = 329 (M?).
[1,2-Dihydro-1-(4-methylphenyl)-3H-naphtho-
[1,2-e][1,3]oxazine-3-ylidene]malonaldehyde
(7f, C22H17NO3)
[1,2-Dihydro-1-(4-nitrophenyl)-3H-naphtho-
[1,2-e][1,3]oxazine-3-ylidene]malonaldehyde
(7b, C21H14N2O5)
IR (KBr): vꢀ = 3,408, 1,632, 1,515, 1,453, 1,221, 828 cm-1
IR (KBr): vꢀ = 3,408, 1,628, 1,515, 1,453, 1,219,
;
821 cm-1 1H NMR (400 MHz, CDCl3): d = 2.30 (s,
;
1H NMR (400 MHz, CDCl3): d = 6.23 (s, 1H), 7.10–7.14
(d, J = 7.6 Hz, 2H), 7.17–7.21 (d, J = 7.6 Hz, 2H),
7.46–7.49 (t, J = 7.6 Hz, 3H), 7.61 (d, J = 7.8 Hz, 1H),
7.88 (d, J = 7.8 Hz, 1H), 7.96 (d, J = 7.7 Hz, 1H), 10.02 (br
s, 2H, CHO), 12.25 (s, 1H) ppm; 13C NMR (100 MHz,
CDCl3): d = 50.3, 101.3, 113.4, 117.9, 123.3, 125.7, 127.3,
128.5, 128.9, 129.6, 130.4, 131.7, 131.8, 132.9, 134.5, 143.6,
144.9, 148.4, 162.6, 187.0 ppm; MS (EI): m/z = 374 (M?).
3H), 6.20 (s, 1H), 7.10–7.13 (d, J = 7.6 Hz, 2H),
7.15–7.20 (d, J = 7.6 Hz, 2H), 7.42–7.48 (t, J = 7.7 Hz,
3H), 7.58 (d, J = 7.8 Hz, 1H), 7.84 (d, J = 7.7 Hz, 1H),
7.97 (d, J = 7.7 Hz, 1H), 10.03 (br s, 2H, CHO), 12.26 (s,
1H) ppm; 13C NMR (100 MHz, CDCl3): d = 23.3, 50.2,
101.1, 113.4, 117.9, 123.3, 125.7, 127.3, 128.5, 128.9,
129.6, 130.4, 131.7, 131.8, 132.9, 134.5, 142.9, 144.4,
147.8, 162.2, 186.8 ppm; MS (EI): m/z = 343 (M?).
[1,2-Dihydro-1-(2-nitrophenyl)-3H-naphtho-
[1,2-e][1,3]oxazine-3-ylidene]malonaldehyde
(7c, C21H14N2O5)
IR (KBr): vꢀ = 3,399, 1,630, 1,515, 1,453, 1,221, 825 cm-1
[1,2-Dihydro-1-(4-methoxyphenyl)-3H-naphtho-
[1,2-e][1,3]oxazine-3-ylidene]malonaldehyde
(7g, C22H17NO4)
IR (KBr): vꢀ = 3,403, 1,624, 1,513, 1,449, 1,220, 819 cm-1
;
;
1H NMR (400 MHz, CDCl3): d = 6.23 (s, 1H), 7.10–7.14
(d, J = 7.6 Hz, 2H), 7.17–7.21 (t, J = 7.6 Hz, 2H),
7.46–7.49 (t, J = 7.7 Hz, 3H), 7.61 (d, J = 7.8 Hz, 1H),
1H NMR (400 MHz, CDCl3): d = 3.48 (s, 3H), 6.21 (s, 1H),
7.18–7.26 (d, J = 7.6 Hz, 2H), 7.45–7.60 (d, J = 7.7 Hz,
2H), 7.63–7.72 (d, J = 7.8 Hz, 2H), 7.87–7.91 (d,
123

J. Safaei Ghomi et al.
J = 7.8 Hz, 2H), 8.08 (s, 1H), 10.02 (br s, 2H, CHO), 12.24
(s, 1H) ppm; 13C NMR (100 MHz, CDCl3): d = 33.5, 50.1,
101.1, 113.4, 117.2, 123.1, 124.3, 126.8, 128.8, 128.9, 129.6,
130.4, 131.7, 131.8, 131.9, 134.2, 143.5, 145.4, 148.4, 162.2,
187.2 ppm; MS (EI): m/z = 359 (M?).
s, 2H, CHO), 12.28 (s, 1H) ppm; 13C NMR (100 MHz,
CDCl3): d = 50.1, 53.5, 53.6, 101.2, 113.4, 117.2, 123.1,
124.3, 126.8, 128.8, 128.9, 129.6, 130.2, 131.7, 131.8,
131.9, 134.5, 143.0, 144.8, 148.4, 163.6, 186.9 ppm; MS
(EI): m/z = 389 (M?).
[1,2-Dihydro-1-(4-isopropylphenyl)-3H-naphtho-
[1,2-e][1,3]oxazine-3-ylidene]malonaldehyde
(7h, C24H21NO3)
[1,2-Dihydro-1-(naphthalen-1-yl)-3H-naphtho-
[1,2-e][1,3]oxazine-3-ylidene]malonaldehyde
(7m, C25H17NO3)
IR (KBr): vꢀ = 3,407, 1,619, 1,513, 1,454, 1,220, 834 cm-1
;
IR (KBr): vꢀ = 3,404, 1,623, 1,510, 1,449, 1,220,
;
826 cm-1 1H NMR (400 MHz, CDCl3): d = 7.20-7.27
1H NMR (400 MHz, CDCl3): d = 1.19 (d, J = 7.0 Hz, 6H),
2.84 (m, J = 7.0 Hz, 1H), 6.20 (s, 1H), 7.19–7.25 (d,
J = 7.6 Hz, 3H), 7.49–7.62 (t, J = 7.7 Hz, 3H), 7.89–7.93
(t, J = 7.6 Hz, 2H), 8.12 (m, 2H), 10.02 (br s, 2H, CHO),
12.26 (s, 1H) ppm; 13C NMR (100 MHz, CDCl3): d = 23.2,
33.5, 50.3, 101.3, 113.4, 117.2, 123.1, 124.3, 126.8, 128.8,
128.9, 129.6, 130.1, 131.7, 131.8, 131.9, 134.5, 143.0, 144.8,
148.6, 162.1, 186.7 ppm; MS (EI): m/z = 371 (M?).
(m, 3H), 7.36–7.42 (m, 4H), 7.61 (d, J = 8.4 Hz, 1H),
7.70–7.82 (m, 3H), 7.89–8.01 (d, J = 7.6 Hz, 3H), 8.77 (d,
J = 7.6 Hz, 1H), 10.01 (br s, 2H, CHO), 12.27 (s, 1H)
ppm; 13C NMR (100 MHz, DMSO-d6): d = 53.4, 101.1,
118.7, 119.3, 122.8, 123.5, 123.9, 125.5, 125.7, 125.9,
126.5, 126.7, 127.9, 129.0, 129.2, 129.7, 131.5, 133.3,
134.0, 137.8, 144.8, 148.4, 163.6, 186.9 ppm; MS (EI): m/
z = 379 (M?).
[1-(4-Bromophenyl)-1,2-dihydro-3H-naphtho-
[1,2-e][1,3]oxazine-3-ylidene]malonaldehyde
(7j, C21H14BrNO3)
Acknowledgments The authors are grateful to University of
Kashan for supporting this work by Grant No: 159196/XX.
IR (KBr): vꢀ = 3,410, 1,620, 1,513, 1,446, 1,220,
815 cm-1 1H NMR (400 MHz, CDCl3): d = 6.20 (s,
;
1H), 7.13–7.15 (d, J = 7.6 Hz, 2H), 7.18–7.20 (d,
J = 7.6 Hz, 2H), 7.46–7.49 (t, J = 7.7 Hz, 3H), 7.61 (d,
J = 7.8 Hz, 1H), 7.88 (d, J = 7.8 Hz, 1H), 7.96 (d,
J = 7.7 Hz, 1H), 10.01 (br s, 2H, CHO), 12.27 (s, 1H)
ppm; 13C NMR (100 MHz, CDCl3): d = 50.5, 101.1,
113.3, 118.2, 123.5, 124.4, 127.3, 128.8, 128.9, 129.6,
130.2, 131.7, 131.8, 131.9, 134.5, 143.6, 145.4, 148.6,
162.4, 186.8 ppm; MS (EI): m/z = 406 (M?).
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